WO2016072642A2 - Polyketone resin composition with excellent impact resistance - Google Patents

Polyketone resin composition with excellent impact resistance Download PDF

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Publication number
WO2016072642A2
WO2016072642A2 PCT/KR2015/011027 KR2015011027W WO2016072642A2 WO 2016072642 A2 WO2016072642 A2 WO 2016072642A2 KR 2015011027 W KR2015011027 W KR 2015011027W WO 2016072642 A2 WO2016072642 A2 WO 2016072642A2
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Prior art keywords
polyketone
bis
weight
composition
linear alternating
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PCT/KR2015/011027
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French (fr)
Korean (ko)
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WO2016072642A3 (en
Inventor
최종인
윤성균
김가영
김성환
Original Assignee
(주) 효성
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Priority claimed from KR1020140154626A external-priority patent/KR101664260B1/en
Priority claimed from KR1020140154620A external-priority patent/KR101664219B1/en
Priority claimed from KR1020140154617A external-priority patent/KR101611578B1/en
Priority claimed from KR1020140154613A external-priority patent/KR101664264B1/en
Priority claimed from KR1020140154624A external-priority patent/KR101646033B1/en
Priority claimed from KR1020140161993A external-priority patent/KR101611580B1/en
Priority claimed from KR1020140161994A external-priority patent/KR101664918B1/en
Priority claimed from KR1020140161977A external-priority patent/KR101655337B1/en
Priority claimed from KR1020140161992A external-priority patent/KR101664919B1/en
Priority claimed from KR1020140161978A external-priority patent/KR101655336B1/en
Priority claimed from KR1020140162006A external-priority patent/KR101706052B1/en
Priority claimed from KR1020140161982A external-priority patent/KR101664929B1/en
Priority claimed from KR1020140161976A external-priority patent/KR101675828B1/en
Priority claimed from KR1020140161988A external-priority patent/KR101664926B1/en
Priority claimed from KR1020140161981A external-priority patent/KR101684890B1/en
Priority claimed from KR1020140162017A external-priority patent/KR101675286B1/en
Priority claimed from KR1020140162011A external-priority patent/KR101684885B1/en
Priority claimed from KR1020140162004A external-priority patent/KR101706050B1/en
Priority claimed from KR1020150073984A external-priority patent/KR101705621B1/en
Priority claimed from KR1020150074020A external-priority patent/KR101716206B1/en
Priority claimed from KR1020150074024A external-priority patent/KR101716160B1/en
Priority claimed from KR1020150073977A external-priority patent/KR101705633B1/en
Priority claimed from KR1020150073978A external-priority patent/KR101705634B1/en
Priority claimed from KR1020150074028A external-priority patent/KR101716164B1/en
Priority claimed from KR1020150073975A external-priority patent/KR101705617B1/en
Priority claimed from KR1020150073989A external-priority patent/KR101807611B1/en
Priority claimed from KR1020150074035A external-priority patent/KR101716166B1/en
Priority claimed from KR1020150073981A external-priority patent/KR101705619B1/en
Priority claimed from KR1020150073985A external-priority patent/KR101705622B1/en
Priority claimed from KR1020150074032A external-priority patent/KR101734890B1/en
Priority claimed from KR1020150074023A external-priority patent/KR101716159B1/en
Application filed by (주) 효성 filed Critical (주) 효성
Publication of WO2016072642A2 publication Critical patent/WO2016072642A2/en
Publication of WO2016072642A3 publication Critical patent/WO2016072642A3/en

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Classifications

    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
    • A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
    • A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45C—PURSES; LUGGAGE; HAND CARRIED BAGS
    • A45C11/00—Receptacles for purposes not provided for in groups A45C1/00-A45C9/00
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J27/00—Cooking-vessels
    • A47J27/08—Pressure-cookers; Lids or locking devices specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L3/00—Supports for pipes, cables or protective tubing, e.g. hangers, holders, clamps, cleats, clips, brackets
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C5/00—Constructions of non-optical parts

Definitions

  • the present invention relates to a polyketone resin composition having excellent impact resistance, and more particularly, by blending a polyketone resin with glass fiber, an inorganic filler, a mineral reinforcing material, and the like, for a mask, a pipe holder, a transmission bracket, a bumper bracket, and an automobile.
  • junction box car wheel rim, bracket for power line, electronics cover, glasses frame, car air intake manifold, carrier of car front end module, car headlamp bezel, car ashtray, car multifunction switch, car speaker grill, car
  • the present invention relates to a polyketone resin composition applicable to various industrial parts such as a head restraint guide for a vehicle, a navigation base for an automobile, an automotive side molding, a hose connector, a stem bolt for an air conditioner, and the like.
  • the present invention relates to a polyketone composition having excellent mechanical properties, and more particularly, to a polyketone composition manufactured using a blend containing an amorphous semiaromatic polyamide or polyester in a polyketone resin and applicable to industrial parts. will be.
  • the present invention relates to a notebook lower housing manufactured by injection molding a polyketone resin composition, and more particularly to a notebook lower housing having excellent flexural modulus and low temperature impact strength by using a polyketone resin composition.
  • Polyketone (PK) is a material that has lower raw materials and polymerization process costs than general engineering plastic materials such as polyamide, polyester, and polycarbonate.
  • Polyketone (PK) has excellent properties such as heat resistance, chemical resistance, fuel permeability, and abrasion resistance. It is widely applied to.
  • polyketones or polyketone polymers There is a growing interest in a group of linear alternating polymers, consisting of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, known as polyketones or polyketone polymers.
  • U.S. Patent No. 4,880,903 discloses a linear alternating polyketone terpolymer consisting of carbon monoxide and ethylene and other olefinically unsaturated hydrocarbons, such as propylene.
  • the process for preparing polyketone polymers is usually a compound of a Group VIII metal selected from palladium, cobalt or nickel, and anions of non-hydro halogen strong-hydrohalogentic acid. Catalyst compositions produced from bidentate ligands of phosphorus, arsenic or antimones are used.
  • U.S. Pat.No. 4,843,144 describes a process for preparing polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of nonhydrohalogenic acid with a pKa of less than 6, and a catalyst that is a bidentate ligand of phosphorus. It is starting.
  • the mechanical properties of the polyketone blends are diversified in application fields of thermoplastics, and due to industrial demands for more excellent properties, studies on polyketone resin compositions having excellent tensile strength and impact strength are required.
  • Japanese Patent Laid-Open No. 11-71513 discloses a polyketone resin composition which is useful as a housing part and improves fluidity, heat resistance, organic solvent resistance and moldability.
  • This patent discloses the polyketone resin composition which contains 0.01-60 weight part of flame retardants with respect to 100 weight part of polyketone resin which mix
  • an organic bromide, an organophosphorus compound, etc. are used as a flame retardant.
  • flame retardants containing organic halogen (Halogen) is limited because of the use of environmental problems, and a lot of problems of smell and coloring occurs.
  • nylon resins, non-reinforced flame retardant ABS resins and flame retardant PC / ABS resins have low rigidity and are not suitable for the recent thinning requirements. Due to the mobility of electric and electronic devices such as personal computers, telephones, notebooks, and the like, development of housings having lightweight and high strength mechanical properties is required. For example, in the case of a notebook housing, a material is developed to solve the problem that a part is bent and comes into contact with an internal component, and the internal component is broken or the housing itself is destroyed. Japanese Patent Laid-Open No.
  • 2008-34823 discloses a technique for producing an electronic device housing by injection molding a thermoplastic resin member containing glass fibers by interposing a thermosetting resin member containing carbon fibers with an adhesive layer made of a nonwoven fabric of a thermoplastic resin.
  • the conventional carbon fiber reinforced thermoplastic resin composition can achieve high rigidity and light weight, but has a problem of being soft and brittle as a material for a housing.
  • An object of the present invention to provide a polyketone resin composition excellent in tensile strength and impact strength compared to the existing polyketone polymer to solve the above problems.
  • an object of the present invention is to provide a polyketone composition that can improve the bending characteristics while maintaining a certain level of tensile strength, impact strength compared to the existing polyketone composition.
  • an object of the present invention is to obtain a notebook bottom housing characterized by sufficient flexural modulus and excellent low temperature impact resistance by injection molding a polyketone composition.
  • the present invention to solve the above problems
  • a polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), the molecular weight distribution of 1.5 to 2.5, y / x of 0.03 to 0.3 linear alternating polyketone and glass fiber, inorganic filler, It provides a polyketone resin composition with improved impact resistance comprising a mineral reinforcing agent as a means for solving the problem.
  • the present invention may be prepared by further comprising a polyurethane resin, polycarbonate resin, polyamide 6 resin, rubber, ASA and sulfonamide plasticizer in order to solve the above problems more effectively.
  • the polyketone resin composition of the present invention is a glass fiber, inorganic filler, mineral reinforcing agent, polyurethane resin, polycarbonate resin, polyamide 6 resin, rubber, ASA and sulfonamide plasticizer relative to 100 parts by weight of the polyketone copolymer It is characterized in that it is added alone or mixed by 5 to 50 parts by weight.
  • the present invention consists of carbon monoxide and at least one olefinically unsaturated hydrocarbon, 60 to 90% by weight of alternating polyketone and 10 to 40% by weight of linear fiber having a residual amount of palladium catalyst of 5 to 50 ppm and a molecular weight distribution of 1.5 to 3.0. It provides a polyketone composition, characterized in that the blend is prepared by injection molding.
  • Preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bipolar compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And preparing a polyketone automobile air intake manifold by injection molding 100 wt% of the blend containing 60 to 90 wt% of the polyketone resin and 10 to 40 wt% of the glass fiber; Characterized in that the manufacturing method of the polyketone composition comprising a.
  • a mixed solvent including an alcohol (eg, methanol) and water
  • Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymer
  • Intrinsic viscosity is 1.0 ⁇ 2.0dl / g, the impact strength is 10 ⁇ 12kJ / m 2, provides a molded article made of a polyketone-polyurethane resin composition, characterized in that the resilience is 35% to 45% do.
  • the weight ratio of polyketone and glass fiber is 50:50 to 95: 5, and the glass fiber has a diameter of 10 ⁇ m, a length of 4 mm, and is coated with polyurethane, and a ligand of a catalyst composition used in polyketone polymerization.
  • the hardness is 95 or more, and the composition ratio of polycarbonate is 1% by weight to 30% by weight based on the total weight of the polyketone composition, and the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1, 3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and has an inherent viscosity of 1.0 to 2.0 dl / g, as a polyketone composition. Provides manufactured industrial parts.
  • the polyketone spectacle frame has a bending angle of 2 ° or less, and the intrinsic viscosity of the polyketone copolymer provides a polyketone spectacle frame, characterized in that 1.0dl / g to 2.0dl / g.
  • Polyketone high impact mask characterized in that the impact resistance of the polyketone mask is 80kJ / m2 or more, the retention of physical properties after moisture absorption of the polyketone is 85% or more relative to the physical properties before the moisture absorption, the catalyst composition used for the polymerization of polyketone Ligand is a poly (ketone) high impact, characterized in that ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) Provide a mask.
  • preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a double ligand compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And injection molding 100% by weight of the blend of 50 to 90% by weight of the polyketone resin and 10 to 50% by weight of the mineral reinforcing material to manufacture a polyketone pipe holder. It provides a method for producing a polyketone pipe holder comprising a.
  • Linear alternating polyketone polymer, sulfonamide plasticizer, polyurethane, ASA Anarylic Styrene Acrylonitrile consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon and having a residual amount of palladium catalyst of 50 ppm or less and a molecular weight distribution of 1.5 to 2.5 It is prepared by injection molding the blend, wherein the sulfonamide-based plasticizer, polyurethane and ASA is a shoe material, characterized in that 10 to 20% by weight, 15 to 20% by weight and 1 to 10% by weight, respectively, relative to the total blend
  • the ligand of the catalyst composition is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl Phosphine)
  • the flexural modulus is 7000 to 8500MPa to provide a shoe material, characterized in that.
  • Polyketone molded product characterized in that the moisture absorption rate is less than 1.0% at 50 °C, 90% relative humidity conditions, the impact strength is 15kJ / m2 or more, the content of the polyketone terpolymer is 50 to 90% by weight, The content of the glass fiber is 10 to 50% by weight and provides a polyketone molded product, characterized in that the polyketone molded product is an accelerator pedal.
  • the impact strength is 17 kJ / m 2 or more, the molecular weight distribution of the polyketone copolymer is 1.5 to 2.5, the ligand of the catalyst composition used in the polyketone polymerization is ((2,2-dimethyl-1,3-dioxane-5,5 -Diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and provides a polyketone transmission bracket characterized in that the tensile strength retention after moisture absorption of the polyketone transmission bracket is 80% or more.
  • a polyketone bumper bracket produced by injection molding a blend of linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon, polyamide 6 and rubber, wherein the polyketone is 40% by weight of the total blend. To 90% by weight, 5 to 40% by weight of polyamide 6 and 5 to 20% by weight of rubber, 70% by weight of polyketone, 22% by weight of polyamide 6 and 8% by weight of rubber.
  • the impact strength is 75 kJ / m2
  • the polyketone bumper bracket provides a polyketone bumper bracket, characterized in that the tensile strength retention of 75% or more in a 10% calcium chloride solution, the rubber is ethylene propylene diene monomer rubber.
  • the ligand of the catalyst composition used in the polymerization of a polyketone copolymer is characterized in that the impact strength at room temperature is 12 kJ / m 2 or more and the tensile strength retention after moisture absorption is 85% or more relative to the property before absorption.
  • an automotive junction box which is, 2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine).
  • the glass fiber and the inorganic filler are included in an amount of 20 to 50 parts by weight and 5.5 to 15.5 parts by weight, respectively, based on 100 parts by weight of the polyketone copolymer, and the inorganic filler is selected from calcium carbonate, magnesium sulfate, silicon carbide, and calcium oxide, and the catalyst composition.
  • Polyketone electronic device cover characterized in that the content of the glass fiber compared to the blend is 5 to 50% by weight, the product strain of the electronic device cover is less than 0.1%, the electronic device cover is a poly protective cover Provides ketone electronics cover.
  • the linear alternating polyketone is a lid for electrical and electronic products, characterized in that the molar ratio of ethylene and propylene is 9 to 24: 1, the lid for battery electronics has an impact strength of 15 kJ / m 2 or more, 50 °C, relative humidity The moisture absorption rate is less than 1.5% at 90% RH, and the tensile strength measured at 50 ° C and 90% RH is maintained at a level of 85% or higher than the tensile strength measured at 25 ° C and 65% RH.
  • a lid for electrical and electronic products characterized in that for the pressure cooker.
  • Polyketone automotive air intake manifold is a polyketone automotive air intake manifold, characterized in that the impact strength is 8kJ / m2 or more, the tensile strength retention is 100% or more after 300 hours treatment at 120 °C, palladium compound, pKa value
  • a catalyst composition comprising an acid that is less than or equal to 6 and a ligand compound of phosphorus
  • Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin
  • manufacturing a polyketone car air intake manifold by injection molding 100% by weight of the blend containing 60 to 90% by weight of the polyketone resin and 10 to 40% by weight of glass fiber to manufacture a polyketone car air intake manifold.
  • the carrier of the polyketone automotive front end module has an impact strength of 8 kJ / m 2 or more and a tensile strength retention of 100% or more after 300 hours of treatment at 120 ° C., a palladium compound, an acid having a pKa of 6 or less, and a double ligand of phosphorus.
  • Preparing a catalyst composition comprising a compound; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And manufacturing a carrier of the polyketone car front end module by injection molding 100 wt% of the blend containing 60 to 90% by weight of the polyketone resin and 10 to 40% by weight of glass fiber. It provides a method of manufacturing a carrier of a module.
  • Impact strength of automobile headlamp bezel is 20kJ / m 2 or more
  • mineral fillers are talc, kaolin, mica, wollastonite, TiO2-coated mica compact (TiO2- coated mica platelets), silica (silica), alumina (alumina), borosilicate (borosilicates) and oxides (oxides), characterized in that any one selected from the group consisting of, based on 100% by weight of the total blend, the mineral Filler provides an automotive headlamp bezel, characterized in that 5 to 50% by weight.
  • Linear alternating polyketone is a vehicle canister comprising a polyketone blend, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15, characterized in that the canister has an impact strength of 20 kJ / m 2 or more.
  • Consists of carbon monoxide and at least one olefinically unsaturated hydrocarbon containing 5 to 50 ppm of palladium catalyst residue, 60 to 85 wt% of linear alternating polyketone polymer having a molecular weight distribution of 1.5 to 3.0, and 15 to 40 wt% of glass fibers.
  • the interior lamp housing characterized in that the blend is manufactured by injection molding, characterized in that the impact strength is 20kJ / m 2 or more.
  • the ashtray for vehicles has an impact strength of 8 kJ / m 2 or more, and the impact strength measured at 50 ° C. and 90% RH is maintained at a level of 90% or more compared to the impact strength measured at 25 ° C. and 65% RH.
  • An ashtray for a vehicle is provided.
  • Automotive multi-function switch provides a multi-function switch for the automobile, characterized in that the impact strength is 8kJ / m 2 or more, and the property retention is 90% or more.
  • An automobile speaker grill which is produced by injection molding a linear alternating polyketone polymer comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon, having a residual amount of palladium catalyst of 5 to 50 ppm and a molecular weight distribution of 1.5 to 3.0. , Impact strength is characterized in that more than 15kJ / m 2 .
  • the headrest guide for automobiles provides a headrest guide for automobiles, characterized in that the impact strength is 20kJ / m 2 or more.
  • the car navigation support provides a car navigation support, characterized in that the impact strength is more than 15kJ / m 2 .
  • Automotive side moldings provide automotive side moldings characterized in that the impact strength is at least 15 kJ / m 2 .
  • Polyketone hose connector characterized in that the low temperature impact strength at minus 30 °C 4kJ / m2 or more, the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-di
  • the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-di)
  • a polyketone hose connector characterized in that it is oxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine).
  • Stem bolt for polyketone air conditioner is a stem bolt for polyketone air conditioner characterized in that the elongation at break is more than 100%, the impact strength is 10kJ / m2 or more, the ligand of the catalyst composition used for the polymerization of the polyketone copolymer (( Provides a stem bolt for polyketone air conditioner, characterized in that 2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) do.
  • the present invention is a polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), having a molecular weight of 20,000 to 200,000, a molecular weight distribution of 1.5 to 2.5, and y / x of 0.03 to 0.3
  • polyketone compositions comprising phosphorus alternating polyketones and amorphous semiaromatic polyamides, wherein the weight ratio of said polyketones to amorphous semiaromatic polyamides is from 60:40 to 95: 5.
  • the amorphous semiaromatic polyamide is preferably polyhexamethyleneisophthalamide.
  • the flexural strength of the polyketone composition is 65 to 90MPa, the flexural modulus is 1,700MPa or more, the impact strength is preferably 7kJ / m2 or more.
  • the present invention also provides a polyketone molded article made of the polyketone composition.
  • the present invention is a polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), and includes a linear alternating polyketone and a polyester having y / x of 0.03 to 0.3, wherein the polyester Is a polyketone composition, characterized in that 10 to 90% by weight relative to the total weight of the composition.
  • the polyketone preferably has an intrinsic viscosity of 1.0 to 2.0 dl / g.
  • the polyketone composition was heat treated at 300 ° C. for 2 hours by ASTM D-638, and the width of the injection direction portion and the right angle direction of the polyketone composition specimens before and after the treatment were measured by a slide caliper, respectively, 2.0% or less. And 0.5% or less.
  • the present invention also provides a polyketone molded article for an automobile fuel container including the polyketone composition.
  • the present invention is composed of 53 to 71% by weight of a linear alternating polyketone polymer consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon in the polyketone composition, the residual amount of palladium catalyst is 50 ppm or less, molecular weight distribution of 1.5 to 2.5,
  • a polyketone notebook bottom housing which is manufactured by injection molding a blend comprising 25 to 35% by weight of glass fiber, 2 to 12% by weight of phosphorus flame retardant, and 2 to 8% by weight of nylon 6I.
  • the ligand of the catalyst composition during the polymerization of the linear alternating polyketone is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl Phosphine).
  • the intrinsic viscosity of the linear alternating polyketone polymer is preferably 1.0 to 2.0 dl / g.
  • the polyketone notebook lower housing is characterized in that the flexural modulus is 8,000MPa or more, low temperature impact strength is 11.0kJ / m 2 or more.
  • Polyketone resin composition of the present invention is excellent in flexural properties, tensile strength, impact strength, moisture resistance and dimensional stability mask, pipe holder, transmission bracket, bumper bracket, automotive junction box, automotive wheel rim, power line binding bracket, electronics There is an advantage that can be applied to various industrial parts, such as device covers, eyeglass frames.
  • the polyketone composition of the present invention is higher in strength than the nylon resin used as a conventional notebook bottom housing material can obtain a notebook bottom housing with improved impact resistance.
  • the poly ketone resin used in the present invention is an engineering plastic and is a recently developed new resin, and is a thermoplastic synthetic resin that is usefully applied as a material for various molded products or parts due to its excellent mechanical properties and molding properties such as bending characteristics. .
  • Mechanical properties of the polyketone resin belongs to the category of high performance plastics, and is a polymer material that synthesizes carbon monoxide as a raw material.
  • Polyketone resin has lower moisture absorption than nylon material, so it is possible to design various products with little change in dimensions and physical properties due to moisture absorption.
  • polyketone resin has a lower density than aluminum, making it suitable for weight reduction.
  • the polyketones used in the present invention are carbon monoxide, ethylenically unsaturated compounds and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, in particular repeating units derived from carbon monoxide and repeating units derived from ethylenically unsaturated compounds and propylene-like. It is a structure in which repeating units derived from an unsaturated compound are alternately connected to each other, and have excellent mechanical and thermal properties, excellent workability, high wear resistance, chemical resistance and gas barrier properties, and are useful materials for various applications.
  • the high molecular weight of these ternary or higher copolymerized polyketones is considered to be useful as an engineering plastic material having higher processability and thermal properties and excellent economic efficiency.
  • the wear resistance is high, and parts such as automobile gears and chemical resistance are high, and the gas barrier property, such as lining material of chemical transport pipe, is high, so that it can be used for light gasoline tanks and the like.
  • the ultra high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fibers, the fibers can be stretched at a high magnification and have a high strength and a high modulus of elasticity oriented in the stretching direction. It is very suitable for building materials and industrial materials.
  • the polyketone polymer of the present invention is a linear alternating structure, and substantially contains carbon monoxide for each molecule of unsaturated hydrocarbon.
  • Suitable ethylenically unsaturated hydrocarbons for use as precursors of polyketone polymers have up to 20, preferably up to 10 carbon atoms.
  • ethylenically unsaturated hydrocarbons are ethene and ⁇ -olefins such as propene, 1-butene, isobutene, 1-hexene, 1-octene
  • aryl aliphatic hydrocarbons in the ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene and m-isopropyl styrene.
  • the polyketone polymers preferably used in the present invention are copolymers of carbon monoxide and ethene or second ethylenically unsaturated hydrocarbons having at least three carbon atoms with carbon monoxide and ethene, in particular ⁇ -olefins such as propene. Terpolymers.
  • each unit containing the second hydrocarbon moiety in the terpolymer there are at least two units containing the ethylene moiety. It is preferable that there are 10-100 units containing a 2nd hydrocarbon part.
  • Polyketone polymers are prepared by contacting carbon monoxide with hydrocarbon monomers under polymerization conditions in the presence of a palladium compound, a catalyst composition suitably produced from anionic and phosphorus bidentate ligands of less than pKa 6 or preferably less than pKa 2.
  • a liquid phase polymerization may be employed in which an alcohol solvent is carried out in an alcohol solvent through a catalyst composition composed of a carbon monoxide and an olefin with a palladium compound, an acid having a PKa of 6 or less, and a diligand compound of phosphorus.
  • the polymerization reaction temperature is preferably 50 ⁇ 100 °C and the reaction pressure is 40 ⁇ 60bar.
  • the polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.
  • the palladium compound palladium acetate is preferable, and the amount of use thereof is preferably 10 -3 to 10 -1 1 mole.
  • the acid having a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, sulfonic acid, and the like.
  • trifluoroacetic acid is used, and the amount is preferably 6 to 20 equivalents relative to palladium.
  • 1, 3-bis [di (2-methoxy phenylphosphino)] propane is preferable as a bidentate coordination compound of phosphorus, and 1-1.2 equivalents are preferable with respect to palladium.
  • the process for producing polyketones is characterized by the presence of an organometallic complex catalyst consisting of a ligand having an element of (a) Group 9, Group 10 or Group 11, and (b) Group 15.
  • an organometallic complex catalyst consisting of a ligand having an element of (a) Group 9, Group 10 or Group 11, and (b) Group 15.
  • the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (eg methanol) and water to form a linear terpolymer, the mixture
  • a mixed solvent eg methanol
  • the content of the water in the mixed solvent is less than 2 parts by weight of ketal may be formed, the heat stability during the process may be lowered, if more than 10 parts by weight may lower the mechanical properties of the product.
  • a liquid medium a mixed solvent consisting of 7090 vol% acetic acid and 1030 vol% water is used, and benzophenone is added during polymerization.
  • a mixed solvent consisting of acetic acid and water is used as a liquid medium, without using methanol, dichloromethane, or nitromethane, which have been mainly used in the production of polyketone.
  • a mixed solvent of acetic acid and water is used as the liquid medium in the production of the polyketone it is possible to improve the catalytic activity while reducing the production cost of the polyketone.
  • the catalyst is composed of a ligand having an element of (a) Group 9, Group 10 or Group 11 transition metal compound (b) Group 15 of the Periodic Table (IUPAC Inorganic Chemistry Nomenclature, 1989).
  • Examples of the Group 9 transition metal compound in the Group 9, 10 or 11 transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamate salts, sulfonates, and the like. Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, trifluoro ruthenium acetate, ruthenium acetylacetate, trifluoromethane sulfonate ruthenium and the like.
  • Examples of the Group 10 transition metal compound include a complex of nickel or palladium, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include nickel acetate, nickel, acetylacetate, palladium acetate and trifluoroacetic acid.
  • Examples of the Group 11 transition metal compound include a complex of copper or silver, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include copper acetate, trifluoroacetate, copper acetylacetate, silver acetate, Silver trifluoroacetic acid, silver acetyl acetate, silver trifluoromethane sulfonic acid, etc. are mentioned.
  • transition metal compounds (a) are nickel and copper compounds
  • preferred transition metal compounds (a) are palladium compounds in terms of yield and molecular weight of polyketones, and in terms of improving catalytic activity and intrinsic viscosity.
  • palladium acetate is used in the process.
  • Examples of the ligand (b) having a group 15 atom include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picolin , Nitrogen ligands such as 2,2'-bikinolin, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) Butane, 1,3-bis [di (2-methyl) phosphino] propane, 1,3-bis [di (2-isopropyl) phosphino] propane, 1,3-bis [di (2-methoxyphenyl ) Pinospino] propane, 1,3-bis [di (2-methoxy-4-sulfonic acid-phenyl) phosphino] propane, 1,2-bis (diphenylphosphino) cyclohexane, 1,2-bis (
  • the ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and particularly, in view of the yield of polyketone, a phosphorus ligand is preferably 1,3-bis [di (2- Methoxyphenyl) phosphino] propane, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, and 2-hydroxy-1,3-bis [in terms of molecular weight of the polyketone.
  • Preferred ligand (b) having an atom of group 15 is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) propane, most preferably 1,3-bis [di (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2 Methoxyphenyl) phosphine).
  • the method for preparing a ligand for a polyketone polymerization catalyst is as follows. Using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and sodium hydride (NaH) ((2,2-dimethyl) ((2,2-dimethyl) ((2,2-dimethyl) ((2,2-dimethyl) Provided is a method for producing a ligand for a polyketone polymerization catalyst, characterized by obtaining -1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine). .
  • the method for preparing a ligand for a polyketone polymerization catalyst of the present invention is conventionally 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane Unlike the synthesis method of ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially mass synthesized.
  • the method for preparing a ligand for a polyketone polymerization catalyst of the present invention is (a) adding bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) to a reaction vessel under a nitrogen atmosphere and hydrogenated at room temperature.
  • DMSO dimethylsulfoxide
  • the amount of the Group 9, Group 10 or Group 11 transition metal compound (a) to be used varies uniformly since the appropriate value varies depending on the type of the ethylenic and propylene unsaturated compounds selected or other polymerization conditions. Although not limited, it is usually 0.01-100 mmol, preferably 0.01-10 mmol, per liter of the capacity of the reaction zone.
  • the capacity of the reaction zone means the capacity of the liquid phase of the reactor.
  • the amount of the ligand (b) to be used is not particularly limited, but is usually 0.1 to 3 mol, preferably 1 to 3 mol, per mol of the transition metal compound (a).
  • the molar ratio of the (a) Group 9, Group 10 or Group 11 transition metal compound and benzophenone is 1: 5 to 100, preferably 1:40 to 60.
  • the molar ratio of genus and benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the polyketone produced is not satisfactory. If the molar ratio of transition metal and benzophenone is greater than 1: 100, the polyketone catalytic activity is rather decreased. It is not preferable because it tends to.
  • Examples of ethylenically unsaturated compounds copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 ⁇ -olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and ⁇ -methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl
  • preferred ethylenically unsaturated compounds are ⁇ -olefins, more preferably ⁇ -olefins having 2 to 4 carbon atoms, most preferably ethylene, and 120 mol% propylene is added in the production of terpolymer copolyketones.
  • the input ratio of carbon monoxide and ethylenically unsaturated compound is 1: 12 (molar ratio) and to adjust propylene to 120 mol% relative to the total mixed gas.
  • polyketone it is common to set the ratio of carbon monoxide and ethylenically unsaturated compound to 1: 1, but in the present invention using a mixed solvent of acetic acid and water as a liquid medium and adding benzophenone during polymerization, carbon monoxide and ethylenic
  • the ratio of the unsaturated compound to 1: 12 and propylene is adjusted to 120 mol% of the total mixed gas, it was found that not only the processability was improved but also the catalytic activity and the intrinsic viscosity were simultaneously improved.
  • the amount of propylene is less than 1 mol%, the effect of three-way copolymerization to lower the melting temperature cannot be obtained. If it exceeds 20 mol%, there is a problem of inhibiting the intrinsic viscosity and the improvement of catalyst activity. desirable.
  • a mixed solvent of acetic acid and water is used as a liquid medium, benzophenone is added during polymerization, and carbon monoxide and ethylenically unsaturated compound and one or more olefinically unsaturated compounds are added to the catalytic activity and intrinsic viscosity of the polyketone.
  • the polymerization time should be at least 10 hours to improve the intrinsic viscosity, but it is possible to prepare a terpolymer copolymer polyketone having a high intrinsic viscosity even if the polymerization time is about 12 hours.
  • the catalyst is produced by contacting the two components.
  • Arbitrary methods can be employ
  • the molar ratio of the ethylenically unsaturated compound and the propylene unsaturated compound is preferably 99: 1 to 85:15. If the molar ratio of propylene is less than 1%, it is difficult to process the molded part, and if it exceeds 15%, There is a problem that the mechanical properties fall.
  • the present invention may further include conventionally known additives such as antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials to improve processability and physical properties of the polymer.
  • additives such as antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials to improve processability and physical properties of the polymer.
  • the polymerization method a solution polymerization method using a liquid medium, a suspension polymerization method, a gas phase polymerization method in which a small amount of a polymer is impregnated with a high concentration of a catalyst solution are used.
  • the polymerization may be either batchwise or continuous.
  • polymerization can use a well-known thing as it is or processing it.
  • polymerization Usually, it is normal pressure-20 MPa, Preferably it is 4-15 MPa.
  • Linear alternating polyketones are formed by the polymerization method as described above.
  • the polymer ring of the polyketone polymer preferred in the present invention may be represented by the following formula (2).
  • G is an ethylenically unsaturated hydrocarbon, in particular, a part obtained from an ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is preferably at least 1: 0.01.
  • the polyketone polymer is a copolymer composed of repeating units represented by General Formulas (1) and (2), and it is preferable that y / x is 0.03 to 0.3.
  • y / x is 0.03 to 0.3.
  • y / x is more preferably 0.03 to 0.1.
  • the melting point of the polymer may be controlled by controlling the ratio of ethylene and propylene of the polyketone polymer.
  • the melting point is about 220 ° C. when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46: 4: 50, but the melting point is adjusted to 235 ° C. when the molar ratio is adjusted to 47.3: 2.7: 50.
  • polyketone polymers having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000, as measured by gel permeation chromatography.
  • the physical properties of the polymer depend on the molecular weight, on whether the polymer is a copolymer or terpolymer, and in the case of terpolymers, on the nature of the second hydrocarbon moiety present.
  • fusing point of the conversion of the polymer used by this invention is 175 degreeC-300 degreeC, and is 210 degreeC-270 degreeC generally.
  • the ultimate viscosity number (LVN) of the polymer measured at 60 ° C.
  • HFIP Hexafluoroisopropylalcohol
  • the polyketone molding of the present invention is composed of a blend consisting of a combination of polyketone and glass fiber, it is characterized in that the stiffness, processability and dimensional stability compared to the conventional materials used.
  • the glass fiber preferably has a particle diameter of 10 to 13 ⁇ m.
  • the particle diameter of the glass fiber is less than 10 ⁇ m, the shape of the glass fiber may change and mechanical properties may decrease.
  • the composition ratio of the polyketone and glass fiber is preferably comprised of 60 to 90% by weight of polyketone polymer and 10 to 40% by weight of glass fiber. If the glass fiber content is less than 15% by weight, the mechanical rigidity may be lowered. If the glass fiber content is more than 40% by weight, the viscosity may be excessively increased, thereby reducing extrusion and injection workability.
  • additives may include, for example, antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials.
  • the polyketone as described above may be produced by extrusion molding or injection molding.
  • the blend composition of the polyketone and glass fibers of the present invention as described above is molded by a method such as extrusion, injection, and the like is produced as a polyketone molding, which is characterized by excellent rigidity, processability and dimensional stability.
  • the polyketone molded article has a product moisture absorption rate of 2.0% or less and the moisture content retention rate of 70% or more.
  • the impact strength is 10 kJ / m 2 or more, preferably 15 kJ / m 2 or more.
  • a liquid phase polymerization may be employed in which an alcohol solvent is carried out in an alcohol solvent through a catalyst composition consisting of a carbon monoxide and an olefin with a palladium compound, an acid having a PKa of 6 or less, and a binary ligand compound of phosphorus.
  • the polymerization reaction temperature is preferably 50 ⁇ 100 °C and the reaction pressure is 40 ⁇ 60bar.
  • the polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.
  • palladium acetate and a palladium compound in the amount of 10 -3 to 10-2 1mole preferred.
  • the acid having a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, sulfonic acid, and the like. In the present invention, trifluoroacetic acid is used, and the amount is preferably 6 to 20 equivalents relative to palladium.
  • 1, 3-bis [di (2-methoxy phenylphosphino)] propane is preferable as a bidentate coordination compound of phosphorus, and 1-1.2 equivalents are preferable with respect to palladium.
  • the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. Less than 1.5 had a poor polymerization yield, and more than 2.5 had a problem of poor moldability.
  • the glass fiber which is a subcomponent of this invention is demonstrated. It is also called glass fiber or glass wool by melting and processing the glass containing silicate as a main component to make it into a fiber shape. Glass fiber is classified according to manufacturing method and divided into short fiber and long fiber. In addition, there are optical fibers for image transmission and glass fibers (optical fibers) for optical communication. Glass has been known for its craft use since ancient times because it stretches like snow at high temperatures. It was the first time that industrialized short fibers were manufactured in Germany as a substitute for natural asbestos during World War I. Long fibers were industrialized in the United States in the 1930s and optical fibers in the 60s. Short fibers are simple to manufacture and are made of felt and used for insulation.
  • Optical fibers are a regular bundle of thousands of hundreds to hundreds of thousands of specially structured fibers, and when an image is inserted at one end of the bundle, it is transmitted to the other end according to the bundle's refraction. It also has a wide range of uses besides fiber scopes.
  • glass fibers are thin, so the specific surface area is very large. For example, if a glass bead with a diameter of 1 cm is stretched into a fiber having a diameter of 1 ⁇ m, its length is about 4,000 m and its area is nearly 400 times larger, thus having a chemical composition (E glass) that is not easily eroded by moisture.
  • C-glass is acid-resistant, and alkali-resistant fibers, such as battery cells, have recently been put to practical use and are used for cement reinforcement.
  • Method for producing a polyketone resin composition excellent in impact resistance of the present invention comprises the steps of preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a double ligand compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone resin; And mixing and extruding glass fibers, inorganic fillers, mineral reinforcing materials, and the like into the polyketone resin.
  • a mixed solvent polymer solvent
  • a solvent eg, alcohol and acetone
  • polyurethane resin polycarbonate, polyamide 6 resin, rubber, ASA (Acrylic Styrene Acrylonitrile), etc. can be further mixed to further improve impact resistance and elasticity, and sulfonamide to improve processability and formability.
  • Systemic plasticizers can be added.
  • Palladium acetate may be used as the palladium compound constituting the catalyst composition, and the amount of the palladium compound is preferably 10 -3 to 10 -1 mole.
  • the acid having a pKa value of 6 or less constituting the catalyst composition one or more selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid, and sulfonic acid may be used, and preferably trifluoroacetic acid is used. 6-20 (molar) equivalents to the compound are appropriate.
  • Examples of the phosphorus double ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (eg, 1,3-bis [di (2-methoxyphenylphosphino)] propane, 1,3- Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane and ((2,2-dimethyl-1,3-diox
  • One or more selected ones can be used, and the amount used is 1 to 1.2 (mol) compared to the palladium compound.
  • the carbon monoxide, ethylene, and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer.
  • the mixed solvent may be a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water. If the content of the water in the mixed solvent is less than 2 parts by weight of ketal may be formed, the heat stability during the process may be lowered, if more than 10 parts by weight may lower the mechanical properties of the product.
  • the polymerization temperature is 50 ⁇ 100 °C
  • the reaction pressure is suitable for the range of 40 ⁇ 60bar.
  • the resulting polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.
  • the obtained polyketone resin is mixed with glass fiber, inorganic filler, mineral reinforcing material, polyurethane resin, polycarbonate, polyamide 6 resin, rubber, Acrylic Styrene Acrylonitrile (ASA), sulfonamide plasticizer as necessary.
  • Extrusion with an extruder finally yields the blend composition.
  • the blend is prepared by melt kneading and extrusion into a twin screw extruder.
  • the extrusion temperature is 230 ⁇ 260 °C
  • screw rotation speed is preferably in the range of 100 ⁇ 300rpm. If the extrusion temperature is less than 230 °C kneading may not occur properly, if it exceeds 260 °C may cause problems with the heat resistance of the resin. In addition, if the screw rotational speed is less than 100rpm it may not be a smooth kneading, if it exceeds 300rpm conductive carbon black or elastic polyurethane or carbon fiber may be destroyed and mechanical properties may be reduced.
  • the glass fiber is added to improve the tensile strength and impact strength is 10 ⁇ m in diameter, 4mm in length, preferably coated with polyurethane.
  • the blending efficiency with the polyketone is excellent, and when the composition is manufactured as an industrial part, the mechanical properties are excellent.
  • the present invention is not limited thereto.
  • the inorganic filler is added to further improve the mechanical properties of the polyketone blend resin composition, but calcium carbonate, magnesium sulfate, silicon carbide, calcium oxide and the like are used, but are not necessarily limited thereto.
  • the mineral reinforcing material is to improve impact resistance and dimensional stability, such as talc, kaolin, mica, wollastonite, TiO2-coated mica platelets, It is preferably one of silica, alumina, borosilicates and oxides.
  • a blend of the linear alternating polyketone and the mineral filler is used, wherein the mineral filler is talc, kaolin, mica, wollastonite, TiO 2 -coated.
  • Mica plates TiO 2 -coated mica platelets
  • silica silica
  • alumina alumina
  • borosilicates and oxides a blend of the linear alternating polyketone and the mineral filler
  • the content of the mineral filler is 5 to 50% by weight. Preferably it is 30 to 40% by weight.
  • the mineral filler is added in less than 5% by weight, the dimensional stability is lowered, and when it exceeds 50% by weight, the injection moldability is lowered.
  • the polyurethane resin is added as necessary to improve the impact strength and resilience of the polyketone resin.
  • the polycarbonate is added as necessary to improve the hardness of the polyketone resin.
  • the polyamide 6 resin and rubber are intended to improve impact resistance, water resistance, and the like.
  • the melt index of the polyamide (240 ° C., 21.2 N) is preferably 5 to 70 g / 10 min. If it is less than 5 g / 10 min, the moldability of parts becomes weak, and if the flow index is more than 70 g / 10 min, physical properties such as impact strength are lowered.
  • EPDM ethylene propylene diene monomer
  • EPDM ethylene propylene diene monomer
  • the ASA (Acrylic Styrene Acrylonitrile) is about 90 kcal / mol of dissociation energy of hydrogen in the rubber main chain, and has a characteristic of dissociating in light having a high wavelength energy of 300 nm or less, and thus, it is difficult to basically cause weathering degradation. Therefore, it is possible to enhance the elasticity and weather resistance of the polyketone resin due to the addition of the ASA.
  • the glass fiber, inorganic filler, mineral reinforcing material, polyurethane resin, polycarbonate, polyamide 6 resin, rubber, ASA (Acrylic Styrene Acrylonitrile), sulfonamide-based plasticizer may be blended alone or mixed, the amount is added 5 to 50 parts by weight relative to 100 parts by weight of the polyketone terpolymer is good, preferably 10 to 20 parts by weight. If the added content is less than 5 parts by weight, it is not possible to give the desired tensile strength and impact strength, and if it exceeds 50 parts by weight, the mechanical strength, dimensional stability and molding characteristics of polyketones may be lowered and thus, may lack practicality.
  • Polyketone resin composition according to the production method of the present invention is excellent in tensile strength and impact strength mask, pipe holder, transmission bracket, bumper bracket, automotive junction box, automobile wheel rim, power line binding bracket, electronic device cover, eyeglass frame, etc. There is an advantage that can be applied to industrial parts of various fields.
  • the polyketone composition according to an embodiment of the present invention is characterized in that the bending properties are excellently improved by containing an amorphous semiaromatic polyamide in the polyketone.
  • Non-limiting examples of such amorphous semiaromatic polyamides include poly hexamethyleneisophthalamide (nylon 6I), hexamethyleneisophthalamide / hexamethylene terephthalamide copolymer (nylon 6I / 6T), poly (methazyl Yleneisophthalamide) (nylon MXDI), caprolactam / methaxylyleneisophthalamide copolymer (nylon 6 / MXDI), caprolactam / hexamethyleneisophthalamide copolymer (nylon 6 / 6I), and the like.
  • poly hexamethyleneisophthalamide (nylon 6I) can be particularly preferably used.
  • the polyketone composition of the present invention is composed of a blend made of a combination of polyketone and amorphous semiaromatic polyamide, and is characterized by improving bending characteristics.
  • the weight of the amorphous semiaromatic polyamide is 5 to 40% by weight relative to the total weight. Preferably it is 10-30 weight%, More preferably, it is 10-20 weight%. If the content of the polyketone resin is less than 60% by weight, the mechanical strength, dimensional stability, and molding properties of the polyketone resin are inferior, resulting in a lack of practicality and workability, and exceeding 95% of the amorphous semiaromatic polyamide. Relative content reduction can make it difficult to impart desired levels of flexural properties.
  • carbon fibers, mica and talc may be added to the composition to reinforce the mechanical properties.
  • antioxidants, pigments and the like can be added as desired. Such additives may be suitably used by those skilled in the art.
  • the polyketone composition according to another embodiment of the present invention is characterized by having excellent moisture resistance and dimensional stability by containing polyester in the polyketone.
  • polyester resin which is a subcomponent of the said polyketone composition is demonstrated.
  • the polyketone composition of the present invention is composed of a blend consisting of a polyketone and a polyester combination, characterized in that to improve moisture resistance.
  • the weight of the polyester is 10 to 90% by weight relative to the total weight. Preferably it is 10-60 weight%, More preferably, it is 20-60 weight%. If the content of the polyketone resin is less than 10% by weight, the mechanical strength, dimensional stability, and molding characteristics of the polyketone resin may be lowered, thereby causing a lack of practicality. It can be difficult to impart moisture resistance.
  • carbon fibers, mica and talc may be added to the composition to reinforce the mechanical properties.
  • antioxidants, pigments and the like can be added as desired. Such additives may be suitably used by those skilled in the art.
  • the polyketone notebook bottom housing is composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon in the polyketone composition, the residual amount of palladium catalyst is 50 ppm or less, and the molecular weight distribution is 1.5 to 2.5. It is prepared by injection molding a blend comprising 53 to 71% by weight of the linear alternating polyketone polymer, 25 to 35% by weight of glass fiber, 2 to 12% by weight of phosphorus flame retardant, and 2 to 8% by weight of nylon 6I. do. If the content of the polyketone, glass fiber, phosphorus-based flame retardant and nylon 6I is less than or above the above range, mechanical properties are poor for use in a notebook housing.
  • Glass fibers are mixed to enhance the mechanical strength of the polyketone resin composition.
  • the amount to be mixed is 20 to 40% by weight, preferably 25 to 35% by weight, more preferably 35% by weight relative to the total weight. If it is less than 20% by weight, the mechanical strength such as impact resistance is not excellent, and if it exceeds 40% by weight, there is a problem that the improvement effect of the mechanical strength is insignificant compared to the economic cost increase due to mixing.
  • the present invention further mixes a flame retardant and nylon 6I to enhance the heat and flame resistance of the final notebook product.
  • the mixing amount is 5 to 10% by weight of the flame retardant, 2 to 8% by weight of nylon 6I relative to the total weight%, preferably 7% by weight of flame retardant, 5% by weight of nylon.
  • the flame retardant used in the present invention is non-halogen-based, particularly preferably a phosphorus flame retardant.
  • Representative phosphorus flame retardants are Cyclic Phosphate Phosphonic, P- [3-[(hydroxymethyl) amino] -3-oxopropyl] -dimethyl ester, Dimethyl methyl phosphonate, Phosphonic, P-[[bis (2-hydroxyethyl) amino] methyl] -diethyl esters, Triethyl Phosphate, Isopropyl phenyl diphenyl phosphate, Tris (2-chloroethyl) phosphate, Tetrakis hydroxymethyl phosphonium sulfate, etc., but are not necessarily limited thereto.
  • a manufacturing method for manufacturing a notebook lower housing of the present invention is as follows.
  • a method of manufacturing a notebook lower housing comprises the steps of preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a double ligand compound of phosphorus, preparing a mixed solvent of methanol-water (polymerization solvent); Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone polymer; And mixing and extruding 52 wt% of the polyketone polymer, 30 wt% of glass fiber, 7 wt% of trimethyl phosphate, and 5 wt% of nylon 6I to prepare a blend; And injection molding the blend, but is not limited thereto.
  • a solvent eg, alcohol and acetone
  • the notebook lower housing made of the polyketone composition as described above is characterized in that the flexural modulus is 8000 MPa or more, and the impact strength is 11 kJ / m 2 or more. Accordingly, the polyketone composition may be usefully applied to a notebook lower housing having excellent flexural modulus and impact resistance.
  • Polyketone manufacturing method for industrial parts comprises the steps of preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a double ligand compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone polymer; Preparing a blend by mixing and extruding 60 to 90 wt% of the polyketone polymer and 10 to 40 wt% of glass fibers; And injection molding the blend, but is not limited thereto.
  • a mixed solvent polymer solvent
  • a solvent eg, methanol
  • Palladium acetate may be used as the palladium compound constituting the catalyst composition, and the amount of palladium acetate is preferably 10 ⁇ 3 to 10 ⁇ 1 moles, but is not limited thereto.
  • the acid having a pKa value of 6 or less constituting the catalyst composition may be at least one selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid and sulfonic acid, preferably trifluoroacetic acid.
  • the use amount is 6-20 (mole) equivalents with respect to a palladium compound.
  • 1,3-bis [diphenylphosphino] propane for example, 1,3-bis [di (2-methoxyphenylphosphino)] propane, 1 , 3-bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane and ((2,2-dimethyl-1,3-dioxane-5,5-diyl ) Bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) may be used one or more selected from the group consisting of, the amount of 1 to 20 (mole) equivalent to the palladium compound is appropriate.
  • the carbon monoxide, ethylene, and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer.
  • the mixed solvent may be a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water. If the content of the water in the mixed solvent is less than 2 parts by weight of ketal may be formed, the heat stability during the process may be lowered, if more than 10 parts by weight may lower the mechanical properties of the product.
  • the polymerization temperature is 50 ⁇ 100 °C
  • the reaction pressure is suitable for the range of 40 ⁇ 60bar.
  • the resulting polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.
  • the obtained polyketone polymer is mixed with glass fibers and then extruded with an extruder to finally obtain a blend composition.
  • the blend may be prepared by melt kneading and extrusion into a twin screw extruder.
  • the extrusion temperature is 230 ⁇ 260 °C
  • screw rotation speed is preferably in the range of 100 ⁇ 300rpm. If the extrusion temperature is less than 230 °C kneading may not occur properly, if it exceeds 260 °C may cause problems with the heat resistance of the resin. In addition, if the screw rotational speed is less than 100rpm may not be smooth kneading, if the screw speed exceeds 300rpm glass fiber may be destroyed and mechanical properties may be reduced.
  • Industrial parts may be manufactured by preparing a blend in the same manner as described above and extruding or injection molding it.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C.
  • polyketone terpolymer prepared by Example 1 100 parts by weight of polyketone terpolymer prepared by Example 1 3 parts by weight of glass fiber, 3 parts by weight of calcium carbonate, 3 parts by weight of talc, 5 parts by weight of polyurethane resin, 2 parts by weight of polycarbonate, polyamide 4 parts by weight of the resin were mixed and prepared into pellets on an extruder using a biaxial screw with a diameter of 2.5 cm and operating at 250 rpm.
  • PA66 70 parts by weight (A218V30) 3 parts by weight of glass fiber, 5 parts by weight of calcium carbonate, 5 parts by weight of talc, 5 parts by weight of polyurethane resin, 2 parts by weight of polycarbonate to operate at 250rpm It was made into pellets on an extruder using a biaxial screw with a diameter of 2.5 cm and L / D 32.
  • PA66 A218V30 product
  • glass fiber 3 parts by weight of glass fiber
  • calcium carbonate 3 parts by weight of talc
  • polyurethane resin 2 parts by weight of polycarbonate
  • polyamide resin 4 parts by weight
  • PA66 70 parts by weight (A218V30) 2 parts by weight of glass fiber, 2 parts by weight of calcium carbonate, 3 parts by weight of talc, 3 parts by weight of polyurethane resin, 2 parts by weight of polycarbonate, 2 parts by weight of polyamide resin Part, 2 parts by weight of rubber, 2 parts by weight of ASA and 2 parts by weight of sulfonamide-based plasticizer were mixed into pellets on an extruder by using a biaxial screw having a diameter of 2.5 cm and operating at 250 rpm. Prepared.
  • the prepared polyketone composition of the above Example was prepared as a specimen, and then compared with the product of the comparative example, the physical properties were evaluated in the following manner, and the results are shown in Table 1 below.
  • Example 1 Item Tensile Strength (MPa) Impact Strength (kJ / m 2 ) Flexural modulus Product Strain Rate (Vertical%) Product strain rate (horizontal%)
  • Example 1 148 18 7800 0.08 0.05
  • Example 2 155 17 7800 0.08 0.06
  • Example 3 156 16 8200 0.09 0.07
  • Example 4 158 16 8400 0.07 0.05
  • Example 5 158 15 8400 0.11 0.07 Comparative Example 1 120 5 6400 0.84 0.75 Comparative Example 2 125 4 6600 0.75 0.66 Comparative Example 3 130 4 7000 0.72 0.62 Comparative Example 4 134 5 7200 0.77 0.68 Comparative Example 5 136 4 7400 0.64 0.58
  • the polyketone resin composition of the present invention through Table 1 was confirmed that not only excellent impact resistance, such as tensile strength, impact strength, but also excellent retention of properties after elasticity and moisture absorption. Therefore, the polyketone resin composition of the present invention is expected to be applied to industrial parts in various fields such as masks, pipe holders, transmission brackets, bumper brackets, automotive junction boxes, automobile wheel rims, power line binding brackets, electronic device covers, eyeglass frames, and the like. .
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Example 6 Except for setting the content of the polyketone in Example 6 80% by weight, the glass fiber content 20% by weight is the same as in Example 6.
  • the glass fiber content 30% by weight is the same as in Example 6.
  • the glass fiber content 40% by weight is the same as in Example 6.
  • the air intake manifold manufactured through the embodiment of the present invention exhibits better impact resistance and long-term heat resistance than the comparative example used as a conventional air intake manifold material, and thus is more suitable for application as an air intake manifold. Do.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Example 10 Except for setting the content of the polyketone in Example 10 80% by weight, the content of the glass fiber 20% by weight is the same as in Example 10.
  • Example 10 Except for setting the content of the polyketone in Example 10 70% by weight, the glass fiber content of 30% by weight is the same as in Example 10.
  • Example 10 is the same as in Example 10 except that the content of the polyketone 60% by weight, the glass fiber content of 40% by weight.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 °C
  • LVN measured at 25 °C by hexa-fluoroisopropano (HFIP) was 1.4dl / g.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • Example 14 Example 15
  • Example 16 Izod impact strength (KJ / m 2 ) 6 23 24 22 Formability usually Great Great Great Great
  • Example was evaluated to be excellent in impact strength and injection properties compared to the comparative example.
  • the automobile headlamp bezel manufactured according to the embodiment of the present invention was excellent in impact resistance and injection resistance, it was very suitable for application as an automobile headlamp bezel.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • the canister manufactured through the embodiment of the present invention exhibits excellent dimensional stability than that of the comparative example used as a conventional canister material, and thus is more suitable for application as a canister.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • a screw was used to make pellets on an extruder, and then injection molded to prepare specimens of an indoor lamp housing.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • Example 21 Example 22
  • Example 23 Example 24 Comparative Example 10 Impact strength (kJ / m2) 25 23 28 27 18 Formability Great Great Great Great usually Dimensional rate of change (%) 1.3 1.1 1.2 1.5 5.2
  • the interior lamp housing manufactured through the embodiment of the present invention exhibits excellent moldability, impact resistance and dimensional stability than the case of the comparative example used as a conventional interior lamp housing material, it is more suitable for application to the interior lamp housing.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • Example 25 Except for setting the content of the polyketone in Example 25 80% by weight, the glass fiber content 20% by weight is the same as in Example 25.
  • Example 25 Except for setting the content of the polyketone in Example 25, 70% by weight, the glass fiber content of 30% by weight is the same as in Example 25.
  • Example 25 Except for setting the content of the polyketone in Example 25, 60% by weight, and the content of glass fiber 40% by weight is the same as in Example 25.
  • the impact strength was improved compared to the comparative example, and the impact strength retention was 90% or more.
  • the flame retardant properties were found to be equal or higher than those of the comparative examples.
  • the ashtray for vehicles according to the present invention has excellent impact resistance and physical property retention rate, and shows excellent flame retardant properties, and thus, has been shown to be more suitable for use as a vehicle ashtray.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • Example 29 Except for setting the content of the polyketone in Example 29 80% by weight, the glass fiber content 20% by weight is the same as in Example 29.
  • the glass fiber content 30% by weight is the same as in Example 29.
  • Example 29 Except for setting the content of the polyketone in Example 29 60% by weight, the content of the glass fiber 40% by weight is the same as in Example 29.
  • the impact strength was improved compared to the comparative example, the impact strength retention was found to be 90% or more.
  • the multifunction switch for automobiles according to the present invention has been found to be more suitable for being used as a multifunction switch for automobiles because of its excellent impact strength and physical property retention rate.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 °C and two stages of 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 °C and two stages of 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • the headrest guide manufactured through the embodiment of the present invention exhibits excellent moldability and dimensional stability than the comparative example used as a conventional headrest guide material, and thus is more suitable for application as a headrest guide for automobiles. .
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 °C and two stages of 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • Example 39 Example 40
  • Example 41 Comparative Example 14 Impact strength (kJ / m2) 18 20 22 7 Formability Great Great Great usually Dimensional rate of change (%) 1.3 1.1 1.2 5.2
  • the navigation pedestal produced through the embodiment of the present invention exhibits excellent moldability and dimensional stability than the case of the comparative example used as a conventional navigation pedestal material, it is more suitable for application as a navigation for automobiles.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 220 ° C
  • LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g
  • MWD was 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 °C and two stages of 84 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 °C and two stages of 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • the side molding prepared through the embodiment of the present invention exhibits excellent moldability and dimensional stability than the case of the comparative example used as a conventional side molding, it is more suitable for application as an automotive side molding.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 235 ° C
  • LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 2.0 dl / g
  • MWD was 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 225 ° C
  • LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 2.0 dl / g
  • MWD was 2.0.
  • Example 46 Comparative Example 16 Low temperature elongation (%) 40 35 25 Low temperature impact strength (kJ / m2) 7.0 4.8 3.5 Freeze test Good Good Destruction
  • the polyketone hose connector manufactured through the embodiment of the present invention exhibits better low temperature tensile elongation and impact resistance than that of the comparative example, and thus is more suitable for application to the hose connector.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15.
  • the melting point of the polyketone terpolymer was 235 ° C
  • LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 2.0 dl / g
  • MWD was 2.0.
  • the stem bolt for polyketone air conditioner manufactured through the embodiment of the present invention shows better elongation at break and impact resistance than the case of the comparative example, it is more suitable for applying to the air conditioner stem bolt.
  • a polyketone-polyurethane resin composition was prepared by blending 99% by weight of the prepared polyketone terpolymer and 1% by weight of thermoplastic polyurethane.
  • Polyketone-polyurethane resin composition was prepared by blending 90% by weight of polyketone terpolymer and 10% by weight of thermoplastic polyurethane prepared in the same manner as in Example 48.
  • Polyketone-polyurethane resin composition was prepared by blending 80% by weight of polyketone terpolymer and 20% by weight of thermoplastic polyurethane prepared in the same manner as in Example 48.
  • Polyketone-polyurethane resin compositions were prepared using 90% by weight of Rhodia PA66 (available from A218V30) and 10% of thermoplastic polyurethane instead of polyketone.
  • the prepared polyketone composition of the Example was prepared as a specimen, and then evaluated for physical properties in the following manner compared to the product of the comparative example, the results are shown in Table 15 below.
  • Example 48 Example 49 Example 50 Comparative Example 18 Comparative Example 19 Resilience (%) 35 38 42 25 37 Impact Strength (KJ / m 2 ) 12 11.8 12.2 11.8 5.4
  • Polyketone-polyurethane resin composition of the present invention in Table 15 is excellent in resilience (35% to 45%) and impact strength (10 ⁇ 12kJ / m 2 ) compared to PA66 to be used as a thermoplastic plastic for industrial use Was evaluated as suitable for.
  • Example 54 It is the same as Example 54 except the intrinsic viscosity of polyketone is 1.0.
  • Specimens were prepared in the same manner as in Example 54 except for 70% by weight of Rhodia PA66 (manufactured by A218V30) instead of polyketone.
  • the prepared polyketone composition of the Example was prepared as a specimen, and then evaluated for physical properties in the following manner compared to the product of the comparative example, the results are shown in Table 16 below.
  • Example 51 Example 52 Example 53 Example 54 Example 55 Example 56 Example 57 Comparative Example 20 Furtherance PK95% / GF5% PK90% / GF10% PK80% / GF20% PK70% / GF30% PK60% / GF40% PK50% / GF50% PK70% / GF30% PA70% / GF30% Tensile Strength Rating (MPa) 148 155 156 158 162 170 180 130 Impact Strength (KJ / m2) 18 20 21 18 20 17 23 12
  • Example 51 As shown in Table 16, in Example 51, the tensile strength and the impact strength were superior to those of Comparative Example 20.
  • Example 51 the polyketone composition prepared in Example 51 rather than Comparative Example 20 was evaluated to be suitable for use as a thermoplastic plastic used for industrial bar having excellent electrical properties.
  • Example 58 Same as Example 58 except for 90 weight percent polyketone terpolymer and 10 weight percent polycarbonate.
  • Example 58 Same as Example 58 except 80 wt% polyketone terpolymer and 20 wt% polycarbonate.
  • Example 58 Same as Example 58 except for 70 weight percent polyketone terpolymer and 30 weight percent polycarbonate.
  • a specimen was prepared in the same manner as in Example 58, except that 100 wt% polyketone was used.
  • the prepared polyketone composition of the Example was prepared as a specimen, and then evaluated for physical properties in the following manner compared to the product of the comparative example, the results are shown in Table 17 below.
  • Hardness measurement Hardness was measured according to the following method in R scale of Rockwell hardness.
  • Example 58 Example 59 Example 60 Example 61 Comparative Example 21 Furtherance PK98% / PC2% PK90% / PC10% PK80% / PC20% PK70% / PC30% PA base Rockwell Hardness Measurement 99 103 110 108 90
  • the polyketone composition prepared according to the examples rather than the comparative example was evaluated to be suitable for use as a thermoplastic plastic used for industrial bar having excellent mechanical properties.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 80 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.4 dl / g, a MI (Melt index) of 60 g / 10 min, and an MWD of 1.8.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.2.
  • PEI specimens which were conventionally used as materials for eyeglass frames, were used as comparative examples.
  • the bending angle of the final specimen was measured after 100 repeated measurements of flexural modulus in accordance with ASTM D790.
  • Example 62 Example 63 Example 64 Example 65 Example 66 Comparative Example 22 Properties IV: 1.2MWD: 2.0 IV: 1.4 MWD: 2.0 IV: 1.6MWD: 2.0 IV: 1.4 MWD: 1.8 IV: 1.4 MWD: 2.2 PEI Formability Good Good Good Good Good Medium (standard) Elastic restoring force (bending angle) 1.5 ° 1.3 ° 1.2 ° 1.5 ° 1.6 ° 2.5 °
  • the spectacle frame manufactured through the embodiment of the present invention has excellent elastic restoring power, and thus, was very suitable for application to the spectacle frame.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 80 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • the test specimen was injection molded on a molding machine having a clamping force of 80 tons to prepare a mask specimen. Notched Izod impact strength of the final mask specimen was measured by the test method of ASTM D256, and the tensile property retention after moisture absorption was measured.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • the test specimen was injection molded on a molding machine having a clamping force of 80 tons to prepare a mask specimen. Notched Izod impact strength of the final mask specimen was measured by the test method of ASTM D256, and the tensile property retention after moisture absorption was measured.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • HFIP hexa-fluoroisopropano
  • the test specimen was injection molded on a molding machine having a clamping force of 80 tons to prepare a mask specimen. Notched Izod impact strength of the final mask specimen was measured by the test method of ASTM D256, and the tensile property retention after moisture absorption was measured.
  • polyamide 66 (polyamide 66, PA66) were measured as a material of DuPont, which was previously used as a high-impact mask material.
  • Comparative Example is a product that is currently used in a high impact mask, the high impact mask produced through the embodiment of the present invention was very suitable for applying as a high impact mask having excellent impact resistance and physical properties.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the melting point of the polyketone terpolymer was 220 °C
  • LVN measured at 25 °C by hexa-fluoroisopropano (HFIP) was 1.4dl / g
  • MI (Melt index) was 60g / 10min.
  • 70% by weight of the polyketone terpolymer prepared above and 30% by weight of kaolin as a mineral reinforcing material at a diameter of 40 mm operating at 250 rpm, and prepared in pellet form on an extruder using a biaxial screw with L / D 32. Injection molding was performed to prepare specimens for pipe holders.
  • Example 70 Except that the content of the polyketone terpolymer and kaolin was adjusted as shown in Table 20, through the same procedure as in Example 70 were prepared for the pipe holder specimens, respectively.
  • Izod impact strength evaluation It was performed according to ASTM D256.
  • the examples prepared by blending polyketone and mineral reinforcement are excellent in impact resistance and impact stability at 10 KJ / m 2 or more and dimensional change rate of 0.1% or less compared to the comparative example. Was evaluated.
  • the pipe holder manufactured according to the embodiment of the present invention was very suitable for application as a pipe holder because it is very excellent in impact resistance and dimensional stability.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • the residual amount of palladium catalyst was 5 ppm.
  • 65% by weight of the polyketone terpolymer prepared in the same manner as in Example 73 and 16% by weight of sulfonamide-based plasticizer were prepared by adding 18% by weight of ASA and 1% by weight of ASA, and the prepared composition was operated at 250 rpm.
  • the diameter of 40cm, using a biaxial screw of L / D 32 to produce a pellet (pellet) on the extruder, and then injection molding to prepare a shoe material.
  • 65% by weight of the polyketone terpolymer prepared in the same manner as in Example 73 and 12% by weight of sulfonamide-based plasticizer were prepared by adding 20% by weight of polyurethane and 3% by weight of ASA, and the prepared composition was operated at 250 rpm.
  • the diameter of 40cm, using a biaxial screw of L / D 32 to produce a pellet (pellet) on the extruder, and then injection molding to prepare a shoe material.
  • Adhesiveness It hold
  • Examples 73 to 75 was found to be very suitable for use as a shoe material due to excellent flexural strength, elastic modulus and adhesiveness and deformation compared to the comparative example.
  • the shoe material including the polyketone blend of the present invention has excellent flexural modulus of 7000 to 8500 MPa.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 80 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • HFIP hexa-fluoroisopropano
  • a specimen was prepared in the same manner as in Example 77 except for 60 wt% of the polyketone terpolymer and 40 wt% of the glass fiber of Example 2.
  • a specimen was prepared in the same manner as in Example 77 except for 90 wt% of the polyketone terpolymer and 10 wt% of the glass fiber of Example 2.
  • Rhodia PA66 80% by weight Glass Fiber 20%, (A218V30) was prepared in the same manner as in Example 77.
  • Izod impact strength It was conducted according to ASTM D256.
  • Example 27 As shown in Table 22, in the case of Example compared to Comparative Example 27, the product moisture absorption was lower, the impact strength was found to be more excellent. Thus, the specimens prepared through the examples rather than the comparative examples were found to be more advantageous for use as an accelerator pedal.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 80 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • HFIP hexa-fluoroisopropano
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.4 dl / g, a MI (Melt index) of 60 g / 10 min, and an MWD of 1.8.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.2.
  • the blend composition of 90% by weight of the polyketone terpolymer prepared in Example 82 and 10% by weight of glass fiber was introduced into a twin screw extruder of L / D32 and D 40 and extruded through melt kneading at a temperature of 240 ° C. at a 250 rpm screw rotation speed. After the pellet was prepared by injection molding to prepare a transmission bracket specimen.
  • the blend composition of 60% by weight of polyketone terpolymer and 40% by weight of glass fiber prepared in Example 82 was introduced into a twin screw extruder of L / D32 and D40, and extruded through melt kneading at a temperature of 240 ° C. at a 250 rpm screw rotation speed. After the pellet was prepared by injection molding to prepare a transmission bracket specimen.
  • Izod impact strength It was conducted according to ASTM D256.
  • Example 81 Example 82
  • Example 83 Example 84
  • Example 85 Example 86
  • the transmission bracket manufactured according to the embodiment rather than the comparative example has a high impact resistance (impact strength of 17kJ / m2 or more) and high water resistance property retention (tensile strength retention of 80% or more) is more suitable for use as a transmission bracket appear.
  • Example 88 Same as Example 88 except that the intrinsic viscosity of the polyketone was adjusted to 1.1.
  • Example 88 Same as Example 88 except that the intrinsic viscosity of the polyketone was adjusted to 2.0.
  • Rhodia's PA66 Glass Fiber 33% and A218V30 were used.
  • Izod impact strength It was conducted according to ASTM D256.
  • Example 88 Example 89 Example 90 Comparative Example 29 Izod impact strength (kJ / m2) 90 89 92 49 Tensile Strength (MPa) 55 56 57 58 Physical property retention rate (%) (90% relative humidity) 85 84 83 40 Physical property retention rate (%) (10% calcium chloride) 80 78 79 30
  • the tensile strength was similar to that of Comparative Example 29 in the case of Example 88, but the impact strength (75 kJ / m 2 or more) was significantly higher.
  • the physical property retention rate of high humidity and the chemical resistance test of calcium chloride showed that the property retention rate was higher than 75%.
  • the bumper brackets manufactured according to the examples rather than the comparative examples were found to be more suitable for use as bumper brackets because of high impact resistance and high physical property retention.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C.
  • Example 91 Same as Example 91 except that the molar ratio of ethylene and propene in the polyketone terpolymer was adjusted to 47 to 3.
  • Example 91 Same as Example 91 except that the intrinsic viscosity of the polyketone terpolymer was adjusted to 1.1 dl / g.
  • Example 91 Same as Example 91 except that the intrinsic viscosity of the polyketone terpolymer was adjusted to 2.0 dl / g.
  • Example 91 Except for using a polyamide instead of a polyketone terpolymer, a specimen for a car junction box was prepared in the same manner as in Example 91.
  • test piece for an automobile junction box was prepared in the same manner as in Example 91.
  • test box for automobile junction box prepared in Example 91 were evaluated by the following method in comparison with the products of Comparative Examples 30 and 31, and the results are shown in Table 25 below.
  • Example 91 Example 92
  • Example 93 Example 94 Comparative Example 30
  • Comparative Example 31 rescue - Polyketone Polyketone Polyketone Polyketone PA6 Noril
  • Tensile strength retention rate after moisture absorption (%) % 90 88 91 92 60 - Impact strength (room temperature) kJ / m 2 15 16 14 17 6 7 Impact Strength (-40 °C) kJ / m 2 6 7 5 8 3 4
  • the Example showed higher physical property retention after moisture absorption and better impact strength at room temperature and low temperature than the comparative example.
  • the impact strength at room temperature was excellent at 12 KJ / m 2 or more, and the tensile strength retention after moisture absorption was more than 85% compared to before the moisture absorption.
  • the specimen produced by the embodiments of the present invention is suitable for use as a junction box for automobiles.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • HFIP hexa-fluoroisopropano
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 1.8.
  • polyketone polymer 20 parts by weight of glass fiber, 10 parts by weight of calcium carbonate, and 3.5 parts by weight of polyvinyl acetate were mixed with 60 parts by weight of 60% by weight of carbon fiber and 100% by weight of the composite resin composition of polyester. It was put in a twin screw extruder and extruded through melt kneading at a 250 rpm screw rotational speed at a temperature of 240 °C.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 80 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 74 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.4 dl / g, a MI (Melt index) of 60 g / 10 min, and an MWD of 1.8.
  • Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine).
  • the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 °C polymerization temperature 78 °C.
  • the molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4.
  • the polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.2.
  • Example 99 Same as Example 99 except that high impact PBT is used instead of the polyketone of Example 99.
  • the polyketone resin composition pellets of the above examples were molded (injected) to prepare bracket specimens for power line binding, and then evaluated for physical properties in the following manner compared to the products of Comparative Examples, and the results are shown in Table 27 below.
  • Izod impact strength It was conducted according to ASTM D256.
  • Cycle time injection molding evaluation sec: The time until the pellets prepared in Examples or Comparative Examples before the crystallization after melting was measured in seconds.

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Abstract

The present invention relates to a polyketone resin composition prepared by mixing a glass fiber, inorganic filler, a mineral reinforcing agent and the like with a polyketone terpolymer comprising a repeat unit represented by general formulae (1) and (2) below, wherein the composition has excellent impact resistance, elastic modulus and property maintenance after water absorption, and thus is applicable to industrial components such as masks, pipe holders, transmission brackets, bumper brackets, junction boxes for automobiles, wheel rims for automobiles, brackets for connecting power lines, covers of electronic equipment, glasses frames, air intake manifolds for automobiles, carriers for front end modules of automobiles, bezels for headlamps of automobiles, housings of interior lights, ashtrays for automobiles, multi-function switches for automobiles, speaker grills for automobiles, headrest guides for automobiles, navigation pedestals for automobiles, side moldings for automobiles, hose connectors, stem bolts for air conditioners, etc.: -[-CH2CH2-CO]x- (1) -[-CH2-CH(CH3)-CO]y- (2) Also, the present invention relates to a composition in which an amorphous semi-aromatic polyamide and polyester are blended as a polyketone polymer, wherein the polyketone composition enhances flexural properties, resistance to humidity, and dimension stability in use as industrial plastic over prior thermoplastic materials. In addition, the present invention relates to a lower housing of a polyketone laptop computer prepared by injection molding the polyketone composition and, more particularly, to a lower housing of a laptop computer having excellent flexural modulus and low-temperature impact strength, prepared by injection molding a polyketone blend comprising a linear alternative polyketone polymer, a glass fiber, a phosphorous-based flame retardant, and nylon 6I.

Description

내충격성이 우수한 폴리케톤 수지 조성물Polyketone resin composition excellent in impact resistance
본 발명은 내충격성이 우수한 폴리케톤 수지 조성물에 관한 것으로, 보다 상세하게는 폴리케톤 수지에 유리섬유, 무기충전제, 미네랄 보강재 등을 블렌딩하여 제조됨으로써 마스크, 파이프 홀더, 변속기 브라켓, 범퍼 브라켓, 자동차용 정션 박스, 자동차 휠림, 전력선 결속용 브라켓, 전자기기 커버, 안경테, 자동차 에어 인테이크 매니폴드, 자동차 프론트엔드모듈의 캐리어, 자동차 헤드램프베젤, 차량용 재떨이, 자동차용 멀티펑션 스위치, 자동차용 스피커 그릴, 자동차용 헤드레스트 가이드, 자동차용 내비게이션 받침대, 자동차용 사이드 몰딩, 호스 커넥터, 에어컨용 스템 볼트 등 다양한 분야의 산업용 부품으로 적용 가능한 폴리케톤 수지 조성물에 관한 것이다.The present invention relates to a polyketone resin composition having excellent impact resistance, and more particularly, by blending a polyketone resin with glass fiber, an inorganic filler, a mineral reinforcing material, and the like, for a mask, a pipe holder, a transmission bracket, a bumper bracket, and an automobile. Junction box, car wheel rim, bracket for power line, electronics cover, glasses frame, car air intake manifold, carrier of car front end module, car headlamp bezel, car ashtray, car multifunction switch, car speaker grill, car The present invention relates to a polyketone resin composition applicable to various industrial parts such as a head restraint guide for a vehicle, a navigation base for an automobile, an automotive side molding, a hose connector, a stem bolt for an air conditioner, and the like.
또한, 본 발명은 기계적 물성이 우수한 폴리케톤 조성물에 관한 것으로서, 상세하게는 폴리케톤 수지에 비정질 반방향족 폴리아미드 또는 폴리에스테르를 포함하는 블렌드를 이용하여 제조되고 산업용 부품으로 적용 가능한 폴리케톤 조성물에 관한 것이다.In addition, the present invention relates to a polyketone composition having excellent mechanical properties, and more particularly, to a polyketone composition manufactured using a blend containing an amorphous semiaromatic polyamide or polyester in a polyketone resin and applicable to industrial parts. will be.
아울러, 본 발명은 폴리케톤 수지 조성물을 사출성형하여 제조되는 노트북 하단 하우징에 관한 것으로, 보다 상세하게는 폴리케톤 수지 조성물을 사용함으로써 우수한 굴곡탄성율과 저온충격강도를 갖는 노트북 하단 하우징에 관한 것이다.In addition, the present invention relates to a notebook lower housing manufactured by injection molding a polyketone resin composition, and more particularly to a notebook lower housing having excellent flexural modulus and low temperature impact strength by using a polyketone resin composition.
폴리케톤(Polyketone, PK)은 폴리아미드, 폴리에스터 및 폴리카보네이트 등의 일반 엔지니어링 플라스틱 소재 대비 원료 및 중합 공정비가 저렴한 소재인데, 내열성, 내화학성, 내연료투과성 및 내마모성 등의 물성이 우수하여 각종 산업에 폭넓게 적용되고 있다. 때문에 폴리케톤 또는 폴리케톤 폴리머로 알려져 있는, 일산화탄소와 적어도 1종의 에틸렌계 불포화 탄화수소로 되는 한 무리의 선상 교대 폴리머에 대한 관심이 높아지고 있다. 미국특허 제4,880,903호는 일산화탄소와 에틸렌과 타 올레핀계 불포화 탄화수소, 예를 들면 프로필렌(propylene)으로 이루어진 선상 교대 폴리케톤 터폴리머 (polyketone terpolymer)를 개시하고 있다.Polyketone (PK) is a material that has lower raw materials and polymerization process costs than general engineering plastic materials such as polyamide, polyester, and polycarbonate. Polyketone (PK) has excellent properties such as heat resistance, chemical resistance, fuel permeability, and abrasion resistance. It is widely applied to. There is a growing interest in a group of linear alternating polymers, consisting of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, known as polyketones or polyketone polymers. U.S. Patent No. 4,880,903 discloses a linear alternating polyketone terpolymer consisting of carbon monoxide and ethylene and other olefinically unsaturated hydrocarbons, such as propylene.
폴리케톤 폴리머의 제조 방법은 통상 팔라듐(palladium), 코발트 (cobalt) 또는 니켈(nikel)중으로부터 선택된 제VIII족 금속의 화합물과, 비하이드로 할로겐(hydro halogen) 강산(strongon-hydrohalogentic acid)의 음이온과, 인, 비소 또는 안티몬(Antimon)의 2좌 배위자로부터 생성되는 촉매 조성물을 사용한다. 미국특허 제4,843,144는 팔라튬 화합물과, pKa가 6 미만의 비하이드로할로겐산의 음이온과, 인의 2좌 배위자로 되는 촉매를 사용하여 일산화탄소와 적어도 1개의 에틸렌계 불포화 탄화수소와의 폴리머를 제조하는 방법을 개시하고 있다.The process for preparing polyketone polymers is usually a compound of a Group VIII metal selected from palladium, cobalt or nickel, and anions of non-hydro halogen strong-hydrohalogentic acid. Catalyst compositions produced from bidentate ligands of phosphorus, arsenic or antimones are used. U.S. Pat.No. 4,843,144 describes a process for preparing polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of nonhydrohalogenic acid with a pKa of less than 6, and a catalyst that is a bidentate ligand of phosphorus. It is starting.
또한, 최근 플라스틱의 고부가가치화, 고성능화에의 요망, 그리고 하이테크 산업의 진전에 있어서 폴리케톤에 여러 충전제를 사용하고 있다. 충전제의 역할은 원가절감, 물성 또는 성질의 개선, 기능부여 및 가공성 개선 등으로 볼 수 있다.In recent years, many fillers have been used in polyketones for the high value of plastics, the desire for high performance, and the development of high-tech industries. The role of the filler can be seen as cost reduction, improvement of physical properties or properties, functionalization and processability improvement.
이에 따라 상기 폴리케톤 블렌드의 기계적 특성은 열가소성 플라스틱의 응용 산업분야가 다양화 되고 더욱 우수한 특성을 요구하는 산업계의 요청으로 인해 인장강도, 충격강도가 우수한 폴리케톤 수지 조성물에 대한 연구가 요구되고 있다.Accordingly, the mechanical properties of the polyketone blends are diversified in application fields of thermoplastics, and due to industrial demands for more excellent properties, studies on polyketone resin compositions having excellent tensile strength and impact strength are required.
그러나 내마모성, 내충격성 및 내화학성 등의 기능적 장점이 있는 폴리케톤을 자동차, 전기전자, 산업용 등 다양한 분야에 단독으로 적용하기에는 PA66, PBT, POM보다 기계적 물성 특히 굴곡 모듈러스가 낮은 문제점이 있다. 상기 문제점을 해결하기 위해 폴리케톤과 다양한 수지와의 블렌딩이 제안되었으나, 상용성 부족으로 작업성이 떨어지거나, 2차 가공시 신율 및 충격강도 등 다른 물성 값이 저하되어 적용하기 어려운 문제점이 있었다.However, in order to apply polyketone having functional advantages such as abrasion resistance, impact resistance, and chemical resistance to various fields such as automobiles, electric electronics, and industrial applications alone, there is a problem in that mechanical properties, particularly flexural modulus, are lower than those of PA66, PBT, and POM. In order to solve the above problems, blending of polyketone and various resins has been proposed, but it is difficult to apply due to lack of compatibility due to lack of workability or other property values such as elongation and impact strength during secondary processing.
한편, 일본특개평 제11-71513호에는 하우징(housing) 부품으로서 유용하고 유동성, 내열성, 내유기 용매성 및 성형성을 개선된 폴리케톤 수지 조성물을 개시하고 있다. 이 특허에서는 폴리케톤 수지 50∼99.00중량% 및 액정성 수지 0.01∼ 50중량%을 배합한 폴리케톤 수지 100중량부에 대하여, 난연제를 0.01∼60 중량부 함유시킨 폴리케톤 수지 조성물이 개시되어 있다. 이 특허에는 난연제로서 유기 브로화물, 유기인 화합물 등을 사용하고 있다. 그렇지만 유기 할로겐(Halogen)을 함유하는 난연제는 환경문제가 야기되기 때문에 그 사용이 제한되고 있고, 냄새 및 착색의 문제가 많이 발생하고 있다.On the other hand, Japanese Patent Laid-Open No. 11-71513 discloses a polyketone resin composition which is useful as a housing part and improves fluidity, heat resistance, organic solvent resistance and moldability. This patent discloses the polyketone resin composition which contains 0.01-60 weight part of flame retardants with respect to 100 weight part of polyketone resin which mix | blended 50-99.00 weight% of polyketone resins and 0.01-50 weight% of liquid crystalline resins. In this patent, an organic bromide, an organophosphorus compound, etc. are used as a flame retardant. However, flame retardants containing organic halogen (Halogen) is limited because of the use of environmental problems, and a lot of problems of smell and coloring occurs.
종래의 전자 기기 하우징용 재료 중, 나일론 수지, 비강화의 난연 ABS 수지나 난연 PC/ABS 수지는 강성이 낮고, 최근의 박형화의 요구에는 적합하지 않다. 퍼스널 컴퓨터, 전화기, 노트북 등 전기, 전자 기기의 모바일화로 인해 경량성이면서 고강도의 기계적 특성을 갖는 하우징의 개발이 요구되고 있다. 예를 들어 노트북 하우징의 경우, 일부가 휘어서 내부 부품과 접촉되어 내부 부품이 파손되거나, 하우징 자체가 파괴되거나 하는 문제점을 해결하기 위한 재료가 개발되고 있다. 일본 특개 제2008-34823호에는 탄소 섬유를 포함하는 열경화성 수지 부재에 열가소성 수지의 부직포 등으로 이루어지는 접착층을 개재시켜서 유리 섬유를 포함하는 열가소성 수지 부재를 사출 성형함으로써 전자 기기 하우징을 제조하는 기술이 개시되어 있다. 그러나, 종래의 탄소 섬유 강화 열가소성 수지 조성물은 고강성, 경량화를 도모할 수 있는 반면에, 하우징용의 재료로서는 무르고 갈라지기 쉽다는 문제점을 가진다.Of the conventional electronic device housing materials, nylon resins, non-reinforced flame retardant ABS resins and flame retardant PC / ABS resins have low rigidity and are not suitable for the recent thinning requirements. Due to the mobility of electric and electronic devices such as personal computers, telephones, notebooks, and the like, development of housings having lightweight and high strength mechanical properties is required. For example, in the case of a notebook housing, a material is developed to solve the problem that a part is bent and comes into contact with an internal component, and the internal component is broken or the housing itself is destroyed. Japanese Patent Laid-Open No. 2008-34823 discloses a technique for producing an electronic device housing by injection molding a thermoplastic resin member containing glass fibers by interposing a thermosetting resin member containing carbon fibers with an adhesive layer made of a nonwoven fabric of a thermoplastic resin. have. However, the conventional carbon fiber reinforced thermoplastic resin composition can achieve high rigidity and light weight, but has a problem of being soft and brittle as a material for a housing.
본 발명은 상기한 문제점을 해결하고자 기존 폴리케톤 폴리머에 비해 인장강도 및 충격강도가 우수한 폴리케톤 수지 조성물을 제공하는 것을 목적으로 한다.An object of the present invention to provide a polyketone resin composition excellent in tensile strength and impact strength compared to the existing polyketone polymer to solve the above problems.
또한, 본 발명은 상기 문제점을 해결하고자, 기존 폴리케톤 조성물에 비해 인장강도, 충격강도는 일정수준을 유지하면서 굴곡특성을 향상시킬 수 있는 폴리케톤 조성물을 제공하는 것을 목적으로 한다.In addition, to solve the above problems, an object of the present invention is to provide a polyketone composition that can improve the bending characteristics while maintaining a certain level of tensile strength, impact strength compared to the existing polyketone composition.
아울러, 본 발명은 폴리케톤 조성물을 사출성형하여 충분한 굴곡탄성율, 우수한 저온내충격성을 특징으로 하는 노트북 하단 하우징을 얻는 것을 목적으로 한다.In addition, an object of the present invention is to obtain a notebook bottom housing characterized by sufficient flexural modulus and excellent low temperature impact resistance by injection molding a polyketone composition.
상기한 과제를 해결하기 위하여 본 발명은The present invention to solve the above problems
하기 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, 분자량 분포가 1.5 내지 2.5이고, y/x가 0.03 내지 0.3인 선상 교대 폴리케톤과 유리섬유, 무기충전제, 미네랄 보강제를 포함하여 구성되는 것을 특징으로 한 내충격성이 향상된 폴리케톤 수지 조성물을 과제 해결을 위한 수단으로 제공한다.A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), the molecular weight distribution of 1.5 to 2.5, y / x of 0.03 to 0.3 linear alternating polyketone and glass fiber, inorganic filler, It provides a polyketone resin composition with improved impact resistance comprising a mineral reinforcing agent as a means for solving the problem.
-[-CH2CH2-CO]x- (1)-[-CH2CH2-CO] x- (1)
-[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
(x, y는 폴리머 중의 일반식 (1) 및 (2)의 각각의 몰%를 나타낸다.(x, y represents each mol% of General Formula (1) and (2) in a polymer.
한편 본 발명은 상기한 과제를 보다 효과적으로 해결하기 위하여 폴리우레탄 수지, 폴리카보네이트 수지, 폴리아미드6 수지와, 고무, ASA 및 설폰아미드계 가소제를 더 포함하여 제조될 수 있다. On the other hand, the present invention may be prepared by further comprising a polyurethane resin, polycarbonate resin, polyamide 6 resin, rubber, ASA and sulfonamide plasticizer in order to solve the above problems more effectively.
본 발명의 상기 폴리케톤 수지 조성물은 상기 폴리케톤 공중합체 100 중량부 대비 유리섬유, 무기충전제, 미네랄 보강제, 폴리우레탄 수지, 폴리카보네이트 수지, 폴리아미드 6수지와, 고무, ASA 및 설폰아미드계 가소제가 5 내지 50 중량부 만큼 단독 또는 혼합하여 첨가되는 것을 특징으로 한다.The polyketone resin composition of the present invention is a glass fiber, inorganic filler, mineral reinforcing agent, polyurethane resin, polycarbonate resin, polyamide 6 resin, rubber, ASA and sulfonamide plasticizer relative to 100 parts by weight of the polyketone copolymer It is characterized in that it is added alone or mixed by 5 to 50 parts by weight.
본 발명은 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 60 내지 90중량%와 유리섬유 10 내지 40 중량%를 혼합한 블렌드를 사출성형하여 제조되는 것을 특징으로 폴리케톤 조성물을 제공한다.The present invention consists of carbon monoxide and at least one olefinically unsaturated hydrocarbon, 60 to 90% by weight of alternating polyketone and 10 to 40% by weight of linear fiber having a residual amount of palladium catalyst of 5 to 50 ppm and a molecular weight distribution of 1.5 to 3.0. It provides a polyketone composition, characterized in that the blend is prepared by injection molding.
팔라듐 화합물, pKa값이 6 이하인 산, 및 인의 2배위자 화합물을 포함하는 촉매 조성물을 준비하는 단계; 알코올(예컨대, 메탄올)과 물을 포함하는 혼합용매(중합용매)를 준비하는 단계; 상기 촉매 조성물 및 혼합용매의 존재 하에서 중합을 진행하여 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머를 제조하는 단계; 상기 선상 터폴리머에서 남은 촉매 조성물을 용매로 제거하여 폴리케톤 수지를 수득하는 단계; 및 상기 폴리케톤 수지 60 내지 90중량%와 유리섬유 10 내지 40중량%를 혼합한 블렌드 100중량%를 사출성형하여 폴리케톤 자동차 에어 인테이크 매니폴드를 제조하는 단계; 를 포함하는 폴리케톤 조성물의 제조방법을 특징으로 한다.Preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bipolar compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And preparing a polyketone automobile air intake manifold by injection molding 100 wt% of the blend containing 60 to 90 wt% of the polyketone resin and 10 to 40 wt% of the glass fiber; Characterized in that the manufacturing method of the polyketone composition comprising a.
고유점도(LVN)는 1.0~2.0dl/g이고, 충격강도가 10~12kJ/m2, 반발탄성이 35% 내지 45%인 것을 특징으로 하는 폴리케톤-폴리우레탄 수지 조성물로 제조된 성형품을 제공한다.Intrinsic viscosity (LVN) is 1.0 ~ 2.0dl / g, the impact strength is 10 ~ 12kJ / m 2, provides a molded article made of a polyketone-polyurethane resin composition, characterized in that the resilience is 35% to 45% do.
폴리케톤과 유리섬유의 중량비가 50:50 내지 95:5, 유리섬유는 직경이 10 μm이고, 길이가 4mm이며, 폴리우레탄으로 코팅된 것을 특징으로 하며, 폴리케톤 중합시 사용되는 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 폴리케톤 조성물로 제조된 폴리케톤 성형품을 제공한다.The weight ratio of polyketone and glass fiber is 50:50 to 95: 5, and the glass fiber has a diameter of 10 μm, a length of 4 mm, and is coated with polyurethane, and a ligand of a catalyst composition used in polyketone polymerization. Is a ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) prepared as a polyketone composition, characterized in that Polyketone molded articles.
경도가 95 이상, 폴리케톤 조성물 전체 중량에 대하여 폴리카보네이트의 조성비는 1중량% 내지 30중량%이며, 폴리케톤 공중합체의 중합시 사용되는 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하며, 고유점도는 1.0 내지 2.0 dl/g이며, 폴리케톤 조성물로 제조된 산업용 부품을 제공한다.The hardness is 95 or more, and the composition ratio of polycarbonate is 1% by weight to 30% by weight based on the total weight of the polyketone composition, and the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1, 3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and has an inherent viscosity of 1.0 to 2.0 dl / g, as a polyketone composition. Provides manufactured industrial parts.
폴리케톤 안경테는 굽힘각도가 2°이하이며, 폴리케톤 공중합체의 고유점도는 1.0dl/g 내지 2.0dl/g 인 것을 특징으로 하는 폴리케톤 안경테를 제공한다.The polyketone spectacle frame has a bending angle of 2 ° or less, and the intrinsic viscosity of the polyketone copolymer provides a polyketone spectacle frame, characterized in that 1.0dl / g to 2.0dl / g.
폴리케톤 마스크의 내충격성이 80kJ/m2이상인 것을 특징으로 하는 폴리케톤 고충격 마스크로, 폴리케톤의 흡습 후 물성 유지율이 흡습 전 물성에 대하여 85%이상이며, 폴리케톤의 중합에 사용되는 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 폴리케톤 고충격 마스크를 제공한다.Polyketone high impact mask, characterized in that the impact resistance of the polyketone mask is 80kJ / m2 or more, the retention of physical properties after moisture absorption of the polyketone is 85% or more relative to the physical properties before the moisture absorption, the catalyst composition used for the polymerization of polyketone Ligand is a poly (ketone) high impact, characterized in that ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) Provide a mask.
일산화탄소와 적어도 1종의 올레핀계 탄화수소로 이루어진 선상 교대 폴리케톤 50 내지 90중량%와 미네랄 보강재를 10 내지 50 중량%를 혼합한 블렌드를 사출성형하여 제조되고, 충격강도가 10kJ/m2 이상인 것을 특징으로 하는 폴리케톤 파이프 홀더로서, 에틸렌과 프로필렌의 몰비가 45:5 내지 48:2, 폴리케톤 파이프 홀더의 치수변화율이 0.1% 이하이며, 네랄 보강재는 탈크(Talc), 카오린(Kaolin), 마이카(Mica), 월라스토나이트(wollastonite), TiO2-코팅된 마이카 소형판 (TiO2-coated mica platelets), 실리카(silica), 알루미나(alumina), 붕규산염 (borosilicates) 및 산화물 (oxides)로 이루어진 군에서 선택된 1종인 것을 특징으로 한다.It is produced by injection molding a blend of 50 to 90% by weight of linear alternating polyketone consisting of carbon monoxide and at least one olefinic hydrocarbon and 10 to 50% by weight of mineral reinforcing material, and has an impact strength of 10 kJ / m 2 or more. Polyketone pipe holder, the molar ratio of ethylene and propylene is 45: 5 to 48: 2, the dimensional change rate of the polyketone pipe holder is 0.1% or less, the neural reinforcing material is Talc, Kaolin, Mica ), Wollastonite, TiO2-coated mica platelets, 1 selected from the group consisting of silica, alumina, borosilicates and oxides It is characterized by being a species.
또한, 팔라듐 화합물, pKa값이 6 이하인 산, 및 인의 2배위자 화합물을 포함하는 촉매 조성물을 준비하는 단계; 알코올(예컨대, 메탄올)과 물을 포함하는 혼합용매(중합용매)를 준비하는 단계; 상기 촉매 조성물 및 혼합용매의 존재 하에서 중합을 진행하여 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머를 제조하는 단계; 상기 선상 터폴리머에서 남은 촉매 조성물을 용매로 제거하여 폴리케톤 수지를 수득하는 단계; 및 상기 폴리케톤 수지 50 내지 90중량%와 미네랄 보강재 10 내지 50중량%를 혼합한 블렌드 100중량%를 사출성형하여 폴리케톤 파이프 홀더를 제조하는 단계; 를 포함하는 폴리케톤 파이프 홀더의 제조방법을 제공한다.In addition, preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a double ligand compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And injection molding 100% by weight of the blend of 50 to 90% by weight of the polyketone resin and 10 to 50% by weight of the mineral reinforcing material to manufacture a polyketone pipe holder. It provides a method for producing a polyketone pipe holder comprising a.
일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 50ppm이하 이고, 분자량 분포가 1.5 내지 2.5인 선상 교대 폴리케톤 폴리머 와 설폰아미드계 가소제, 폴리우레탄, ASA(Acrylic Styrene Acrylonitrile)를 포함하는 블렌드를 사출성형하여 제조되고, 상기 설폰아미드계 가소제, 폴리우레탄 및 ASA는 블렌드 전체 대비 각각 10 내지 20중량%, 15 내지 20중량% 및 1 내지 10중량% 인 것을 특징으로 하는 신발용 소재로, 상기 선상 교대 폴리케톤의 중합시 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)이며, 굴곡탄성율이 7000 내지 8500MPa인 것을 특징으로 하는 신발용 소재를 제공한다.Linear alternating polyketone polymer, sulfonamide plasticizer, polyurethane, ASA (Acrylic Styrene Acrylonitrile) consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon and having a residual amount of palladium catalyst of 50 ppm or less and a molecular weight distribution of 1.5 to 2.5 It is prepared by injection molding the blend, wherein the sulfonamide-based plasticizer, polyurethane and ASA is a shoe material, characterized in that 10 to 20% by weight, 15 to 20% by weight and 1 to 10% by weight, respectively, relative to the total blend In the polymerization of the linear alternating polyketone, the ligand of the catalyst composition is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl Phosphine), the flexural modulus is 7000 to 8500MPa to provide a shoe material, characterized in that.
50℃, 90%의 상대습도 조건에서의 흡습율이 1.0% 미만이고, 충격강도가 15kJ/m2 이상인 것을 특징으로 하는 폴리케톤 성형제품으로, 폴리케톤 터폴리머의 함량은 50 내지 90 중량% 이고, 유리섬유의 함량은 10 내지 50 중량%이며, 폴리케톤 성형제품이 엑셀레이터 페달인 것을 특징으로 하는 폴리케톤 성형제품을 제공한다.Polyketone molded product characterized in that the moisture absorption rate is less than 1.0% at 50 ℃, 90% relative humidity conditions, the impact strength is 15kJ / m2 or more, the content of the polyketone terpolymer is 50 to 90% by weight, The content of the glass fiber is 10 to 50% by weight and provides a polyketone molded product, characterized in that the polyketone molded product is an accelerator pedal.
충격강도가 17kJ/m2이상, 폴리케톤 공중합체의 분자량 분포는 1.5 내지 2.5 이며, 폴리케톤 중합시 사용되는 촉매 조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)이며, 폴리케톤 변속기 브라켓의 흡습 후 인장강도 유지율이 80% 이상인 것을 특징으로 하는 폴리케톤 변속기 브라켓을 제공한다.The impact strength is 17 kJ / m 2 or more, the molecular weight distribution of the polyketone copolymer is 1.5 to 2.5, the ligand of the catalyst composition used in the polyketone polymerization is ((2,2-dimethyl-1,3-dioxane-5,5 -Diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and provides a polyketone transmission bracket characterized in that the tensile strength retention after moisture absorption of the polyketone transmission bracket is 80% or more.
일산화탄소와 적어도 일종의 올레핀계 불포화 탄화수소로 이루어진 선상 교대 폴리케톤과 폴리아미드6 및 고무를 포함하는 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 폴리케톤 범퍼 브라켓으로, 렌드 전체 중량%에 대하여 폴리케톤은 40 내지 90중량%, 폴리아미드 6는 5 내지 40 중량% 및 고무는 5 내지 20중량%, 폴리케톤은 70중량%, 폴리아미드 6는 22중량% 및 고무는 8중량%이며, 폴리케톤 범퍼 브라켓의 충격강도는 75kJ/m2, 폴리케톤 범퍼 브라켓은 염화칼슘 10% 수용액에서 인장강도 유지율이 75%이상이고, 고무는 에틸렌프로필렌 디엔모노머 고무인 것을 특징으로 하는 폴리케톤 범퍼 브라켓을 제공한다.A polyketone bumper bracket produced by injection molding a blend of linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon, polyamide 6 and rubber, wherein the polyketone is 40% by weight of the total blend. To 90% by weight, 5 to 40% by weight of polyamide 6 and 5 to 20% by weight of rubber, 70% by weight of polyketone, 22% by weight of polyamide 6 and 8% by weight of rubber. The impact strength is 75 kJ / m2, the polyketone bumper bracket provides a polyketone bumper bracket, characterized in that the tensile strength retention of 75% or more in a 10% calcium chloride solution, the rubber is ethylene propylene diene monomer rubber.
자동차용 정션 박스는 상온에서 충격강도가 12kJ/m2 이상, 흡습 후 인장강도 유지율이 흡습 전 물성에 대하여 85%이상인 것을 특징으로 하는 폴리케톤 공중합체의 중합시 사용되는 촉매 조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 자동차용 정션 박스를 제공한다.In the junction box for automobiles, the ligand of the catalyst composition used in the polymerization of a polyketone copolymer is characterized in that the impact strength at room temperature is 12 kJ / m 2 or more and the tensile strength retention after moisture absorption is 85% or more relative to the property before absorption. Provided is an automotive junction box which is, 2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine).
유리섬유와 무기 충전제는 폴리케톤 공중합체 100중량부 대비 각각 20~50중량부, 5.5~15.5 중량부만큼 포함되며, 무기 충전제는 탄산칼슘, 황산마그네슘, 실리콘 카바이드, 산화칼슘으로부터 선택되고, 촉매 조성물을 구성하는 인의 2배위자 화합물로 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)을 사용하는 것을 특징으로 한 자동차 휠의 림을 제공한다.The glass fiber and the inorganic filler are included in an amount of 20 to 50 parts by weight and 5.5 to 15.5 parts by weight, respectively, based on 100 parts by weight of the polyketone copolymer, and the inorganic filler is selected from calcium carbonate, magnesium sulfate, silicon carbide, and calcium oxide, and the catalyst composition. ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) as a double ligand compound of phosphorus It provides a rim of a car wheel, characterized in that.
일산화탄소와 적어도 1종의 에틸렌계 불포화 탄화수소로 이루어진 선상 교대 폴리케톤을 사출성형하여 제조되는 것을 특징으로 하는 전력선 결속용 브라켓으로, 충격강도가 8kJ/m2 이상, 에틸렌과 프로필렌의 몰비%가 9 내지 24 : 1, 고유점도는 1.0 내지 2.0 dl/g이 바람직하고, 폴리케톤의 중합시 사용되는 촉매 조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 전력선 결속용 브라켓을 제공한다.A power line binding bracket manufactured by injection molding a linear alternating polyketone made of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, the impact strength of 8 kJ / m 2 or more, and the molar ratio of ethylene and propylene of 9 to 24 : 1, the intrinsic viscosity is preferably 1.0 to 2.0 dl / g, the ligand of the catalyst composition used in the polymerization of polyketone is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (Methylene)) bis (bis (2-methoxyphenyl) phosphine) provides a power line binding bracket.
블렌드 대비 유리섬유의 함량은 5 내지 50중량%인 것을 특징으로 하는 폴리케톤 전자기기 커버로, 전자기기 커버의 제품변형율이 0.1% 이하이고, 상기 전자기기 커버는 핸드폰 보호 커버인 것을 특징으로 하는 폴리케톤 전자기기 커버를 제공한다.Polyketone electronic device cover characterized in that the content of the glass fiber compared to the blend is 5 to 50% by weight, the product strain of the electronic device cover is less than 0.1%, the electronic device cover is a poly protective cover Provides ketone electronics cover.
상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비가 9 내지 24:1 인 것을 특징으로 하는 전기전자제품용 뚜껑으로, 전지전자제품용 뚜껑은 충격강도가 15kJ/m2 이상이고, 50℃, 상대습도 90%RH에서 수분 흡습율이 1.5% 미만이며, 50℃, 상대습도 90%RH에서 측정한 인장강도가 25℃, 상대습도 65%RH에서 측정한 인장강도 대비 85% 이상 수준을 유지하며, 뚜껑은 압력밥솥용인 것을 특징으로 하는 전기전자제품용 뚜껑을 제공한다.The linear alternating polyketone is a lid for electrical and electronic products, characterized in that the molar ratio of ethylene and propylene is 9 to 24: 1, the lid for battery electronics has an impact strength of 15 kJ / m 2 or more, 50 ℃, relative humidity The moisture absorption rate is less than 1.5% at 90% RH, and the tensile strength measured at 50 ° C and 90% RH is maintained at a level of 85% or higher than the tensile strength measured at 25 ° C and 65% RH. Provides a lid for electrical and electronic products, characterized in that for the pressure cooker.
폴리케톤 자동차 에어 인테이크 매니폴드는 충격강도가 8kJ/m2 이상이고, 120℃에서 300시간 처리 후 인장강도 유지율이 100% 이상인 것을 특징으로 하는 폴리케톤 자동차 에어 인테이크 매니폴드로, 팔라듐 화합물, pKa값이 6 이하인 산, 및 인의 2배위자 화합물을 포함하는 촉매 조성물을 준비하는 단계; 알코올(예컨대, 메탄올)과 물을 포함하는 혼합용매(중합용매)를 준비하는 단계; 상기 촉매 조성물 및 혼합용매의 존재 하에서 중합을 진행하여 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머를 제조하는 단계; 상기 선상 터폴리머에서 남은 촉매 조성물을 용매로 제거하여 폴리케톤 수지를 수득하는 단계; 및 상기 폴리케톤 수지 60 내지 90중량%와 유리섬유 10 내지 40중량%를 혼합한 블렌드 100중량%를 사출성형하여 폴리케톤 자동차 에어 인테이크 매니폴드를 제조하는 단계;를 포함하는 폴리케톤 자동차 에어 인테이크 매니폴드의 제조방법을 제공한다.Polyketone automotive air intake manifold is a polyketone automotive air intake manifold, characterized in that the impact strength is 8kJ / m2 or more, the tensile strength retention is 100% or more after 300 hours treatment at 120 ℃, palladium compound, pKa value Preparing a catalyst composition comprising an acid that is less than or equal to 6 and a ligand compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And manufacturing a polyketone car air intake manifold by injection molding 100% by weight of the blend containing 60 to 90% by weight of the polyketone resin and 10 to 40% by weight of glass fiber to manufacture a polyketone car air intake manifold. Provided are methods of making folds.
폴리케톤 자동차 프론트엔드모듈의 캐리어는 충격강도가 8kJ/m2 이상이고, 120℃에서 300시간 처리 후 인장강도 유지율이 100% 이상이 바람직하며, 팔라듐 화합물, pKa값이 6 이하인 산, 및 인의 2배위자 화합물을 포함하는 촉매 조성물을 준비하는 단계; 알코올(예컨대, 메탄올)과 물을 포함하는 혼합용매(중합용매)를 준비하는 단계; 상기 촉매 조성물 및 혼합용매의 존재 하에서 중합을 진행하여 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머를 제조하는 단계; 상기 선상 터폴리머에서 남은 촉매 조성물을 용매로 제거하여 폴리케톤 수지를 수득하는 단계; 및 상기 폴리케톤 수지 60 내지 90중량%와 유리섬유 10 내지 40중량%를 혼합한 블렌드 100중량%를 사출성형하여 폴리케톤 자동차 프론트엔드모듈의 캐리어를 제조하는 단계;를 포함하는 폴리케톤 자동차 프론트엔드모듈의 캐리어의 제조방법을 제공한다.The carrier of the polyketone automotive front end module has an impact strength of 8 kJ / m 2 or more and a tensile strength retention of 100% or more after 300 hours of treatment at 120 ° C., a palladium compound, an acid having a pKa of 6 or less, and a double ligand of phosphorus. Preparing a catalyst composition comprising a compound; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And manufacturing a carrier of the polyketone car front end module by injection molding 100 wt% of the blend containing 60 to 90% by weight of the polyketone resin and 10 to 40% by weight of glass fiber. It provides a method of manufacturing a carrier of a module.
자동차 헤드램프베젤의 충격강도가 20kJ/m2 이상이고, 미네랄 필러는 탈크(Talc), 카오린(Kaolin), 마이카(Mica), 월라스토나이트(wollastonite), TiO2-코팅된 마이카 소형판 (TiO2-coated mica platelets), 실리카(silica), 알루미나(alumina), 붕규산염 (borosilicates) 및 산화물 (oxides)로 이루어진 군에서 선택된 어느 하나인 것을 특징으로 하며, 상기 블렌드 전체 100 중량%를 기준으로, 상기 미네랄 필러는 5 내지 50 중량%인 것을 특징으로 하는 자동차 헤드램프베젤을 제공한다.Impact strength of automobile headlamp bezel is 20kJ / m 2 or more, mineral fillers are talc, kaolin, mica, wollastonite, TiO2-coated mica compact (TiO2- coated mica platelets), silica (silica), alumina (alumina), borosilicate (borosilicates) and oxides (oxides), characterized in that any one selected from the group consisting of, based on 100% by weight of the total blend, the mineral Filler provides an automotive headlamp bezel, characterized in that 5 to 50% by weight.
선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15 인 것을 특징으로 하는 폴리케톤 블렌드를 포함하는 차량용 캐니스터로, 캐니스터는 충격강도가 20kJ/m2 이상인 것을 특징으로 한다.Linear alternating polyketone is a vehicle canister comprising a polyketone blend, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15, characterized in that the canister has an impact strength of 20 kJ / m 2 or more.
일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 폴리머 60 내지 85 중량%와 유리섬유 15 내지 40 중량%를 포함하는 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 실내등 하우징으로, 충격강도가 20kJ/m2 이상인 것을 특징으로 한다.Consists of carbon monoxide and at least one olefinically unsaturated hydrocarbon, containing 5 to 50 ppm of palladium catalyst residue, 60 to 85 wt% of linear alternating polyketone polymer having a molecular weight distribution of 1.5 to 3.0, and 15 to 40 wt% of glass fibers. The interior lamp housing, characterized in that the blend is manufactured by injection molding, characterized in that the impact strength is 20kJ / m 2 or more.
차량용 재떨이는 충격강도가 8kJ/m2 이상이고, 50℃, 상대습도 90%RH에서 측정한 충격강도가 25℃, 상대습도 65%RH에서 측정한 충격강도 대비 90% 이상 수준을 유지하는 것을 특징으로 하는 차량용 재떨이를 제공한다.The ashtray for vehicles has an impact strength of 8 kJ / m 2 or more, and the impact strength measured at 50 ° C. and 90% RH is maintained at a level of 90% or more compared to the impact strength measured at 25 ° C. and 65% RH. An ashtray for a vehicle is provided.
자동차용 멀티펑션 스위치는 충격강도가 8kJ/m2 이상이고, 물성유지율이 90% 이상인 것을 특징으로 하는 자동차용 멀티펑션 스위치를 제공한다.Automotive multi-function switch provides a multi-function switch for the automobile, characterized in that the impact strength is 8kJ / m 2 or more, and the property retention is 90% or more.
일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 폴리머를 사출성형하여 제조되는 것을 특징으로 하는 자동차용 스피커 그릴로서, 충격강도가 15kJ/m2 이상인 것을 특징으로 한다.An automobile speaker grill, which is produced by injection molding a linear alternating polyketone polymer comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon, having a residual amount of palladium catalyst of 5 to 50 ppm and a molecular weight distribution of 1.5 to 3.0. , Impact strength is characterized in that more than 15kJ / m 2 .
자동차용 헤드레스트 가이드는 충격강도가 20kJ/m2 이상인 것을 특징으로 하는 자동차용 헤드레스트 가이드를 제공한다.The headrest guide for automobiles provides a headrest guide for automobiles, characterized in that the impact strength is 20kJ / m 2 or more.
자동차용 내비게이션 받침대는 충격강도가 15kJ/m2 이상인 것을 특징으로 하는 자동차용 내비게이션 받침대를 제공한다.The car navigation support provides a car navigation support, characterized in that the impact strength is more than 15kJ / m 2 .
자동차용 사이드 몰딩은 충격강도가 15kJ/m2 이상인 것을 특징으로 하는 자동차용 사이드 몰딩을 제공한다.Automotive side moldings provide automotive side moldings characterized in that the impact strength is at least 15 kJ / m 2 .
영하 30℃에서의 저온 충격강도가 4kJ/m2 이상인 것을 특징으로 하는 폴리케톤 호스 커넥터로, 폴리케톤 공중합체의 중합에 사용되는 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 폴리케톤 호스 커넥터를 제공한다.Polyketone hose connector, characterized in that the low temperature impact strength at minus 30 ℃ 4kJ / m2 or more, the ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-di Provided is a polyketone hose connector characterized in that it is oxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine).
폴리케톤 에어컨용 스템 볼트는 파단신율이 100% 이상이고, 충격강도가 10kJ/m2 이상인 것을 특징으로 하는 폴리케톤 에어컨용 스템 볼트이며, 폴리케톤 공중합체의 중합에 사용되는 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 폴리케톤 에어컨용 스템 볼트를 제공한다.Stem bolt for polyketone air conditioner is a stem bolt for polyketone air conditioner characterized in that the elongation at break is more than 100%, the impact strength is 10kJ / m2 or more, the ligand of the catalyst composition used for the polymerization of the polyketone copolymer (( Provides a stem bolt for polyketone air conditioner, characterized in that 2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) do.
또한, 본 발명은 하기 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, 분자량이 20,000 내지 200,000이며, 분자량 분포가 1.5 내지 2.5이고, y/x가 0.03 내지 0.3인 선상 교대 폴리케톤과 비정질 반방향족 폴리아미드를 포함하며, 상기 폴리케톤과 비정질 반방향족 폴리아미드의 중량비가 60:40 내지 95:5 인 것을 특징으로 하는 폴리케톤 조성물도 제공한다.In addition, the present invention is a polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), having a molecular weight of 20,000 to 200,000, a molecular weight distribution of 1.5 to 2.5, and y / x of 0.03 to 0.3 Also provided are polyketone compositions comprising phosphorus alternating polyketones and amorphous semiaromatic polyamides, wherein the weight ratio of said polyketones to amorphous semiaromatic polyamides is from 60:40 to 95: 5.
-[-CH2CH2-CO]x- (1)-[-CH2CH2-CO] x- (1)
-[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
(x, y는 폴리머 중의 일반식 (1) 및 (2)의 각각의 몰%를 나타낸다.)(x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)
이때, 상기 비정질 반방향족 폴리아미드는 폴리헥사메틸렌이소프탈아미드인 것이 바람직하다.In this case, the amorphous semiaromatic polyamide is preferably polyhexamethyleneisophthalamide.
또한, 상기 폴리케톤 조성물의 굴곡강도는 65 내지 90MPa 이고, 굴곡탄성률은 1,700MPa 이상이며, 충격강도는 7kJ/m2 이상인 것이 바람직하다.In addition, the flexural strength of the polyketone composition is 65 to 90MPa, the flexural modulus is 1,700MPa or more, the impact strength is preferably 7kJ / m2 or more.
아울러, 본 발명은 상기 폴리케톤 조성물로 제조된 폴리케톤 성형품도 제공한다.In addition, the present invention also provides a polyketone molded article made of the polyketone composition.
또한, 본 발명은 하기 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, y/x가 0.03 내지 0.3인 선상 교대 폴리케톤과 폴리에스테르를 포함하고, 상기 폴리에스테르는 조성물 전체중량 대비 10 내지 90 중량%인 것을 특징으로 하는 폴리케톤 조성물을 제공한다.In addition, the present invention is a polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), and includes a linear alternating polyketone and a polyester having y / x of 0.03 to 0.3, wherein the polyester Is a polyketone composition, characterized in that 10 to 90% by weight relative to the total weight of the composition.
-[-CH2CH2-CO]x- (1)-[-CH2CH2-CO] x- (1)
-[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
(x, y는 폴리머 중의 일반식 (1) 및 (2)의 각각의 몰%를 나타낸다.)(x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)
이때, 상기 폴리케톤은 고유점도가 1.0 내지 2.0 dl/g인 것이 바람직하다.At this time, the polyketone preferably has an intrinsic viscosity of 1.0 to 2.0 dl / g.
또한, 상기 폴리케톤 조성물은 ASTM D-638에 의해 300℃에서 2시간 열처리하여, 상기 처리전후의 폴리케톤 조성물 시편의 사출방향부분 및 직각방향의 폭을 슬라이드캘리퍼에 의해 측정 시, 각각 2.0%이하 및 0.5%이하인 것이 바람직하다.In addition, the polyketone composition was heat treated at 300 ° C. for 2 hours by ASTM D-638, and the width of the injection direction portion and the right angle direction of the polyketone composition specimens before and after the treatment were measured by a slide caliper, respectively, 2.0% or less. And 0.5% or less.
아울러, 본 발명은 상기 폴리케톤 조성물을 포함하는 자동차 연료 용기용 폴리케톤 성형품도 제공한다.In addition, the present invention also provides a polyketone molded article for an automobile fuel container including the polyketone composition.
또한, 본 발명은 폴리케톤 조성물 중 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 50ppm이하 이고, 분자량 분포가 1.5 내지 2.5인 선상 교대 폴리케톤 폴리머 53 내지 71중량%와, 유리섬유 25 내지 35중량%와, 인계 난연제 2 내지 12중량%와, 나일론 6I 2 내지 8중량%를 포함하는 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 폴리케톤 노트북 하단 하우징을 제공한다.In addition, the present invention is composed of 53 to 71% by weight of a linear alternating polyketone polymer consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon in the polyketone composition, the residual amount of palladium catalyst is 50 ppm or less, molecular weight distribution of 1.5 to 2.5, Provided is a polyketone notebook bottom housing, which is manufactured by injection molding a blend comprising 25 to 35% by weight of glass fiber, 2 to 12% by weight of phosphorus flame retardant, and 2 to 8% by weight of nylon 6I.
이때, 상기 선상 교대 폴리케톤의 중합시 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것이 바람직하다.At this time, the ligand of the catalyst composition during the polymerization of the linear alternating polyketone is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl Phosphine).
또한, 상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.0 내지 2.0dl/g인 것이 바람직하다.In addition, the intrinsic viscosity of the linear alternating polyketone polymer is preferably 1.0 to 2.0 dl / g.
또한, 상기 폴리케톤 노트북 하단 하우징의 굴곡 탄성율이 8,000MPa 이상이고, 저온 충격강도가 11.0kJ/m2 이상인 것을 특징으로 한다.In addition, the polyketone notebook lower housing is characterized in that the flexural modulus is 8,000MPa or more, low temperature impact strength is 11.0kJ / m 2 or more.
본 발명의 폴리케톤 수지 조성물은 굴곡특성, 인장강도, 충격강도, 내습성 및 치수안정성이 우수하여 마스크, 파이프 홀더, 변속기 브라켓, 범퍼 브라켓, 자동차용 정션 박스, 자동차 휠림, 전력선 결속용 브라켓, 전자기기 커버, 안경테 등 다양한 분야의 산업용 부품으로 적용 가능한 장점이 있다.Polyketone resin composition of the present invention is excellent in flexural properties, tensile strength, impact strength, moisture resistance and dimensional stability mask, pipe holder, transmission bracket, bumper bracket, automotive junction box, automotive wheel rim, power line binding bracket, electronics There is an advantage that can be applied to various industrial parts, such as device covers, eyeglass frames.
또한, 본 발명의 폴리케톤 조성물은 기존의 노트북 하단 하우징 소재로 사용되는 나일론 수지에 비해 강도가 높아서 내충격성이 향상된 노트북 하단 하우징을 얻을 수 있다.In addition, the polyketone composition of the present invention is higher in strength than the nylon resin used as a conventional notebook bottom housing material can obtain a notebook bottom housing with improved impact resistance.
이하, 폴리케톤 폴리머에 대해 설명하면 다음과 같다.Hereinafter, the polyketone polymer will be described.
본 발명에서 사용되는 폴리케톤(poly ketone)수지는 엔지니어링 플라스틱이며 근래 개발된 새로운 수지로서, 굴곡특성 등과 같은 기계적 물성 및 성형 특성이 탁월하여 각종 성형품이나 부품의 소재로 유용하게 적용되고 있는 열가소성 합성수지이다. 폴리케톤 수지의 기계적 물성은 고성능 플라스틱의 범주에 속하며, 일산화탄소를 원료로 합성하는 고분자 물질인 바, 친환경 소재로서도 크게 주목받고 있다.The poly ketone resin used in the present invention is an engineering plastic and is a recently developed new resin, and is a thermoplastic synthetic resin that is usefully applied as a material for various molded products or parts due to its excellent mechanical properties and molding properties such as bending characteristics. . Mechanical properties of the polyketone resin belongs to the category of high performance plastics, and is a polymer material that synthesizes carbon monoxide as a raw material.
폴리케톤 수지는 나일론 재질에 비하여 수분흡습도가 낮아 수분 흡습에 따른 치수 및 물성변화가 적고 다양한 제품 설계가 가능한 소재이다. 특히 폴리케톤 수지는 알루미늄 재질에 비하여 밀도가 낮아 제품 경량화에도 매우 적합하다.Polyketone resin has lower moisture absorption than nylon material, so it is possible to design various products with little change in dimensions and physical properties due to moisture absorption. In particular, polyketone resin has a lower density than aluminum, making it suitable for weight reduction.
본 발명에 사용되는 폴리케톤은 일산화탄소, 에틸렌성 불포화 화합물 및 하나 또는 그 이상의 올레핀성 불포화 탄화수소 화합물, 삼 또는 그 이상의 공중합체, 특히 일산화탄소 유래의 반복단위 및 에틸렌성 불포화 화합물 유래의 반복단위와 프로필렌성 불포화 화합물 유래의 반복단위가 실질적으로 교대로 연결된 구조로서, 기계적 성질 및 열적 성질이 우수하고, 가공성이 뛰어나며 내마모성, 내약품성, 가스배리어성이 높아서, 여러 가지 용도에 유용한 재료이다. 이 삼원 또는 그 이상의 공중합 폴리케톤의 고분자량체는 더욱 높은 가공성 및 열적 성질을 가지고, 경제성이 우수한 엔지니어링 플라스틱재로서 유용하다고 여겨진다. 특히, 내마모성이 높아서 자동차의 기어 등의 부품, 내약품성이 높아서 화학수송 파이프의 라이닝재 등, 가스배리어성이 높아서 경량 가솔린 탱크 등에 이용가능하다. 또한, 고유점도가 2 이상의 초고분자량 폴리케톤을 섬유에 이용한 경우, 고배율의 연신이 가능해지고, 연신방향으로 배향된 고강도 및 고탄성율을 가지는 섬유로서, 벨트, 고무호스의 보강재나 타이어 코드, 콘크리트 보강재등 건축재료나 산업자재 용도에 매우 적합한 재료가 된다.The polyketones used in the present invention are carbon monoxide, ethylenically unsaturated compounds and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, in particular repeating units derived from carbon monoxide and repeating units derived from ethylenically unsaturated compounds and propylene-like. It is a structure in which repeating units derived from an unsaturated compound are alternately connected to each other, and have excellent mechanical and thermal properties, excellent workability, high wear resistance, chemical resistance and gas barrier properties, and are useful materials for various applications. The high molecular weight of these ternary or higher copolymerized polyketones is considered to be useful as an engineering plastic material having higher processability and thermal properties and excellent economic efficiency. In particular, the wear resistance is high, and parts such as automobile gears and chemical resistance are high, and the gas barrier property, such as lining material of chemical transport pipe, is high, so that it can be used for light gasoline tanks and the like. In addition, when the ultra high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fibers, the fibers can be stretched at a high magnification and have a high strength and a high modulus of elasticity oriented in the stretching direction. It is very suitable for building materials and industrial materials.
본 발명의 폴리케톤 폴리머는 선상 교대 구조체이고, 또 불포화 탄화수소 1분자 마다 실질적으로 일산화탄소를 포함하고 있다. 폴리케톤 폴리머의 전구체로서 사용하는데 적당한 에틸렌계 불포화 탄화수소는 20개까지, 바람직한 것은 10개까지의 탄소 원자를 가진다. 또한 에틸렌계 불포화 탄화수소는 에텐 및 α-올레핀, 예를 들면 프로펜(propene), 1-부텐(butene), 아이소부텐(iso-butene), 1-헥센(hexene), 1-옥텐(octene)과 같은 지방족이거나 또는 다른 지방족 분자상에 아릴(aryl) 치환기를 포함하고, 특히 에틸렌계 불포화 탄소 원자상에 아릴 치환기를 포함하고 있는 아릴 지방족이다. 에틸렌계 불포화 탄화 수소 중 아릴 지방족 탄화수소의 예로서는 스틸렌(styrene), p-메틸스틸렌(methyl styrene), p-에틸스틸렌(ethyl styrene) 및 m-이소프로필 스틸렌(isopropyl styrene)을 들 수 있다. 본 발명에서 바람직하게 사용되는 폴리케톤 폴리머는 일산화탄소와 에텐(ethene)과의 코폴리머 또는 일산화탄소와 에텐과 적어도 3개의 탄소원자를 가지는 제2의 에틸렌계 불포화 탄화수소, 특히 프로펜(propene) 같은 α-올레핀과의 터폴리머(terpolymer)이다.The polyketone polymer of the present invention is a linear alternating structure, and substantially contains carbon monoxide for each molecule of unsaturated hydrocarbon. Suitable ethylenically unsaturated hydrocarbons for use as precursors of polyketone polymers have up to 20, preferably up to 10 carbon atoms. In addition, ethylenically unsaturated hydrocarbons are ethene and α-olefins such as propene, 1-butene, isobutene, 1-hexene, 1-octene Aryl aliphatic groups containing aryl substituents on aliphatic or other aliphatic molecules, such as aryl substituents on ethylenically unsaturated carbon atoms. Examples of the aryl aliphatic hydrocarbons in the ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene and m-isopropyl styrene. The polyketone polymers preferably used in the present invention are copolymers of carbon monoxide and ethene or second ethylenically unsaturated hydrocarbons having at least three carbon atoms with carbon monoxide and ethene, in particular α-olefins such as propene. Terpolymers.
상기 폴리케톤 터폴리머를 본 발명 블랜드의 주요 폴리머 성분으로서 사용할 때에, 터폴리머내의 제2의 탄화수소 부분을 포함하고 있는 각단위에 대하여, 에틸렌 부분을 포함하고 있는 단위가 적어도 2개 있다. 제2의 탄화수소 부분을 포함하고 있는 단위가 10~100개 있는 것이 바람직하다.When the polyketone terpolymer is used as the main polymer component of the blend of the present invention, for each unit containing the second hydrocarbon moiety in the terpolymer, there are at least two units containing the ethylene moiety. It is preferable that there are 10-100 units containing a 2nd hydrocarbon part.
폴리케톤 폴리머의 바람직한 제조 방법은 미국 특허 제4,843,144호에 개시되어 있다. 팔라튬 화합물과(18℃의 수중에서 측정했다.) pKa 6미만 또는 바람직하게는 pKa 2미만의 비하이드로 할로겐산의 음이온과 인의 2좌 배위자로부터 적절히 생성되는 촉매 조성물의 존재 하에서 일산화탄소와 탄화수소 모노머를 중합 조건하에서 접촉시켜서 폴리케톤 폴리머를 제조한다.Preferred methods of preparing polyketone polymers are disclosed in US Pat. No. 4,843,144. Carbon monoxide and hydrocarbon monomers were prepared in the presence of a palladium compound and a catalyst composition suitably produced from anionic and phosphorus bidentate ligands of less than 6 pKa or preferably less than pKa 2 and preferably less than pKa 2. Polyketone polymers are prepared by contacting under polymerization conditions.
폴리케톤 폴리머의 바람직한 제조 방법은 미국특허 제4,843,144호에 개시되어 있다. 팔라듐 화합물, pKa 6 미만 또는 바람직하게는 pKa 2 미만의 하이드로 할로겐산의 음이온 및 인의 2좌 배위자로부터 적절히 생성되는 촉매 조성물의 존재하에서 일산화탄소와 탄화수소 모노머를 중합 조건하에서 접촉시켜서 폴리케톤 폴리머를 제조한다.Preferred methods for preparing polyketone polymers are disclosed in US Pat. No. 4,843,144. Polyketone polymers are prepared by contacting carbon monoxide with hydrocarbon monomers under polymerization conditions in the presence of a palladium compound, a catalyst composition suitably produced from anionic and phosphorus bidentate ligands of less than pKa 6 or preferably less than pKa 2.
폴리케톤 수지의 제조법으로는 일산화탄소와 올레핀을 팔라듐 화합물, PKa가 6이하인 산, 인의 이배위자 화합물로 이루어진 촉매 조성물을 통해 알코올 용매하에 실시되는 액상 중합을 채용할 수 있다. 중합 반응 온도는 50~100℃가 바람직하며 반응 압력은 40~60bar이다. 폴리머는 중합 후 여과, 정제 공정을 통해 회수하며 남은 촉매 조성물은 알코올이나 아세톤 등의 용매로 제거한다. 여기에서 팔라듐 화합물로서는 초산 팔라듐이 바람직하며 사용량은 10-3~10-1 1mole이 바람직하다. pKa값이 6이하인 산의 구체적인 예로서, 트리플루오르초산, p-톨리엔술폰산, 황산, 술폰산 등을 들 수 있다. 본 발명에서는 트리플루오르초산을 사용하였으며 사용량은 팔라듐 대비 6~20당량이 바람직하다. 또 인의 이좌배위좌 화합물로는 1,3-비스[다이(2-메톡시 페닐포스피노)]프로판이 바람직하며, 사용량은 팔라듐 대비 1~1.2당량이 바람직하다.As a method for producing a polyketone resin, a liquid phase polymerization may be employed in which an alcohol solvent is carried out in an alcohol solvent through a catalyst composition composed of a carbon monoxide and an olefin with a palladium compound, an acid having a PKa of 6 or less, and a diligand compound of phosphorus. The polymerization reaction temperature is preferably 50 ~ 100 ℃ and the reaction pressure is 40 ~ 60bar. The polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone. As the palladium compound, palladium acetate is preferable, and the amount of use thereof is preferably 10 -3 to 10 -1 1 mole. Specific examples of the acid having a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, sulfonic acid, and the like. In the present invention, trifluoroacetic acid is used, and the amount is preferably 6 to 20 equivalents relative to palladium. Moreover, 1, 3-bis [di (2-methoxy phenylphosphino)] propane is preferable as a bidentate coordination compound of phosphorus, and 1-1.2 equivalents are preferable with respect to palladium.
이하, 상기 폴리케톤 수지의 중합 공정을 상세히 설명한다.Hereinafter, the polymerization process of the polyketone resin will be described in detail.
폴리케톤의 제조방법은 (a) 제 9족, 제 10족 또는 제 11족 전이금속 화합물, (b) 제 15족의 원소를 가지는 리간드로 이루어지는 유기금속 착체 촉매의 존재 하에, 액상 매체 중에서 일산화탄소와 에틸렌성 및 프로필렌성 불포화 화합물을 삼원 공중합시켜 폴리케톤을 제조하는 방법에 있어서, 상기 일산화탄소, 에틸렌 및 프로필렌은 알코올(예컨대, 메탄올)과 물의 혼합용매에서 액상 중합되어 선상 터폴리머를 생성하는데, 상기 혼합용매로는 메탄올 100 중량부 및 물 2~10 중량부의 혼합물을 사용할 수 있다. 혼합용매에서 물의 함량이 2 중량부 미만이면 케탈이 형성되어 공정시 내열안정성이 저하될 수 있으며, 10 중량부를 초과하면 제품의 기계적 물성이 저하될 수 있다. 액상 매체로서 7090용량%의 초산과 1030용량%의 물로 이루어지는 혼합용매를 사용하고, 중합시 벤조페논을 첨가하는 것을 특징으로 한다.The process for producing polyketones is characterized by the presence of an organometallic complex catalyst consisting of a ligand having an element of (a) Group 9, Group 10 or Group 11, and (b) Group 15. In the method for producing polyketone by terpolymerization of ethylenic and propylene unsaturated compounds, the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (eg methanol) and water to form a linear terpolymer, the mixture As a solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of the water in the mixed solvent is less than 2 parts by weight of ketal may be formed, the heat stability during the process may be lowered, if more than 10 parts by weight may lower the mechanical properties of the product. As a liquid medium, a mixed solvent consisting of 7090 vol% acetic acid and 1030 vol% water is used, and benzophenone is added during polymerization.
여기서 액상 매체로서 종래 폴리케톤의 제조에 주로 사용되어 오던 메탄올, 디클로로메탄 또는 니트로메탄 등을 사용하지 않고, 초산과 물로 이루어지는 혼합용매를 사용하는 것이 특징이다. 이는 폴리케톤의 제조에 액상 매체로서 초산과 물의 혼합용매를 사용함으로써 폴리케톤의 제조비용을 절감시키면서 촉매활성도 향상시킬 수 있기 때문이다. In this case, a mixed solvent consisting of acetic acid and water is used as a liquid medium, without using methanol, dichloromethane, or nitromethane, which have been mainly used in the production of polyketone. This is because by using a mixed solvent of acetic acid and water as the liquid medium in the production of the polyketone it is possible to improve the catalytic activity while reducing the production cost of the polyketone.
액상매체로서 초산과 물의 혼합용매를 사용시, 물의 농도가 10용량% 미만으로 적을 때는 촉매활성에 영향을 덜미치지만, 10용량% 이상의 농도가 되면 촉매활성이 급격히 증가한다. 반면, 물의 농도가 30용량%를 초과하면 촉매활성은 감소하는 경향을 보인다.. When a mixed solvent of acetic acid and water is used as the liquid medium, when the concentration of water is less than 10% by volume, the catalytic activity is less affected. However, when the concentration is more than 10% by volume, the catalytic activity rapidly increases. On the other hand, when the concentration of water exceeds 30% by volume, catalytic activity tends to decrease.
여기서 촉매는, 주기율표(IUPAC 무기화학 명명법 개정판, 1989)의 (a) 제 9족, 제 10족 또는 제 11족 전이금속 화합물, (b) 제 15족의 원소를 가지는 리간드로 이루어지는 것이다.The catalyst is composed of a ligand having an element of (a) Group 9, Group 10 or Group 11 transition metal compound (b) Group 15 of the Periodic Table (IUPAC Inorganic Chemistry Nomenclature, 1989).
제 9족, 제 10족 또는 제 11족 전이금속 화합물(a) 중 제 9족 전이금속 화합물의 예로서는, 코발트 또는 루테늄의 착체, 카본산염, 인산염, 카바민산염, 술폰산염 등을 들 수 있고, 그 구체예로서는 초산 코발트, 코발트 아세틸아세테이트, 초산 루테늄, 트리플루오로 초산 루테늄, 루테늄 아세틸아세테이트, 트리플루오로 메탄 술폰산루테늄 등을 들 수 있다.Examples of the Group 9 transition metal compound in the Group 9, 10 or 11 transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamate salts, sulfonates, and the like. Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, trifluoro ruthenium acetate, ruthenium acetylacetate, trifluoromethane sulfonate ruthenium and the like.
제 10족 전이금속 화합물의 예로서는, 니켈 또는 팔라듐의 착체, 카본산염, 인산염, 카바민산염, 술폰산염 등을 들 수 있고, 그 구체예로서는 초산 니켈, 니켈, 아세틸아세테이트, 초산 팔라듐, 트리플루오로 초산 팔라듐, 팔라듐 아세틸아세테이트, 염화 팔라듐, 비스(N,N-디에틸카바메이트)비스(디에틸아민)팔라듐, 황산 팔라듐 등을 들 수 있다.Examples of the Group 10 transition metal compound include a complex of nickel or palladium, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include nickel acetate, nickel, acetylacetate, palladium acetate and trifluoroacetic acid. Palladium, palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium, palladium sulfate and the like.
제 11족 전이금속 화합물의 예로서는, 구리 또는 은의 착체, 카본산염, 인산염, 카바민산염, 술폰산염 등을 들 수 있고, 그 구체예로서는 초산 구리, 트리플루오로 초산 구리, 구리 아세틸아세테이트, 초산 은, 트리플루오로초산 은, 은 아세틸아세테이트, 트리플루오로메탄 술폰산 은 등을 들 수 있다.Examples of the Group 11 transition metal compound include a complex of copper or silver, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include copper acetate, trifluoroacetate, copper acetylacetate, silver acetate, Silver trifluoroacetic acid, silver acetyl acetate, silver trifluoromethane sulfonic acid, etc. are mentioned.
이들 중에서 값싸고 경제적으로 바람직한 전이금속 화합물(a)은 니켈 및 구리 화합물이고, 폴리케톤의 수득량 및 분자량의 면에서 바람직한 전이금속 화합물(a)은 팔라듐 화합물이며, 촉매활성 및 고유점도 향상의 면에서 초산 팔라듐을 사용하는 것이 가장 바람직하다.Among these, inexpensive and economically preferable transition metal compounds (a) are nickel and copper compounds, and preferred transition metal compounds (a) are palladium compounds in terms of yield and molecular weight of polyketones, and in terms of improving catalytic activity and intrinsic viscosity. Most preferably, palladium acetate is used in the process.
제 15족의 원자를 가지는 리간드(b)의 예로서는, 2,2'-비피리딜, 4,4'-디메틸-2,2'-비피리딜, 2,2'-비-4-피콜린, 2,2'-비키놀린 등의 질소 리간드, 1,2-비스 (디페닐포스피노)에탄, 1,3-비스(디페닐포스피노)프로판, 1,4-비스(디페닐포스피노)부탄, 1,3-비스[디(2-메틸)포스피노]프로판, 1,3-비스[디(2-이소프로필)포스피노]프로판, 1,3-비스[디(2-메톡시페닐)포스피노]프로판, 1,3-비스[디(2-메톡시-4-술폰산나트륨-페닐)포스피노]프로판, 1,2-비스(디페닐포스피노)시클로헥산, 1,2-비스(디페닐포스피노)벤젠, 1,2-비스[(디페닐포스피노)메틸]벤젠, 1,2-비스[[디(2-메톡시페닐)포스피노]메틸]벤젠, 1,2-비스[[디(2-메톡시-4-술폰산나트륨-페닐)포스피노]메틸]벤젠, 1,1'-비스(디페닐포스피노)페로센, 2-히드록시-1,3-비스[디(2-메톡시페닐)포스피노]프로판, 2,2-디메틸-1,3-비스[디(2-메톡시페닐)포스피노]프로판 등의 인 리간드 등을 들 수 있다.Examples of the ligand (b) having a group 15 atom include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picolin , Nitrogen ligands such as 2,2'-bikinolin, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) Butane, 1,3-bis [di (2-methyl) phosphino] propane, 1,3-bis [di (2-isopropyl) phosphino] propane, 1,3-bis [di (2-methoxyphenyl ) Pinospino] propane, 1,3-bis [di (2-methoxy-4-sulfonic acid-phenyl) phosphino] propane, 1,2-bis (diphenylphosphino) cyclohexane, 1,2-bis (Diphenylphosphino) benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, 1,2- Bis [[di (2-methoxy-4-sulfonate-phenyl) phosphino] methyl] benzene, 1,1'-bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) Spinosyns; there may be mentioned a ligand, such as propane.
이들 중에서 바람직한 제 15족의 원소를 가지는 리간드(b)는, 제 15족의 원자를 가지는 인 리간드이고, 특히 폴리케톤의 수득량의 면에서 바람직한 인 리간드는 1,3-비스[디(2-메톡시페닐)포스피노]프로판, 1,2-비스[[디(2-메톡시페닐)포스피노]메틸]벤젠이고, 폴리케톤의 분자량의 측면에서는 2-히드록시-1,3-비스[디(2-메톡시페닐)포스피노]프로판, 2,2-디메틸-1,3-비스[디(2-메톡시페닐)포스피노]프로판이고, 유기용제를 필요로 하지 않고 안전하다는 면에서는 수용성의 1,3-비스[디(2-메톡시-4-술폰산나트륨-페닐)포스피노]프로판, 1,2-비스[[디(2-메톡시-4-술폰산나트륨-페닐)포스피노]메틸]벤젠이고, 합성이 용이하고 대량으로 입수가 가능하고 경제면에 있어서 바람직한 것은 1,3-비스(디페닐포스피노)프로판, 1,4-비스(디페닐포스피노)부탄이다. 바람직한 제 15족의 원자를 가지는 리간드(b)는 1,3-비스[디(2-메톡시페닐)포스피노]프로판 또는 1,3-비스(디페닐포스피노)프로판이고, 가장 바람직하게는 1,3-비스[디(2-메톡시페닐)포스피노]프로판 또는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)이다.Among them, the ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and particularly, in view of the yield of polyketone, a phosphorus ligand is preferably 1,3-bis [di (2- Methoxyphenyl) phosphino] propane, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, and 2-hydroxy-1,3-bis [in terms of molecular weight of the polyketone. Di (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) phosphino] propane, and do not require an organic solvent in terms of safety Water-soluble 1,3-bis [di (2-methoxy-4-sulfonate-phenyl) phosphino] propane, 1,2-bis [[di (2-methoxy-4-sulfonate-phenyl) phosphino ] Methyl] benzene, the synthesis | combination is easy, it is available in large quantities, and economically preferable is 1, 3-bis (diphenyl phosphino) propane and 1, 4-bis (diphenyl phosphino) butane. Preferred ligand (b) having an atom of group 15 is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) propane, most preferably 1,3-bis [di (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2 Methoxyphenyl) phosphine).
[화학식 1][Formula 1]
Figure PCTKR2015011027-appb-I000001
Figure PCTKR2015011027-appb-I000001
상기 화학식 1의 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)은 현재까지 소개된 폴리케톤 중합촉매 중 최고활성을 보이는 것으로 알려진 3,3-비스-[비스-(2-메톡시페닐)포스파닐메틸]-1,5-디옥사-스파이로[5,5]운데칸과 동등한 활성 발현을 보이되 그 구조는 더욱 단순하고 분자량 또한 더욱 낮은 물질이다. 그 결과, 본 발명은 당 분야의 폴리케톤 중합촉매로서 최고활성을 확보하면서도 그 제조비용 및 원가는 더욱 절감된 신규한 폴리케톤 중합촉매를 제공할 수 있게 되었다. 폴리케톤 중합촉매용 리간드의 제조방법은은 다음과 같다. 비스(2-메톡시페닐)포스핀, 5,5-비스(브로모메틸)-2,2-디메틸-1,3-디옥산 및 수소화나트륨(NaH)을 사용하여 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)을 얻는 것을 특징으로 하는 폴리케톤 중합촉매용 리간드의 제조방법이 제공된다. 본 발명의 폴리케톤 중합촉매용 리간드 제조방법은 종래 3,3-비스-[비스-(2-메톡시페닐)포스파닐메틸]-1,5-디옥사-스파이로[5,5]운데칸의 합성법과는 달리 리튬이 사용되지 않는 안전한 환경하에서 용이한 프로세스를 통해 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)을 상업적으로 대량합성할 수 있다.((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) of Formula 1 is a polyketone introduced to date Activity equivalent to 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, known to exhibit the highest activity in the polymerization catalyst The structure is simpler and has a lower molecular weight. As a result, the present invention is able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst in the art while further reducing the production cost and cost. The method for preparing a ligand for a polyketone polymerization catalyst is as follows. Using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and sodium hydride (NaH) ((2,2-dimethyl Provided is a method for producing a ligand for a polyketone polymerization catalyst, characterized by obtaining -1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine). . The method for preparing a ligand for a polyketone polymerization catalyst of the present invention is conventionally 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane Unlike the synthesis method of ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially mass synthesized.
바람직한 일 구체예에서, 본 발명의 폴리케톤 중합촉매용 리간드 제조방법은 (a) 질소 대기하에서 비스(2-메톡시페닐)포스핀 및 디메틸설폭시드(DMSO)를 반응용기에 투입하고 상온에서 수소화나트륨을 가한 뒤 교반하는 단계; (b) 얻어진 혼합액에 5,5-비스(브로모메틸)-2,2-디메틸-1,3-디옥산 및 디메틸설폭시드를 가한뒤 교반하여 반응시키는 단계; (c) 반응 완료 후 메탄올을 투입하고 교반하는 단계;(d) 톨루엔 및 물을 투입하고 층분리 후 유층을 물로 세척한 다음 무수황산나트륨으로 건조 후 감압 여과를 하고 감압 농축하는 단계; 및 (e) 잔류물을 메탄올 하에서 재결정하여 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)를 얻는 단계;를 거쳐 수행될 수 있다.In a preferred embodiment, the method for preparing a ligand for a polyketone polymerization catalyst of the present invention is (a) adding bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) to a reaction vessel under a nitrogen atmosphere and hydrogenated at room temperature. Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the obtained mixture, followed by stirring to react; (c) adding and stirring methanol after completion of the reaction; (d) adding toluene and water, washing the oil layer with water after separating the layers, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue is recrystallized under methanol ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) It can be performed through;
제 9족, 제 10족 또는 제 11족 전이금속 화합물(a)의 사용량은, 선택되는 에틸렌성 및 프로필렌성 불포화 화합물의 종류나 다른 중합조건에 따라 그 적합한 값이 달라지기 때문에, 일률적으로 그 범위를 한정할 수는 없으나, 통상 반응대역의 용량 1리터당 0.01~100밀리몰, 바람직하게는 0.01~10밀리몰이다. 반응대역의 용량이라는 것은, 반응기의 액상의 용량을 말한다. 리간드(b)의 사용량도 특별히 제한되지는 않으나, 전이금속 화합물 (a) 1몰당, 통상 0.1~3몰, 바람직하게는 1~3몰이다.The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) to be used varies uniformly since the appropriate value varies depending on the type of the ethylenic and propylene unsaturated compounds selected or other polymerization conditions. Although not limited, it is usually 0.01-100 mmol, preferably 0.01-10 mmol, per liter of the capacity of the reaction zone. The capacity of the reaction zone means the capacity of the liquid phase of the reactor. The amount of the ligand (b) to be used is not particularly limited, but is usually 0.1 to 3 mol, preferably 1 to 3 mol, per mol of the transition metal compound (a).
또한, 폴리케톤의 중합시 벤조페논을 첨가하는 것을 또 다른 특징으로 한다.In addition, the addition of benzophenone during the polymerization of polyketones is another feature.
본 발명에서는 폴리케톤의 중합시 벤조페논을 첨가함으로써 폴리케톤의 고유점도가향상되는 효과를 달성할 수 있다. 상기 (a) 제 9족, 제 10족 또는 제 11족 전이금속 화합물과 벤조페논의 몰비는 1 : 5~100, 바람직하게는 1 : 40∼60 이다. 전이금In the present invention, it is possible to achieve the effect of improving the intrinsic viscosity of the polyketone by adding benzophenone during the polymerization of the polyketone. The molar ratio of the (a) Group 9, Group 10 or Group 11 transition metal compound and benzophenone is 1: 5 to 100, preferably 1:40 to 60. Transfer money
속과 벤조페논의 몰비가 1 : 5 미만이면 제조되는 폴리케톤의 고유점도 향상의 효과가 만족스럽지 못하고, 전이금속과 벤조페논의 몰비가 1 : 100을 초과하면 제조되는 폴리케톤 촉매활성이 오히려 감소하는 경향이 있으므로 바람직하지 않다.If the molar ratio of genus and benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the polyketone produced is not satisfactory. If the molar ratio of transition metal and benzophenone is greater than 1: 100, the polyketone catalytic activity is rather decreased. It is not preferable because it tends to.
일산화탄소와 공중합하는 에틸렌성 불포화 화합물의 예로서는, 에틸렌, 프로필렌, 1-부텐, 1-헥센, 4-메틸-1-펜텐, 1-옥텐, 1-데센, 1-도데센, 1-테트라데센, 1-헥사데센, 비닐시클로헥산 등의 α-올레핀; 스티렌, α-메틸스티렌 등의 알케닐 방향족 화합물; 시클로펜텐, 노르보르넨, 5-메틸노르보르넨, 5-페닐노르보르넨, 테트라시클로도데센, 트리시클로도데센, 트리시클로운데센, 펜타시클로펜타데센, 펜타시클로헥사데센, 8-에틸테트라시클로도데센 등의 환상 올레핀; 염화비닐 등의 할로겐화 비닐; 에틸아크릴레이트, 메틸아크릴레이트 등의 아크릴산 에스테르 등을 들 수 있다. 이들 중에서 바람직한 에틸렌성 불포화 화합물은 α-올레핀이고, 더욱 바람직하게는 탄소수가 2~4인 α-올레핀, 가장 바람직하게는 에틸렌이며 삼원 공중합 폴리케톤 제조에 있어서는 120mol% 프로필렌을 투입하는 것이다.Examples of ethylenically unsaturated compounds copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 Α-olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and α-methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Acrylic esters, such as ethyl acrylate and methyl acrylate, etc. are mentioned. Among these, preferred ethylenically unsaturated compounds are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, most preferably ethylene, and 120 mol% propylene is added in the production of terpolymer copolyketones.
여기에서 일산화탄소와 에틸렌성 불포화 화합물의 투입비를 1 : 12(몰비)로 조절하고 프로필렌을 전체 혼합가스 대비 120mol%로 조절하는 것이 바람직하다. 폴리케톤의 제조시, 일산화탄소와 에틸렌성 불포화 화합물의 투입비를 1 : 1로 하는 것이 일반적이지만, 액상 매체로서 초산과 물의 혼합용매를 사용하고, 중합시 벤조페논을 첨가하는 본 발명에서는 일산화탄소와 에틸렌성 불포화 화합물의 투입비를 1 : 12로 하고 프로필렌을 전체 혼합가스 대비 120mol%로 조절하는 경우 가공성이 향상될 뿐 아니라 촉매활성 및 고유점도 향상을 동시에 달성할 수 있음을 발견하였다. 프로필렌의 투입량이 1mol% 미만일 경우 용융온도를 낮추고자 하는 삼원공중합의 효과를 얻을 수 없고 20mol%를 초과하는 경우에는 고유점도 및 촉매 활성 향상을 저해하는 문제점이 생기게 되므로 투입비를 120mol%로 조절하는 것이 바람직하다.Here, it is preferable to adjust the input ratio of carbon monoxide and ethylenically unsaturated compound to 1: 12 (molar ratio) and to adjust propylene to 120 mol% relative to the total mixed gas. In the production of polyketone, it is common to set the ratio of carbon monoxide and ethylenically unsaturated compound to 1: 1, but in the present invention using a mixed solvent of acetic acid and water as a liquid medium and adding benzophenone during polymerization, carbon monoxide and ethylenic When the ratio of the unsaturated compound to 1: 12 and propylene is adjusted to 120 mol% of the total mixed gas, it was found that not only the processability was improved but also the catalytic activity and the intrinsic viscosity were simultaneously improved. If the amount of propylene is less than 1 mol%, the effect of three-way copolymerization to lower the melting temperature cannot be obtained. If it exceeds 20 mol%, there is a problem of inhibiting the intrinsic viscosity and the improvement of catalyst activity. desirable.
또한, 중합 공정에서는 액상 매체로서 초산과 물의 혼합용매를 사용하고, 중합시 벤조페논을 첨가하며 일산화탄소와 에틸렌성 불포화 화합물 및 하나 또는 그 이상의 올레핀성 불포화 화합물을 투입함으로써 폴리케톤의 촉매활성 및 고유점도가 향상되는 것 뿐 아니라, 종래 기술에서는 고유점도 향상을 위해 중합시간을 최소한 10시간 이상으로 해야 했던 것과는 달리, 중합시간을 12시간 정도로만 해도 높은 고유점도를 가진 삼원 공중합 폴리케톤의 제조가 가능하다. In addition, in the polymerization process, a mixed solvent of acetic acid and water is used as a liquid medium, benzophenone is added during polymerization, and carbon monoxide and ethylenically unsaturated compound and one or more olefinically unsaturated compounds are added to the catalytic activity and intrinsic viscosity of the polyketone. Not only is not only improved, but in the prior art, the polymerization time should be at least 10 hours to improve the intrinsic viscosity, but it is possible to prepare a terpolymer copolymer polyketone having a high intrinsic viscosity even if the polymerization time is about 12 hours.
일산화탄소와 상기 에틸렌성 불포화 화합물 및 프로필렌성 불포화 화합물 삼원 공중합은 상기 제 9족, 제 10족 또는 제 11족 전이금속 화합물(a), 제 15족의 원소를 가지는 리간드(b) 로 이루어지는 유기금속 착체 촉매에 의해 일어나는 것으로, 상기 촉매는 상기 2성분을 접촉시킴으로써 생성된다. 접촉시키는 방법으로서는 임의의 방법을 채용할 수 있다. 즉, 적당한 용매 중에서 2성분을 미리 혼합한 용액으로 만들어 사용해도 좋고, 중합계에 2성분을 각각 따로따로 공급하여 중합계 내에서 접촉시켜도 좋다. 이때, 상기 에틸렌성 불포화 화합물 및 프로필렌성 불포화 화합물의 몰비%는 99:1 내지 85:15인 것이 바람직한데 프로필렌의 몰비%가 1%미만이면 성형부품의 가공이 어렵고, 15%를 초과하게 되면, 기계적 물성이 떨어지게 되는 문제점이 있다.Ternary copolymerization of carbon monoxide, the ethylenically unsaturated compound and the propylene unsaturated compound is an organometallic complex comprising a Group 9, Group 10 or Group 11 transition metal compound (a) and a ligand (b) having an element of Group 15 As a result of the catalyst, the catalyst is produced by contacting the two components. Arbitrary methods can be employ | adopted as a method of making it contact. That is, you may make and use the solution which mixed two components previously in a suitable solvent, and may respectively supply two components separately to a polymerization system, and may contact them in a polymerization system. At this time, the molar ratio of the ethylenically unsaturated compound and the propylene unsaturated compound is preferably 99: 1 to 85:15. If the molar ratio of propylene is less than 1%, it is difficult to process the molded part, and if it exceeds 15%, There is a problem that the mechanical properties fall.
본 발명에서는 폴리머의 가공성이나 물성을 개선하기 위하여 종래 알려져 있는 첨가제, 예를 들면 산화방지제, 안정제, 충전제, 내화재료, 이형제, 착색제 및 기타재료를 추가적으로 포함할 수 있다. The present invention may further include conventionally known additives such as antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials to improve processability and physical properties of the polymer.
중합법으로서는 액상 매체를 사용하는 용액중합법, 현탁중합법, 소량의 중합체에 고농도의 촉매 용액을 함침시키는 기상중합법 등이 사용된다. 중합은 배치식 또는 연속식 중 어느 것이어도 좋다. 중합에 사용하는 반응기는, 공지의 것을 그대로, 또는 가공하여 사용할 수 있다. 중합온도에 대해서는 특별히 제한은 없고, 일반적으로 40~180℃, 바람직하게는 50~120℃가 채용된다. 중합시의 압력에 대해서도 제한은 없으나, 일반적으로 상압~20MPa, 바람직하게는 4~15MPa이다.As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, a gas phase polymerization method in which a small amount of a polymer is impregnated with a high concentration of a catalyst solution are used. The polymerization may be either batchwise or continuous. The reactor used for superposition | polymerization can use a well-known thing as it is or processing it. There is no restriction | limiting in particular about polymerization temperature, Generally 40-180 degreeC, Preferably 50-120 degreeC is employ | adopted. Although there is no restriction | limiting also about the pressure at the time of superposition | polymerization, Usually, it is normal pressure-20 MPa, Preferably it is 4-15 MPa.
상기와 같은 중합법에 의하여 선상 교대 폴리케톤이 형성된다.Linear alternating polyketones are formed by the polymerization method as described above.
본 발명에서 바람직한 폴리케톤 폴리머의 폴리머 고리는 하기 화학식 2로 나타낼 수 있다.The polymer ring of the polyketone polymer preferred in the present invention may be represented by the following formula (2).
[화학식 2][Formula 2]
-[CO-(-CH2-CH2-)-]x-[CO-(G)]y--[CO-(-CH2-CH2-)-] x- [CO- (G)] y-
상기 화학식 2 중, G는 에틸렌계 불포화 탄화수소로서, 특히 적어도 3개의탄소 원자를 가지는 에틸렌계 불포화 탄화수소로부터 얻어지는 부분이고, x:y는 적어도 1:0.01인 것이 바람직하다.In the formula (2), G is an ethylenically unsaturated hydrocarbon, in particular, a part obtained from an ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is preferably at least 1: 0.01.
다른 구체예로, 상기 폴리케톤 폴리머는 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 공중합체로서, y/x가 0.03~0.3 인 것이 바람직하다. 상기 y/x값의 수치가 0.03 미만인 경우, 용융성 및 가공성이 떨어지는 한계가 있고, 0.3을 초과하는 경우는 기계적 물성이 떨어진다. 또한 y/x는 더욱 바람직하게 0.03 내지 0.1이다.In another embodiment, the polyketone polymer is a copolymer composed of repeating units represented by General Formulas (1) and (2), and it is preferable that y / x is 0.03 to 0.3. When the value of the y / x value is less than 0.03, there is a limit inferior in meltability and workability, and when it exceeds 0.3, mechanical properties are inferior. And y / x is more preferably 0.03 to 0.1.
-[-CH2CH2-CO]x- (1) -[-CH2CH2-CO] x- (1)
-[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
또한, 폴리케톤 폴리머의 에틸렌과 프로필렌의 비를 조절하여 폴리머의 융점을 조절할 수 있다. 일례로, 에틸렌 : 프로필렌 : 일산화탄소의 몰비를 46 : 4 :50으로 조절하는 경우 융점은 약 220℃이나, 몰비를 47.3 : 2.7 : 50 으로 조절하는 경우의 융점은 235℃로 조절된다.In addition, the melting point of the polymer may be controlled by controlling the ratio of ethylene and propylene of the polyketone polymer. For example, the melting point is about 220 ° C. when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46: 4: 50, but the melting point is adjusted to 235 ° C. when the molar ratio is adjusted to 47.3: 2.7: 50.
겔 투과 크로마토그래피(chromatography)에 의하여 측정한 수평균 분자량이 100~200,000 특별히 20,000~90,000의 폴리케톤 폴리머가 특히 바람직하다. 폴리머의 물리적 특성은 분자량에 따라서, 폴리머가 코폴리머인, 또는 터폴리머인 것에따라서, 또 터폴리머의 경우에는 존재하는 제2의 탄화 수소부분의 성질에 따라서 정해진다. 본 발명에서 사용하는 폴리머의 통산의 융점은 175℃~300℃이고, 또한 일반적으로는 210℃~270℃ 이다. 표준 세관점도 측정장치를 사용하고HFIP(Hexafluoroisopropylalcohol)로 60℃에 측정한 폴리머의 극한 점도 수(LVN)는 0.5dl/g~10dl/g, 또한 바람직하게는 0.8dl/g~4dl/g이며, 더욱 바람직하게는, 1.0dl/g~2.0dl/g 이다. 이 때 극한 점도 수가 0.5dl/g 미만이면 기계적 물성이 떨어지고, 10dl/g 을 초과하면 가공성이 떨어지는 문제점이 발생한다.Particularly preferred are polyketone polymers having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer depend on the molecular weight, on whether the polymer is a copolymer or terpolymer, and in the case of terpolymers, on the nature of the second hydrocarbon moiety present. Melting | fusing point of the conversion of the polymer used by this invention is 175 degreeC-300 degreeC, and is 210 degreeC-270 degreeC generally. The ultimate viscosity number (LVN) of the polymer measured at 60 ° C. using a standard tubular viscosity measuring device and HFIP (Hexafluoroisopropylalcohol) is 0.5 dl / g to 10 dl / g, more preferably 0.8 dl / g to 4 dl / g, More preferably, they are 1.0 dl / g-2.0 dl / g. At this time, if the intrinsic viscosity number is less than 0.5dl / g, the mechanical properties are inferior, and if it exceeds 10dl / g, there is a problem of poor workability.
한편, 본 발명의 폴리케톤 성형물은 폴리케톤과 유리섬유의 조합으로 이루어진 블렌드로 구성되는 것으로서, 기존에 사용되던 소재와 비교하여 강성, 가공성 및 치수안정성을 향상시키는 것을 특징으로 한다.On the other hand, the polyketone molding of the present invention is composed of a blend consisting of a combination of polyketone and glass fiber, it is characterized in that the stiffness, processability and dimensional stability compared to the conventional materials used.
여기서 상기 유리섬유는 그 입경이 10 내지 13㎛인 것이 바람직하다. 유리섬유의 입경이 10㎛ 미만이면 유리섬유의 형상이 변하여 기계적 물성이 저하될 수 있다. Herein, the glass fiber preferably has a particle diameter of 10 to 13 μm. When the particle diameter of the glass fiber is less than 10㎛, the shape of the glass fiber may change and mechanical properties may decrease.
상기 폴리케톤과 유리섬유의 조성비는 폴리케톤 폴리머 60 내지 90 중량%와 유리섬유 10 내지 40 중량%로 포함되는 것이 바람직하다. 유리섬유의 함량이 15 중량% 미만이면 기계적 강성이 저하될 수 있으며, 40 중량%를 초과하면 점도가 지나치게 상승하여 압출, 사출 작업성이 떨어질 수 있다.The composition ratio of the polyketone and glass fiber is preferably comprised of 60 to 90% by weight of polyketone polymer and 10 to 40% by weight of glass fiber. If the glass fiber content is less than 15% by weight, the mechanical rigidity may be lowered. If the glass fiber content is more than 40% by weight, the viscosity may be excessively increased, thereby reducing extrusion and injection workability.
본 발명에서는 폴리머의 가공성이나 물성을 개선하기 위하여 종래 알려져 있는 첨가제, 예를 들면 산화방지제, 안정제, 충전제, 내화재료, 이형제, 착색제 및 기타재료를 포함할 수 있다. 상기와 같은 폴리케톤을 압출 성형 또는 사출 성형에 의하여 성형물을 제조할 수 있다.In the present invention, in order to improve the processability and physical properties of the polymer, conventionally known additives may include, for example, antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials. The polyketone as described above may be produced by extrusion molding or injection molding.
한편, 상기와 같은 본 발명의 폴리케톤 및 유리섬유의 블렌드 조성물은 압출, 사출 등의 방법으로 성형되어 폴리케톤 성형물로 제조되며, 이는 강성, 가공성 및 치수안정성이 우수한 특징이 있다. 이 때, 상기 폴리케톤 성형물은 제품 흡습율이 2.0% 이하이고 수분흡수 시 물성유지율이 70% 이상이다. 또한 충격강도는 10kJ/m2 이상으로, 바람직하게는 15kJ/m2 이상이다.On the other hand, the blend composition of the polyketone and glass fibers of the present invention as described above is molded by a method such as extrusion, injection, and the like is produced as a polyketone molding, which is characterized by excellent rigidity, processability and dimensional stability. At this time, the polyketone molded article has a product moisture absorption rate of 2.0% or less and the moisture content retention rate of 70% or more. The impact strength is 10 kJ / m 2 or more, preferably 15 kJ / m 2 or more.
폴리케톤 폴리머의 제조법으로는 일산화탄소와 올레핀을 팔라듐 화합물, PKa가 6이하인 산, 인의 이배위자 화합물로 이루어진 촉매 조성물을 통해 알코올 용매하에 실시되는 액상 중합을 채용할 수 있다. 중합 반응 온도는 50~100℃가 바람직하며 반응 압력은 40~60bar이다. 폴리머는 중합 후 여과, 정제 공정을 통해 회수하며 남은 촉매 조성물은 알코올이나 아세톤 등의 용매로 제거한다.As a method for producing a polyketone polymer, a liquid phase polymerization may be employed in which an alcohol solvent is carried out in an alcohol solvent through a catalyst composition consisting of a carbon monoxide and an olefin with a palladium compound, an acid having a PKa of 6 or less, and a binary ligand compound of phosphorus. The polymerization reaction temperature is preferably 50 ~ 100 ℃ and the reaction pressure is 40 ~ 60bar. The polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.
여기에서 팔라듐 화합물로서는 초산 팔라듐이 바람직하며 사용량은 10-3~10-1mole이 바람직하다. pKa값이 6이하인 산의 구체적인 예로서, 트리플루오르초산, p-톨리엔술폰산, 황산, 술폰산 등을 들 수 있다. 본 발명에서는 트리플루오르초산을 사용하였으며 사용량은 팔라듐 대비 6~20당량이 바람직하다. 또 인의 이좌배위좌 화합물로는 1,3-비스[다이(2-메톡시 페닐포스피노)]프로판이 바람직하며, 사용량은 팔라듐 대비 1~1.2당량이 바람직하다.This is preferred as palladium acetate and a palladium compound in the amount of 10 -3 to 10-2 1mole preferred. Specific examples of the acid having a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, sulfonic acid, and the like. In the present invention, trifluoroacetic acid is used, and the amount is preferably 6 to 20 equivalents relative to palladium. Moreover, 1, 3-bis [di (2-methoxy phenylphosphino)] propane is preferable as a bidentate coordination compound of phosphorus, and 1-1.2 equivalents are preferable with respect to palladium.
한편, 폴리케톤의 분자량 분포는 1.5 내지 2.5인 것이 좋고, 보다 바람직하게는 1.8~2.2이 좋다. 1.5 미만은 중합수율이 떨어지며, 2.5 이상은 성형성이 떨어지는 문제점이 있었다. 상기 분자량 분포를 조절하기 위해서는 팔라듐 촉매의 양과 중합온도에 따라 비례하여 조절이 가능하다. 즉, 팔라듐 촉매의 양이 많아지거나, 중합온도가 100℃이상이면 분자량 분포가 커지는 양상을 보인다.On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. Less than 1.5 had a poor polymerization yield, and more than 2.5 had a problem of poor moldability. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of palladium catalyst and polymerization temperature. That is, when the amount of the palladium catalyst increases or the polymerization temperature is 100 ° C. or more, the molecular weight distribution is increased.
본 발명의 부성분인 유리섬유에 대해서 설명한다. 규산염을 주성분으로 하는 유리를 용융가공하여 섬유 모양으로 가공한 것으로 글라스 파이버 또는 글라스 울이라고도 한다. 유리섬유를 제법용도에 따라 분류하면 단(短)섬유와 장(長)섬유로 나눈다. 이 밖에 화상전송용인 광학섬유, 광통신용인 유리섬유(광섬유)가 있다. 유리는 고온상태에서 쉽게 설처럼 늘어나므로 고대부터 공예적인 용도로 알려져 있었다. 이것이 공업화된 것은 제1차 세계대전중 천연석면의 대용품으로 독일에서 고온단열용의 단섬유가 제조된 것이 처음이다. 장섬유는 1930년대에, 또 광학섬유는 60년대에 모두 미국에서 공업화되었다. 단섬유는 제조도 간단하며 펠트처럼 만들어 단열재에 이용되고, 장섬유는 직물로서 유리섬유보강플라스티(FRP)절연재 등으로 널리 사용되고 있다. 광학섬유는 수천 개에서 수십만 개 정도로 특수한 구조를 가진 섬유를 규칙적으로 묶은 것이며 다발의 한쪽 끝에서 화상을 집어넣으면 다발의 굴절에 따라 다른 끝에 전송된다. 또 파이버스코프 외에 넓은 용도가 있다. 일반적으로 유리섬유는 가늘므로 비표면적(比表面積)이 매우 크다. 예를 들면 지름 1cm인 유리구슬을 지름이 1μm의 섬유로 늘이면 길이가 약 4,000m나 되고 면적도 400배 가까이 늘어나므로 습기에 잘 침식되지 않는 화학조성(E유리)을 가지게 된다. C유리는 내산성(耐酸性)이고 축전지의 격벽(隔壁) 등에 내(耐)알칼리 섬유는 최근에 실용화된 것으로 시멘트 강화용에 사용되고 있다.The glass fiber which is a subcomponent of this invention is demonstrated. It is also called glass fiber or glass wool by melting and processing the glass containing silicate as a main component to make it into a fiber shape. Glass fiber is classified according to manufacturing method and divided into short fiber and long fiber. In addition, there are optical fibers for image transmission and glass fibers (optical fibers) for optical communication. Glass has been known for its craft use since ancient times because it stretches like snow at high temperatures. It was the first time that industrialized short fibers were manufactured in Germany as a substitute for natural asbestos during World War I. Long fibers were industrialized in the United States in the 1930s and optical fibers in the 60s. Short fibers are simple to manufacture and are made of felt and used for insulation. Long fibers are widely used as glass fiber reinforced plastic (FRP) insulation as fabric. Optical fibers are a regular bundle of thousands of hundreds to hundreds of thousands of specially structured fibers, and when an image is inserted at one end of the bundle, it is transmitted to the other end according to the bundle's refraction. It also has a wide range of uses besides fiber scopes. In general, glass fibers are thin, so the specific surface area is very large. For example, if a glass bead with a diameter of 1 cm is stretched into a fiber having a diameter of 1 μm, its length is about 4,000 m and its area is nearly 400 times larger, thus having a chemical composition (E glass) that is not easily eroded by moisture. C-glass is acid-resistant, and alkali-resistant fibers, such as battery cells, have recently been put to practical use and are used for cement reinforcement.
본 발명의 내 충격성이 우수한 폴리케톤 수지 조성물의 제조방법은 팔라듐 화합물, pKa값이6 이하인 산, 및 인의 2배위자 화합물을 포함하는 촉매 조성물을 준비하는 단계; 알코올(예컨대, 메탄올)과 물을 포함하는 혼합용매(중합용매)를 준비하는 단계; 상기 촉매 조성물 및 혼합용매의 존재 하에서 중합을 진행하여 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머를 제조하는 단계; 상기 선상 터폴리머에서 남은 촉매 조성물을 용매(예컨대, 알코올 및 아세톤)로 제거하여 폴리케톤 수지를 수득하는 단계; 및 상기 폴리케톤 수지에 유리섬유, 무기충전제, 미네랄 보강재 등을 혼합, 압출하는 단계;를 포함하여 이루어진다.Method for producing a polyketone resin composition excellent in impact resistance of the present invention comprises the steps of preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a double ligand compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone resin; And mixing and extruding glass fibers, inorganic fillers, mineral reinforcing materials, and the like into the polyketone resin.
또한 필요에 따라 내충격성과 탄성 등을 더욱 향상시키기 위하여 폴리우레탄 수지, 폴리카보네이트, 폴리아미드6 수지, 고무, ASA(Acrylic Styrene Acrylonitrile) 등을 더 혼합할 수 있고 가공성과 성형성을 향상시키기 위하여 설폰아미드계 가소제를 첨가할 수 있다.Also, if necessary, polyurethane resin, polycarbonate, polyamide 6 resin, rubber, ASA (Acrylic Styrene Acrylonitrile), etc. can be further mixed to further improve impact resistance and elasticity, and sulfonamide to improve processability and formability. Systemic plasticizers can be added.
촉매 조성물을 구성하는 상기 팔라듐 화합물로는 초산 팔라듐을 사용할 수 있으며, 그 사용량은 10-3~10-1몰이 적절하다.Palladium acetate may be used as the palladium compound constituting the catalyst composition, and the amount of the palladium compound is preferably 10 -3 to 10 -1 mole.
촉매 조성물을 구성하는 상기 pKa값이 6 이하인 산으로는 트리플루오르 초산, p-톨루엔술폰산, 황산 및 술폰산으로 이루어진 군에서 선택된 1종 이상, 바람직하게는 트리플루오르 초산을 사용할 수 있으며, 그 사용량은 팔라듐 화합물 대비6~20 (몰)당량이 적절하다.As the acid having a pKa value of 6 or less constituting the catalyst composition, one or more selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid, and sulfonic acid may be used, and preferably trifluoroacetic acid is used. 6-20 (molar) equivalents to the compound are appropriate.
촉매 조성물을 구성하는 상기 인의 2배위자 화합물로는 1,3-비스[다이페닐포스피노]프로판(예컨대, 1,3-비스[다이(2-메톡시페닐포스피노)]프로판, 1,3-비스[비스[아니실]포스피노메틸]-1,5-디옥사스피로[5,5]운데칸 및 ((2,2-디메틸-1,3-디옥Examples of the phosphorus double ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (eg, 1,3-bis [di (2-methoxyphenylphosphino)] propane, 1,3- Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane and ((2,2-dimethyl-1,3-diox
산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로 이루어진 군에서Acid-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine)
선택된 1종 이상을 사용할 수 있으며, 그 사용량은 팔라듐 화합물 대비 1~1.2 (몰)One or more selected ones can be used, and the amount used is 1 to 1.2 (mol) compared to the palladium compound.
당량이 적절하다.Equivalence is appropriate.
상기 일산화탄소, 에틸렌 및 프로필렌은 알코올(예컨대, 메탄올)과 물의 혼합용매에서 액상 중합되어 선상 터폴리머를 생성하는데, 상기 혼합용매로는 메탄올 100 중량부 및 물 2~10 중량부의 혼합물을 사용할 수 있다. 혼합용매에서 물의 함량이 2 중량부 미만이면 케탈이 형성되어 공정시 내열안정성이 저하될 수 있으며, 10 중량부를 초과하면 제품의 기계적 물성이 저하될 수 있다.The carbon monoxide, ethylene, and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer. The mixed solvent may be a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water. If the content of the water in the mixed solvent is less than 2 parts by weight of ketal may be formed, the heat stability during the process may be lowered, if more than 10 parts by weight may lower the mechanical properties of the product.
또한, 상기 중합시 반응온도는 50~100℃, 반응압력은 40~60bar의 범위가 적절하다. 생성된 폴리머는 중합 후 여과, 정제 공정을 통해 회수하며, 남은 촉매 조성물은 알코올 또는 아세톤 등의 용매로 제거한다.In addition, the polymerization temperature is 50 ~ 100 ℃, the reaction pressure is suitable for the range of 40 ~ 60bar. The resulting polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.
본 발명에서는 상기 얻어진 폴리케톤 수지에 필요에 따라 유리섬유, 무기충전제, 미네랄 보강재, 폴리우레탄 수지, 폴리카보네이트, 폴리아미드6 수지, 고무, ASA(Acrylic Styrene Acrylonitrile), 설폰아미드계 가소제를 혼합한 다음 압출기로 압출하여 최종적으로 블렌드 조성물을 수득한다. 상기 블렌드는 2축 압출기에 투입하여 용융혼련 및 압출함으로써 제조된다.In the present invention, the obtained polyketone resin is mixed with glass fiber, inorganic filler, mineral reinforcing material, polyurethane resin, polycarbonate, polyamide 6 resin, rubber, Acrylic Styrene Acrylonitrile (ASA), sulfonamide plasticizer as necessary. Extrusion with an extruder finally yields the blend composition. The blend is prepared by melt kneading and extrusion into a twin screw extruder.
이때, 압출온도는 230~260℃, 스크류 회전속도는 100~300rpm의 범위가 바람직하다. 압출온도가 230℃ 미만이면 혼련이 적절히 일어나지 않을 수 있으며, 260℃를 초과하면 수지의 내열성 관련 문제가 발생할 수 있다. 또한 스크류 회전속도가 100rpm 미만이면 원활한 혼련이 일어나지 않을 수 있으며, 300rpm을 초과하면 전도성 카본블랙 또는 탄성 폴리우레탄 또는 탄소섬유가 파괴되어 기계적 물성이 저하될 수 있다.At this time, the extrusion temperature is 230 ~ 260 ℃, screw rotation speed is preferably in the range of 100 ~ 300rpm. If the extrusion temperature is less than 230 ℃ kneading may not occur properly, if it exceeds 260 ℃ may cause problems with the heat resistance of the resin. In addition, if the screw rotational speed is less than 100rpm it may not be a smooth kneading, if it exceeds 300rpm conductive carbon black or elastic polyurethane or carbon fiber may be destroyed and mechanical properties may be reduced.
상기 유리섬유는 인장강도와 충격강도를 향상시키기 위하여 첨가되는 것으로 직경이 10μm 이고, 길이가 4mm이며, 폴리우레탄으로 코팅된 것이 바람직하다. 상기 유리섬유를 사용하는 경우 폴리케톤과의 블렌딩 효율이 우수하며, 조성물을 산업용 부품으로 제조시 기계적 물성이 우수하다. 그러나 본 발명이 이에 한정되는 것은 아니다.The glass fiber is added to improve the tensile strength and impact strength is 10μm in diameter, 4mm in length, preferably coated with polyurethane. When the glass fiber is used, the blending efficiency with the polyketone is excellent, and when the composition is manufactured as an industrial part, the mechanical properties are excellent. However, the present invention is not limited thereto.
상기 무기충전제는 폴리케톤 블렌드 수지 조성물의 기계적 물성을 더욱 향상시키기 위하여 첨가되는 것으로 탄산칼슘, 황산마그네슘, 실리콘 카바이드, 산화칼슘 등을 사용하지만 반드시 이에 한정되는 것은 아니다. The inorganic filler is added to further improve the mechanical properties of the polyketone blend resin composition, but calcium carbonate, magnesium sulfate, silicon carbide, calcium oxide and the like are used, but are not necessarily limited thereto.
상기 미네랄 보강재는 내충격성과 치수안정성을 향상시키기 위한 것으로 탈크(Talc), 카오린(Kaolin), 마이카(Mica), 월라스토나이트(wollastonite), TiO2-코팅된 마이카 소형판 (TiO2-coated mica platelets), 실리카 (silica), 알루미나(alumina), 붕규산염(borosilicates) 및 산화물 (oxides)중 어느 하나인 것이 바람직하다.The mineral reinforcing material is to improve impact resistance and dimensional stability, such as talc, kaolin, mica, wollastonite, TiO2-coated mica platelets, It is preferably one of silica, alumina, borosilicates and oxides.
본 발명에서는 상기 선상 교대 폴리케톤과 미네랄 필러를 혼합한 블렌드를 사용하는데, 여기서 상기 미네랄 필러는 탈크(Talc), 카오린(Kaolin), 마이카(Mica), 월라스토나이트(wollastonite), TiO2-코팅된 마이카 소형판 (TiO2-coated mica platelets), 실리카 (silica), 알루미나(alumina), 붕규산염(borosilicates) 및 산화물 (oxides)중 어느 하나이다.In the present invention, a blend of the linear alternating polyketone and the mineral filler is used, wherein the mineral filler is talc, kaolin, mica, wollastonite, TiO 2 -coated. Mica plates (TiO 2 -coated mica platelets), silica, alumina, borosilicates and oxides.
또한, 상기 미네랄 필러의 함량은 5 내지 50중량%이다. 바람직하게는 30 내지 40중량%인 것이 좋다. 여기서, 미네랄 필러가 5중량% 미만으로 첨가되면 치수안정성이 떨어지고, 50중량% 초과하면 사출 성형성이 떨어진다.In addition, the content of the mineral filler is 5 to 50% by weight. Preferably it is 30 to 40% by weight. Herein, when the mineral filler is added in less than 5% by weight, the dimensional stability is lowered, and when it exceeds 50% by weight, the injection moldability is lowered.
상기 폴리우레탄 수지는 폴리케톤 수지의 충격강도, 반발탄성을 향상시키기 위하여 필요에 따라 첨가된다.The polyurethane resin is added as necessary to improve the impact strength and resilience of the polyketone resin.
상기 폴리카보네이트는 폴리케톤 수지의 경도를 향상시키기 위하여 필요에 따라 첨가된다. The polycarbonate is added as necessary to improve the hardness of the polyketone resin.
상기 폴리아미드6 수지와 고무는 내충격성, 내수성 등을 향상시키기 위한 것으로 폴리아미드의 유동지수 (Melt Index)(240 ℃, 21.2 N)는 각각 5 ~ 70 g/10 min이 바람직하며, 유동지수가 5 g/10 min 미만일 경우에는 부품 성형성이 취약해 지며, 유동지수가 70 g/10 min 초과일 경우에는 충격 강도 등의 물성이 저하된다. 또한 고무는 주쇄에 이중결합이 존재하지 않은 비극성 고무인 에틸렌프로필렌 디엔모노머(ethylene propylene diene monomer (M-class) rubber, EPDM) 고무를 사용하는 것이 내후성과 내오존성 등에 있어서 효과적이나, 반드시 이에 한정되는 것은 아니다. The polyamide 6 resin and rubber are intended to improve impact resistance, water resistance, and the like. The melt index of the polyamide (240 ° C., 21.2 N) is preferably 5 to 70 g / 10 min. If it is less than 5 g / 10 min, the moldability of parts becomes weak, and if the flow index is more than 70 g / 10 min, physical properties such as impact strength are lowered. In addition, the use of ethylene propylene diene monomer (M-class) rubber (EPDM) rubber, which is a nonpolar rubber having no double bond in the main chain, is effective in weatherability and ozone resistance, but is not limited thereto. no.
상기 ASA(Acrylic Styrene Acrylonitrile)는 고무 주쇄 중 수소의 해리에너지가 약 90 kcal/mol인데, 300nm 이하의 파장 에너지가 높은 광에서 해리되는 특성을 가지고 있어서, 기본적으로 내후열화가 일어나기 어렵다. 따라서 상기 ASA의 첨가로 인하여 폴리케톤 수지의 탄성 및 내후성을 강화시킬 수 있다.The ASA (Acrylic Styrene Acrylonitrile) is about 90 kcal / mol of dissociation energy of hydrogen in the rubber main chain, and has a characteristic of dissociating in light having a high wavelength energy of 300 nm or less, and thus, it is difficult to basically cause weathering degradation. Therefore, it is possible to enhance the elasticity and weather resistance of the polyketone resin due to the addition of the ASA.
상기 유리섬유, 무기충전제, 미네랄 보강재, 폴리우레탄 수지, 폴리카보네이트, 폴리아미드6 수지, 고무, ASA(Acrylic Styrene Acrylonitrile), 설폰아미드계 가소제는 단독으로 또는 혼합하여 블렌딩할 수 있고, 첨가되는 함량은 폴리케톤 터폴리머 100 중량부 대비 5내지 50 중량부가 좋고, 바람직하게는 10 내지 20 중량부가 좋다. 첨가되는 함량이 5 중량부 미만이면 원하는 인장강도 및 충격강도를 부여할 수 없고, 50 중량부를 초과하면 폴리케톤 고유의 기계적 강도, 치수안정성 및 성형특성 등이 저하되어 실용성이 결여될 수 있다.The glass fiber, inorganic filler, mineral reinforcing material, polyurethane resin, polycarbonate, polyamide 6 resin, rubber, ASA (Acrylic Styrene Acrylonitrile), sulfonamide-based plasticizer may be blended alone or mixed, the amount is added 5 to 50 parts by weight relative to 100 parts by weight of the polyketone terpolymer is good, preferably 10 to 20 parts by weight. If the added content is less than 5 parts by weight, it is not possible to give the desired tensile strength and impact strength, and if it exceeds 50 parts by weight, the mechanical strength, dimensional stability and molding characteristics of polyketones may be lowered and thus, may lack practicality.
본 발명의 제조방법에 의한 폴리케톤 수지 조성물은 인장강도, 충격강도가 우수하여 마스크, 파이프 홀더, 변속기 브라켓, 범퍼 브라켓, 자동차용 정션 박스, 자동차 휠림, 전력선 결속용 브라켓, 전자기기 커버, 안경테 등 다양한 분야의 산업용 부품으로 적용 가능한 장점이 있다. Polyketone resin composition according to the production method of the present invention is excellent in tensile strength and impact strength mask, pipe holder, transmission bracket, bumper bracket, automotive junction box, automobile wheel rim, power line binding bracket, electronic device cover, eyeglass frame, etc. There is an advantage that can be applied to industrial parts of various fields.
한편, 본 발명에 실시예에 따른 폴리케톤 조성물은 폴리케톤에 비정질 반방향족 폴리아미드를 함유시킴으로써, 굴곡특성이 우수하게 개선된 것을 특징으로 하고 있다.On the other hand, the polyketone composition according to an embodiment of the present invention is characterized in that the bending properties are excellently improved by containing an amorphous semiaromatic polyamide in the polyketone.
이하, 상기 폴리케톤 조성물의 부성분인 비정질 반방향족 폴리아미드에 대해서 설명한다. Hereinafter, the amorphous semiaromatic polyamide which is a subcomponent of the polyketone composition will be described.
상기 비정질 반방향족 폴리아미드의 비제한적인 예를 들면, 폴리 헥사메틸렌이소프탈아미드(나일론 6I), 헥사메틸렌이소프탈아미드/헥사메틸렌테레프탈아미드 코폴리머(나일론 6I/6T), 폴리(메타자일릴렌이소프탈아미드)(나일론 MXDI), 카프로락탐/메타자일릴렌이소프탈아미드 코폴리머(나일론 6/MXDI), 카프로락탐/헥사메틸렌이소프탈아미드 코폴리머(나일론6/6I) 등이 있다. 이들 중에서도 폴리 헥사메틸렌이소프탈아미드(나일론 6I)가 특히 바람직하게 사용될 수 있다.Non-limiting examples of such amorphous semiaromatic polyamides include poly hexamethyleneisophthalamide (nylon 6I), hexamethyleneisophthalamide / hexamethylene terephthalamide copolymer (nylon 6I / 6T), poly (methazyl Yleneisophthalamide) (nylon MXDI), caprolactam / methaxylyleneisophthalamide copolymer (nylon 6 / MXDI), caprolactam / hexamethyleneisophthalamide copolymer (nylon 6 / 6I), and the like. . Among them, poly hexamethyleneisophthalamide (nylon 6I) can be particularly preferably used.
구체적으로, 본 발명의 폴리케톤 조성물은 폴리케톤과 비정질 반방향족 폴리아미드의 조합으로 이루어진 블렌드로 구성되는 것으로서, 굴곡특성을 향상시키는 것을 특징으로 한다.Specifically, the polyketone composition of the present invention is composed of a blend made of a combination of polyketone and amorphous semiaromatic polyamide, and is characterized by improving bending characteristics.
비정질 반방향족 폴리아미드의 중량은 전체중량 대비 5내지 40 중량%이다. 바람직하게는 10 내지 30 중량%이며, 더욱 바람직하게는 10 내지 20 중량%인 것이 좋다. 여기서 폴리케톤 수지의 함량이 60 중량% 미만이면 폴리케톤 수지 고유의 기계적 강도, 치수안정성 및 성형 특성 등이 저하되어 실용성이 결여 및 작업성이 현저히 떨어지며, 95%를 초과하면 비정질 반방향족 폴리아미드의 상대적 함량 감소로 원하는 수준의 굴곡특성을 부여하기 어려워질 수 있다.The weight of the amorphous semiaromatic polyamide is 5 to 40% by weight relative to the total weight. Preferably it is 10-30 weight%, More preferably, it is 10-20 weight%. If the content of the polyketone resin is less than 60% by weight, the mechanical strength, dimensional stability, and molding properties of the polyketone resin are inferior, resulting in a lack of practicality and workability, and exceeding 95% of the amorphous semiaromatic polyamide. Relative content reduction can make it difficult to impart desired levels of flexural properties.
이외에, 상기 조성물에 보강재로 카본 화이버, 마이카 및 탈크 등을 첨가하여 기계적인 물성을 보강시킬 수 있다. 또한, 산화 방지제 및 안료 등을 목적하는 바에 따라 첨가할 수 있다. 이러한 첨가제는 이 분야에서 통상의 지식을 가진 자에 의하여 적절히 사용될 수 있다.In addition, carbon fibers, mica and talc may be added to the composition to reinforce the mechanical properties. In addition, antioxidants, pigments and the like can be added as desired. Such additives may be suitably used by those skilled in the art.
한편, 본 발명에 다른 실시예에 따른 폴리케톤 조성물은 폴리케톤에 폴리에스테르를 함유시킴으로써, 내습성 및 치수안정성이 우수하게 개선된 것을 그 특징으로 하고 있다.On the other hand, the polyketone composition according to another embodiment of the present invention is characterized by having excellent moisture resistance and dimensional stability by containing polyester in the polyketone.
이하, 상기 폴리케톤 조성물의 부성분인 폴리에스테르 수지에 대해서 설명한다.Hereinafter, the polyester resin which is a subcomponent of the said polyketone composition is demonstrated.
구체적으로, 본 발명의 폴리케톤 조성물은 폴리케톤과 폴리에스테르 조합으로 이루어진 블렌드로 구성되는 것으로서, 내습성를 향상시키는 것을 특징으로 한다.Specifically, the polyketone composition of the present invention is composed of a blend consisting of a polyketone and a polyester combination, characterized in that to improve moisture resistance.
폴리에스테르의 중량은 전체중량 대비 10 내지 90 중량%이다. 바람직하게는 10 내지 60 중량%이며, 더욱 바람직하게는 20 내지 60 중량%인 것이 좋다. 여기서 폴리케톤 수지의 함량이 10 중량% 미만이면 폴리케톤 수지 고유의 기계적 강도, 치수안정성 및 성형 특성 등이 저하되어 실용성이 결여될 수 있으며, 90%를 초과하면 폴리에스테르의 상대적 함량 감소로 원하는 수준의 내습성을 부여하기 어려워질 수 있다.The weight of the polyester is 10 to 90% by weight relative to the total weight. Preferably it is 10-60 weight%, More preferably, it is 20-60 weight%. If the content of the polyketone resin is less than 10% by weight, the mechanical strength, dimensional stability, and molding characteristics of the polyketone resin may be lowered, thereby causing a lack of practicality. It can be difficult to impart moisture resistance.
이외에, 상기 조성물에 보강재로 카본 화이버, 마이카 및 탈크 등을 첨가하여 기계적인 물성을 보강시킬 수 있다. 또한, 산화 방지제 및 안료 등을 목적하는 바에 따라 첨가할 수 있다. 이러한 첨가제는 이 분야에서 통상의 지식을 가진 자에 의하여 적절히 사용될 수 있다.In addition, carbon fibers, mica and talc may be added to the composition to reinforce the mechanical properties. In addition, antioxidants, pigments and the like can be added as desired. Such additives may be suitably used by those skilled in the art.
한편, 본 발명의 또 다른 실시예에 따른 폴리케톤 노트북 하단 하우징은 폴리케톤 조성물 중 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 50ppm이하 이고, 분자량 분포가 1.5 내지 2.5인 선상 교대 폴리케톤 폴리머 53 내지 71중량%와, 유리섬유 25 내지 35중량%와, 인계 난연제 2 내지 12중량%와, 나일론 6I 2 내지 8중량%를 포함하는 블렌드를 사출성형하여 제조되는 것을 특징으로 한다. 상기 폴리케톤, 유리섬유, 인계 난연제 및 나일론 6I의 함량이 상기 범위 미만이거나 초과하면, 노트북 하우징에 사용하기에는 기계적 물성이 떨어진다.Meanwhile, the polyketone notebook bottom housing according to another embodiment of the present invention is composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon in the polyketone composition, the residual amount of palladium catalyst is 50 ppm or less, and the molecular weight distribution is 1.5 to 2.5. It is prepared by injection molding a blend comprising 53 to 71% by weight of the linear alternating polyketone polymer, 25 to 35% by weight of glass fiber, 2 to 12% by weight of phosphorus flame retardant, and 2 to 8% by weight of nylon 6I. do. If the content of the polyketone, glass fiber, phosphorus-based flame retardant and nylon 6I is less than or above the above range, mechanical properties are poor for use in a notebook housing.
상기 폴리케톤 수지 조성물의 기계적 강도를 강화시키기 위하여 유리섬유를 혼합한다. 혼합되는 양은 전체 중량%대비 20~40중량%, 바람직하게는 25~35중량%, 보다 바람직하게는 35중량%가 좋다. 20중량%미만이면 내충격성 등 기계적 강도가 우수하지 못하고 40중량%를 초과하면 혼합에 따른 경제적 비용상승 대비 기계적 강도의 향상 효과가 미미한 문제점이 발생된다.Glass fibers are mixed to enhance the mechanical strength of the polyketone resin composition. The amount to be mixed is 20 to 40% by weight, preferably 25 to 35% by weight, more preferably 35% by weight relative to the total weight. If it is less than 20% by weight, the mechanical strength such as impact resistance is not excellent, and if it exceeds 40% by weight, there is a problem that the improvement effect of the mechanical strength is insignificant compared to the economic cost increase due to mixing.
또한, 본 발명은 최종 제품인 노트북의 내열성 및 난연성을 강화시키기 위하여 난연제 및 나일론 6I를 추가로 혼합한다. 혼합하는 양은 전체 중량%대비 난연제 5~10중량%, 나일론 6I 2~8중량%가 좋고, 바람직하게는 난연제 7중량%, 나일론 5중량%가 좋다. In addition, the present invention further mixes a flame retardant and nylon 6I to enhance the heat and flame resistance of the final notebook product. The mixing amount is 5 to 10% by weight of the flame retardant, 2 to 8% by weight of nylon 6I relative to the total weight%, preferably 7% by weight of flame retardant, 5% by weight of nylon.
본 발명에서 사용되는 난연제는 비할로겐계로서 특히 인계 난연제가 바람직하다. 대표적인 인계 난연제는 Cyclic Phosphate Phosphonic, P-[3-[(hydroxymethyl)amino]-3-oxopropyl]-dimethyl ester, Dimethyl methyl phosphonate, Phosphonic,P-[[bis(2-hydroxyethyl)amino]methyl]-diethyl ester, Triethyl Phosphate, Isopropyl phenyl diphenyl phosphate, Tris(2-chloroethyl)phosphate, Tetrakis hydroxymethyl phosphonium sulfate 등이 있으나 반드시 이에 한정되는 것은 아니다.The flame retardant used in the present invention is non-halogen-based, particularly preferably a phosphorus flame retardant. Representative phosphorus flame retardants are Cyclic Phosphate Phosphonic, P- [3-[(hydroxymethyl) amino] -3-oxopropyl] -dimethyl ester, Dimethyl methyl phosphonate, Phosphonic, P-[[bis (2-hydroxyethyl) amino] methyl] -diethyl esters, Triethyl Phosphate, Isopropyl phenyl diphenyl phosphate, Tris (2-chloroethyl) phosphate, Tetrakis hydroxymethyl phosphonium sulfate, etc., but are not necessarily limited thereto.
이하, 본 발명의 노트북 하단 하우징을 제조하기 위한 제조방법은 다음과 같다.Hereinafter, a manufacturing method for manufacturing a notebook lower housing of the present invention is as follows.
본 발명에 따른 노트북 하단 하우징의 제조방법은 팔라듐 화합물, pKa값이 6 이하인 산, 및 인의 2배위자 화합물을 포함하는 촉매 조성물을 준비하는 단계 메탄올-물의 혼합용매(중합용매)를 준비하는 단계; 상기 촉매 조성물 및 혼합용매의 존재 하에서 중합을 진행하여 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머를 제조하는 단계; 상기 선상 터폴리머에서 남은 촉매 조성물을 용매(예컨대, 알코올 및 아세톤)로 제거하여 폴리케톤 폴리머를 수득하는 단계; 및 상기 폴리케톤 폴리머 52중량%에 유리섬유 30중량%, 트리메틸 포스페이트(Triethyl Phosphate) 7중량%, 나일론 6I 5중량%를 혼합, 압출하여 블렌드를 제조하는 단계; 및 상기 블렌드를 사출성형하는 단계를 포함할 수 있으나, 이에 한정되는 것은 아니다.A method of manufacturing a notebook lower housing according to the present invention comprises the steps of preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a double ligand compound of phosphorus, preparing a mixed solvent of methanol-water (polymerization solvent); Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone polymer; And mixing and extruding 52 wt% of the polyketone polymer, 30 wt% of glass fiber, 7 wt% of trimethyl phosphate, and 5 wt% of nylon 6I to prepare a blend; And injection molding the blend, but is not limited thereto.
상기와 같은 폴리케톤 조성물로 제조된 노트북 하단 하우징은 굴곡 탄성율이 8000MPa 이상, 충격강도가 11kJ/m2 이상인 것을 특징으로 한다. 이에 따라, 상기 폴리케톤 조성물을 사용하여 우수한 굴곡탄성율 및 내충격성을 갖는 노트북 하단 하우징으로 유용하게 적용할 수 있다.The notebook lower housing made of the polyketone composition as described above is characterized in that the flexural modulus is 8000 MPa or more, and the impact strength is 11 kJ / m 2 or more. Accordingly, the polyketone composition may be usefully applied to a notebook lower housing having excellent flexural modulus and impact resistance.
이하, 본 발명의 산업용 부품의 제조방법은 다음과 같다.Hereinafter, the manufacturing method of the industrial component of the present invention is as follows.
본 발명에 따른 산업용 부품용 폴리케톤 제조방법은 팔라듐 화합물, pKa값이 6 이하인 산, 및 인의 2배위자 화합물을 포함하는 촉매 조성물을 준비하는 단계; 알코올(예컨대, 메탄올)과 물을 포함하는 혼합용매(중합용매)를 준비하는 단계; 상기 촉매 조성물 및 혼합용매의 존재 하에서 중합을 진행하여 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머를 제조하는 단계; 상기 선상 터폴리머에서 남은 촉매 조성물을 용매(예컨대, 알코올 및 아세톤)로 제거하여 폴리케톤 폴리머를 수득하는 단계; 및 상기 폴리케톤 폴리머 60 내지 90중량%와 유리섬유 10 내지 40중량%를 혼합, 압출하여 블렌드를 제조하는 단계; 및 상기 블렌드를 사출성형하는 단계를 포함할 수 있으나, 이에 한정되는 것은 아니다.Polyketone manufacturing method for industrial parts according to the present invention comprises the steps of preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a double ligand compound of phosphorus; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent; Removing the remaining catalyst composition from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone polymer; Preparing a blend by mixing and extruding 60 to 90 wt% of the polyketone polymer and 10 to 40 wt% of glass fibers; And injection molding the blend, but is not limited thereto.
상기 촉매 조성물을 구성하는 상기 팔라듐 화합물로는 초산 팔라듐을 사용할 수 있으며, 그 사용량은 10-3~10-1 몰이 적절하나, 이에 한정되는 것은 아니다.Palladium acetate may be used as the palladium compound constituting the catalyst composition, and the amount of palladium acetate is preferably 10 −3 to 10 −1 moles, but is not limited thereto.
또한, 상기 촉매 조성물을 구성하는 상기 pKa값이 6 이하인 산으로는 트리플루오르 초산, p-톨루엔술폰산, 황산 및 술폰산으로 이루어진 군에서 선택된 1종 이상, 바람직하게는 트리플루오르 초산을 사용할 수 있으며, 그 사용량은 팔라듐 화합물 대비 6~20 (몰)당량이 적절하다.In addition, the acid having a pKa value of 6 or less constituting the catalyst composition may be at least one selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid and sulfonic acid, preferably trifluoroacetic acid. The use amount is 6-20 (mole) equivalents with respect to a palladium compound.
또한, 상기 촉매 조성물을 구성하는 상기 인의 2배위자 화합물로는 1,3-비스[다이페닐포스피노]프로판(예컨대, 1,3-비스[다이(2-메톡시페닐포스피노)]프로판, 1,3-비스[비스[아니실]포스피노메틸]-1,5-디옥사스피로[5,5]운데칸 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로 이루어진 군에서 선택된 1종 이상을 사용할 수 있으며, 그 사용량은 팔라듐 화합물 대비 1~20 (몰)당량이 적절하다.In addition, as the double ligand compound of phosphorus constituting the catalyst composition, 1,3-bis [diphenylphosphino] propane (for example, 1,3-bis [di (2-methoxyphenylphosphino)] propane, 1 , 3-bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane and ((2,2-dimethyl-1,3-dioxane-5,5-diyl ) Bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) may be used one or more selected from the group consisting of, the amount of 1 to 20 (mole) equivalent to the palladium compound is appropriate.
상기 일산화탄소, 에틸렌 및 프로필렌은 알코올(예컨대, 메탄올)과 물의 혼합용매에서 액상 중합되어 선상 터폴리머를 생성하는데, 상기 혼합용매로는 메탄올 100 중량부 및 물 2~10 중량부의 혼합물을 사용할 수 있다. 혼합용매에서 물의 함량이 2 중량부 미만이면 케탈이 형성되어 공정시 내열안정성이 저하될 수 있으며, 10 중량부를 초과하면 제품의 기계적 물성이 저하될 수 있다.The carbon monoxide, ethylene, and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer. The mixed solvent may be a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water. If the content of the water in the mixed solvent is less than 2 parts by weight of ketal may be formed, the heat stability during the process may be lowered, if more than 10 parts by weight may lower the mechanical properties of the product.
또한, 상기 중합시 반응온도는 50~100℃, 반응압력은 40~60bar의 범위가 적절하다. 생성된 폴리머는 중합 후 여과, 정제 공정을 통해 회수하며, 남은 촉매 조성물은 알코올 또는 아세톤 등의 용매로 제거한다.In addition, the polymerization temperature is 50 ~ 100 ℃, the reaction pressure is suitable for the range of 40 ~ 60bar. The resulting polymer is recovered through polymerization and filtration and purification, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.
본 발명에서는 상기 얻어진 폴리케톤 폴리머를 유리섬유와 혼합한 다음 압출기로 압출하여 최종적으로 블렌드 조성물을 수득한다. 상기 블렌드는 2축 압출기에 투입하여 용융혼련 및 압출함으로써 제조될 수 있다.In the present invention, the obtained polyketone polymer is mixed with glass fibers and then extruded with an extruder to finally obtain a blend composition. The blend may be prepared by melt kneading and extrusion into a twin screw extruder.
이때, 압출온도는 230~260℃, 스크류 회전속도는 100~300rpm의 범위가 바람직하다. 압출온도가 230℃ 미만이면 혼련이 적절히 일어나지 않을 수 있으며, 260℃를 초과하면 수지의 내열성 관련 문제가 발생할 수 있다. 또한 스크류 회전속도가 100rpm 미만이면 원활한 혼련이 일어나지 않을 수 있으며, 300rpm을 초과하면 유리섬유가 파괴되어 기계적 물성이 저하될 수 있다.At this time, the extrusion temperature is 230 ~ 260 ℃, screw rotation speed is preferably in the range of 100 ~ 300rpm. If the extrusion temperature is less than 230 ℃ kneading may not occur properly, if it exceeds 260 ℃ may cause problems with the heat resistance of the resin. In addition, if the screw rotational speed is less than 100rpm may not be smooth kneading, if the screw speed exceeds 300rpm glass fiber may be destroyed and mechanical properties may be reduced.
상기와 같은 방법으로 블렌드를 제조하고 이를 압출 성형 또는 사출 성형함으로써 산업용 부품을 제조할 수 있다.Industrial parts may be manufactured by preparing a blend in the same manner as described above and extruding or injection molding it.
이하, 실시예를 통해 본 발명을 구체적으로 설명한다. 그러나 이들 실시예는 본 발명의 이해를 돕기 위한 것일 뿐 어떠한 의미로든 본 발명의 범위가 이들 실시예로 한정되는 것은 아니다. 비제한적인 이하의 실시예에 의하여 본 발명을 자세히 설명한다.Hereinafter, the present invention will be described in detail through examples. However, these examples are only for the understanding of the present invention, and the scope of the present invention in any sense is not limited to these examples. The invention is illustrated in detail by the following non-limiting examples.
실시예Example 1 One
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexafluoroisopropano)로 25℃에 측정한 LVN이 1.3dl/g이며, MI(Melt index)가 48g/10min 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexafluoroisopropano) at 1.3 dl / g, and a MI (Melt index) of 48 g / 10 min. The polyketone terpolymer prepared above was prepared in pellet form on an extruder using a biaxial screw with a diameter of 2.5 cm operating at 250 rpm and L / D = 32.
실시예Example 2 2
실시예 1에 의하여 제조된 폴리케톤 터폴리머 100 중량부에 유리섬유 5 중량부, 탄산칼슘 10 중량부, 탈크(Talc) 5중량부를 혼합하여 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다.100 parts by weight of the polyketone terpolymer prepared in Example 1, 5 parts by weight of glass fiber, 10 parts by weight of calcium carbonate, 5 parts by weight of talc (2.5 cm) operating at 250rpm, L / D = 32 The pellets were prepared on an extruder using a phosphorous biaxial screw.
실시예Example 3 3
실시예 1에 의하여 제조된 폴리케톤 터폴리머 100 중량부에 유리섬유 3 중량부, 탄산칼슘 5 중량부, 탈크(Talc) 5 중량부, 폴리우레탄 수지 5 중량부, 폴리카보네이트 2 중량부를 혼합하여 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다.250 rpm by mixing 3 parts by weight of glass fibers, 5 parts by weight of calcium carbonate, 5 parts by weight of talc, 5 parts by weight of polyurethane resin, and 2 parts by weight of polycarbonate to 100 parts by weight of the polyketone terpolymer prepared according to Example 1. It was made into pellets on an extruder using a biaxial screw with a diameter of 2.5 cm and L / D = 32.
실시예Example 4 4
실시예 1에 의하여 제조된 폴리케톤 터폴리머 100 중량부에 유리섬유 3 중량부, 탄산칼슘 3 중량부, 탈크(Talc) 3 중량부, 폴리우레탄 수지 5 중량부, 폴리카보네이트 2 중량부, 폴리아미드 수지 4 중량부를 혼합하여 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다.100 parts by weight of polyketone terpolymer prepared by Example 1 3 parts by weight of glass fiber, 3 parts by weight of calcium carbonate, 3 parts by weight of talc, 5 parts by weight of polyurethane resin, 2 parts by weight of polycarbonate, polyamide 4 parts by weight of the resin were mixed and prepared into pellets on an extruder using a biaxial screw with a diameter of 2.5 cm and operating at 250 rpm.
실시예Example 5 5
실시예 1에 의하여 제조된 폴리케톤 터폴리머 100 중량부에 유리섬유 2 중량부, 탄산칼슘 2 중량부, 탈크(Talc) 3 중량부, 폴리우레탄 수지 3 중량부, 폴리카보네이트 2 중량부, 폴리아미드 수지 2 중량부, 고무 2 중량부, ASA 2 중량부, 설폰아미드계 가소제 2 중량부를 혼합하여 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다.2 parts by weight of glass fibers, 2 parts by weight of calcium carbonate, 3 parts by weight of talc, 3 parts by weight of polyurethane resin, 2 parts by weight of polycarbonate, 2 parts by weight of polyketone terpolymer prepared by Example 1 2 parts by weight of resin, 2 parts by weight of rubber, 2 parts by weight of ASA and 2 parts by weight of sulfonamide-based plasticizer were mixed and pelletized on an extruder by using a biaxial screw having a diameter of 2.5 cm and operating at 250 rpm. ) Phase.
비교예Comparative example 1 One
PA66 70 중량%(A218V30 제품)을 사용하여 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다.A pellet was prepared on an extruder using a biaxial screw with a diameter of 2.5 cm operating at 250 rpm using L / D = 32 using 70 weight percent PA66 (available from A218V30).
비교예Comparative example 2 2
PA66 70 중량%(A218V30 제품) 100 중량부에 유리섬유 5 중량부, 탄산칼슘 10 중량부, 탈크(Talc) 5중량부를 혼합하여 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다.70 parts by weight of PA66 (A218V30), 5 parts by weight of glass fiber, 10 parts by weight of calcium carbonate, and 5 parts by weight of talc, 2.5 cm in diameter, operating at 250 rpm, 2-axis with L / D = 32 The screw was used to make pellets on an extruder.
비교예Comparative example 3 3
PA66 70 중량%(A218V30 제품) 100 중량부에 유리섬유 3 중량부, 탄산칼슘 5 중량부, 탈크(Talc) 5 중량부, 폴리우레탄 수지 5 중량부, 폴리카보네이트 2 중량부를 혼합하여 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다.100 parts by weight of PA66 70 parts by weight (A218V30) 3 parts by weight of glass fiber, 5 parts by weight of calcium carbonate, 5 parts by weight of talc, 5 parts by weight of polyurethane resin, 2 parts by weight of polycarbonate to operate at 250rpm It was made into pellets on an extruder using a biaxial screw with a diameter of 2.5 cm and L / D = 32.
비교예Comparative example 4 4
PA66 70 중량%(A218V30 제품) 100 중량부에 유리섬유 3 중량부, 탄산칼슘 3 중량부, 탈크(Talc) 3 중량부, 폴리우레탄 수지 5 중량부, 폴리카보네이트 2 중량부, 폴리아미드 수지 4 중량부를 혼합하여 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다.70 parts by weight of PA66 (A218V30 product) 3 parts by weight of glass fiber, 3 parts by weight of calcium carbonate, 3 parts by weight of talc, 5 parts by weight of polyurethane resin, 2 parts by weight of polycarbonate, 4 parts by weight of polyamide resin The parts were mixed and made into pellets on an extruder using a biaxial screw with a diameter of 2.5 cm and operating at 250 rpm, L / D = 32.
비교예Comparative example 5 5
PA66 70 중량%(A218V30 제품) 100 중량부에 유리섬유 2 중량부, 탄산칼슘 2 중량부, 탈크(Talc) 3 중량부, 폴리우레탄 수지 3 중량부, 폴리카보네이트 2 중량부, 폴리아미드 수지 2 중량부, 고무 2 중량부, ASA 2 중량부, 설폰아미드계 가소제 2 중량부를 혼합하여 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다.70 parts by weight of PA66 70 parts by weight (A218V30) 2 parts by weight of glass fiber, 2 parts by weight of calcium carbonate, 3 parts by weight of talc, 3 parts by weight of polyurethane resin, 2 parts by weight of polycarbonate, 2 parts by weight of polyamide resin Part, 2 parts by weight of rubber, 2 parts by weight of ASA and 2 parts by weight of sulfonamide-based plasticizer were mixed into pellets on an extruder by using a biaxial screw having a diameter of 2.5 cm and operating at 250 rpm. Prepared.
물성평가Property evaluation
상기 실시예의 제조된 폴리케톤 조성물을 시편으로 제조한 다음, 비교예의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 1에 나타내었다.The prepared polyketone composition of the above Example was prepared as a specimen, and then compared with the product of the comparative example, the physical properties were evaluated in the following manner, and the results are shown in Table 1 below.
1. 인장강도 평가 : ASTM D638에 의거하여 실시하였다.1. Tensile strength evaluation: It was performed according to ASTM D638.
2. 충격강도평가(노치드 아이조드) : ASTM D638에 의거하여 실시하였다.2. Impact strength evaluation (notched Izod): It was carried out according to ASTM D638.
3. 굴곡탄성율 평가: ASTM D790에 의거하여 실시하였다.3. Flexural modulus evaluation: It was carried out in accordance with ASTM D790.
4. 치수안정성 평가: 온도 50℃, 상대습도 90%의 조건에서 수직 및 수평방향에 대해 MS211-47에 따라 평가하였다.4. Dimensional Stability Evaluation: Evaluation was made in accordance with MS211-47 for vertical and horizontal directions at a temperature of 50 ° C. and a relative humidity of 90%.
항목Item 인장강도 (MPa)Tensile Strength (MPa) 충격강도 (kJ/m2)Impact Strength (kJ / m 2 ) 굴곡탄성율Flexural modulus 제품변형율 (수직%)Product Strain Rate (Vertical%) 제품변형율 (수평%)Product strain rate (horizontal%)
실시예1Example 1 148148 1818 78007800 0.080.08 0.050.05
실시예2Example 2 155155 1717 78007800 0.080.08 0.060.06
실시예3Example 3 156156 1616 82008200 0.090.09 0.070.07
실시예4Example 4 158158 1616 84008400 0.070.07 0.050.05
실시예5Example 5 158158 1515 84008400 0.110.11 0.070.07
비교예1Comparative Example 1 120120 55 64006400 0.840.84 0.750.75
비교예2Comparative Example 2 125125 44 66006600 0.750.75 0.660.66
비교예3Comparative Example 3 130130 44 70007000 0.720.72 0.620.62
비교예4Comparative Example 4 134134 55 72007200 0.770.77 0.680.68
비교예5Comparative Example 5 136136 44 74007400 0.640.64 0.580.58
상기 표 1을 통해 본 발명의 폴리케톤 수지 조성물은 인장강도, 충격강도 등 내충격성이 우수할 뿐만 아니라 탄성 및 수분흡수 후 물성유지율이 탁월한 것으로 확인되었다. 따라서 본 발명의 폴리케톤 수지 조성물은 마스크, 파이프 홀더, 변속기 브라켓, 범퍼 브라켓, 자동차용 정션 박스, 자동차 휠림, 전력선 결속용 브라켓, 전자기기 커버, 안경테 등 다양한 분야의 산업용 부품으로 적용할 것으로 예상된다.The polyketone resin composition of the present invention through Table 1 was confirmed that not only excellent impact resistance, such as tensile strength, impact strength, but also excellent retention of properties after elasticity and moisture absorption. Therefore, the polyketone resin composition of the present invention is expected to be applied to industrial parts in various fields such as masks, pipe holders, transmission brackets, bumper brackets, automotive junction boxes, automobile wheel rims, power line binding brackets, electronic device covers, eyeglass frames, and the like. .
실시예Example 6 6
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MWD가 2.0 이었다. Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. In addition, the melting point of the polyketone terpolymer was 220 ° C, LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g, MWD was 2.0.
상기 제조된 폴리케톤 터폴리머 90중량%와 유리섬유 10중량%를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차 에어 인테이크 매니폴드를 제조하여 물성을 평가하였다.90 wt% of the prepared polyketone terpolymer and 10 wt% of glass fiber were 40 mm in diameter operating at 250 rpm, and manufactured by injection molding into pellets on an extruder using a biaxial screw having L / D = 32. An automobile air intake manifold was prepared to evaluate the physical properties.
실시예Example 7 7
실시예 6중 폴리케톤의 함량을 80중량%, 유리섬유의 함량을 20중량% 설정한 것 이외에는 실시예 6과 동일하다.Except for setting the content of the polyketone in Example 6 80% by weight, the glass fiber content 20% by weight is the same as in Example 6.
실시예Example 8 8
실시예 6중 폴리케톤의 함량을 70중량%, 유리섬유의 함량을 30중량% 설정한 것 이외에는 실시예 6과 동일하다.Except for setting the content of the polyketone in Example 6 70% by weight, the glass fiber content 30% by weight is the same as in Example 6.
실시예Example 9 9
실시예 6중 폴리케톤의 함량을 60중량%, 유리섬유의 함량을 40중량% 설정한 것 이외에는 실시예 6과 동일하다.Except for setting the content of the polyketone in Example 6 60% by weight, the glass fiber content 40% by weight is the same as in Example 6.
비교예Comparative example 6 6
나일론 6 수지 70중량%와 유리섬유 30중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 자동차 에어 인테이크 매니폴드의 시편을 제조하였다.70 wt% of nylon 6 resin and 30 wt% of glass fiber were added to prepare a composition, and the prepared composition was pelleted on an extruder using a biaxial screw having a diameter of 40 cm and operating at 250 rpm. And then injection molded to prepare a specimen of the automotive air intake manifold.
물성평가Property evaluation
상기 실시예 6 내지 9 및 비교예 6에서 각각 제조된 시편을 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 2에 나타내었다.Physical properties of the specimens prepared in Examples 6 to 9 and Comparative Example 6 were evaluated in the following manner, and the results are shown in Table 2 below.
1. 인장강도 평가 : ASTM D638에 의거하여 실시하였다. 1. Tensile strength evaluation: It was performed according to ASTM D638.
2. 굴곡강도 평가 : ASTM D790에 의거하여 실시하였다.2. Flexural strength evaluation: It was performed according to ASTM D790.
3. 충격강도 평가 : ISO 179에 의거하여 실시하였다.3. Impact strength evaluation: It was carried out according to ISO 179.
4. 인장강도 유지율 평가 : ASTM D648에 의거하여 실시하였다.4. Evaluation of Tensile Strength Retention Rate: A test was performed according to ASTM D648.
비중importance 인장강도 (MPa)Tensile Strength (MPa) 굴곡강도 (MPa)Flexural Strength (MPa) 굴곡탄성율 (MPa)Flexural modulus (MPa) Charpy notched (KJ/m2)Charpy notched (KJ / m2) 120℃, 300시간 인장강도 유지율(%)120 ℃, 300 hours tensile strength retention (%)
실시예 6Example 6 1.301.30 113113 161161 44004400 8.08.0 110110
실시예 7Example 7 1.371.37 129129 178178 50005000 9.79.7 113113
실시예 8Example 8 1.441.44 156156 213213 69006900 12.412.4 115115
실시예 9Example 9 1.521.52 173173 237237 93009300 14.914.9 116116
비교예 6Comparative Example 6 1.381.38 160160 230230 90009000 66 8080
상기 표 2에서 알 수 있는 바와 같이, 실시예의 경우 비교예 6 대비 충격강도 및 인장강도 유지율이 우수한 것으로 나타났다. 따라서, 본 발명의 실시예를 통해 제조된 에어 인테이크 매니폴드는 기존의 에어 인테이크 매니폴드 소재로 사용되는 비교예의 경우보다 우수한 내충격성 및 장기내열성을 나타내므로, 에어 인테이크 매니폴드로 적용하기에 더욱 적합하다.As can be seen in Table 2, in the case of the Example it was found that the impact strength and tensile strength retention is superior to Comparative Example 6. Therefore, the air intake manifold manufactured through the embodiment of the present invention exhibits better impact resistance and long-term heat resistance than the comparative example used as a conventional air intake manifold material, and thus is more suitable for application as an air intake manifold. Do.
실시예Example 10 10
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MWD가 2.0 이었다. Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. In addition, the melting point of the polyketone terpolymer was 220 ° C, LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g, MWD was 2.0.
상기 제조된 폴리케톤 터폴리머 85중량%와 유리섬유 15중량%를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차 프론트엔드모듈의 캐리어 시편을 제조하였다.85 wt% of the prepared polyketone terpolymer and 15 wt% of glass fiber were 40 mm in diameter operating at 250 rpm, and manufactured by injection molding by pelletizing on an extruder using a biaxial screw having L / D = 32. A carrier specimen of the vehicle front end module was prepared.
실시예Example 11 11
실시예 10중 폴리케톤의 함량을 80중량%, 유리섬유의 함량을 20중량% 설정한 것 이외에는 실시예 10과 동일하다.Except for setting the content of the polyketone in Example 10 80% by weight, the content of the glass fiber 20% by weight is the same as in Example 10.
실시예Example 12 12
실시예 10중 폴리케톤의 함량을 70중량%, 유리섬유의 함량을 30중량% 설정한 것 이외에는 실시예 10과 동일하다.Except for setting the content of the polyketone in Example 10 70% by weight, the glass fiber content of 30% by weight is the same as in Example 10.
실시예Example 13 13
실시예 10중 폴리케톤의 함량을 60중량%, 유리섬유의 함량을 40중량% 설정한 것 이외에는 실시예 10과 동일하다.Example 10 is the same as in Example 10 except that the content of the polyketone 60% by weight, the glass fiber content of 40% by weight.
비교예Comparative example 7 7
나일론 6 수지와 유리섬유 30중량% 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 자동차 프론트엔드모듈의 캐리어 시편을 제조하였다.30 wt% of nylon 6 resin and glass fiber were added to prepare a composition, and the prepared composition was prepared in pellet form on an extruder using a biaxial screw having a diameter of 40 cm and operating at 250 rpm. After the injection molding, a carrier specimen of the front end module of the vehicle was manufactured.
물성평가Property evaluation
상기 실시예 10 내지 13 및 비교예 7에서 각각 제조된 시편을 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 3에 나타내었다.Physical properties of the specimens prepared in Examples 10 to 13 and Comparative Example 7 were evaluated in the following manner, and the results are shown in Table 3 below.
1. 인장강도 평가 : ASTM D638에 의거하여 실시하였다. 1. Tensile strength evaluation: It was performed according to ASTM D638.
2. 굴곡강도 평가 : ASTM D790에 의거하여 실시하였다.2. Flexural strength evaluation: It was performed according to ASTM D790.
3. 충격강도 평가 : ISO 179에 의거하여 실시하였다.3. Impact strength evaluation: It was carried out according to ISO 179.
4. 인장강도 유지율 평가 : ASTM D648에 의거하여 실시하였다.4. Evaluation of Tensile Strength Retention Rate: A test was performed according to ASTM D648.
비중importance 인장강도 (MPa)Tensile Strength (MPa) 굴곡강도 (MPa)Flexural Strength (MPa) 굴곡탄성율 (MPa)Flexural modulus (MPa) Charpy notched (KJ/m2)Charpy notched (KJ / m2) 120℃, 300시간 인장강도 유지율(%)120 ℃, 300 hours tensile strength retention (%)
실시예 10Example 10 1.301.30 113113 161161 44004400 8.08.0 110110
실시예 11Example 11 1.371.37 129129 178178 50005000 9.79.7 113113
실시예 12Example 12 1.441.44 156156 213213 69006900 12.412.4 115115
실시예 13Example 13 1.521.52 173173 237237 93009300 14.914.9 116116
비교예 7Comparative Example 7 1.381.38 160160 230230 90009000 66 8080
상기 표 3에서 알 수 있는 바와 같이, 실시예의 경우 비교예 7 대비 충격강도 및 인장강도 유지율이 우수한 것으로 나타났다. 따라서, 본 발명의 실시예를 통해 제조된 자동차 프론트엔드모듈의 캐리어는 기존의 자동차 프론트엔드모듈의 캐리어 소재로 사용되는 비교예의 경우보다 우수한 충격강도 및 일장강도 유지율을 나타내므로, 자동차 프론트엔드모듈의 캐리어로 적용하기에 더욱 적합하다.As can be seen in Table 3, in the case of the Example it was found that the impact strength and tensile strength retention is superior to Comparative Example 7. Therefore, since the carrier of the vehicle front end module manufactured through the embodiment of the present invention exhibits better impact strength and work strength retention than that of the comparative example used as a carrier material of the existing vehicle front end module, It is more suitable for application as a carrier.
실시예 14Example 14
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이었다. 상기에서 제조된 폴리케톤 터폴리머 70중량%와 미네랄 필러 30중량%를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차 헤드램프베젤 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. In addition, the melting point of the polyketone terpolymer was 220 ℃, LVN measured at 25 ℃ by hexa-fluoroisopropano (HFIP) was 1.4dl / g. 70 wt% of the polyketone terpolymer and 30 wt% of the mineral filler prepared above were injection molded by pelletizing on an extruder using a biaxial screw having a diameter of 40 mm operating at 250 rpm and having an L / D = 32. Automobile headlamp bezel specimens were prepared.
실시예 15Example 15
폴리케톤 터폴리머 80중량%와 미네랄 필러 20중량%를 제외하고는 실시예 14과 동일하다.Except for 80% by weight polyketone terpolymer and 20% by weight mineral filler is the same as in Example 14.
실시예 16Example 16
폴리케톤 터폴리머 90중량%와 미네랄 필러 10중량%를 제외하고는 실시예 14과 동일하다.Except for 90% by weight of polyketone terpolymer and 10% by weight of the mineral filler is the same as in Example 14.
비교예 8Comparative Example 8
폴리부틸렌 테레프탈레이트(polybutylene terephtalate, PBT) 와 폴리에틸렌 테레프탈레이트(polyethylene terephtalate PET)의 블렌드 조성물 60중량%과 미네랄 필러 40중량%를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차 헤드램프베젤 시편을 제조하였다.60-mm blend composition of polybutylene terephtalate (PBT) and polyethylene terephtalate PET and 40% by weight mineral filler at 40 rpm with a diameter of 40 mm, L / D = 32 biaxial screw Using a pellet (pellet) on the extruder using an injection molding to prepare an automobile headlamp bezel specimen.
물성평가Property evaluation
상기 실시예의 제조된 펠렛을 사출 성형하여 자동차 헤드램프베젤용 시편을 제조한 다음, 비교예의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 4에 나타내었다.After injection molding the prepared pellets of the above Example to prepare a specimen for the headlamp bezel of the automobile, and compared with the product of the comparative example to evaluate the physical properties in the following manner, the results are shown in Table 4 below.
1. 아이조드 충격강도 평가 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength evaluation: It was performed according to ASTM D256.
2. 성형성 평가 : 동일한 금형에서 단위시간당 정상품으로 사출되는 사출품의 수로 평가, 기준 대비 많은 수를 사출할 수 있을 경우 우수, 기준 대비 적은 수를 사출 할 수 있을 경우 미흡 판정.2. Evaluation of moldability: It is evaluated by the number of injection molded products per unit time in the same mold. If it can inject a large number of standards, it is judged as good.
항목Item 비교예 8Comparative Example 8 실시예 14Example 14 실시예 15Example 15 실시예 16Example 16
아이조드 충격강도 (KJ/m2)Izod impact strength (KJ / m 2 ) 66 2323 2424 2222
성형성Formability 보통usually 우수Great 우수Great 우수Great
상기 표 4에서 보듯이, 실시예의 경우 비교예 대비 충격강도와 사출성이 우수한 것으로 평가되었다.As shown in Table 4, the Example was evaluated to be excellent in impact strength and injection properties compared to the comparative example.
따라서, 본 발명의 실시예를 통해 제조된 자동차 헤드램프베젤은 내충격성, 사출성이 우수하여 자동차 헤드렘프베젤로 적용하기에 매우 적합하였다.Therefore, the automobile headlamp bezel manufactured according to the embodiment of the present invention was excellent in impact resistance and injection resistance, it was very suitable for application as an automobile headlamp bezel.
실시예 17Example 17
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 일산화탄소는 50mol%이고, 에틸렌은 46mol%이며, 프로필렌은 4mol%이었다. 또한, 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MWD가 2.0 이었다. Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. In the polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. Further, the melting point of the polyketone terpolymer was 220 ° C, LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, and MWD was 2.0.
상기 제조된 폴리케톤 터폴리머 70중량%와 유리섬유 30중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 캐니스터의 시편을 제조하였다. 70 wt% of the prepared polyketone terpolymer and 30 wt% of glass fiber were prepared to prepare a composition, and the prepared composition was operated on an extruder by using a biaxial screw having a diameter of 40 cm and a L / D = 32 operating at 250 rpm. After the pellets (pellets) were prepared, and injection molding to prepare a specimen of the canister.
실시예 18Example 18
실시예 17과 동일한 방법으로 제조된 폴리케톤 터폴리머 75중량%와 유리섬유 25중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 캐니스터의 시편을 제조하였다. 75 wt% polyketone terpolymer and 25 wt% glass fiber prepared in the same manner as in Example 17 to prepare a composition, the composition is a biaxial shaft 40cm in diameter, operating at 250rpm, L / D = 32 A screw was used to produce pellets on an extruder and then injection molded to prepare specimens of the canister.
실시예 19Example 19
실시예 17과 동일한 방법으로 제조된 폴리케톤 터폴리머 80중량%와 유리섬유 20중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 캐니스터의 시편을 제조하였다. 80 wt% of polyketone terpolymer and 20 wt% of glass fiber prepared in the same manner as in Example 17 to prepare a composition, the prepared composition is a biaxial shaft 40cm in diameter, operating at 250rpm, L / D = 32 A screw was used to produce pellets on an extruder and then injection molded to prepare specimens of the canister.
실시예 20Example 20
실시예 17과 동일한 방법으로 제조된 폴리케톤 터폴리머 85중량%와 유리섬유 15중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 캐니스터의 시편을 제조하였다. 85 wt% of polyketone terpolymer and 15 wt% of glass fiber were prepared in the same manner as in Example 17 to prepare a composition, and the prepared composition was biaxially formed with a diameter of 40 cm and a L / D = 32 operating at 250 rpm. A screw was used to produce pellets on an extruder and then injection molded to prepare specimens of the canister.
비교예 9Comparative Example 9
나일론 66 수지 70중량%와 유리섬유 30중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 캐니스터의 시편을 제조하였다.70 wt% of nylon 66 resin and 30 wt% of glass fiber were prepared to prepare a composition, and the prepared composition was pelleted on an extruder using a biaxial screw having a diameter of 40 cm and operating at 250 rpm, and having an L / D = 32. And then injection molded to prepare a canister specimen.
물성 평가Property evaluation
상기 실시예 17 내지 20 및 비교예 9에서 각각 제조된 시편을 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 5에 나타내었다.The physical properties of the specimens prepared in Examples 17 to 20 and Comparative Example 9 were evaluated in the following manner, and the results are shown in Table 5 below.
1. 아이조드 충격강도 평가 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength evaluation: It was performed according to ASTM D256.
2. 치수 변화율 평가 : 온도 50℃, 상대습도 90%의 조건에서 수직 및 수평방향에 대해 MS211-47에 따라 평가하였다.2. Evaluation of dimensional change rate: It was evaluated according to MS211-47 for the vertical and horizontal directions under the conditions of temperature 50 ℃, relative humidity 90%.
구분division 충격강도Impact strength 치수변화율Dimensional change rate
KJ/m2 KJ / m 2 %%
실시예 17Example 17 2525 1.31.3
실시예 18Example 18 2323 1.11.1
실시예 19Example 19 2828 1.21.2
실시예 20Example 20 2727 1.51.5
비교예 9Comparative Example 9 1818 5.25.2
상기 표 5에서 알 수 있는 바와 같이, 실시예의 경우 비교예 9 대비 치수안정성이 우수한 것으로 나타났다. 따라서 본 발명의 실시예를 통해 제조된 캐니스터는 기존의 캐니스터 소재로 사용되는 비교예의 경우보다 우수한 치수안정성을 나타내므로, 캐니스터로 적용하기에 더욱 적합하다.As can be seen in Table 5, in the case of the Example was shown to be superior in dimensional stability compared to Comparative Example 9. Therefore, the canister manufactured through the embodiment of the present invention exhibits excellent dimensional stability than that of the comparative example used as a conventional canister material, and thus is more suitable for application as a canister.
실시예 21Example 21
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 일산화탄소는 50mol%이고, 에틸렌은 46mol%이며, 프로필렌은 4mol%이었다. 또한, 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MWD가 2.0 이었다. Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. In the polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. Further, the melting point of the polyketone terpolymer was 220 ° C, LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, and MWD was 2.0.
상기 제조된 폴리케톤 터폴리머 70중량%와 유리섬유 30중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 실내등 하우징의 시편을 제조하였다. 70 wt% of the prepared polyketone terpolymer and 30 wt% of glass fiber were prepared to prepare a composition, and the prepared composition was operated on an extruder by using a biaxial screw having a diameter of 40 cm and a L / D = 32 operating at 250 rpm. After the pellet (pellet) was prepared, and injection molding to prepare a specimen of the interior lamp housing.
실시예 22Example 22
실시예 21과 동일한 방법으로 제조된 폴리케톤 터폴리머 75중량%와 유리섬유 25중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 실내등 하우징의 시편을 제조하였다. 75 wt% of polyketone terpolymer and 25 wt% of glass fiber were prepared in the same manner as in Example 21, to prepare a composition, and the resulting composition was 40 cm in diameter, operating at 250 rpm, and biaxial with L / D = 32. A screw was used to make pellets on an extruder, and then injection molded to prepare specimens of an indoor lamp housing.
실시예 23Example 23
실시예 21과 동일한 방법으로 제조된 폴리케톤 터폴리머 80중량%와 유리섬유 20중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 실내등 하우징의 시편을 제조하였다. 80 wt% of polyketone terpolymer and 20 wt% of glass fiber prepared in the same manner as in Example 21 to prepare a composition, the composition is a biaxial axis of 40cm in diameter, operating at 250rpm, L / D = 32 A screw was used to make pellets on an extruder, and then injection molded to prepare specimens of an indoor lamp housing.
실시예 24Example 24
실시예 21과 동일한 방법으로 제조된 폴리케톤 터폴리머 85중량%와 유리섬유 15중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 실내등 하우징의 시편을 제조하였다. 85 wt% of polyketone terpolymer and 15 wt% of glass fiber were prepared in the same manner as in Example 21 to prepare a composition, and the resulting composition was 40 cm in diameter, operating at 250 rpm, and biaxial with L / D = 32. A screw was used to make pellets on an extruder, and then injection molded to prepare specimens of an indoor lamp housing.
비교예 10Comparative Example 10
나일론 66 수지와 유리섬유 30중량% 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 실내등 하우징의 시편을 제조하였다.30 wt% of nylon 66 resin and glass fiber were added to prepare a composition, and the prepared composition was prepared in pellet form on an extruder using a biaxial screw having a diameter of 40 cm operating at 250 rpm and having an L / D = 32. After injection molding, a specimen of the interior lamp housing was manufactured.
물성 평가Property evaluation
상기 실시예 21 내지 24 및 비교예 10에서 각각 제조된 시편을 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 6에 나타내었다.Physical properties of the specimens prepared in Examples 21 to 24 and Comparative Example 10 were evaluated in the following manner, and the results are shown in Table 6 below.
1. 아이조드 충격강도 평가 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength evaluation: It was performed according to ASTM D256.
2. 성형성 평가 : 동일한 금형에서 단위시간당 정상품으로 사출되는 사출품의 수로 평가, 기준 대비 많은 수를 사출할 수 있을 경우 우수, 기준 대비 적은 수를 사출 할 수 있을 경우 미흡 판정.2. Evaluation of moldability: It is evaluated by the number of injection molded products per unit time in the same mold. If it can inject a large number of standards, it is judged as good.
3. 치수 변화율 평가 : 온도 50℃, 상대습도 90%의 조건에서 수직 및 수평방향에 대해 MS211-47에 따라 평가하였다.3. Evaluation of dimensional change rate: It was evaluated according to MS211-47 for the vertical and horizontal directions under the conditions of temperature 50 ℃, relative humidity 90%.
항목Item 실시예 21Example 21 실시예 22Example 22 실시예 23Example 23 실시예 24Example 24 비교예 10Comparative Example 10
충격강도 (kJ/m2)Impact strength (kJ / m2) 2525 2323 2828 2727 1818
성형성Formability 우수Great 우수Great 우수Great 우수Great 보통usually
치수변화율 (%)Dimensional rate of change (%) 1.31.3 1.11.1 1.21.2 1.51.5 5.25.2
상기 표 6에서 알 수 있는 바와 같이, 실시예의 경우 비교예 10 대비 단위시간당 많은 양을 사출할 수 있어서 성형성은 우수한 것으로 판정되며, 내충격성 및 치수안정성도 우수한 것으로 나타났다. 따라서, 본 발명의 실시예를 통해 제조된 실내등 하우징은 기존의 실내등 하우징 소재로 사용되는 비교예의 경우보다 우수한 성형성, 내충격성 및 치수안정성을 나타내므로, 실내등 하우징으로 적용하기에 더욱 적합하다.As can be seen in Table 6, in the case of Example can be injected a large amount per unit time compared to Comparative Example 10 was determined to be excellent moldability, it was also shown that the impact resistance and dimensional stability is also excellent. Therefore, the interior lamp housing manufactured through the embodiment of the present invention exhibits excellent moldability, impact resistance and dimensional stability than the case of the comparative example used as a conventional interior lamp housing material, it is more suitable for application to the interior lamp housing.
실시예 25Example 25
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 일산화탄소는 50mol%이고, 에틸렌은 46mol%이며, 프로필렌은 4mol%이었다. 또한, 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MWD가 2.0 이었다. Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. In the polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. Further, the melting point of the polyketone terpolymer was 220 ° C, LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, and MWD was 2.0.
상기 제조된 폴리케톤 터폴리머 90중량%와 유리섬유 10중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 차량용 재떨이의 시편을 제조하였다. 90 wt% of the prepared polyketone terpolymer and 10 wt% of glass fiber were prepared to prepare a composition, and the prepared composition was extruded on an extruder using a biaxial screw having a diameter of 40 cm and a L / D = 32 operating at 250 rpm. After the pellets (pellets) were prepared in the injection molding, a vehicle ashtray specimens were prepared.
실시예 26Example 26
실시예 25중 폴리케톤의 함량을 80중량%, 유리섬유의 함량을 20중량% 설정한 것 이외에는 실시예 25와 동일하다.Except for setting the content of the polyketone in Example 25 80% by weight, the glass fiber content 20% by weight is the same as in Example 25.
실시예 27Example 27
실시예 25중 폴리케톤의 함량을 70중량%, 유리섬유의 함량을 30중량% 설정한 것 이외에는 실시예 25와 동일하다.Except for setting the content of the polyketone in Example 25, 70% by weight, the glass fiber content of 30% by weight is the same as in Example 25.
실시예 28Example 28
실시예 25중 폴리케톤의 함량을 60중량%, 유리섬유의 함량을 40중량% 설정한 것 이외에는 실시예 25과 동일하다.Except for setting the content of the polyketone in Example 25, 60% by weight, and the content of glass fiber 40% by weight is the same as in Example 25.
비교예 11Comparative Example 11
나일론 66 수지와 유리섬유 30중량% 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 차량용 재떨이의 시편을 제조하였다.30 wt% of nylon 66 resin and glass fiber were added to prepare a composition, and the prepared composition was prepared in pellet form on an extruder using a biaxial screw having a diameter of 40 cm operating at 250 rpm and having an L / D = 32. After injection molding, a specimen of the ashtray for a vehicle was manufactured.
물성 평가Property evaluation
상기 실시예 25 내지 28 및 비교예 11에서 각각 제조된 시편을 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 7에 나타내었다.Physical properties of the specimens prepared in Examples 25 to 28 and Comparative Example 11 were evaluated in the following manner, and the results are shown in Table 7 below.
1. 충격강도 평가 : ISO 179에 의거하여 실시하였다.1. Impact strength evaluation: It was conducted according to ISO 179.
2. 물성 유지율 평가 : ASTM D648, ISO 179에 의거하여 실시하였다.2. Evaluation of retention of physical properties: It was carried out according to ASTM D648, ISO 179.
(50℃, 상대습도 90%RH에서 측정한 충격강도 대비 25℃, 상대습도 65%RH에서 측정한 충격강도 유지율)(Impact strength retention at 25 ° C and 65% RH relative to impact strength at 50 ° C and 90% RH)
3. 난연성 평가 : UL94에 의거하여 실시하였다.3. Flame retardancy evaluation: It was carried out according to UL94.
항목Item 실시예 25Example 25 실시예 26Example 26 실시예 27Example 27 실시예 28Example 28 비교예 11Comparative Example 11
충격강도 (kJ/m2)Impact strength (kJ / m2) 88 1010 1313 1515 77
물성 유지율 (%)Physical property retention rate (%) 9090 9393 9595 100100 7575
난연성 평가 (UL94, 1/16")Flame Retardant Rating (UL94, 1/16 ") V-0V-0 V-0V-0 V-0V-0 V-0V-0 V-0V-0
상기 표 7에서 알 수 있는 바와 같이, 실시예의 경우 비교예 대비 충격강도가 향상되었고, 충격강도 유지율이 90% 이상으로 물성 유지율이 우수한 것으로 나타났다. 또한, 실시예의 경우 비교예에 비하여 난연특성이 동등 혹은 그 이상인 것으로 나타났다.As can be seen in Table 7, in the case of the example, the impact strength was improved compared to the comparative example, and the impact strength retention was 90% or more. In the case of the examples, the flame retardant properties were found to be equal or higher than those of the comparative examples.
따라서, 본 발명에 따른 차량용 재떨이는 내충격성 및 물성 유지율이 우수하고, 우수한 난연특성을 보이는 바, 차량용 재떨이로 쓰이기에 더욱 적합한 것으로 나타났다.Therefore, the ashtray for vehicles according to the present invention has excellent impact resistance and physical property retention rate, and shows excellent flame retardant properties, and thus, has been shown to be more suitable for use as a vehicle ashtray.
실시예 29Example 29
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 일산화탄소는 50mol%이고, 에틸렌은 46mol%이며, 프로필렌은 4mol%이었다. 또한, 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MWD가 2.0 이었다. Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. In the polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. Further, the melting point of the polyketone terpolymer was 220 ° C, LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, and MWD was 2.0.
상기 제조된 폴리케톤 터폴리머 90중량%와 유리섬유 10중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 자동차용 멀티펑션 스위치의 시편을 제조하였다. 90 wt% of the prepared polyketone terpolymer and 10 wt% of glass fiber were prepared to prepare a composition, and the prepared composition was extruded on an extruder using a biaxial screw having a diameter of 40 cm and a L / D = 32 operating at 250 rpm. After the pellets (pellet) was prepared, and injection molding to prepare a test piece of the automotive multi-function switch.
실시예 30Example 30
실시예 29중 폴리케톤의 함량을 80중량%, 유리섬유의 함량을 20중량% 설정한 것 이외에는 실시예 29와 동일하다.Except for setting the content of the polyketone in Example 29 80% by weight, the glass fiber content 20% by weight is the same as in Example 29.
실시예 31Example 31
실시예 29중 폴리케톤의 함량을 70중량%, 유리섬유의 함량을 30중량% 설정한 것 이외에는 실시예 29와 동일하다.Except for setting the content of the polyketone in Example 29 70% by weight, the glass fiber content 30% by weight is the same as in Example 29.
실시예 32Example 32
실시예 29중 폴리케톤의 함량을 60중량%, 유리섬유의 함량을 40중량% 설정한 것 이외에는 실시예 29와 동일하다.Except for setting the content of the polyketone in Example 29 60% by weight, the content of the glass fiber 40% by weight is the same as in Example 29.
비교예 11Comparative Example 11
나일론 66 수지 70중량%와 유리섬유 30중량% 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 자동차용 멀티펑션 스위치의 시편을 제조하였다.70 wt% of nylon 66 resin and 30 wt% of glass fiber were prepared to prepare a composition, and the prepared composition was pelleted on an extruder using a biaxial screw having a diameter of 40 cm and operating at 250 rpm, and having an L / D = 32. After the preparation, the injection molding was carried out to prepare a specimen of a multi-function switch for automobiles.
물성 평가Property evaluation
상기 실시예 29 내지 32 및 비교예 11에서 각각 제조된 시편을 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 8에 나타내었다.The physical properties of the specimens prepared in Examples 29 to 32 and Comparative Example 11 were evaluated in the following manner, and the results are shown in Table 8 below.
1. 인장강도 평가 : ASTM D638에 의거하여 실시하였다. 1. Tensile strength evaluation: It was performed according to ASTM D638.
2. 굴곡강도 평가 : ASTM D790에 의거하여 실시하였다.2. Flexural strength evaluation: It was performed according to ASTM D790.
3. 충격강도 평가 : ISO 179에 의거하여 실시하였다.3. Impact strength evaluation: It was carried out according to ISO 179.
4. 물성 유지율 평가 : ASTM D648, ISO 179에 의거하여 실시하였다.4. Evaluation of retention of physical properties: It was carried out according to ASTM D648, ISO 179.
인장강도 (MPa)Tensile Strength (MPa) 굴곡강도 (MPa)Flexural Strength (MPa) 굴곡탄성율 (MPa)Flexural modulus (MPa) Charpy notched (KJ/m2)Charpy notched (KJ / m2) 충격강도 유지율 (%)Impact Strength Retention Rate (%)
실시예 29Example 29 113113 161161 43004300 8.08.0 9090
실시예 30Example 30 129129 178178 50005000 1010 9393
실시예 31Example 31 156156 213213 69006900 1313 9595
실시예 32Example 32 173173 237237 93009300 1515 100100
비교예 11Comparative Example 11 160160 230230 90009000 66 7575
상기 표 8에서 알 수 있는 바와 같이, 실시예의 경우 비교예 대비 충격강도가 향상되었고, 충격강도 유지율이 90% 이상인 것을 알 수 있었다.As can be seen in Table 8, in the case of the embodiment, the impact strength was improved compared to the comparative example, the impact strength retention was found to be 90% or more.
따라서, 본 발명에 따른 자동차용 멀티펑션 스위치는 충격강도 및 물성유지율이 우수한 바, 자동차용 멀티펑션 스위치로 쓰이기에 더욱 적합한 것으로 나타났다.Therefore, the multifunction switch for automobiles according to the present invention has been found to be more suitable for being used as a multifunction switch for automobiles because of its excellent impact strength and physical property retention rate.
실시예 33Example 33
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 11배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조 후, 사출성형하여 자동차용 스피커 그릴의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 ℃ and two stages of 84 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. In addition, the melting point of the polyketone terpolymer was 220 ° C, LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g, MWD was 2.0. The polyketone terpolymer prepared above is 40mm in diameter operating at 250rpm and manufactured in pellet form on an extruder using a biaxial screw with L / D = 32, and then injection molded to produce a specimen of an automobile speaker grill. Prepared.
실시예 34Example 34
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.6dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차용 스피커 그릴의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 ℃ and two stages of 84 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0. The polyketone terpolymer prepared above was 40mm in diameter operating at 250rpm and manufactured by pelletizing on an extruder using a biaxial screw with L / D = 32 to produce a specimen of an automobile speaker grill by injection molding. It was.
실시예 35Example 35
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 72℃의 1단계와 78℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 2.0dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차용 스피커 그릴의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 ℃ and two stages of 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0. The polyketone terpolymer prepared above was 40mm in diameter operating at 250rpm and manufactured by pelletizing on an extruder using a biaxial screw with L / D = 32 to produce a specimen of an automobile speaker grill by injection molding. It was.
비교예 12Comparative Example 12
폴리옥시메틸렌 수지를 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 자동차용 스피커 그릴의 시편을 제조하였다.The polyoxymethylene resin was manufactured in pellet form on an extruder using a biaxial screw having a diameter of 40 cm operating at 250 rpm and L / D = 32, followed by injection molding to prepare a specimen of an automobile speaker grill. .
물성 평가Property evaluation
상기 실시예 33 내지 35 및 비교예 12에서 각각 제조된 시편을 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 9에 나타내었다.Physical properties of the specimens prepared in Examples 33 to 35 and Comparative Example 12 were evaluated in the following manner, and the results are shown in Table 9 below.
1. 아이조드 충격강도 평가 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength evaluation: It was performed according to ASTM D256.
2. 성형성 평가 : 동일한 금형에서 단위시간당 정상품으로 사출되는 사출품의 수로 평가, 기준 대비 많은 수를 사출할 수 있을 경우 우수, 기준 대비 적은 수를 사출 할 수 있을 경우 미흡 판정.2. Evaluation of moldability: It is evaluated by the number of injection molded products per unit time in the same mold. If it can inject a large number of standards, it is judged as good.
항목Item 실시예 33Example 33 실시예 34Example 34 실시예 35Example 35 비교예 12Comparative Example 12
충격강도 (kJ/m2)Impact strength (kJ / m2) 1818 1717 2121 88
성형성Formability 우수Great 우수Great 우수Great 보통usually
상기 표 9에서 알 수 있는 바와 같이, 실시예의 경우 비교예 12 대비 단위시간당 많은 시편을 사출할 수 있어서 성형성은 양호한 것으로 판정되며, 충격강도가 우수하여 자동차용 스피커 그릴로 적용하기에 더욱 적합하다.As can be seen in Table 9, in the case of the embodiment can be injected more specimens per unit time compared to Comparative Example 12, the moldability is determined to be good, the impact strength is excellent, it is more suitable to apply to the automotive speaker grill.
실시예 36Example 36
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 11배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조 후, 사출성형하여 자동차용 헤드레스트 가이드의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 ℃ and two stages of 84 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. In addition, the melting point of the polyketone terpolymer was 220 ° C, LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g, MWD was 2.0. The polyketone terpolymer prepared above is 40mm in diameter operating at 250rpm and manufactured in pellet form on an extruder using a biaxial screw with L / D = 32, followed by injection molding to test the specimen of the headrest guide for automobiles. Was prepared.
실시예 37Example 37
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.6dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차용 헤드레스트 가이드의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 ℃ and two stages of 84 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0. The polyketone terpolymer prepared above was 40mm in diameter operating at 250rpm, and was manufactured by injection molding into pellets on an extruder using a biaxial screw having L / D = 32 to test the specimen of the headrest guide for automobiles. Prepared.
실시예 38Example 38
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 72℃의 1단계와 78℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 2.0dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차용 헤드레스트 가이드의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 ℃ and two stages of 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0. The polyketone terpolymer prepared above was 40mm in diameter operating at 250rpm, and was manufactured by injection molding into pellets on an extruder using a biaxial screw having L / D = 32 to test the specimen of the headrest guide for automobiles. Prepared.
비교예 13Comparative Example 13
나일론6 수지를 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 자동차용 헤드레스트 가이드의 시편을 제조하였다.The nylon 6 resin was manufactured in pellet form on an extruder by using a biaxial screw having a diameter of 40 cm and operating at 250 rpm, and having an L / D = 32, followed by injection molding to prepare a specimen of an automobile headrest guide. .
물성 평가Property evaluation
상기 실시예 36 내지 38 및 비교예 13에서 각각 제조된 시편을 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 10에 나타내었다.Physical properties of the specimens prepared in Examples 36 to 38 and Comparative Example 13 were evaluated in the following manner, and the results are shown in Table 10 below.
1. 아이조드 충격강도 평가 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength evaluation: It was performed according to ASTM D256.
2. 성형성 평가 : 동일한 금형에서 단위시간당 정상품으로 사출되는 사출품의 수로 평가, 기준 대비 많은 수를 사출할 수 있을 경우 우수, 기준 대비 적은 수를 사출 할 수 있을 경우 미흡 판정.2. Evaluation of moldability: It is evaluated by the number of injection molded products per unit time in the same mold. If it can inject a large number of standards, it is judged as good.
3. 치수 변화율 평가 : 온도 50℃, 상대습도 90%의 조건에서 수직 및 수평방향에 대해 MS211-47에 따라 평가하였다.3. Evaluation of dimensional change rate: It was evaluated according to MS211-47 for the vertical and horizontal directions under the conditions of temperature 50 ℃, relative humidity 90%.
항목Item 실시예 36Example 36 실시예 37Example 37 실시예 38Example 38 비교예 13Comparative Example 13
충격강도 (kJ/m2)Impact strength (kJ / m2) 2525 2323 2828 88
성형성Formability 우수Great 우수Great 우수Great 보통usually
치수변화율 (%)Dimensional rate of change (%) 1.31.3 1.11.1 1.21.2 5.25.2
상기 표 10에서 알 수 있는 바와 같이, 실시예의 경우 비교예 13 대비 단위시간당 많은 시편을 사출할 수 있어서 성형성은 양호한 것으로 판정되며, 치수안정성도 우수한 것으로 나타났다. 따라서, 본 발명의 실시예를 통해 제조된 헤드레스트 가이드는 기존의 헤드레스트 가이드 소재로 사용되는 비교예의 경우보다 우수한 성형성 및 치수안정성을 나타내므로, 자동차용 헤드레스트 가이드로 적용하기에 더욱 적합하다.As can be seen in Table 10, in the case of the embodiment can be injected more specimens per unit time compared to Comparative Example 13, the moldability was determined to be good, and the dimensional stability was also excellent. Therefore, the headrest guide manufactured through the embodiment of the present invention exhibits excellent moldability and dimensional stability than the comparative example used as a conventional headrest guide material, and thus is more suitable for application as a headrest guide for automobiles. .
실시예 39Example 39
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 11배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조 후, 사출성형하여 자동차용 내비게이션 받침대의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 ℃ and two stages of 84 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. In addition, the melting point of the polyketone terpolymer was 220 ° C, LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g, MWD was 2.0. The polyketone terpolymer prepared above is 40mm in diameter operating at 250rpm and manufactured in pellet form on an extruder using a biaxial screw with L / D = 32, followed by injection molding to test the specimen of the vehicle navigation support. Prepared.
실시예 40Example 40
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.6dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차용 내비게이션 받침대의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 ℃ and two stages of 84 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0. The polyketone terpolymer prepared above was 40mm in diameter operating at 250rpm and manufactured by pelletizing on an extruder using a biaxial screw having L / D = 32 to produce a specimen of a vehicle navigation pedestal for injection molding. It was.
실시예 41Example 41
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 72℃의 1단계와 78℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 2.0dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차용 내비게이션 받침대의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 ℃ and two stages of 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0. The polyketone terpolymer prepared above was 40mm in diameter operating at 250rpm and manufactured by pelletizing on an extruder using a biaxial screw having L / D = 32 to produce a specimen of a vehicle navigation pedestal for injection molding. It was.
비교예 14Comparative Example 14
폴리아미드 수지를 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 자동차용 내비게이션 받침대의 시편을 제조하였다.The polyamide resin was manufactured in pellet form on an extruder using a biaxial screw having a diameter of 40 cm and operated at 250 rpm, and L / D = 32, followed by injection molding to prepare a specimen of a vehicle navigation bracket.
물성 평가Property evaluation
상기 실시예 39 내지 41 및 비교예 14에서 각각 제조된 시편을 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 11에 나타내었다.Physical properties of the specimens prepared in Examples 39 to 41 and Comparative Example 14 were evaluated in the following manner, and the results are shown in Table 11 below.
1. 아이조드 충격강도 평가 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength evaluation: It was performed according to ASTM D256.
2. 성형성 평가 : 동일한 금형에서 단위시간당 정상품으로 사출되는 사출품의 수로 평가, 기준 대비 많은 수를 사출할 수 있을 경우 우수, 기준 대비 적은 수를 사출 할 수 있을 경우 미흡 판정.2. Evaluation of moldability: It is evaluated by the number of injection molded products per unit time in the same mold. If it can inject a large number of standards, it is judged as good.
3. 치수 변화율 평가 : 온도 50℃, 상대습도 90%의 조건에서 수직 및 수평방향에 대해 MS211-47에 따라 평가하였다.3. Evaluation of dimensional change rate: It was evaluated according to MS211-47 for the vertical and horizontal directions under the conditions of temperature 50 ℃, relative humidity 90%.
항목Item 실시예 39Example 39 실시예 40Example 40 실시예 41Example 41 비교예 14Comparative Example 14
충격강도 (kJ/m2)Impact strength (kJ / m2) 1818 2020 2222 77
성형성Formability 우수Great 우수Great 우수Great 보통usually
치수변화율 (%)Dimensional rate of change (%) 1.31.3 1.11.1 1.21.2 5.25.2
상기 표 11에서 알 수 있는 바와 같이, 실시예의 경우 비교예 14 대비 단위시간당 많은 시편을 사출할 수 있어서 성형성은 양호한 것으로 판정되며, 치수안정성도 우수한 것으로 나타났다. 따라서, 본 발명의 실시예를 통해 제조된 내비게이션 받침대는 기존의 네이게이션 받침대 소재로 사용되는 비교예의 경우보다 우수한 성형성 및 치수안정성을 나타내므로, 자동차용 내비게이션로 적용하기에 더욱 적합하다.As can be seen in Table 11, in the case of the Example can be injected more specimens per unit time compared to Comparative Example 14, the moldability was determined to be good, and the dimensional stability was also excellent. Therefore, the navigation pedestal produced through the embodiment of the present invention exhibits excellent moldability and dimensional stability than the case of the comparative example used as a conventional navigation pedestal material, it is more suitable for application as a navigation for automobiles.
실시예 42Example 42
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 11배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조 후, 사출성형하여 자동차용 사이드 몰딩의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and goes through a first stage of the polymerization temperature 78 ℃ and two stages of 84 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. In addition, the melting point of the polyketone terpolymer was 220 ° C, LVN measured at 25 ° C by hexa-fluoroisopropano (HFIP) was 1.4 dl / g, MWD was 2.0. The polyketone terpolymer prepared above was 40mm in diameter operating at 250rpm and manufactured as pellets on an extruder using a biaxial screw having a L / D = 32, and then injection molded to test a vehicle side molding specimen. Prepared.
실시예 43Example 43
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.6dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차용 사이드 몰딩의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and goes through a first stage of the polymerization temperature 74 ℃ and two stages of 84 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, and an MWD of 2.0. The polyketone terpolymer prepared above was 40mm in diameter operating at 250rpm and manufactured by pelletizing on an extruder using a biaxial screw with L / D = 32 to produce a specimen for automobile side molding. It was.
실시예 44Example 44
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 72℃의 1단계와 78℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 2.0dl/g이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 자동차용 사이드 몰딩의 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and goes through a first stage of the polymerization temperature 72 ℃ and two stages of 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 2.0 dl / g, and MWD at 2.0. The polyketone terpolymer prepared above was 40mm in diameter operating at 250rpm and manufactured by pelletizing on an extruder using a biaxial screw with L / D = 32 to produce a specimen for automobile side molding. It was.
비교예 15Comparative Example 15
나일론6 수지를 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 자동차용 사이드 몰딩의 시편을 제조하였다.The nylon 6 resin was manufactured in pellet form on an extruder using a biaxial screw having a diameter of 40 cm and operated at 250 rpm, and then L / D = 32, followed by injection molding to prepare a vehicle side molding specimen.
물성 평가Property evaluation
상기 실시예 42 내지 44 및 비교예 15에서 각각 제조된 시편을 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 12에 나타내었다.The physical properties of the specimens prepared in Examples 42 to 44 and Comparative Example 15 were evaluated in the following manner, and the results are shown in Table 12 below.
1. 아이조드 충격강도 평가 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength evaluation: It was performed according to ASTM D256.
2. 성형성 평가 : 동일한 금형에서 단위시간당 정상품으로 사출되는 사출품의 수로 평가, 기준 대비 많은 수를 사출할 수 있을 경우 우수, 기준 대비 적은 수를 사출 할 수 있을 경우 미흡 판정.2. Evaluation of moldability: It is evaluated by the number of injection molded products per unit time in the same mold. If it can inject a large number of standards, it is judged as good.
3. 치수 변화율 평가 : 온도 50℃, 상대습도 90%의 조건에서 수직 및 수평방향에 대해 MS211-47에 따라 평가하였다.3. Evaluation of dimensional change rate: It was evaluated according to MS211-47 for the vertical and horizontal directions under the conditions of temperature 50 ℃, relative humidity 90%.
항목Item 실시예 42Example 42 실시예 43Example 43 실시예 44Example 44 비교예 15Comparative Example 15
충격강도 (kJ/m2)Impact strength (kJ / m2) 1818 2020 2222 77
성형성Formability 우수Great 우수Great 우수Great 보통usually
치수변화율 (%)Dimensional rate of change (%) 1.31.3 1.11.1 1.21.2 5.25.2
상기 표 12에서 알 수 있는 바와 같이, 실시예의 경우 비교예 15 대비 단위시간당 많은 시편을 사출할 수 있어서 성형성은 양호한 것으로 판정되며, 치수안정성도 우수한 것으로 나타났다. 따라서, 본 발명의 실시예를 통해 제조된 사이드 몰딩은 기존의 사이드 몰딩으로 사용되는 비교예의 경우보다 우수한 성형성 및 치수안정성을 나타내므로, 자동차용 사이드 몰딩으로 적용하기에 더욱 적합하다.As can be seen in Table 12, in the case of the Example can be injected more specimens per unit time compared to Comparative Example 15, it was determined that the moldability is good, the dimensional stability is also excellent. Therefore, the side molding prepared through the embodiment of the present invention exhibits excellent moldability and dimensional stability than the case of the comparative example used as a conventional side molding, it is more suitable for application as an automotive side molding.
실시예 45Example 45
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 235℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 2.0dl/g이며, MWD가 2.0 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 74 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. In addition, the melting point of the polyketone terpolymer was 235 ° C, LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 2.0 dl / g, and MWD was 2.0.
상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 호스 커넥터의 시편을 제조하였다.The polyketone terpolymer prepared above was 40 mm in diameter, operating at 250 rpm, and manufactured by pelletizing on an extruder using a biaxial screw having a L / D = 32 to produce a specimen of a hose connector.
실시예 46Example 46
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 225℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 2.0dl/g이며, MWD가 2.0 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 74 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. Further, the melting point of the polyketone terpolymer was 225 ° C, LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 2.0 dl / g, and MWD was 2.0.
상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 호스 커넥터의 시편을 제조하였다.The polyketone terpolymer prepared above was 40 mm in diameter, operating at 250 rpm, and manufactured by pelletizing on an extruder using a biaxial screw having a L / D = 32 to produce a specimen of a hose connector.
비교예 16Comparative Example 16
폴리옥시메틸렌 수지를 폴리옥시메틸렌 수지를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 호스 커넥터의 시편을 제조하였다.The polyoxymethylene resin was manufactured by pelletizing a pellet on a extruder using a biaxial screw having a diameter of 40 mm and operating a polyoxymethylene resin at 250 rpm, and having an L / D = 32, and then injection-molding the specimen of the hose connector. Was prepared.
물성평가Property evaluation
상기 실시예 45, 46 및 비교예 16에서 각각 제조된 호스 커넥터의 물성을 하기와 같은 방법으로 평가하였으며, 그 결과는 하기 표 13에 나타내었다.The physical properties of the hose connectors prepared in Examples 45, 46 and Comparative Example 16, respectively, were evaluated in the following manner, and the results are shown in Table 13 below.
1) 충격강도 평가 : ASTM D256에 의거하여 실시하였다. 이때, 영하 30℃에서 측정하였다.1) Impact strength evaluation: It was performed according to ASTM D256. At this time, it measured at minus 30 degreeC.
2) 인장물성 평가 : ASTM D638에 의거하여 실시하였다. 이때, 영하 30℃에서 측정하였다.2) Tensile property evaluation: It was performed according to ASTM D638. At this time, it measured at minus 30 degreeC.
3) 동결시험 평가 : 호스 커넥터에 물을 채우고, 영하 30℃에서 냉각한 후, 24시간 동안 방치하여 파손 여부를 확인하였다.3) Evaluation of freezing test: After filling the hose connector with water, cooled to minus 30 ℃, it was left for 24 hours to check for damage.
항목Item 실시예 45Example 45 실시예 46Example 46 비교예 16Comparative Example 16
저온 신율 (%)Low temperature elongation (%) 4040 3535 2525
저온 충격강도 (kJ/m2)Low temperature impact strength (kJ / m2) 7.07.0 4.84.8 3.53.5
동결시험Freeze test 양호Good 양호Good 파괴Destruction
상기 표 13에서 알 수 있는 바와 같이, 실시예의 경우 비교예 대비 저온 인장신율 및 충격강도가 우수한 것으로 나타났으며, 동결시험에서도 실시예의 경우 양호한 것으로 나타났다. 따라서, 본 발명의 실시예를 통해 제조된 폴리케톤 호스 커넥터는 비교예의 경우보다 우수한 저온 인장신율 및 내충격성을 나타내므로, 호스 커넥터에 적용하기에 더욱 적합하다.As can be seen in Table 13, in the case of the Example was shown to be superior to the low-temperature tensile elongation and impact strength compared to the Comparative Example, it was found to be good for the Example even in the freezing test. Therefore, the polyketone hose connector manufactured through the embodiment of the present invention exhibits better low temperature tensile elongation and impact resistance than that of the comparative example, and thus is more suitable for application to the hose connector.
실시예 47Example 47
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 85대 15였다. 또한 상기 폴리케톤 터폴리머의 융점은 235℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 2.0dl/g이며, MWD가 2.0 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 74 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 85 to 15. In addition, the melting point of the polyketone terpolymer was 235 ° C, LVN measured at 25 ° C by HFIP (hexa-fluoroisopropano) was 2.0 dl / g, and MWD was 2.0.
상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 에어컨용 스템 볼트의 시편을 제조하였다.The polyketone terpolymer prepared above was 40mm in diameter operating at 250rpm and manufactured by pelletizing on an extruder using a biaxial screw with L / D = 32 to produce a specimen of stem bolt for air conditioner. It was.
비교예 17Comparative Example 17
황동을 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 에어컨용 스템 볼트의 시편을 제조하였다.Brass was 40 mm in diameter, operating at 250 rpm, and prepared by pelletizing on an extruder using a biaxial screw having a diameter of L / D = 32 to injection molding to prepare a specimen of a stem bolt for an air conditioner.
물성평가Property evaluation
상기 실시예 47 및 비교예 17에서 각각 제조된 에어컨용 스템 볼트의 물성을 하기와 같은 방법으로 평가하였으며, 그 결과는 하기 표 14에 나타내었다.The physical properties of the stem bolts for air conditioners prepared in Example 47 and Comparative Example 17, respectively, were evaluated in the following manner, and the results are shown in Table 14 below.
1) 인장물성 평가 : ASTM D638에 의거하여 실시하였다.1) Tensile property evaluation: It was performed according to ASTM D638.
2) 충격강도 평가 : ASTM D256에 의거하여 실시하였다.2) Impact strength evaluation: It was performed according to ASTM D256.
항목Item 실시예 47Example 47 비교예 17Comparative Example 17
파단신율 (%)Elongation at Break (%) 300300 1111
충격강도 (kJ/m2)Impact strength (kJ / m2) 5050 --
상기 표 14에서 알 수 있는 바와 같이, 실시예의 경우 비교예 대비 파단신율 및 충격강도가 우수한 것으로 나타났다. 따라서, 본 발명의 실시예를 통해 제조된 폴리케톤 에어컨용 스템 볼트는 비교예의 경우보다 우수한 파단신율 및 내충격성을 나타내므로, 에어컨용 스템 볼트에 적용하기에 더욱 적합하다.As can be seen in Table 14, in the case of the Example it was found that the elongation at break and impact strength is superior to the comparative example. Therefore, the stem bolt for polyketone air conditioner manufactured through the embodiment of the present invention shows better elongation at break and impact resistance than the case of the comparative example, it is more suitable for applying to the air conditioner stem bolt.
실시예 48Example 48
초산 팔라듐, 트리플루오르 초산의 음이온 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로 구성되는 촉매 조성물의 존재하에, 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머(terpolymer)를 메탄올 100중량부 대비 물 5중량부 이고, 70~90℃의 용매에서 중합하였다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 한편, 상기 제조된 폴리케톤 터폴리머의 융점은 220℃이고, 1,1,1,3,3,3-HFIP에 측정된 고유점도(LVN)는 1.4 dl/g이었다.Palladium acetate, anion of trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) In the presence of the catalyst composition, a linear terpolymer of carbon monoxide, ethylene and propylene was polymerized in a solvent at 70 to 90 ° C. with 5 parts by weight of water relative to 100 parts by weight of methanol. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. Meanwhile, the melting point of the prepared polyketone terpolymer was 220 ° C., and the intrinsic viscosity (LVN) measured in 1,1,1,3,3,3-HFIP was 1.4 dl / g.
상기 제조된 폴리케톤 터폴리머 99중량% 및 열가소성 폴리우레탄 1중량%를 블렌딩하여 폴리케톤-폴리우레탄 수지 조성물을 제조하였다.A polyketone-polyurethane resin composition was prepared by blending 99% by weight of the prepared polyketone terpolymer and 1% by weight of thermoplastic polyurethane.
실시예 49Example 49
실시예 48과 동일하게 제조된 폴리케톤 터폴리머 90중량% 및 열가소성 폴리우레탄 10중량%를 블렌딩하여 폴리케톤-폴리우레탄 수지 조성물을 제조하였다.Polyketone-polyurethane resin composition was prepared by blending 90% by weight of polyketone terpolymer and 10% by weight of thermoplastic polyurethane prepared in the same manner as in Example 48.
실시예 50Example 50
실시예 48과 동일하게 제조된 폴리케톤 터폴리머 80중량% 및 열가소성 폴리우레탄 20중량%를 블렌딩하여 폴리케톤-폴리우레탄 수지 조성물을 제조하였다.Polyketone-polyurethane resin composition was prepared by blending 80% by weight of polyketone terpolymer and 20% by weight of thermoplastic polyurethane prepared in the same manner as in Example 48.
비교예 18Comparative Example 18
실시예 48과 동일하게 제조된 폴리케톤 터폴리머 100중량%를 사용하였다.100 wt% of the polyketone terpolymer prepared in the same manner as in Example 48 was used.
비교예 19Comparative Example 19
폴리케톤 대신 Rhodia 사 PA66 90 중량%(A218V30 제품) 및 열가소성 폴리우레탄 10%을 사용하여 폴리케톤-폴리우레탄 수지 조성물을 제조하였다.Polyketone-polyurethane resin compositions were prepared using 90% by weight of Rhodia PA66 (available from A218V30) and 10% of thermoplastic polyurethane instead of polyketone.
물성평가Property evaluation
상기 실시예의 제조된 폴리케톤 조성물을 시편으로 제조한 다음, 비교예의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 15에 나타내었다.The prepared polyketone composition of the Example was prepared as a specimen, and then evaluated for physical properties in the following manner compared to the product of the comparative example, the results are shown in Table 15 below.
1. 반발탄성 평가 : ASTM 2632에 의하여 측정하였다.1. Evaluation of resilience: It was measured according to ASTM 2632.
2. 충격강도평가(노치드 아이조드) : ASTM D638에 의거하여 실시하였다.2. Impact strength evaluation (notched Izod): It was carried out according to ASTM D638.
실시예48Example 48 실시예49Example 49 실시예50Example 50 비교예18Comparative Example 18 비교예19Comparative Example 19
반발탄성 (%)Resilience (%) 3535 3838 4242 2525 3737
충격강도(KJ/m2)Impact Strength (KJ / m 2 ) 1212 11.811.8 12.212.2 11.811.8 5.45.4
상기 표 15에서 본 발명의 폴리케톤-폴리우레탄 수지 조성물은 PA66에 비하여 반발탄성(35% 내지 45%)과 충격강도(10~12kJ/m2)가 우수하여 산업용으로 사용되는 열가소성 플라스틱으로 사용되기에 적합한 것으로 평가되었다.Polyketone-polyurethane resin composition of the present invention in Table 15 is excellent in resilience (35% to 45%) and impact strength (10 ~ 12kJ / m 2 ) compared to PA66 to be used as a thermoplastic plastic for industrial use Was evaluated as suitable for.
실시예 51Example 51
초산 팔라듐, 트리플루오르 초산의 음이온 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로 구성되는 촉매 조성물의 존재하에, 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머(terpolymer)를 메탄올 100중량부 대비 물 5중량부이고, 70~90℃의 용매에서 중합하였다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 한편, 상기 제조된 폴리케톤 터폴리머의 융점은 220℃이고, 1,1,1,3,3,3-HFIP에 측정된 고유점도(LVN)는 1.4 dl/g이었다.Palladium acetate, anion of trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) In the presence of the catalyst composition, a linear terpolymer of carbon monoxide, ethylene and propylene was polymerized in a solvent at 70 to 90 ° C. with 5 parts by weight of water relative to 100 parts by weight of methanol. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. Meanwhile, the melting point of the prepared polyketone terpolymer was 220 ° C., and the intrinsic viscosity (LVN) measured in 1,1,1,3,3,3-HFIP was 1.4 dl / g.
상기 제조된 폴리케톤 터폴리머 95중량% 및 열가소성 유리섬유은 5중량%를 블렌딩 하여 폴리케톤 조성물을 제조하였다.95 wt% of the prepared polyketone terpolymer and 5 wt% of the thermoplastic glass fibers were blended to prepare a polyketone composition.
실시예 52Example 52
폴리케톤 터폴리머 90중량%, 유리섬유 10중량%를 제외하고는 실시예 51과 동일하다.Except for 90% by weight of polyketone terpolymer, 10% by weight of glass fiber was the same as in Example 51.
실시예 53Example 53
폴리케톤 터폴리머 80중량%, 유리섬유 20중량%를 제외하고는 실시예 51과 동일하다.Except for 80% by weight polyketone terpolymer, 20% by weight glass fibers, the same as in Example 51.
실시예 54Example 54
폴리케톤 터폴리머 70중량%, 유리섬유 30중량%를 제외하고는 실시예 51과 동일하다.Except for 70% by weight polyketone terpolymer, 30% by weight glass fibers, the same as in Example 51.
실시예 55Example 55
폴리케톤 터폴리머 60중량%, 유리섬유 40중량%를 제외하고는 실시예 51과 동일하다.Except for 60% by weight of polyketone terpolymer, 40% by weight of glass fiber was the same as in Example 51.
실시예 56Example 56
폴리케톤 터폴리머 50중량%, 유리섬유 50중량%를 제외하고는 실시예 51과 동일하다.Except for 50% by weight of polyketone terpolymer, 50% by weight of glass fiber, the same as in Example 51.
실시예 57Example 57
폴리케톤의 고유점도가 1.0 인 것을 제외하고는 실시예 54와 동일하다.It is the same as Example 54 except the intrinsic viscosity of polyketone is 1.0.
비교예 20Comparative Example 20
폴리케톤 대신에 Rhodia 사 PA66 70 중량%(A218V30 제품)을 제외하고는 상기 실시예 54와 동일한 방법으로 시편을 제조하였다.Specimens were prepared in the same manner as in Example 54 except for 70% by weight of Rhodia PA66 (manufactured by A218V30) instead of polyketone.
물성평가Property evaluation
상기 실시예의 제조된 폴리케톤 조성물을 시편으로 제조한 다음, 비교예의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 16에 나타내었다.The prepared polyketone composition of the Example was prepared as a specimen, and then evaluated for physical properties in the following manner compared to the product of the comparative example, the results are shown in Table 16 below.
1. 인장강도 평가 : ASTM D638에 의거하여 실시하였다.1. Tensile strength evaluation: It was performed according to ASTM D638.
2. 충격강도평가(노치드 아이조드) : ASTM D638에 의거하여 실시하였다.2. Impact strength evaluation (notched Izod): It was carried out according to ASTM D638.
실시예 51Example 51 실시예 52Example 52 실시예 53Example 53 실시예 54Example 54 실시예 55Example 55 실시예 56Example 56 실시예 57Example 57 비교예 20Comparative Example 20
조성Furtherance PK95%/GF5%PK95% / GF5% PK90%/GF10%PK90% / GF10% PK80%/GF20%PK80% / GF20% PK70%/GF30%PK70% / GF30% PK60%/GF40%PK60% / GF40% PK50%/GF50%PK50% / GF50% PK70%/GF30%PK70% / GF30% PA70%/GF30%PA70% / GF30%
인장강도 평가 (MPa)Tensile Strength Rating (MPa) 148148 155155 156156 158158 162162 170170 180180 130130
충격강도 (KJ/m2)Impact Strength (KJ / m2) 1818 2020 2121 1818 2020 1717 2323 1212
상기 표 16에서 보듯이, 실시예 51 경우 비교예 20에 비하여 인장강도 및 충격강도가 우수한 것으로 나타났다.As shown in Table 16, in Example 51, the tensile strength and the impact strength were superior to those of Comparative Example 20.
따라서, 비교예 20보다는 실시예 51를 통해 제조된 폴리케톤 조성물은 전기적 특성이 우수한 바 산업용으로 사용되는 열가소성 플라스틱으로 사용되기에 적합한 것으로 평가되었다.Therefore, the polyketone composition prepared in Example 51 rather than Comparative Example 20 was evaluated to be suitable for use as a thermoplastic plastic used for industrial bar having excellent electrical properties.
실시예 58Example 58
초산 팔라듐, 트리플루오르 초산의 음이온 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로 구성되는 촉매 조성물의 존재하에, 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머(terpolymer)를 메탄올 100중량부 대비 물 5중량부 이고, 70~90℃의 용매에서 중합하였다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 한편, 상기 제조된 폴리케톤 터폴리머의 융점은 220℃이고, 1,1,1,3,3,3-HFIP에 측정된 고유점도(LVN)는 1.4 dl/g이었다.Palladium acetate, anion of trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) In the presence of the catalyst composition, a linear terpolymer of carbon monoxide, ethylene and propylene was polymerized in a solvent at 70 to 90 ° C. with 5 parts by weight of water relative to 100 parts by weight of methanol. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. Meanwhile, the melting point of the prepared polyketone terpolymer was 220 ° C., and the intrinsic viscosity (LVN) measured in 1,1,1,3,3,3-HFIP was 1.4 dl / g.
상기 제조된 폴리케톤 터폴리머 98중량% 및 열가소성 폴리카보네이트은 2중량%를 블렌딩 하여 폴리케톤 조성물을 제조하였다. 98 wt% of the prepared polyketone terpolymer and 2 wt% of the thermoplastic polycarbonate were blended to prepare a polyketone composition.
실시예 59Example 59
폴리케톤 터폴리머 90중량%, 폴리카보네이트 10중량%를 제외하고는 실시예 58과 동일하다.Same as Example 58 except for 90 weight percent polyketone terpolymer and 10 weight percent polycarbonate.
실시예 60Example 60
폴리케톤 터폴리머 80중량%, 폴리카보네이트 20중량%를 제외하고는 실시예 58과 동일하다.Same as Example 58 except 80 wt% polyketone terpolymer and 20 wt% polycarbonate.
실시예 61Example 61
폴리케톤 터폴리머 70중량%, 폴리카보네이트 30중량%를 제외하고는 실시예 58과 동일하다.Same as Example 58 except for 70 weight percent polyketone terpolymer and 30 weight percent polycarbonate.
비교예 21Comparative Example 21
폴리케톤 100중량%을 사용한 것을 제외하고는 실시예 58과 동일한 방법으로 시편을 제조하였다.A specimen was prepared in the same manner as in Example 58, except that 100 wt% polyketone was used.
물성평가Property evaluation
상기 실시예의 제조된 폴리케톤 조성물을 시편으로 제조한 다음, 비교예의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 17에 나타내었다.The prepared polyketone composition of the Example was prepared as a specimen, and then evaluated for physical properties in the following manner compared to the product of the comparative example, the results are shown in Table 17 below.
1. 경도(Hardness) 측정 : 경도는 Rockwell 경도의 R 스케일로 하기의 방법에 따라 측정하였다.1. Hardness measurement: Hardness was measured according to the following method in R scale of Rockwell hardness.
a . 강철 볼에 예비부하(Minor load) 를 가하여 시편표면을 누른다. a. Press the specimen surface by applying a minor load to the steel ball.
b . 값이 안정화 되면 게이지눈금을 0 으로 조정한다.b. When the value stabilizes, adjust the gauge scale to zero.
c . 본부하(Major load) 를 15 초 동안 가한 후 제거하되 예비부하는 그대로 둔다.c. Apply the main load for 15 seconds and remove it but leave the preload alone.
d . 1 5 초 후에 게이지 눈금을 측정한다. ( - RB : Total indentation under load)d. 1 After 5 seconds, measure the gauge scale. (-RB: Total indentation under load)
e . Rockwell 경도을 계산한다.e. Calculate Rockwell hardness.
실시예 58Example 58 실시예 59Example 59 실시예 60Example 60 실시예 61Example 61 비교예 21Comparative Example 21
조성Furtherance PK98%/PC2%PK98% / PC2% PK90%/PC10%PK90% / PC10% PK80%/PC20%PK80% / PC20% PK70%/PC30%PK70% / PC30% PA basePA base
Rockwell 경도측정Rockwell Hardness Measurement 9999 103103 110110 108108 9090
상기 표 17에서 보듯이, 실시예 경우 비교예에 비하여 Rockwell 경도(95이상)가 더 우수한 것으로 평가되었다.As shown in Table 17, the Rockwell hardness (95 or more) was evaluated to be superior to the comparative example compared to the comparative example.
따라서, 비교예 보다는 실시예를 통해 제조된 폴리케톤 조성물은 기계적 특성이 우수한 바 산업용으로 사용되는 열가소성 플라스틱으로 사용되기에 적합한 것으로 평가되었다.Therefore, the polyketone composition prepared according to the examples rather than the comparative example was evaluated to be suitable for use as a thermoplastic plastic used for industrial bar having excellent mechanical properties.
실시예 62Example 62
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 11배의 몰비이고, 중합온도 80℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.2dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조 후, 사출성형하여 안경테 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 80 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0. The polyketone terpolymer prepared above was 40 mm in diameter operating at 250 rpm, and was manufactured in pellet form on an extruder using a biaxial screw having L / D = 32, followed by injection molding to prepare spectacle frames.
실시예 63Example 63
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 안경테 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0. The polyketone terpolymer prepared above was 40 mm in diameter operating at 250 rpm, and prepared by pelletizing on an extruder using a biaxial screw having an L / D = 32 to produce an eyeglass frame specimen.
실시예 64Example 64
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.6dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 안경테 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 74 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0. The polyketone terpolymer prepared above was 40 mm in diameter operating at 250 rpm, and prepared by pelletizing on an extruder using a biaxial screw having an L / D = 32 to produce an eyeglass frame specimen.
실시예 65Example 65
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 1.8 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 안경테 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.4 dl / g, a MI (Melt index) of 60 g / 10 min, and an MWD of 1.8. The polyketone terpolymer prepared above was 40 mm in diameter operating at 250 rpm, and prepared by pelletizing on an extruder using a biaxial screw having an L / D = 32 to produce an eyeglass frame specimen.
실시예 66Example 66
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.2 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 안경테 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.2. The polyketone terpolymer prepared above was 40 mm in diameter operating at 250 rpm, and prepared by pelletizing on an extruder using a biaxial screw having an L / D = 32 to produce an eyeglass frame specimen.
비교예 22Comparative Example 22
종래에 안경테의 소재로 사용되던 PEI 시편을 비교예로 사용하였다.PEI specimens, which were conventionally used as materials for eyeglass frames, were used as comparative examples.
물성평가Property evaluation
상기 실시예의 제조된 펠렛을 사출 성형하여 안경테용 시편을 제조한 다음, 비교예와 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 18에 나타내었다. After injection molding the prepared pellets of the above Example to prepare a spectacle frame for the spectacle, and compared with the comparative example to evaluate the physical properties in the following manner, the results are shown in Table 18 below.
1. 성형성 평가1. Moldability Evaluation
동일한 금형에서 단위시간당 정상품으로 사출되는 사출품의 수로 평가, 기준 대비 많은 수를 사출할 수 있을 경우 우수, 기준 대비 적은 수를 사출 할 수 있을 경우 미흡 판정.It is evaluated by the number of injection molded products per unit time in the same mold, and excellent when it is possible to inject a large number compared to the standard.
2. 탄성복원력(굽힘각도)2. Elastic restoring force (bending angle)
ASTM D790에 의거한 굴곡탄성율을 100회 반복 측정후 최종 시편의 굽어진 각도를 측정함.The bending angle of the final specimen was measured after 100 repeated measurements of flexural modulus in accordance with ASTM D790.
실시예와 비교예의 물성은 하기 표 18과 같았다.Physical properties of the Examples and Comparative Examples were as shown in Table 18 below.
항목Item 실시예62Example 62 실시예63Example 63 실시예64Example 64 실시예65Example 65 실시예66Example 66 비교예22Comparative Example 22
물성Properties IV : 1.2MWD : 2.0IV: 1.2MWD: 2.0 IV : 1.4MWD : 2.0IV: 1.4 MWD: 2.0 IV : 1.6MWD : 2.0IV: 1.6MWD: 2.0 IV : 1.4MWD : 1.8IV: 1.4 MWD: 1.8 IV : 1.4MWD : 2.2IV: 1.4 MWD: 2.2 PEIPEI
성형성Formability 양호Good 양호Good 양호Good 양호Good 양호Good 보통 (기준)Medium (standard)
탄성복원력 (굽힘각도)Elastic restoring force (bending angle) 1.5°1.5 ° 1.3°1.3 ° 1.2°1.2 ° 1.5°1.5 ° 1.6°1.6 ° 2.5°2.5 °
상기 표 18에서 보듯이, 실시예의 경우 비교예22 대비 단위시간당 많은 시편을 사출할 수 있어서 성형성은 양호한 것으로 판정되며, 탄성복원력을 나타내는 굽힘각도가 더 우수한 것으로 나타났다. 따라서, 본 발명의 실시예를 통해 제조된 안경테는 탄성복원력이 우수하므로, 안경테로 적용되기에 매우 적합하였다.As shown in Table 18, in the case of the embodiment can be injected more specimens per unit time than Comparative Example 22, the moldability was determined to be good, the bending angle indicating the elastic restoring force was better. Therefore, the spectacle frame manufactured through the embodiment of the present invention has excellent elastic restoring power, and thus, was very suitable for application to the spectacle frame.
실시예 67Example 67
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 11배의 몰비이고, 중합온도 80℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.2dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 80 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다. 제조된 시험편을 형체력 80톤의 성형기 상에서 사출성형하여 마스크 시편을 제조하였다. 최종 제조된 마스크시편의 노치드 이조드(Notched Izod) 충격강도를 ASTM D256의 시험방법으로 측정하고, 흡습 후 인장물성 유지율을 측정하였다.The polyketone terpolymer prepared above was prepared in pellet form on an extruder using a biaxial screw with a diameter of 2.5 cm operating at 250 rpm and L / D = 32. The test specimen was injection molded on a molding machine having a clamping force of 80 tons to prepare a mask specimen. Notched Izod impact strength of the final mask specimen was measured by the test method of ASTM D256, and the tensile property retention after moisture absorption was measured.
실시예 68Example 68
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다. 제조된 시험편을 형체력 80톤의 성형기 상에서 사출성형하여 마스크 시편을 제조하였다. 최종 제조된 마스크시편의 노치드 이조드(Notched Izod) 충격강도를 ASTM D256의 시험방법으로 측정하고, 흡습 후 인장물성 유지율을 측정하였다.The polyketone terpolymer prepared above was prepared in pellet form on an extruder using a biaxial screw with a diameter of 2.5 cm operating at 250 rpm and L / D = 32. The test specimen was injection molded on a molding machine having a clamping force of 80 tons to prepare a mask specimen. Notched Izod impact strength of the final mask specimen was measured by the test method of ASTM D256, and the tensile property retention after moisture absorption was measured.
실시예 69Example 69
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.6dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 74 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하였다. 제조된 시험편을 형체력 80톤의 성형기 상에서 사출성형하여 마스크 시편을 제조하였다. 최종 제조된 마스크시편의 노치드 이조드(Notched Izod) 충격강도를 ASTM D256의 시험방법으로 측정하고, 흡습 후 인장물성 유지율을 측정하였다.The polyketone terpolymer prepared above was prepared in pellet form on an extruder using a biaxial screw with a diameter of 2.5 cm operating at 250 rpm and L / D = 32. The test specimen was injection molded on a molding machine having a clamping force of 80 tons to prepare a mask specimen. Notched Izod impact strength of the final mask specimen was measured by the test method of ASTM D256, and the tensile property retention after moisture absorption was measured.
비교예 23Comparative Example 23
기존에 고충격 마스크 소재로 사용되던 DuPont 사(社)의 소재로서 폴리아마이드66(Polyamide66, PA66)의 충격강도 및 흡습 후 물성 유지율을 측정하였다.The impact strength and retention of physical properties after absorption of polyamide 66 (polyamide 66, PA66) were measured as a material of DuPont, which was previously used as a high-impact mask material.
실시예와 비교예의 물성은 하기 표 19와 같았다.Physical properties of the Examples and Comparative Examples were as shown in Table 19 below.
물성 유지율 평가: Property retention rate:
1) 온도 50℃, 상대습도 90%에서 24시간 처리1) 24 hours at 50 ℃ and 90% RH
2) 인장물성 평가 : ASTM D638에 의하여 인장강도 측정2) Tensile property evaluation: Tensile strength measurement according to ASTM D638
3) 사출즉시 물성으로부터 유지율 산출3) Calculation of retention rate from physical properties immediately after injection
시험항목Test Items 실시예67Example 67 실시예68Example 68 실시예69Example 69 비교예23Comparative Example 23
Notched Izod 충격강도(kJ/m2)(23℃, ASTM D256)Notched Izod Impact Strength (kJ / m2) (23 ℃, ASTM D256) 8585 9090 9292 5050
흡습 후 물성유지율 (%)Property retention rate after moisture absorption (%) 9191 9090 8686 6060
상기 표 19에서 보듯이, 실시예의 경우 비교예 대비 충격강도 및 흡습 후 물성유지율이 매우 우수한 것으로 평가되었다.As shown in Table 19, in the case of the Example it was evaluated that the impact strength and the property retention after moisture absorption is very excellent compared to the comparative example.
비교예는 현재 고충격 마스크에 사용되어지는 제품으로서, 본 발명의 실시예를 통해 제조된 고충격 마스크는 내충격성 및 물성유지가 매우 우수한 고충격 마스크로 적용하기에 매우 적합하였다.Comparative Example is a product that is currently used in a high impact mask, the high impact mask produced through the embodiment of the present invention was very suitable for applying as a high impact mask having excellent impact resistance and physical properties.
실시예 70Example 70
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min 이었다. 상기에서 제조된 폴리케톤 터폴리머 70중량%와 미네랄 보강재로 카오린 30중량%를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조 후 사출 성형하여 파이프 홀더용 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. In addition, the melting point of the polyketone terpolymer was 220 ℃, LVN measured at 25 ℃ by hexa-fluoroisopropano (HFIP) was 1.4dl / g, MI (Melt index) was 60g / 10min. 70% by weight of the polyketone terpolymer prepared above and 30% by weight of kaolin as a mineral reinforcing material at a diameter of 40 mm operating at 250 rpm, and prepared in pellet form on an extruder using a biaxial screw with L / D = 32. Injection molding was performed to prepare specimens for pipe holders.
실시예 71 내지 72Examples 71-72
폴리케톤 터폴리머 및 카오린의 함량을 하기 표 20에 기재된 바와 같이 조절한 것을 제외하고는, 실시예 70과 동일한 과정을 통하여 파이프 홀더용 시편을 각각 제조하였다.Except that the content of the polyketone terpolymer and kaolin was adjusted as shown in Table 20, through the same procedure as in Example 70 were prepared for the pipe holder specimens, respectively.
비교예 24Comparative Example 24
기존에 DuPont 사(社)의 소재로서 PA66 70중량%과 미네랄 보강재로 카오린 30중량%를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조 후 사출 성형하여 파이프 홀더용 시편을 제조하였다.Conventionally, the material of DuPont, 70% by weight of PA66 and 30% by weight of kaolin as mineral reinforcement, is 40 mm in diameter, operating at 250 rpm, and pelletized on an extruder using a biaxial screw with L / D = 32. After the injection molding to prepare a specimen for a pipe holder.
비교예 25Comparative Example 25
PA66과 카오린의 함량을 하기 표 20에 기재된 바와 같이 조절한 것을 제외하고는, 비교예 1과 동일한 과정을 통하여 파이프 홀더용 시편을 제조하였다.Except that the content of PA66 and kaolin was adjusted as shown in Table 20, the specimen for the pipe holder was prepared through the same process as in Comparative Example 1.
물성평가Property evaluation
상기 실시예 70 내지 72에서 각각 제조된 파이프 홀더용 시편을 비교예 24 및 25의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하였으며, 그 결과를 하기 표 20에 나타내었다.The physical properties of the pipe holder specimens prepared in Examples 70 to 72 were evaluated by the following method in comparison with the products of Comparative Examples 24 and 25, and the results are shown in Table 20 below.
1. 아이조드 충격강도 평가 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength evaluation: It was performed according to ASTM D256.
2. 치수변화율 평가 : 온도 50℃, 상대습도 90%의 조건에서 수직 및 수평방향에 대해 MS211-47에 따라 평가하였다.2. Evaluation of dimensional change rate: Vertical and horizontal directions were evaluated according to MS211-47 at a temperature of 50 ° C and a relative humidity of 90%.
구분division 배합비Compounding cost 충격강도Impact strength 치수변화율 수직Dimensional change rate vertical 치수변화율 수평Dimensional change rate horizontal
KJ/m2 KJ / m 2 %% %%
실시예70Example 70 폴리케톤 70% 미네랄보강재 30%Polyketone 70% Mineral Reinforcement 30% 1616 0.080.08 0.050.05
실시예71Example 71 폴리케톤 60% 미네랄보강재 40%Polyketone 60% Mineral Reinforcement 40% 1414 0.070.07 0.040.04
실시예72Example 72 폴리케톤 50% 미네랄보강재 50%Polyketone 50% Mineral Reinforcement 50% 1212 0.050.05 0.020.02
비교예24Comparative Example 24 PA66 70% 미네랄 보강재 30%PA66 70% Mineral Reinforcement 30% 5.55.5 0.350.35 0.230.23
비교예25Comparative Example 25 PA66 60% 미네랄 보강재 40%PA66 60% Mineral Reinforcement 40% 4.54.5 0.300.30 0.210.21
상기 표 20에서 보듯이, 폴리케톤과 미네랄보강재를 블렌딩하여 제조된 실시예들은 비교예에 비하여 충격강도가 10 KJ/m2 이상으로 내충격성이 우수하고 치수변화율이 0.1% 이하로 치수안정성이 우수한 것으로 평가되었다.As shown in Table 20, the examples prepared by blending polyketone and mineral reinforcement are excellent in impact resistance and impact stability at 10 KJ / m 2 or more and dimensional change rate of 0.1% or less compared to the comparative example. Was evaluated.
따라서, 본 발명의 실시예를 통해 제조된 파이프 홀더는 내충격성, 치수안정성이 매우 우수하여 파이프 홀더로 적용하기에 매우 적합하였다.Therefore, the pipe holder manufactured according to the embodiment of the present invention was very suitable for application as a pipe holder because it is very excellent in impact resistance and dimensional stability.
실시예 73Example 73
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 일산화탄소는 50mol%이고, 에틸렌은 46mol%이며, 프로필렌은 4mol%이었다. 또한, 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. 또한, 팔라듐 촉매 잔량이 5 ppm 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. In the polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0. In addition, the residual amount of palladium catalyst was 5 ppm.
상기 제조된 폴리케톤 터폴리머 65중량%와 설폰아미드계 가소제 15중량%, 폴리우레탄 17중량% 및 ASA 3중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 신발용 소재의 시편을 제조하였다. 65 wt% of the prepared polyketone terpolymer, 15 wt% of sulfonamide-based plasticizer, 17 wt% of polyurethane, and 3 wt% of ASA were added to prepare a composition, and the prepared composition was 40 cm in diameter operating at 250 rpm, and L A biaxial screw with a / D = 32 was used to produce pellets on an extruder, followed by injection molding to prepare shoe specimens.
실시예 74Example 74
실시예 73과 동일한 방법으로 제조된 상기 폴리케톤 터폴리머 65중량%와 설폰아미드계 가소제 16중량%를 폴리우레탄 18중량% ASA 1중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 신발용 소재의 시편을 제조하였다. 65% by weight of the polyketone terpolymer prepared in the same manner as in Example 73 and 16% by weight of sulfonamide-based plasticizer were prepared by adding 18% by weight of ASA and 1% by weight of ASA, and the prepared composition was operated at 250 rpm. The diameter of 40cm, using a biaxial screw of L / D = 32 to produce a pellet (pellet) on the extruder, and then injection molding to prepare a shoe material.
실시예 75Example 75
실시예 73과 동일한 방법으로 제조된 상기 폴리케톤 터폴리머 65중량%와 설폰아미드계 가소제 12중량%를 폴리우레탄 20중량% ASA 3중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 신발용 소재의 시편을 제조하였다. 65% by weight of the polyketone terpolymer prepared in the same manner as in Example 73 and 12% by weight of sulfonamide-based plasticizer were prepared by adding 20% by weight of polyurethane and 3% by weight of ASA, and the prepared composition was operated at 250 rpm. The diameter of 40cm, using a biaxial screw of L / D = 32 to produce a pellet (pellet) on the extruder, and then injection molding to prepare a shoe material.
비교예 26Comparative Example 26
기존 신발용 소재로 듀폰사의 나이론 66 85중량%와 설폰아미드계 가소제 15중량%을 혼합하여 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 신발용 소재의 시편을 제조하였다. DuPont's nylon 66 85% by weight and sulfonamide plasticizer 15% by weight was mixed with the existing shoe material to prepare a composition, the composition is 40cm in diameter operating at 250rpm, L / D = 32 Using a screw to produce a pellet (pellet) on the extruder, and then injection molding to prepare a specimen of the shoe material.
물성 평가Property evaluation
상기 실시예 및 비교예에서 각각 제조된 시편을 (10cm 변, 두께 0.3mm, 0.5mm, 0.7mm의 3종류)에 있어서, 접착성 및 변형을 이하의 기준으로 평가하였다.In each of the specimens prepared in the above Examples and Comparative Examples (three types of 10 cm side, 0.3 mm, 0.5 mm, 0.7 mm), adhesiveness and deformation were evaluated based on the following criteria.
1. 굴곡탄성율 : ASTM D790에 의거하여 실시하였다.1. Flexural modulus: It was performed according to ASTM D790.
2. 굴곡강도 : ASTM D790에 의거하여 실시하였다.2. Flexural strength: conducted according to ASTM D790.
3. 접착성: 얻어진 시험편에 대해서 온도 23℃, 습도 50%의 조건하에서 4일간 유지한 후, 라디오 펜치로, 시트와 스터드간, 또는 시트와 밑창간을 박리함으로써 행하였다. 얻어진 결과는 이하와 같이 평가하였다.3. Adhesiveness: It hold | maintained for 4 days on the obtained test piece on the conditions of the temperature of 23 degreeC, and 50% of humidity, and peeled between a sheet | seat and a stud, or between a sheet | seat and a sole with a radio pliers. The obtained result was evaluated as follows.
A: 매우 견고(부재간의 계면이 박리되지 않고, 시험편이 파괴)A: Very robust (the interface between members does not peel off, and the test piece breaks)
B: 견고(부재간의 계면이 일부 박리되고, 시험편이 일부 파괴)B: Robust (the interface between members is partially peeled off and the test piece is partially destroyed)
C: 박리(부재간의 계면이 박리)C: peeling (interface between members peeling)
또한, 시트와 스터드간의 평가가 "C"일 경우에는, 시트와 밑창간의 접착성은 시트와 밑창만의 복합 성형체로 평가하였다.In the case where the evaluation between the sheet and the stud was "C", the adhesiveness between the sheet and the sole was evaluated by the composite molded body of the sheet and the sole alone.
4. 변형성: 얻어진 시험편에 대해서, 단부로부터 10cm 변의 영역을 육안 관찰함으로써 행하였다.4. Deformability: The obtained test piece was performed by visually observing an area of 10 cm side from the end.
+: 변형되지 않음+: Not deformed
ㅁ: 일부 변형(단부 또는 접착부의 일부에 대하여 변형 있음)S: some deformation (deformation with respect to the end or part of the bond)
-: 크게 변형(변형된 부분의 면적이 변형되지 않은 부분의 면적보다 큼)-: Large deformation (the area of the deformed part is larger than the area of the undeformed part)
항목Item 굴곡강도 (MPa)Flexural Strength (MPa) 굴곡탄성율 (MPa)Flexural modulus (MPa) 접착성Adhesive 변형성Deformability
실시예 73Example 73 225225 78007800 AA ++
실시예 74Example 74 220220 76007600 AA ++
실시예 75Example 75 230230 82008200 AA ++
비교예 26Comparative Example 26 200200 65006500 BB ㅁM
상기 표 21에서 알 수 있는 바와 같이, 실시예 73~75경우 비교예 대비 굴곡강도, 탄성율 및 접착성과 변형성이 우수하여 신발용 소재로 사용되기에 매우 적합한 것으로 판명되었다. 특히 본 발명의 폴리케톤 블렌드를 포함하는 신발용 소재는 굴곡탄성율이 7000 내지 8500MPa으로 우수하다.As can be seen in Table 21, Examples 73 to 75 was found to be very suitable for use as a shoe material due to excellent flexural strength, elastic modulus and adhesiveness and deformation compared to the comparative example. In particular, the shoe material including the polyketone blend of the present invention has excellent flexural modulus of 7000 to 8500 MPa.
실시예 76Example 76
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 11배의 몰비이고, 중합온도 80℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.2dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 80 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
상기 제조된 폴리케톤 터폴리머 80중량% 및 유리섬유 20중량%를 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하여 펠렛상으로 제조후 사출 성형하여 엑셀레이터 페달용 시편을 제조하였다.80% by weight of the prepared polyketone terpolymer and 20% by weight of glass fiber were introduced into a twin screw extruder of L / D32, D 40 and extruded through melt kneading at a 250 rpm screw rotational speed at a temperature of 240 ° C. to prepare pellets. Injection molding was performed to prepare a specimen for an accelerator pedal.
실시예 77Example 77
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
상기 제조된 폴리케톤 터폴리머 80중량% 및 유리섬유 20중량%를 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하여 펠렛상으로 제조후 사출 성형하여 엑셀레이터 페달용 시편을 제조하였다.80% by weight of the prepared polyketone terpolymer and 20% by weight of glass fiber were introduced into a twin screw extruder of L / D32, D 40 and extruded through melt kneading at a 250 rpm screw rotational speed at a temperature of 240 ° C. to prepare pellets. Injection molding was performed to prepare a specimen for an accelerator pedal.
실시예 78Example 78
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.6dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 74 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
상기 제조된 폴리케톤 터폴리머 80중량% 및 유리섬유 20중량%를 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하여 펠렛상으로 제조후 사출 성형하여 엑셀레이터 페달용 시편을 제조하였다.80% by weight of the prepared polyketone terpolymer and 20% by weight of glass fiber were introduced into a twin screw extruder of L / D32, D 40 and extruded through melt kneading at a 250 rpm screw rotational speed at a temperature of 240 ° C. to prepare pellets. Injection molding was performed to prepare a specimen for an accelerator pedal.
실시예 79Example 79
실시예 2의 폴리케톤 터폴리머 60중량% 및 유리섬유 40중량%를 제외하고는 실시예 77과 동일하게 시편을 제조하였다.A specimen was prepared in the same manner as in Example 77 except for 60 wt% of the polyketone terpolymer and 40 wt% of the glass fiber of Example 2.
실시예 80Example 80
실시예 2의 폴리케톤 터폴리머 90중량% 및 유리섬유 10중량%를 제외하고는 실시예 77과 동일하게 시편을 제조하였다.A specimen was prepared in the same manner as in Example 77 except for 90 wt% of the polyketone terpolymer and 10 wt% of the glass fiber of Example 2.
비교예 27Comparative Example 27
Rhodia 사 PA66 80중량% Glass Fiber 20%,( A218V30 제품)이외에는 실시예 77과 동일하게 제조하였다.Rhodia PA66 80% by weight Glass Fiber 20%, (A218V30) was prepared in the same manner as in Example 77.
물성평가Property evaluation
상기 실시예의 제조된 펠렛을 사출 성형하여 엑셀레이터 페달용 시편을 제조한 다음, 비교예의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 22에 나타내었다.After injection molding the prepared pellet of the Example to prepare a specimen for the accelerator pedal, and compared to the product of the comparative example to evaluate the physical properties in the following manner, the results are shown in Table 22.
1. 아이조드 충격강도 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength: It was conducted according to ASTM D256.
2. 수분흡습 평가 : 온도 50℃, 상대습도 90%에서 24시간 처리후 수분 함유량 측정2. Moisture absorption evaluation: Determination of water content after treatment for 24 hours at temperature 50 ℃, relative humidity 90%
항목Item 실시예 76Example 76 실시예 77Example 77 실시예 78Example 78 실시예 79Example 79 실시예 80Example 80 비교예 27Comparative Example 27
PK의 기본물성Basic Properties of PK IV : 1.2MWD : 2.0IV: 1.2MWD: 2.0 IV : 1.4MWD : 2.0IV: 1.4 MWD: 2.0 IV : 1.6MWD : 2.0IV: 1.6MWD: 2.0 IV : 1.4MWD : 1.8IV: 1.4 MWD: 1.8 IV : 1.4MWD : 2.2IV: 1.4 MWD: 2.2 PA66/GFPA66 / GF
조성비Creation costs PK80%/GF20%PK80% / GF20% PK80%/GF20%PK80% / GF20% PK80%/GF20%PK80% / GF20% PK60%/GF40%PK60% / GF40% PK90%/GF10%PK90% / GF10% PA80%/GF20%PA80% / GF20%
제품 흡습율 (%)Product moisture absorption rate (%) 0.510.51 0.50.5 0.530.53 0.610.61 0.640.64 2.52.5
충격강도 (kJ/m2)Impact strength (kJ / m2) 1717 1818 1919 2222 1616 1212
상기 표 22에서 보듯이, 실시예의 경우 비교예 27에 비하여 제품흡습율이 낮고, 충격강도는 더욱 우수한 것으로 나타났다. 따라서, 비교예보다는 실시예를 통해 제조된 시편은 엑셀레이터 페달로 사용하기에 더 유리한 것으로 나타났다.As shown in Table 22, in the case of Example compared to Comparative Example 27, the product moisture absorption was lower, the impact strength was found to be more excellent. Thus, the specimens prepared through the examples rather than the comparative examples were found to be more advantageous for use as an accelerator pedal.
실시예 81Example 81
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 11배의 몰비이고, 중합온도 80℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.2dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 80 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
상기 제조된 폴리케톤 터폴리머 75중량%, 유리섬유 25중량%인 블렌드 조성물을 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하여 펠렛을 제조 후 사출성형하여 변속기 브라켓 시편을 제조하였다.75% by weight of the prepared polyketone terpolymer, 25% by weight glass fiber blend composition was introduced into a twin screw extruder of L / D32, D 40 and extruded through melt kneading at 250 rpm screw rotation speed at a temperature of 240 ℃ pellets After injection molding, a transmission bracket specimen was prepared.
실시예 82Example 82
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
상기 제조된 폴리케톤 터폴리머 75중량%, 유리섬유 25중량%인 블렌드 조성물을 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하여 펠렛을 제조 후 사출성형하여 변속기 브라켓 시편을 제조하였다.75% by weight of the prepared polyketone terpolymer, 25% by weight glass fiber blend composition was introduced into a twin screw extruder of L / D32, D 40 and extruded through melt kneading at 250 rpm screw rotation speed at a temperature of 240 ℃ pellets After injection molding, a transmission bracket specimen was prepared.
실시예 83Example 83
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.6dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 74 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
상기 제조된 폴리케톤 터폴리머 75중량%, 유리섬유 25중량%인 블렌드 조성물을 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하여 펠렛을 제조 후 사출성형하여 변속기 브라켓 시편을 제조하였다.75% by weight of the prepared polyketone terpolymer, 25% by weight glass fiber blend composition was introduced into a twin screw extruder of L / D32, D 40 and extruded through melt kneading at 250 rpm screw rotation speed at a temperature of 240 ℃ pellets After injection molding, a transmission bracket specimen was prepared.
실시예 84Example 84
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 1.8 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.4 dl / g, a MI (Melt index) of 60 g / 10 min, and an MWD of 1.8.
상기 제조된 폴리케톤 터폴리머 75중량%, 유리섬유 25중량%인 블렌드 조성물을 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하여 펠렛을 제조 후 사출성형하여 변속기 브라켓 시편을 제조하였다.75% by weight of the prepared polyketone terpolymer, 25% by weight glass fiber blend composition was introduced into a twin screw extruder of L / D32, D 40 and extruded through melt kneading at 250 rpm screw rotation speed at a temperature of 240 ℃ pellets After injection molding, a transmission bracket specimen was prepared.
실시예 85Example 85
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.2 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.2.
상기 제조된 폴리케톤 터폴리머 75중량%, 유리섬유 25중량%인 블렌드 조성물을 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하여 펠렛을 제조 후 사출성형하여 변속기 브라켓 시편을 제조하였다.75% by weight of the prepared polyketone terpolymer, 25% by weight glass fiber blend composition was introduced into a twin screw extruder of L / D32, D 40 and extruded through melt kneading at 250 rpm screw rotation speed at a temperature of 240 ℃ pellets After injection molding, a transmission bracket specimen was prepared.
실시예 86Example 86
실시예 82에서 제조된 폴리케톤 터폴리머 90중량%, 유리섬유 10중량%인 블렌드 조성물을 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하여 펠렛을 제조 후 사출성형하여 변속기 브라켓 시편을 제조하였다.The blend composition of 90% by weight of the polyketone terpolymer prepared in Example 82 and 10% by weight of glass fiber was introduced into a twin screw extruder of L / D32 and D 40 and extruded through melt kneading at a temperature of 240 ° C. at a 250 rpm screw rotation speed. After the pellet was prepared by injection molding to prepare a transmission bracket specimen.
실시예 87Example 87
실시예 82에서 제조된 폴리케톤 터폴리머 60중량%, 유리섬유 40중량%인 블렌드 조성물을 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하여 펠렛을 제조 후 사출성형하여 변속기 브라켓 시편을 제조하였다.The blend composition of 60% by weight of polyketone terpolymer and 40% by weight of glass fiber prepared in Example 82 was introduced into a twin screw extruder of L / D32 and D40, and extruded through melt kneading at a temperature of 240 ° C. at a 250 rpm screw rotation speed. After the pellet was prepared by injection molding to prepare a transmission bracket specimen.
비교예 28Comparative Example 28
Rhodia 사 PA66 75% 및 Glass Fiber 25%(A218V30 제품)을 사용하여 실시예 82와 동일하게 제조하였다.It was prepared in the same manner as in Example 82 using Rhodia 75% PA66 and 25% Glass Fiber (A218V30).
물성평가Property evaluation
상기 실시예의 제조된 펠렛을 사출 성형하여 변속기 브라켓용 시편을 제조한 다음, 비교예의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 23에 나타내었다.After injection molding the prepared pellets of the above example to prepare a specimen for a transmission bracket, and compared to the product of the comparative example to evaluate the physical properties in the following manner, the results are shown in Table 23.
1. 아이조드 충격강도 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength: It was conducted according to ASTM D256.
2. 흡습 후 물성(인장물성)유지율 평가2. Evaluation of retention of physical properties (tensile properties) after moisture absorption
1) 온도 50℃, 상대습도 90%에서 24시간 처리 1) 24 hours at 50 ℃ and 90% RH
2) 인장물성 평가 : ASTM D638에 의하여 인장강도 측정 2) Tensile property evaluation: Tensile strength measurement according to ASTM D638
3) 사출즉시 물성으로부터 유지율 산출 3) Calculation of retention rate from physical properties immediately after injection
항목Item 실시예 81Example 81 실시예 82Example 82 실시예 83Example 83 실시예 84Example 84 실시예 85Example 85 실시예 86Example 86 실시예 87Example 87 비교예 28Comparative Example 28
PK물성PK Properties IV : 1.2MWD : 2.0IV: 1.2MWD: 2.0 IV : 1.4MWD : 2.0IV: 1.4 MWD: 2.0 IV : 1.6MWD : 2.0IV: 1.6MWD: 2.0 IV : 1.4MWD : 1.8IV: 1.4 MWD: 1.8 IV : 1.4MWD : 2.2IV: 1.4 MWD: 2.2 IV : 1.4MWD : 2.0IV: 1.4 MWD: 2.0 IV : 1.4MWD : 2.0IV: 1.4 MWD: 2.0 --
조성비Creation costs PK75%/GF25%PK75% / GF25% PK75%/GF25%PK75% / GF25% PK75%/GF25%PK75% / GF25% PK75%/GF25%PK75% / GF25% PK75%/GF25%PK75% / GF25% PK90%/GF10%PK90% / GF10% PK60%/GF40%PK60% / GF40% PA75%/GF25%PA75% / GF25%
제품 내수성 (% 물성유지율)Product Water Resistance (% Property Retention Rate) 8989 9090 8888 8989 9090 8888 8686 6060
아이조드 충격강도 (kJ/m2)Izod impact strength (kJ / m2) 1818 2020 2121 1818 2020 1717 2323 1212
상기 표 23에서 보듯이, 실시예의 경우 비교예 28에 비하여 내수성 물성 유지율이 크게 높은 것으로 나타났다. 또한, 아이조드 충격강도 실험에서도 비교예에 비하여 그 값이 더 높아 충격강도도 더욱 우수한 것으로 나타났다.As shown in Table 23, the case of the Example was found to have a significantly higher water resistance retention compared to Comparative Example 28. In addition, the Izod impact strength test also showed that the value is higher than the comparative example, the impact strength is also excellent.
따라서, 비교예보다는 실시예를 통해 제조된 변속기 브라켓은 내충격성(충격강도가 17kJ/m2 이상)이 높고 내수성 물성유지율(인장강도 유지율이 80%이상)이 높아 변속기 브라켓으로 사용하기에 더 적합한 것으로 나타났다.Therefore, the transmission bracket manufactured according to the embodiment rather than the comparative example has a high impact resistance (impact strength of 17kJ / m2 or more) and high water resistance property retention (tensile strength retention of 80% or more) is more suitable for use as a transmission bracket appear.
실시예 88Example 88
초산 팔라듐, 트리플루오르 초산의 음이온 및((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로 구성되는 촉매 조성물의 존재하에, 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머(terpolymer)를 메탄올 100 중량부에 2 중량부의 물이 첨가된 70~90℃의 용매에서 중합하였다. 제조된 터폴리머의 융점은 220℃이고, 1,1,1,3,3,3-HFIP에 측정된 고유점도(LVN)는 1.4 dl/g이었다.Palladium acetate, anion of trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) In the presence of the resulting catalyst composition, a linear terpolymer of carbon monoxide, ethylene and propylene was polymerized in a solvent at 70-90 ° C. in which 2 parts by weight of water was added to 100 parts by weight of methanol. Melting point of the prepared terpolymer was 220 ℃, intrinsic viscosity (LVN) measured in 1,1,1,3,3,3-HFIP was 1.4 dl / g.
상기 제조된 폴리케톤 터폴리머 70중량%, 나일론 6 22중량% 및 고무(EPDM) 8중량%를 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하여 펠렛을 제조하였다.70 wt% of the polyketone terpolymer prepared above, 22 wt% of nylon 6 and 8 wt% of rubber (EPDM) were put into a twin screw extruder having L / D32 and D 40 to melt kneading at a rotation speed of 250 rpm at a temperature of 240 ° C. Pellets were prepared by extrusion through.
실시예 89Example 89
폴리케톤의 고유점도를 1.1로 조절한 것을 제외하고는 실시예 88과 동일하다.Same as Example 88 except that the intrinsic viscosity of the polyketone was adjusted to 1.1.
실시예 90Example 90
폴리케톤의 고유점도를 2.0로 조절한 것을 제외하고는 실시예 88과 동일하다.Same as Example 88 except that the intrinsic viscosity of the polyketone was adjusted to 2.0.
비교예 29Comparative Example 29
Rhodia 사 PA66 Glass Fiber 33%, A218V30 제품을 사용하였다.Rhodia's PA66 Glass Fiber 33% and A218V30 were used.
물성평가Property evaluation
상기 실시예의 제조된 펠렛을 사출 성형하여 범퍼 브라켓용 시편을 제조한 다음, 비교예의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 24에 나타내었다.After injection molding the prepared pellets of the Example to prepare a specimen for the bumper bracket, and compared to the product of the comparative example to evaluate the physical properties in the following manner, the results are shown in Table 24 below.
1. 아이조드 충격강도 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength: It was conducted according to ASTM D256.
2. 인장강도 : ASTM D638에 의거하여 실시하였다.2. Tensile strength: It was performed according to ASTM D638.
3. 내염화칼슘 인장강도 유지율: ASTM D638에 의거하여 제작된 시편을 2시간 동안 100℃ 물에 침적 후 꺼내어 표면수를 제거하고 30분간 실온에서 방치한 다음 100℃ 염화칼슘 10% 수용액에 2시간 침적 후 꺼내어 1시간 동안 실온에서 방치 후 표면수를 제거하는, 총 5.5시간을 1 주기로 하여 매 5cycle 당 인장강도 의 유지율을 평가하였다. 상기 유지율 평가는 총 20cycle을 실시하였다.3. Tensile strength retention of calcium chloride: The specimen prepared according to ASTM D638 was immersed in water at 100 ° C. for 2 hours, then removed, and the surface water was removed and left at room temperature for 30 minutes, and then immersed in 100% calcium chloride 10% aqueous solution for 2 hours. The retention rate of tensile strength was evaluated every 5 cycles by removing the surface water and removing the surface water after 1 hour at room temperature. The retention rate was carried out a total of 20 cycles.
항목Item 실시예 88Example 88 실시예 89Example 89 실시예 90Example 90 비교예 29Comparative Example 29
아이조드 충격강도 (kJ/m2)Izod impact strength (kJ / m2) 9090 8989 9292 4949
인장강도 (MPa)Tensile Strength (MPa) 5555 5656 5757 5858
물성유지율 (%)(90% 상대습도)Physical property retention rate (%) (90% relative humidity) 8585 8484 8383 4040
물성유지율 (%)(10% 염화칼슘)Physical property retention rate (%) (10% calcium chloride) 8080 7878 7979 3030
상기 표 24에서 보듯이, 실시예 88의 경우 비교예 29에 비하여 인장강도는 비슷한 수치를 보이나 충격강도(75kJ/m2이상)는 크게 높은 것으로 나타났다. 또한, 고습도에 대한 물성유지율과 염화칼슘에 대한 내화학성 실험에서도 물성유지율이 75% 이상으로 높게 나타난 것으로 나타났다.As shown in Table 24, the tensile strength was similar to that of Comparative Example 29 in the case of Example 88, but the impact strength (75 kJ / m 2 or more) was significantly higher. In addition, the physical property retention rate of high humidity and the chemical resistance test of calcium chloride showed that the property retention rate was higher than 75%.
따라서, 비교예보다는 실시예를 통해 제조된 범퍼 브라켓은 내충격성이 높고 물성유지율이 높아 범퍼 브라켓으로 사용하기에 더 적합한 것으로 나타났다.Therefore, the bumper brackets manufactured according to the examples rather than the comparative examples were found to be more suitable for use as bumper brackets because of high impact resistance and high physical property retention.
실시예 91Example 91
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 48g/10min 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조된 펠렛을 사출 성형하여 자동차 정션 박스용 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.4 dl / g, and a MI (Melt index) of 48 g / 10 min. Specimen for automobile junction box by injection molding the pellet prepared in the form of pellets on an extruder using a biaxial screw having a diameter of 2.5cm and a L / D = 32 operating the polyketone terpolymer prepared at 250rpm Was prepared.
실시예 92Example 92
폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비를 47 대 3으로 조절한 것을 제외하고는 실시예 91과 동일하다.Same as Example 91 except that the molar ratio of ethylene and propene in the polyketone terpolymer was adjusted to 47 to 3.
실시예 93Example 93
폴리케톤 터폴리머의 고유 점도를 1.1dl/g로 조절한 것을 제외하고는 실시예 91과 동일하다.Same as Example 91 except that the intrinsic viscosity of the polyketone terpolymer was adjusted to 1.1 dl / g.
실시예 94Example 94
폴리케톤 터폴리머의 고유 점도를 2.0dl/g로 조절한 것을 제외하고는 실시예 91과 동일하다.Same as Example 91 except that the intrinsic viscosity of the polyketone terpolymer was adjusted to 2.0 dl / g.
비교예 30Comparative Example 30
폴리케톤 터폴리머 대신 폴리아미드를 사용한 것을 제외하고는, 실시예 91과 동일한 과정을 통하여 자동차 정션 박스용 시편을 제조하였다.Except for using a polyamide instead of a polyketone terpolymer, a specimen for a car junction box was prepared in the same manner as in Example 91.
비교예 31Comparative Example 31
폴리케톤 터폴리머 대신 노릴GTX를 제외하고는, 실시예 91과 동일한 과정을 통하여 자동차 정션 박스용 시편을 제조하였다.Except for Noryl GTX instead of polyketone terpolymer, a test piece for an automobile junction box was prepared in the same manner as in Example 91.
물성평가Property evaluation
실시예 91 에서 제조된 자동차 정션 박스용 시편을 비교예 30 및 31 제품과 대비하여 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 25에 나타내었다.The physical properties of the test box for automobile junction box prepared in Example 91 were evaluated by the following method in comparison with the products of Comparative Examples 30 and 31, and the results are shown in Table 25 below.
1. 치수안정성: 1. Dimensional stability:
물성 유지율 평가: Property retention rate:
1) 온도 50℃, 상대습도 90%에서 24시간 처리1) 24 hours at 50 ℃ and 90% RH
2) 인장물성 평가 : ASTM D638에 의하여 인장강도 측정2) Tensile property evaluation: Tensile strength measurement according to ASTM D638
3) 사출즉시 물성으로부터 유지율 산출3) Calculation of retention rate from physical properties immediately after injection
2. 충격강도 평가: ASTM D256에 의거하여 실시하였다.2. Impact strength evaluation: It was performed according to ASTM D256.
구분division 단위unit 실시예 91Example 91 실시예 92Example 92 실시예 93Example 93 실시예 94Example 94 비교예 30Comparative Example 30 비교예 31Comparative Example 31
구조rescue -- 폴리케톤Polyketone 폴리케톤Polyketone 폴리케톤Polyketone 폴리케톤Polyketone PA6PA6 노릴Noril
흡습 후 인장강도유지율 (%)Tensile strength retention rate after moisture absorption (%) %% 9090 8888 9191 9292 6060 --
충격강도(상온) Impact strength (room temperature) kJ/m2 kJ / m 2 1515 1616 1414 1717 66 77
충격강도(-40℃)Impact Strength (-40 ℃) kJ/m2 kJ / m 2 66 77 55 88 33 44
상기 표 25에 따르면 실시예은 비교예에 비해 흡습 후 물성 유지율이 높고, 상온 및 저온에서의 충격강도 모두 우수한 것으로 나타났다. 특히 상온에서의 충격강도는 12 KJ/m2 이상으로 우수하였고, 흡습후 인장강도 유지율이 흡습전에 비하여 85% 이상으로 우수하였다. 따라서, 본원발명의 실시예에 의해 제조된 시편은 자동차용 정션 박스로 사용하기에 적합하다.According to Table 25, the Example showed higher physical property retention after moisture absorption and better impact strength at room temperature and low temperature than the comparative example. In particular, the impact strength at room temperature was excellent at 12 KJ / m 2 or more, and the tensile strength retention after moisture absorption was more than 85% compared to before the moisture absorption. Thus, the specimen produced by the embodiments of the present invention is suitable for use as a junction box for automobiles.
실시예 95Example 95
초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머를 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 11배의 몰비이고, 중합온도 80℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.2dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. Catalyst generated from palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) Linear alternating polyketone terpolymers of carbon monoxide, ethylene and propene were prepared in the presence of the composition. In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 80 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0.
상기 제조된 폴리케톤 터폴리머 100중량부에, 유리섬유 20 중량부, 탄산칼슘 10 중량부, 폴리초산 비닐 3.5 중량부를 혼합하여 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하였다.100 parts by weight of the prepared polyketone terpolymer, 20 parts by weight of glass fiber, 10 parts by weight of calcium carbonate, and 3.5 parts by weight of polyvinyl acetate were mixed and introduced into a twin screw extruder of L / D32 and D 40 to 250 rpm at a temperature of 240 ° C. Extruded through melt kneading at a screw rotational speed.
실시예 96Example 96
초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머를 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. Catalyst generated from palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) Linear alternating polyketone terpolymers of carbon monoxide, ethylene and propene were prepared in the presence of the composition. In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0.
상기 제조된 폴리케톤 터폴리머 100중량부에, 유리섬유 40 중량부, 탄산칼슘 10 중량부, 폴리초산 비닐 3.5 중량부를 혼합하여 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하였다.100 parts by weight of the prepared polyketone terpolymer, 40 parts by weight of glass fiber, 10 parts by weight of calcium carbonate, and 3.5 parts by weight of polyvinyl acetate were mixed and introduced into a twin screw extruder of L / D32 and D 40 to 250 rpm at a temperature of 240 ° C. Extruded through melt kneading at a screw rotational speed.
실시예 97Example 97
초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머를 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.6dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. Catalyst generated from palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) Linear alternating polyketone terpolymers of carbon monoxide, ethylene and propene were prepared in the presence of the composition. In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 74 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0.
상기 제조된 폴리케톤 터폴리머 100중량부에, 탄산칼슘 10 중량부, 폴리초산 비닐 3.5 중량부를 혼합하여 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하였다.100 parts by weight of the prepared polyketone terpolymer, 10 parts by weight of calcium carbonate and 3.5 parts by weight of polyvinyl acetate were mixed and introduced into a twin screw extruder of L / D32 and D 40, followed by melt kneading at a rotation speed of 250 rpm at a temperature of 240 ° C. Extruded through.
실시예 98Example 98
초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머를 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 1.8이었다. Catalyst generated from palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) Linear alternating polyketone terpolymers of carbon monoxide, ethylene and propene were prepared in the presence of the composition. In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 1.8.
상기 제조된 폴리케톤 터폴리머 100중량부에, 유리섬유 45 중량부, 탄산칼슘 10 중량부, 폴리초산 비닐 3.5 중량부를 혼합하여 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하였다.100 parts by weight of the prepared polyketone terpolymer, 45 parts by weight of glass fiber, 10 parts by weight of calcium carbonate, and 3.5 parts by weight of polyvinyl acetate were mixed and introduced into a twin screw extruder of L / D32 and D 40 to 250 rpm at a temperature of 240 ° C. Extruded through melt kneading at a screw rotational speed.
비교예 32Comparative Example 32
폴리케톤 폴리머 대신 부피 탄소섬유 60중량%와 폴리에스터 40%의 복합수지 조성물 100중량부에 유리섬유 20 중량부, 탄산칼슘 10 중량부, 폴리초산 비닐 3.5 중량부를 혼합하여 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하였다.Instead of polyketone polymer, 20 parts by weight of glass fiber, 10 parts by weight of calcium carbonate, and 3.5 parts by weight of polyvinyl acetate were mixed with 60 parts by weight of 60% by weight of carbon fiber and 100% by weight of the composite resin composition of polyester. It was put in a twin screw extruder and extruded through melt kneading at a 250 rpm screw rotational speed at a temperature of 240 ℃.
비교예 33Comparative Example 33
폴리케톤 폴리머 대신 부피 탄소섬유 60중량%와 폴리에스터 40%의 복합수지 조성물 100중량부에 직경 30~300μm의 알루미늄 파우더 20중량부, 유리섬유 20 중량부, 탄산칼슘 10 중량부, 폴리초산 비닐 3.5 중량부를 혼합하여 L/D32, D 40인 2축 압출기에 투입하여 온도 240℃에서 250rpm 스크류 회전속도로 용융혼련을 통해 압출하였다.20 parts by weight of aluminum powder with a diameter of 30 to 300 μm, 20 parts by weight of glass fiber, 10 parts by weight of calcium carbonate, polyvinyl acetate 3.5 by weight of 60% by weight of carbon fiber and 100% of composite resin composition by 40% of polyester instead of polyketone polymer The mixture by weight was added to a twin screw extruder, L / D32, D40, and extruded through melt kneading at a temperature of 240 ° C. at a 250 rpm screw rotation speed.
물성평가Property evaluation
상기 실시예의 제조된 펠렛을 사출 성형하여 자동차 휠의 림용으로 0.5mm두께의 판상의 시편 금형을 제조한 다음 선팽창계수, 인장강도, 신율, 비중을 측정하여 그 결과를 표 26을 통해 나타내었다.Injection molding the prepared pellets of the above Example to prepare a plate-shaped specimen mold of 0.5mm thickness for the rim of the automobile wheel, and then measured the coefficient of linear expansion, tensile strength, elongation, specific gravity and the results are shown in Table 26.
항목Item 실시예95Example 95 실시예96Example 96 실시예97Example 97 실시예98Example 98 비교예32Comparative Example 32 비교예33Comparative Example 33
선팽창 계수 α-5 Coefficient of linear expansion α -5 0.470.47 0.550.55 0.440.44 0.520.52 0.780.78 0.880.88
인장강도 kg/mm2 Tensile Strength kg / mm 2 4848 5252 3535 5252 2424 2222
신율 (%)Elongation (%) 1515 1212 1616 1414 1212 1414
중량 (kg)Weight (kg) 7.87.8 7.47.4 7.27.2 6.86.8 12.412.4 13.213.2
상기 표 26에서 보듯이, 실시예 95~98의 경우 비교예 32,33 대비 선팽창계수, 인장강도, 신율, 비중 등 모든 물성이 우수한 것으로 나타나서 자동차 휠의 림의 재질로 사용되기에 적합한 것으로 판명되었다.As shown in Table 26, in the case of Examples 95-98, all physical properties such as coefficient of linear expansion, tensile strength, elongation, specific gravity, etc. were superior to Comparative Examples 32 and 33, and thus, were found to be suitable for use as the material of the rim of an automobile wheel. .
실시예 99Example 99
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 11배의 몰비이고, 중합온도 80℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.2dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조 후, 사출성형하여 전력선 결속용 브라켓 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 11 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 80 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.2 dl / g, a melt index (MI) of 60 g / 10 min, and a MWD of 2.0. The polyketone terpolymer prepared above was 40mm in diameter operating at 250rpm, and was manufactured in pellet form on an extruder using a biaxial screw having L / D = 32, followed by injection molding to prepare a bracket for power line binding bracket. It was.
실시예 100Example 100
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 전력선 결속용 브라켓 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.0. The polyketone terpolymer prepared above was 40 mm in diameter, operating at 250 rpm, and manufactured by pelletizing on an extruder using a biaxial screw having a diameter of L / D = 32 to prepare a bracket for power line binding bracket. .
실시예 101Example 101
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 9배의 몰비이고, 중합온도 74℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.6dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 전력선 결속용 브라켓 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 9 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 74 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.6 dl / g, a MI (Melt index) of 60 g / 10 min, and a MWD of 2.0. The polyketone terpolymer prepared above was 40 mm in diameter, operating at 250 rpm, and manufactured by pelletizing on an extruder using a biaxial screw having a diameter of L / D = 32 to prepare a bracket for power line binding bracket. .
실시예 102Example 102
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 1.8 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 전력선 결속용 브라켓시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.4 dl / g, a MI (Melt index) of 60 g / 10 min, and an MWD of 1.8. The polyketone terpolymer prepared above was 40 mm in diameter operating at 250 rpm, and manufactured by pelletizing on an extruder using a biaxial screw having an L / D = 32 to produce a power line binding bracket specimen. .
실시예 103Example 103
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46 대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.2 이었다. 상기에서 제조된 폴리케톤 터폴리머를 250rpm으로 작동하는 직경 40mm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조하여 사출성형하여 전력선 결속용 브라켓시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46 to 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano), 1.4 dl / g, MI (Melt index) of 60 g / 10 min, and MWD of 2.2. The polyketone terpolymer prepared above was 40 mm in diameter operating at 250 rpm, and manufactured by pelletizing on an extruder using a biaxial screw having an L / D = 32 to produce a power line binding bracket specimen. .
비교예 34Comparative Example 34
실시예 99의 폴리케톤 대신 고충격 PBT를 이용하는 것을 제외하고는 실시예 99와 동일하다.Same as Example 99 except that high impact PBT is used instead of the polyketone of Example 99.
물성평가Property evaluation
상기 실시예의 폴리케톤 수지 조성물 펠렛을 (사출) 성형하여 전력선 결속용 브라켓 시편을 제조한 다음, 비교예의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 27에 나타내었다.The polyketone resin composition pellets of the above examples were molded (injected) to prepare bracket specimens for power line binding, and then evaluated for physical properties in the following manner compared to the products of Comparative Examples, and the results are shown in Table 27 below.
1. 아이조드 충격강도: ASTM D256에 의거하여 실시하였다.1. Izod impact strength: It was conducted according to ASTM D256.
2. cycle time(사출성형성 평가 sec) : 실시예 혹은 비교예에서 제조된 펠렛이 용융 후에 결정화 되기까지의 시간을 sec 단위로 측정하였다.2. Cycle time (injection molding evaluation sec): The time until the pellets prepared in Examples or Comparative Examples before the crystallization after melting was measured in seconds.
3. 치수 변화율 평가3. Evaluation of dimensional change rate
ASTM D-638에 의해 300℃에서 2시간 열처리하여, 상기 처리전후의 보빈용 시편의 평행한 부분의 폭을 슬라이드캘리퍼에 의해 측정하여 치수변화를 관측하였다.After heat treatment at 300 ° C. for 2 hours by ASTM D-638, the width of parallel portions of the bobbin test specimens before and after the treatment was measured by a slide caliper to observe the dimensional change.
실시예 99Example 99 실시예 100Example 100 실시예 101Example 101 실시예 102Example 102 실시예 103Example 103 비교예 34Comparative Example 34
물성Properties IV : 1.2MWD : 2.0IV: 1.2MWD: 2.0 IV : 1.4MWD : 2.0IV: 1.4 MWD: 2.0 IV : 1.6MWD : 2.0IV: 1.6MWD: 2.0 IV : 1.4MWD : 1.8IV: 1.4 MWD: 1.8 IV : 1.4MWD : 2.2IV: 1.4 MWD: 2.2 고충격 PBTHigh Impact PBT
충격강도 (kJ/m2)Impact strength (kJ / m2) 99 1010 1111 9.59.5 9.79.7 6.56.5
cycle time(sec)cycle time (sec) 1414 1515 1717 1616 1616 2525
치수변화율Dimensional change rate 1.3%1.3% 1.2%1.2% 1.2%1.2% 1.4%1.4% 1.3%1.3% 5.2%5.2%
상기 표27 에 따르면 비교예34에 비하여 실시예는 충격강도가 더 높아서 내충격성이 더 우수한 것으로 나타났다. 또한, cycle time 이 단축되어 생산성이 향상되는 것으로 나타났다. 이에 더해, 치수변화율이 낮아 치수안정성이 우수한 것으로 평가되었다. 따라서, 전력선 결속용 브라켓으로 사용하기에 실시예가 더 우수한 것으로 나타났다.According to Table 27 above, the Example had a higher impact strength than the Comparative Example 34, and thus the impact resistance was better. In addition, the cycle time was shortened and productivity was improved. In addition, it was evaluated that the dimensional stability was excellent because of the low rate of dimensional change. Thus, the embodiment was found to be better for use as a power line binding bracket.
실시예 104Example 104
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 또한 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 48g/10min 이었다. 상기에서 제조된 폴리케톤 터폴리머 70중량%와 유리섬유 30중량%를 250rpm으로 작동하는 직경 2.5cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에서 펠렛(pellet) 상으로 제조 후 사출성형하여 전자기기커버 시편을 제조하였다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. The polyketone terpolymer had a melting point of 220 ° C., LVN measured at 25 ° C. with HFIP (hexa-fluoroisopropano) at 1.4 dl / g, and a MI (Melt index) of 48 g / 10 min. 70% by weight of the polyketone terpolymer and 30% by weight of glass fibers prepared above were injected into a pellet on a extruder using a biaxial screw having a diameter of 2.5 cm, operating at 250 rpm, and having an L / D = 32. Molded to prepare an electronic device cover specimen.
실시예 105Example 105
폴리케톤 터폴리머의 고유점도를 1.1 dl/g 로 조절한 것을 제외하고는 실시예 104와 동일하다.Same as Example 104 except that the intrinsic viscosity of the polyketone terpolymer was adjusted to 1.1 dl / g.
실시예 106Example 106
폴리케톤 터폴리머의 고유점도를 2.0 dl/g 로 조절한 것을 제외하고는 실시예 104와 동일하다.It was the same as Example 104 except the intrinsic viscosity of the polyketone terpolymer was adjusted to 2.0 dl / g.
실시예 107Example 107
폴리케톤 터폴리머 90중량% 와 유리섬유 10중량%를 제외하고는 실시예 104와 동일하다.Same as Example 104 except for 90 wt% of polyketone terpolymer and 10 wt% of glass fiber.
실시예 108Example 108
폴리케톤 터폴리머 60중량% 와 유리섬유 40중량%를 제외하고는 실시예 104와 동일하다.Same as Example 104 except for 60 wt% of polyketone terpolymer and 40 wt% of glass fiber.
비교예 35Comparative Example 35
기존에 전자기기 커버의 소재로 사용되던 나일론6 70중량%와 유리섬유30중량%를 블렌딩한 제품을 이용한 것을 제외하고는 실시예 104와 동일하다.Except for using a product in which 70% by weight of nylon 6 and 30% by weight of glass fiber, which was used as a material of the electronic device cover, was used in the same manner as in Example 104.
비교예 36Comparative Example 36
기존에 전자기기 커버의 소재로 사용되던 폴리카보네이트 70중량%와 유리섬유 30중량%를 블렌딩한 제품을 제품을 이용한 것을 제외하고는 실시예 104와 동일하다.Except for using a product that is a blend of 70% by weight of polycarbonate and 30% by weight of glass fiber used as a material of the electronic device cover is the same as in Example 104.
물성평가Property evaluation
상기 실시예의 제조된 펠렛을 사출 성형하여 전자기기 커버용 시편을 제조한 다음, 비교예의 시편과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 28에 나타내었다.After injection molding the prepared pellets of the above Example to prepare a specimen for an electronic device cover, and compared to the specimen of the comparative example to evaluate the physical properties in the following manner, the results are shown in Table 28 below.
1. 아이조드 충격강도 평가: ASTM D256에 의거하여 실시하였다.1. Izod impact strength evaluation: It was performed according to ASTM D256.
2. 치수안정성 평가 : 온도 50℃, 상대습도 90%의 조건에서 수직 및 수평방향에 대해 MS211-47에 따라 평가하였다.2. Evaluation of Dimensional Stability: Evaluation was made in accordance with MS211-47 for the vertical and horizontal directions at a temperature of 50 ° C and a relative humidity of 90%.
실시예와 비교예의 물성은 하기 표 28과 같았다.Physical properties of the Examples and Comparative Examples were as shown in Table 28 below.
항목Item 실시예 104Example 104 실시예 105Example 105 실시예 106Example 106 실시예 107Example 107 실시예 108Example 108 비교예 35Comparative Example 35 비교예 36Comparative Example 36
조성Furtherance 폴리케톤 70%+ Glass Fiber 30%Polyketone 70% + Glass Fiber 30% 폴리케톤 70%+ Glass Fiber 30%Polyketone 70% + Glass Fiber 30% 폴리케톤 70%+ Glass Fiber 30%Polyketone 70% + Glass Fiber 30% 폴리케톤 90%+ Glass Fiber 10%Polyketone 90% + Glass Fiber 10% 폴리케톤 60%+ Glass Fiber 40%Polyketone 60% + Glass Fiber 40% 나일론6 70%+ Glass Fiber 30%Nylon 6 70% + Glass Fiber 30% 폴리카보네이트 70%+ Glass Fiber 30%Polycarbonate 70% + Glass Fiber 30%
충격강도 (kJ/m2)Impact strength (kJ / m2) 1616 1616 1616 1515 1818 66 1414
제품 변형율 (%, 수직)Product strain (%, vertical) 0.080.08 0.080.08 0.090.09 0.050.05 0.100.10 0.80.8 0.070.07
제품 변형율 (%, 수평)Product strain (%, horizontal) 0.050.05 0.050.05 0.060.06 0.030.03 0.080.08 0.750.75 0.060.06
※ 제품 변형율의 측정조건, 50℃, 상대습도 90%※ Measurement condition of product strain, 50 ℃, relative humidity 90%
상기 표 28에서 보듯이, 실시예의 경우 비교예 대비 충격강도 값이 더 높아 내충격성이 매우 우수한 것으로 평가되었다. 또한 치수안정성도 우수한 것으로 나타났다.As shown in Table 28, in the case of the Example was higher impact strength value than the comparative example was evaluated as very excellent impact resistance. In addition, dimensional stability was found to be excellent.
따라서, 본 발명의 실시예를 통해 제조된 폴리케톤 전자기기 커버는 내충격성 및 치수안정성이 매우 우수한 전자기기 커버로 적용하기에 매우 적합하였다.Therefore, the polyketone electronic device cover manufactured through the embodiment of the present invention was very suitable for application as an electronic device cover having excellent impact resistance and dimensional stability.
실시예 109Example 109
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 일산화탄소는 50mol%이고, 에틸렌은 46mol%이며, 프로필렌은 4mol%이었다. 또한, 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이고, 팔라듐 잔존량이 5ppm 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. In the polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. In addition, the melting point of the polyketone terpolymer is 220 ℃, LVN measured at 25 ℃ by hexa-fluoroisopropano (HFIP) is 1.4dl / g, MI (Melt index) is 60g / 10min, MWD is 2.0, The residual amount of palladium was 5 ppm.
상기 제조된 폴리케톤 터폴리머 70중량%와 유리섬유 30중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 전기전자제품용 뚜껑의 시편을 제조하였다.70 wt% of the prepared polyketone terpolymer and 30 wt% of glass fiber were prepared to prepare a composition, and the prepared composition was operated on an extruder by using a biaxial screw having a diameter of 40 cm and a L / D = 32 operating at 250 rpm. After the pellet (pellet) was prepared, and injection molding to prepare a specimen of the lid for electrical and electronic products.
실시예 110Example 110
실시예 109와 동일한 방법으로 제조된 폴리케톤 터폴리머 75중량%와 유리섬유 25중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 전기전자제품용 뚜껑의 시편을 제조하였다. 75 wt% polyketone terpolymer prepared in the same manner as in Example 109 and 25 wt% glass fiber were prepared to prepare a composition, and the prepared composition was biaxially formed with a diameter of 40 cm and a L / D = 32 operating at 250 rpm. The pellets were prepared on pellets on an extruder using a screw, and then injection molded to prepare specimens of lids for electrical and electronic products.
실시예 111Example 111
실시예 109와 동일한 방법으로 제조된 폴리케톤 터폴리머 80중량%와 유리섬유 20중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 전기전자제품용 뚜껑의 시편을 제조하였다. 80 wt% polyketone terpolymer and 20 wt% glass fiber prepared in the same manner as in Example 109 were prepared to prepare a composition, and the resulting composition was 40 cm in diameter, operating at 250 rpm, and biaxial with L / D = 32. The pellets were prepared on pellets on an extruder using a screw, and then injection molded to prepare specimens of lids for electrical and electronic products.
실시예 112Example 112
실시예 109와 동일한 방법으로 제조된 폴리케톤 터폴리머 85중량%와 유리섬유 15중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 전기전자제품용 뚜껑의 시편을 제조하였다. 85 wt% of polyketone terpolymer and 15 wt% of glass fiber were prepared in the same manner as in Example 109, to prepare a composition, and the resulting composition was 40 cm in diameter, operating at 250 rpm, and biaxially having L / D = 32. The pellets were prepared on pellets on an extruder using a screw, and then injection molded to prepare specimens of lids for electrical and electronic products.
비교예 37Comparative Example 37
나일론 66 수지 70중량%와 유리섬유 30중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 전기전자제품용 뚜껑의 시편을 제조하였다.70 wt% of nylon 66 resin and 30 wt% of glass fiber were prepared to prepare a composition, and the prepared composition was pelleted on an extruder using a biaxial screw having a diameter of 40 cm and operating at 250 rpm, and having an L / D = 32. And then injection molded to prepare specimens of lids for electrical and electronic products.
물성 평가Property evaluation
상기 실시예 109 내지 112 및 비교예 37에서 각각 제조된 시편을 하기와 같은 방법으로 물성을 평가하였으며, 그 결과는 하기 표 29에 나타내었다.The physical properties of the specimens prepared in Examples 109 to 112 and Comparative Example 37 were evaluated in the following manner, and the results are shown in Table 29 below.
1. 아이조드 충격강도 평가 : ASTM D256에 의거하여 실시하였다.1. Izod impact strength evaluation: It was performed according to ASTM D256.
2. 제품 흡습율 평가 : 온도 50℃, 상대습도 90%에서 10일동안 처리한 후 수분함유량을 측정하였다.2. Evaluation of Product Hygroscopicity: The moisture content was measured after 10 days of treatment at a temperature of 50 ° C. and a relative humidity of 90%.
3. 내수성 물성유지율 평가 : 시편은 표준 조건(25℃, 65%RH 상대습도, 10일 동안 보관)과 고온 고습 조건(50℃, 90%RH 상대습도, 10일동안 보관)에서 처리 후, ASTM D638에 의거하여 인장강도를 각각 측정하였으며, 각 처리 샘플당 수직 및 수평 방향으로 5회씩 측정한 값의 평균치를 취하였다.3. Evaluation of water resistance retention: Specimens were treated under standard conditions (25 ℃, 65% RH relative humidity, storage for 10 days) and high temperature and high humidity conditions (50 ℃, 90% RH relative humidity, storage for 10 days), followed by ASTM Tensile strengths were measured on the basis of D638, and the average of the five measurements in the vertical and horizontal directions for each treated sample was taken.
항목Item 실시예109Example 109 실시예110Example 110 실시예111Example 111 실시예112Example 112 비교예37Comparative Example 37
제품 흡습율 (%, 50℃, 90%RH)Product Hygroscopicity (%, 50 ℃, 90% RH) 1.01.0 0.90.9 1.11.1 1.21.2 3.03.0
제품 내수성 (%, 인장강도유지율)Product water resistance (%, tensile strength retention) 9090 8989 8787 8686 4040
충격강도 (kJ/m2)Impact strength (kJ / m2) 1717 1515 1515 1515 55
상기 표 29에서 알 수 있는 바와 같이, 실시예의 경우 비교예 대비 충격강도가 향상(15kJ/m2이상)되었고, 50℃, 90%RH 상대습도에서 측정한 인장강도 유지율이 85% 이상으로 물성 유지율이 우수한 것으로 나타났다.As can be seen in Table 29, in the case of the Example, the impact strength was improved (more than 15 kJ / m2) compared to the comparative example, and the tensile strength retention measured at 50 ° C. and 90% RH relative humidity was 85% or more. Found to be excellent.
따라서, 본 발명에 따른 전기전자제품용 뚜껑은 내수성 및 물성 유지율이 우수하고, 이에 따라 압력밥솥용으로 적용하기에 매우 적합하다.Therefore, the lid for electric and electronic products according to the present invention is excellent in water resistance and physical property retention, and thus is very suitable for application for pressure cookers.
실시예 113Example 113
초산 팔라듐, 트리플루오르 초산의 음이온 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로 구성되는 촉매 조성물의 존재하에, 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머(terpolymer)를 메탄올 100 중량부에 2 중량부의 물이 첨가된 70~90의 용매에서 중합하였다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 한편, 상기 제조된 폴리케톤 터폴리머의 융점은 220℃이고, 1,1,1,3,3,3-HFIP에 측정된 고유점도(LVN)는 1.5 dl/g이었으며, 분자량 분포는 2.0이었다.Palladium acetate, anion of trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) In the presence of the resulting catalyst composition, a linear terpolymer of carbon monoxide, ethylene and propylene was polymerized in a solvent of 70-90 in which 2 parts by weight of water was added to 100 parts by weight of methanol. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. On the other hand, the melting point of the prepared polyketone terpolymer is 220 ℃, the intrinsic viscosity (LVN) measured in 1,1,1,3,3,3-HFIP was 1.5 dl / g, the molecular weight distribution was 2.0.
상기 제조된 폴리케톤 터폴리머 95중량% 및 폴리 헥사메틸렌이소프탈아미드 5중량%를 블렌딩 하여 폴리케톤 조성물을 제조하였다. The polyketone composition was prepared by blending 95% by weight of the prepared polyketone terpolymer and 5% by weight of poly hexamethyleneisophthalamide.
실시예 114Example 114
폴리케톤 터폴리머 80중량% 및 폴리 헥사메틸렌이소프탈아미드 20중량%를 제외하고 실시예 113과 동일하다.Same as Example 113 except for 80 wt% polyketone terpolymer and 20 wt% poly hexamethyleneisophthalamide.
실시예 115Example 115
폴리케톤 터폴리머 70중량% 및 폴리 헥사메틸렌이소프탈아미드 30중량%를 제외하고 실시예 113과 동일하다.Same as Example 113 except for 70 weight percent polyketone terpolymer and 30 weight percent poly hexamethyleneisophthalamide.
비교예 38Comparative Example 38
폴리케톤 100 중량%를 제외하고 실시예 113과 동일하다. Same as Example 113 except for 100% by weight of polyketone.
비교예 39Comparative Example 39
Rhodia 사 PA66 80 중량%(A218V30 제품) 및 폴리 헥사메틸렌이소프탈아미드 20중량%을 상기 실시예 113과 동일한 방법으로 시편을 제조하였다.Specimens were prepared in the same manner as in Example 113 above, with 80% by weight of Rhodia PA66 (manufactured by A218V30) and 20% by weight of poly hexamethyleneisophthalamide.
물성평가Property evaluation
상기 실시예의 제조된 폴리케톤 조성물을 시편으로 제조한 다음, 비교예의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 30에 나타내었다.The prepared polyketone composition of the Example was prepared as a specimen, and then evaluated for physical properties in the following manner compared to the product of the comparative example, the results are shown in Table 30 below.
1. 인장강도 평가 : ASTM D638에 의거하여 실시하였다.1. Tensile strength evaluation: It was performed according to ASTM D638.
2. 굴곡강도 평가 : ASTM D790에 의거하여 실시하였다2. Flexural strength evaluation: based on ASTM D790
3. 굴곡탄성율 평가 : ASTM D790에 의거하여 실시하였다.3. Flexural modulus evaluation: It was carried out in accordance with ASTM D790.
4. 충격강도평가(노치드 아이조드) : ASTM D236에 의거하여 실시하였다.4. Impact strength evaluation (notched Izod): It was carried out according to ASTM D236.
항목Item PK/6I ratioPK / 6I ratio 작업성Workability MI (g/10min)MI (g / 10min) 인장강도 (MPa)Tensile Strength (MPa) 파단신율 (%)Elongation at Break (%) 굴곡강도 (MPa)Flexural Strength (MPa) 굴곡탄성률 (MPa)Flexural Modulus (MPa) 충격강도 (kJ/m2) Impact strength (kJ / m 2)
실시예 113Example 113 95:595: 5 우수Great 5757 6565 301301 6565 1,7581,758 10.310.3
실시예 114Example 114 80:2080:20 우수Great 2626 6868 173173 7575 1,9181,918 8.68.6
실시예 115Example 115 70:3070:30 우수Great 5050 7171 3232 8383 2,0522,052 7.47.4
비교예 38Comparative Example 38 100:0100: 0 나쁨Bad 7676 6464 426426 6262 1,6491,649 9.69.6
비교예 39Comparative Example 39 PA6IPA6I -- -- 7373 -- 109109 2,8412,841 7.17.1
상기 표 30에서 보듯이, 실시예들의 경우 비교예 38, 39에 비하여 충격강도는 일정수준 이상을 유지하면서 굴곡강도 및 굴곡탄성율이 우수한 것으로 나타났다.As shown in Table 30, in the case of Examples compared to Comparative Examples 38 and 39, the impact strength was maintained while maintaining a certain level or more was excellent in flexural strength and flexural modulus.
특히, 굴곡강도는 65 내지 90MPa으로 우수하고, 굴곡탄성률은 1,700MPa 이상이며, 충격강도는 7kJ/m2 이상으로 우수하였다.In particular, the flexural strength was excellent at 65 to 90MPa, the flexural modulus was 1700 MPa or more, and the impact strength was excellent at 7 kJ / m 2 or more.
따라서, 비교예 38, 39보다는 실시예들을 통해 제조된 폴리케톤 조성물은 굴곡특성이 우수한바, 산업용으로 사용되는 열가소성 플라스틱으로 사용되기에 적합한 것으로 평가되었다.Therefore, the polyketone composition prepared according to Examples rather than Comparative Examples 38 and 39 was excellent in the bending property, it was evaluated to be suitable for use as a thermoplastic plastic used for industrial use.
실시예 116Example 116
초산 팔라듐, 트리플루오르 초산의 음이온 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로 구성되는 촉매 조성물의 존재하에, 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머(terpolymer)를 메탄올 100중량부 대비 물5중량부 이고, 70~90℃의 용매에서 중합하였다. 상기에서 제조된 폴리케톤 터폴리머에서 에틸렌과 프로펜의 몰비는 46대 4였다. 한편, 상기 제조된 폴리케톤 터폴리머의 융점은 220℃이고, 1,1,1,3,3,3-HFIP에 측정된 고유점도(LVN)는 1.4 dl/g이었다.Palladium acetate, anion of trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) In the presence of the catalyst composition, a linear terpolymer of carbon monoxide, ethylene and propylene was polymerized in a solvent at 70 to 90 ° C. with 5 parts by weight of water relative to 100 parts by weight of methanol. The molar ratio of ethylene and propene in the polyketone terpolymer prepared above was 46: 4. Meanwhile, the melting point of the prepared polyketone terpolymer was 220 ° C., and the intrinsic viscosity (LVN) measured in 1,1,1,3,3,3-HFIP was 1.4 dl / g.
상기 제조된 폴리케톤 터폴리머 70중량% 및 폴리에스테르는 30중량%를 블렌딩 하여 폴리케톤 조성물을 제조하였다. 70 wt% of the prepared polyketone terpolymer and 30 wt% of polyester were blended to prepare a polyketone composition.
실시예 117Example 117
폴리케톤 터폴리머 60중량%, 폴리에스테르 40중량%를 제외하고는 실시예 116과 동일하다.Same as Example 116 except for 60 weight percent polyketone terpolymer and 40 weight percent polyester.
실시예 118Example 118
폴리케톤 터폴리머 80중량%, 폴리에스테르 20중량%를 제외하고는 실시예 116과 동일하다.Same as Example 116 except for 80 wt% polyketone terpolymer and 20 wt% polyester.
비교예 40Comparative Example 40
실시예 116의 폴리케톤 100중량%를 사용한 것을 제외하고는 실시예 116과 동일한 방법으로 시편을 제조하였다.A specimen was prepared in the same manner as in Example 116 except that 100 wt% of the polyketone of Example 116 was used.
물성평가Property evaluation
상기 실시예의 제조된 폴리케톤 조성물을 시편으로 제조한 다음, 비교예의 제품과 대비하여 아래와 같은 방법으로 물성을 평가하고, 그 결과를 하기 표 31에 나타내었다.The prepared polyketone composition of the Example was prepared as a specimen, and then evaluated for physical properties in the following manner compared to the product of the comparative example, the results are shown in Table 31 below.
1. 흡습율 평가 : 85℃ 상대습도 85%RH에서 일주일동안 시편을 방치 후 흡습율을 측정하였다.1. Evaluation of moisture absorption: After leaving the specimen for one week at 85 ℃ relative humidity 85% RH, the moisture absorption was measured.
2. 치수 변화율 평가 : ASTM D-638에 의해 300℃에서 2시간 열처리하여, 상기 처리전후의 시편의 사출방향부분 및 직각방향의 폭을 슬라이드캘리퍼에 의해 측정하여 치수변화를 관측하였다.2. Evaluation of dimensional change rate: After heat treatment at 300 DEG C for 2 hours by ASTM D-638, the width in the injection direction and the right angle direction of the specimen before and after the treatment was measured by a slide caliper to observe the dimensional change.
실시예 116Example 116 실시예 117Example 117 실시예 118Example 118 비교예 40Comparative Example 40
조성Furtherance PK70%/PE30%PK70% / PE30% PK60%/PE40%PK60% / PE40% PK80%/PE20%PK80% / PE20% PK100%PK100%
흡습율 (질량%)Hygroscopicity (mass%) 0.500.50 0.510.51 0.490.49 1.031.03
치수변화율 (%)-사출방향Rate of change of dimension (%)-Injection direction 1.01.0 1.31.3 1.21.2 3.23.2
치수변화율 (%)-직각방향Dimensional rate of change (%)-perpendicular 0.130.13 0.150.15 0.140.14 1.231.23
상기 표 31에서 보듯이, 실시예의 경우 비교예 40에 비하여 내습성 및 치수안정성(사출방향부분 및 직각방향의 폭을 슬라이드캘리퍼에 의해 측정 시, 각각 2.0%이하 및 0.5%이하)이 우수한 것으로 나타났다.As shown in Table 31, the moisture resistance and the dimensional stability (2.0% or less and 0.5% or less, respectively, when measured by the slide caliper in the direction of the injection direction and the right angle) were superior to the comparative example 40 for the example. .
따라서, 비교예 40보다는 실시예를 통해 제조된 폴리케톤 조성물은 내습성, 치수안정성이 우수한바, 산업용으로 사용되는 열가소성 플라스틱으로 사용되기에 적합한 것으로 평가되었다.Therefore, the polyketone composition prepared according to Examples rather than Comparative Example 40 was excellent in moisture resistance and dimensional stability, it was evaluated to be suitable for use as a thermoplastic plastic used for industrial use.
실시예 119Example 119
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 일산화탄소는 50mol%이고, 에틸렌은 46mol%이며, 프로필렌은 4mol%이었다. 또한, 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 2.0dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이고, 팔라듐 잔존량이 5ppm 이었다. Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. In the polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. In addition, the melting point of the polyketone terpolymer is 220 ℃, LVN measured at 25 ℃ by hexa-fluoroisopropano (HFIP) is 2.0dl / g, MI (Melt index) is 60g / 10min, MWD is 2.0, The residual amount of palladium was 5 ppm.
상기 제조된 폴리케톤 터폴리머 58중량%에 유리섬유 30중량%, 트리메틸 포스페이트 7중량% 및 나일론 6I 5중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 노트북 하단 하우징의 시편을 제조하였다. 58 wt% of the prepared polyketone terpolymer, 30 wt% of glass fiber, 7 wt% of trimethyl phosphate, and 5 wt% of nylon 6I were added to prepare a composition, and the prepared composition was 40 cm in diameter operating at 250 rpm, and L / A biaxial screw with a D = 32 was used to produce pellets on an extruder and then injection molded to prepare specimens of a notebook bottom housing.
실시예 120Example 120
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 일산화탄소는 50mol%이고, 에틸렌은 46mol%이며, 프로필렌은 4mol%이었다. 또한, 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.6dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이고, 팔라듐 잔존량이 3ppm 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. In the polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. In addition, the melting point of the polyketone terpolymer is 220 ℃, LVN measured at 25 ℃ by HFIP (hexa-fluoroisopropano) is 1.6dl / g, MI (Melt index) is 60g / 10min, MWD is 2.0, The residual amount of palladium was 3 ppm.
상기 제조된 폴리케톤 터폴리머 58중량%에 유리섬유 30중량%, 트리메틸 포스페이트 7중량% 및 나일론 6I 5중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 노트북 하단 하우징의 시편을 제조하였다. 58 wt% of the prepared polyketone terpolymer, 30 wt% of glass fiber, 7 wt% of trimethyl phosphate, and 5 wt% of nylon 6I were added to prepare a composition, and the prepared composition was 40 cm in diameter operating at 250 rpm, and L / A biaxial screw with a D = 32 was used to produce pellets on an extruder and then injection molded to prepare specimens of a notebook bottom housing.
실시예 121Example 121
일산화탄소와 에틸렌과 프로펜으로 이루어진 선상 교대 폴리케톤 터폴리머는 초산 팔라듐, 트리 플루오르 초산 및 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)으로부터 생성한 촉매 조성물의 존재 하에서 제조했다. 상기에서 팔라듐 대비 트리 플루오르 초산의 함량은 10배의 몰비이고, 중합온도 78℃의 1단계와 84℃의 2단계를 거친다. 상기에서 제조된 폴리케톤 터폴리머에서 일산화탄소는 50mol%이고, 에틸렌은 46mol%이며, 프로필렌은 4mol%이었다. 또한, 상기 폴리케톤 터폴리머의 융점은 220℃이고, HFIP(hexa-fluoroisopropano)로 25℃에 측정한 LVN이 1.4dl/g이며, MI(Melt index)가 60g/10min이며, MWD가 2.0 이고, 팔라듐 잔존량이 6ppm 이었다.Linear alternating polyketone terpolymers consisting of carbon monoxide, ethylene and propene include palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis ( Prepared in the presence of a catalyst composition produced from bis (2-methoxyphenyl) phosphine). In the above, the content of trifluoroacetic acid relative to palladium is 10 times the molar ratio, and the first stage and the second stage of 84 ℃ polymerization temperature 78 ℃. In the polyketone terpolymer prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. In addition, the melting point of the polyketone terpolymer is 220 ℃, LVN measured at 25 ℃ by hexa-fluoroisopropano (HFIP) is 1.4dl / g, MI (Melt index) is 60g / 10min, MWD is 2.0, The residual amount of palladium was 6 ppm.
상기 제조된 폴리케톤 터폴리머 58중량%에 유리섬유 30중량%, 트리메틸 포스페이트 7중량% 및 나일론 6I 5중량%를 투입하여 조성물을 제조하고, 제조된 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 노트북 하단 하우징의 시편을 제조하였다. 58 wt% of the prepared polyketone terpolymer, 30 wt% of glass fiber, 7 wt% of trimethyl phosphate, and 5 wt% of nylon 6I were added to prepare a composition, and the prepared composition was 40 cm in diameter operating at 250 rpm, and L / A biaxial screw with a D = 32 was used to produce pellets on an extruder and then injection molded to prepare specimens of a notebook bottom housing.
비교예 41Comparative Example 41
듀폰사 제조된 나일론 66 70중량%와 나이론 6T 30중량%의 나일론 수지 조성물에 대하여 상기 나일론 수지 조성물 35중량% 대비 유리섬유 50중량%와 트리메틸 포스페이트 15중량%를 포함하는 조성물을 250rpm으로 작동하는 직경 40cm이며, L/D=32인 2축 스크류를 이용하여 압출기 상에 펠렛(pellet) 상으로 제조한 후, 사출성형하여 노트북 하단 하우징의 시편을 제조하였다. A diameter of 50 wt% glass fiber and 15 wt% trimethyl phosphate compared to 35 wt% of the nylon resin composition based on 70 wt% of nylon 66 and 30 wt% of nylon 6T manufactured by DuPont was operated at 250 rpm. The pellets were prepared on pellets on an extruder using a biaxial screw having a diameter of 40 cm and L / D = 32, and then injection molded to prepare specimens of a notebook lower housing.
물성 평가Property evaluation
실시예 119 내지 121 및 비교예 41에서 각각 제조한 노트북 하단 하우징 시편을 하기와 같은 방법으로 물성을 평가하였고, 그 결과를 하기 표 32에 나타내었다.The physical properties of the notebook lower housing specimens prepared in Examples 119 to 121 and Comparative Example 41 were evaluated in the following manner, and the results are shown in Table 32 below.
1. 굴곡탄성율: ASTM D790에 의거하여 실시하였다.1. Flexural modulus: It was performed according to ASTM D790.
2. 저온충격강도 평가: ASTM D256에 의거하여 실시하였다. 저온충격강도는 -40℃에서 30일간 저온챔버에 넣어둔 후, 정확한 측정을 위하여 저온 챔버에서 꺼내 10초 내에 측정하였다.2. Low temperature impact strength evaluation: It was carried out in accordance with ASTM D256. The low temperature impact strength was placed in a low temperature chamber at -40 ° C. for 30 days, and then taken out of the low temperature chamber for 10 minutes to measure accurately.
3. 낙구 충격강도: 사출 성형으로 제작한 시험편(100mm두께)을 사용하여 낙구 충격시험을 행하였다. UL1956 수직 낙구 시험법의 시험기를 사용하고, 500g의 강구를 사용했을 때의 한계 파괴 높이를 조사하였다.3. Falling ball impact strength: The falling ball impact test was done using the test piece (100 mm thickness) produced by injection molding. Using the tester of UL1956 Vertical Fall Ball Test, the limit breaking height when 500 g of steel balls were used was investigated.
항목Item 실시예 119Example 119 실시예 120Example 120 실시예 121Example 121 비교예 41Comparative Example 41
굴곡탄성율(MPa)Flexural modulus (MPa) 8,9008,900 8,8008,800 8,6008,600 7,2007,200
저온충격강도(kJ/m2)Low temperature impact strength (kJ / m 2 ) 12.412.4 11.811.8 11.511.5 7.57.5
낙구 충격강도(cm)Falling ball impact strength (cm) 130130 120120 100100 6060
상기 표 32에 따르면 비교예에 비하여 실시예의 굴곡탄성율와 저온충격강도가 높았으므로, 강도가 더 향상된 것으로 평가되었다.According to Table 32, the flexural modulus and low temperature impact strength of the Example were higher than those of the comparative example, and thus, the strength was evaluated to be improved.
또한, 본 발명의 폴리케톤 수지 조성물을 포함한 실시예의 경우 낙구 충격 강도에 있어서 비교예 대비하여 훨씬 뛰어난 결과가 나타났다. In addition, in the case of the embodiment including the polyketone resin composition of the present invention, much superior results were found in comparison with the comparative example in falling ball impact strength.
따라서, 본 발명에 따른 노트북 하단 하우징은 기존의 노트북 하단 하우징 소재로 사용되는 비교예의 경우보다 우수한 굴곡탄성율(8,000MPa 이상)과 내충격성(저온 충격강도가 11.0kJ/m2이상)의 기계적 특성을 가지므로, 노트북 하단 하우징용으로 적용하기에 더욱 적합하다.Accordingly, the notebook bottom housing according to the present invention exhibits excellent mechanical properties such as flexural modulus (8,000 MPa or more) and impact resistance (low temperature impact strength of 11.0 kJ / m 2 or more) than the comparative example used as a conventional notebook bottom housing material. It is more suitable for application for notebook bottom housing.

Claims (147)

  1. 하기 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, 분자량 분포가 1.5 내지 2.5이고, y/x가 0.03 내지 0.3인 선상 교대 폴리케톤과 유리섬유, 무기충전제, 미네랄 보강제를 포함하여 구성되는 것을 특징으로 한 내충격성이 향상된 폴리케톤 수지 조성물.A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), the molecular weight distribution of 1.5 to 2.5, y / x of 0.03 to 0.3 linear alternating polyketone and glass fiber, inorganic filler, Impact resistance polyketone resin composition, characterized in that comprising a mineral reinforcing agent.
    -[-CH2CH2-CO]x- (1)-[-CH2CH2-CO] x- (1)
    -[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
    (x, y는 폴리머 중의 일반식 (1) 및 (2)의 각각의 몰%를 나타낸다.(x, y represents each mol% of General Formula (1) and (2) in a polymer.
  2. 제 1항에 있어서,The method of claim 1,
    상기 폴리케톤 수지 조성물은 폴리우레탄 수지, 폴리카보네이트 수지를 더 포함하는 것을 특징으로 한 내충격성이 우수한 폴리케톤 수지 조성물.The polyketone resin composition is excellent polyketone resin composition, characterized in that it further comprises a polyurethane resin, polycarbonate resin.
  3. 제 2항에 있어서,The method of claim 2,
    상기 폴리케톤 수지 조성물은 폴리아미드 6수지와, 고무, ASA 및 설폰아미드계 가소제를 더 포함하는 것을 특징으로 한 내충격성이 우수한 폴리케톤 수지 조성물.The polyketone resin composition is a polyketone resin composition excellent in impact resistance, characterized in that it further comprises a polyamide 6 resin, rubber, ASA and sulfonamide plasticizer.
  4. 제 1항 내지 제 3항 중 어느 하나의 항에 있어서,The method according to any one of claims 1 to 3,
    상기 폴리케톤 수지 조성물은 상기 폴리케톤 공중합체 100 중량부 대비 유리섬유, 무기충전제, 미네랄 보강제, 폴리우레탄 수지, 폴리카보네이트 수지, 폴리아미드 6수지와, 고무, ASA 및 설폰아미드계 가소제가 5 내지 50 중량부 만큼 단독 또는 혼합하여 첨가되는 것을 특징으로 한 내충격성이 우수한 폴리케톤 수지 조성물.The polyketone resin composition is a glass fiber, inorganic filler, mineral reinforcing agent, polyurethane resin, polycarbonate resin, polyamide 6 resin, rubber, ASA and sulfonamide-based plasticizer 5 to 50 parts by weight of the polyketone copolymer Polyketone resin composition excellent in impact resistance, characterized in that added by weight alone or in combination.
  5. 제 1항 내지 제 4항의 폴리케톤 수지 조성물로 제조되는 것을 특징으로 한 마스크, 파이프 홀더, 변속기 브라켓, 범퍼 브라켓, 자동차용 정션 박스, 자동차 휠림, 전력선 결속용 브라켓, 전자기기 커버, 안경테A mask, a pipe holder, a transmission bracket, a bumper bracket, an automobile junction box, an automobile wheel rim, a power line binding bracket, an electronic device cover, and an eyeglass frame, which are made of the polyketone resin composition of claim 1.
  6. 일산화탄소와 적어도 1종의 에틸렌계 불포화 탄화수소로 이루어진 선상 교대 폴리케톤과 열가소성 폴리우레탄 수지를 포함하고, 상기 폴리우레탄의 함량은 폴리케톤 중량대비 1~20중량%인 것을 특징으로 한 폴리케톤-폴리우레탄 수지 조성물.A polyketone-polyurethane comprising linear alternating polyketone and a thermoplastic polyurethane resin composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, wherein the content of the polyurethane is 1 to 20% by weight based on the weight of the polyketone. Resin composition.
  7. 제 6항에 있어서,The method of claim 6,
    상기 폴리케톤은 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 공중합체로서, y/x가 0.03~0.3 이고, 고유점도(LVN)는 1.0~2.0dl/g이고 분자량 분포가 1.5~2.5인 것을 특징으로 한 폴리케톤-폴리우레탄 수지 조성물.The polyketone is a copolymer consisting of repeating units represented by formulas (1) and (2), y / x is 0.03 to 0.3, intrinsic viscosity (LVN) is 1.0 to 2.0 dl / g and molecular weight distribution is 1.5 Polyketone polyurethane resin composition characterized in that ~ 2.5.
    -[-CH2CH2-CO]x- (1)-[-CH2CH2-CO] x- (1)
    -[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
  8. 제 6항에 있어서,The method of claim 6,
    상기 폴리케톤-폴리우레탄 수지 조성물은 충격강도가 10~12kJ/m2인 것을 특징으로 하는 폴리케톤-폴리우레탄 수지 조성물.The polyketone-polyurethane resin composition is a polyketone-polyurethane resin composition, characterized in that the impact strength is 10 ~ 12kJ / m 2 .
  9. 제 6항에 있어서,The method of claim 6,
    상기 폴리케톤-폴리우레탄 수지 조성물은 반발탄성이 35% 내지 45%인 것을 특징으로 하는 폴리케톤-폴리우레탄 수지 조성물.The polyketone-polyurethane resin composition is a polyketone-polyurethane resin composition, characterized in that the resilience is 35% to 45%.
  10. 제 6항 내지 제 9항 중 어느 한 항에 기재된 폴리케톤-폴리우레탄 수지 조성물로 제조된 성형품.The molded article manufactured from the polyketone-polyurethane resin composition in any one of Claims 6-9.
  11. 하기 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, 분자량 분포가 1.5 내지 2.5이고, y/x가 0.03 내지 0.3인 선상 교대 폴리케톤과 유리섬유를 포함하며, 상기 폴리케톤과 유리섬유의 중량비가 50:50 내지 95:5 인 것을 특징으로 하는 폴리케톤 조성물.A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), comprising a linear alternating polyketone and a glass fiber having a molecular weight distribution of 1.5 to 2.5 and y / x of 0.03 to 0.3, The polyketone composition, characterized in that the weight ratio of the polyketone and glass fiber is 50:50 to 95: 5.
    -[-CH2CH2-CO]x- (1)-[-CH2CH2-CO] x- (1)
    -[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
    (x, y는 폴리머 중의 일반식 (1) 및 (2)의 각각의 몰%를 나타낸다.)(x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)
  12. 제 11항에 있어서,The method of claim 11,
    상기 유리섬유는 직경이 10 μm이고, 길이가 4mm이며, 폴리우레탄으로 코팅된 것을 특징으로 하는 폴리케톤 조성물The glass fiber is 10 μm in diameter, 4 mm in length, polyketone composition, characterized in that coated with polyurethane
  13. 제 11항에 있어서,The method of claim 11,
    상기 폴리케톤의 고유점도는 1.0 내지 2.0 dl/g인 것을 특징으로 하는 폴리케톤 조성물Polyketone composition, characterized in that the intrinsic viscosity of the polyketone is 1.0 to 2.0 dl / g
  14. 제 11항에 있어서,The method of claim 11,
    상기 폴리케톤 중합시 사용되는 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 폴리케톤 조성물.The ligand of the catalyst composition used in the polyketone polymerization is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine Polyketone composition, characterized in that).
  15. 제 11항 내지 제 14항 중 어느 한 항에 기재된 폴리케톤 조성물로 제조된 폴리케톤 성형품.A polyketone molded article made of the polyketone composition according to any one of claims 11 to 14.
  16. 하기 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, y/x가 0.03 내지 0.3인 선상 교대 폴리케톤과 폴리카보네이트를 포함하며, 경도가 95 이상인 것을 특징으로 하는 폴리케톤 조성물.A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), the linear alternating polyketone having y / x of 0.03 to 0.3 and polycarbonate, and having a hardness of 95 or more Polyketone composition.
    -[-CH2CH2-CO]x- (1)-[-CH2CH2-CO] x- (1)
    -[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
    (x, y는 폴리머 중의 일반식 (1) 및 (2)의 각각의 몰%를 나타낸다.)(x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)
  17. 제 16항에 있어서,The method of claim 16,
    상기 폴리케톤 조성물 전체 중량에 대하여 폴리카보네이트의 조성비는 1중량% 내지 30중량%인 것을 특징으로 하는 폴리케톤 조성물.The composition ratio of the polycarbonate to the total weight of the polyketone composition, characterized in that the polyketone composition, characterized in that 1% to 30% by weight.
  18. 제 16항에 있어서,The method of claim 16,
    상기 폴리케톤 공중합체의 중합시 사용되는 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 폴리케톤 조성물.The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl Phosphine) polyketone composition.
  19. 제 16항에 있어서,The method of claim 16,
    상기 폴리케톤 공중합체의 고유점도는 1.0 내지 2.0 dl/g인 것을 특징으로 하는 폴리케톤 조성물.Intrinsic viscosity of the polyketone copolymer is a polyketone composition, characterized in that 1.0 to 2.0 dl / g.
  20. 제 16항 내지 제 19항 중 어느 한 항에 기재된 폴리케톤 조성물로 제조된 산업용 부품.An industrial part made from the polyketone composition according to any one of claims 16 to 19.
  21. 하기 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어지고, y/x가 0.03 내지 0.3인 선상 교대 폴리케톤 공중합체를 사출성형 하여 제조되는 것을 특징으로 하는 폴리케톤 안경테.A polyketone spectacle frame comprising a repeating unit represented by the following general formulas (1) and (2) and manufactured by injection molding a linear alternating polyketone copolymer having y / x of 0.03 to 0.3.
    -[-CH2-CH2-CO]x- (1)-[-CH2-CH2-CO] x- (1)
    -[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
    (x, y는 폴리머 중의 일반식 (1) 및 (2)의 각각의 몰%를 나타낸다.)(x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)
  22. 제 21항에 있어서, The method of claim 21,
    상기 폴리케톤 안경테는 굽힘각도가 2°이하인 것을 특징으로 하는 폴리케톤 안경테.The polyketone spectacle frame is characterized in that the bending angle is less than 2 ° polyketone spectacle frame.
  23. 제 21항에 있어서,The method of claim 21,
    상기 y/x 는 0.03 내지 0.1인 것을 특징으로 하는 폴리케톤 안경테.The y / x is polyketone spectacle frame, characterized in that from 0.03 to 0.1.
  24. 제 21항에 있어서,The method of claim 21,
    상기 폴리케톤 공중합체의 고유점도는 1.0dl/g 내지 2.0dl/g 인 것을 특징으로 하는 폴리케톤 안경테.Polyketone spectacle frame, characterized in that the intrinsic viscosity of the polyketone copolymer is 1.0dl / g to 2.0dl / g.
  25. 일산화탄소와 적어도 1종의 올레핀계 탄화수소로 이루어진 선상 교대 폴리케톤을 사출성형하여 제조된 폴리케톤 마스크의 내충격성이 80kJ/m2이상인 것을 특징으로 하는 폴리케톤 고충격 마스크.A polyketone high impact mask, characterized in that the impact resistance of a polyketone mask produced by injection molding a linear alternating polyketone made of carbon monoxide and at least one olefinic hydrocarbon is 80 kJ / m 2 or more.
  26. 제 25항에 있어서,The method of claim 25,
    상기 폴리케톤의 흡습 후 물성 유지율이 흡습 전 물성에 대하여 85%이상인 것을 특징으로 하는 폴리케톤 고충격 마스크.The polyketone high-impact mask, characterized in that the retention of physical properties after the moisture absorption of the polyketone is 85% or more relative to the physical properties before the moisture absorption.
  27. 제 25항에 있어서,The method of claim 25,
    상기 폴리케톤의 고유 점도가 1.0 내지 2.0 인 것을 특징으로 하는 폴리케톤 고충격 마스크.Polyketone high impact mask, characterized in that the intrinsic viscosity of the polyketone is 1.0 to 2.0.
  28. 제 25항에 있어서,The method of claim 25,
    상기 폴리케톤의 중합에 사용되는 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 폴리케톤 고충격 마스크.The ligand of the catalyst composition used for the polymerization of the polyketone is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) force Pin) polyketone high impact mask characterized in that.
  29. 일산화탄소와 적어도 1종의 올레핀계 탄화수소로 이루어진 선상 교대 폴리케톤 50 내지 90중량%와 미네랄 보강재를 10 내지 50 중량%를 혼합한 블렌드를 사출성형하여 제조되고, 충격강도가 10kJ/m2 이상인 것을 특징으로 하는 폴리케톤 파이프 홀더.It is produced by injection molding a blend of 50 to 90% by weight of linear alternating polyketone consisting of carbon monoxide and at least one olefinic hydrocarbon and 10 to 50% by weight of mineral reinforcing material, and has an impact strength of 10 kJ / m 2 or more. Polyketone pipe holder.
  30. 제 29항에 있어서The method of claim 29
    상기 선상교대 폴리케톤은 에틸렌과 프로필렌의 몰비가 45:5 내지 48:2인 것을 특징으로 하는 폴리케톤 파이프 홀더.Said linear alternating polyketone is a polyketone pipe holder, characterized in that the molar ratio of ethylene and propylene is 45: 5 to 48: 2.
  31. 제 29항에 있어서,The method of claim 29,
    상기 폴리케톤 파이프 홀더의 치수변화율이 0.1% 이하인 것을 특징으로 하는 폴리케톤 파이프 홀더.Polyketone pipe holder, characterized in that the dimensional change rate of the polyketone pipe holder is 0.1% or less.
  32. 제 29항에 있어서,The method of claim 29,
    상기 미네랄 보강재는 탈크(Talc), 카오린(Kaolin), 마이카(Mica), 월라스토나이트(wollastonite), TiO2-코팅된 마이카 소형판 (TiO2-coated mica platelets), 실리카(silica), 알루미나(alumina), 붕규산염 (borosilicates) 및 산화물 (oxides)로 이루어진 군에서 선택된 1종인 것을 특징으로 하는 폴리케톤 파이프 홀더.The mineral reinforcing material is talc, kaolin, mica, mica, wollastonite, TiO2-coated mica platelets, silica, alumina, alumina , Borosilicates (borosilicates) and oxides (oxides) polyketone pipe holder, characterized in that one selected from the group consisting of.
  33. 팔라듐 화합물, pKa값이 6 이하인 산, 및 인의 2배위자 화합물을 포함하는 촉매 조성물을 준비하는 단계;Preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bipolar compound of phosphorus;
    알코올(예컨대, 메탄올)과 물을 포함하는 혼합용매(중합용매)를 준비하는 단계;Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water;
    상기 촉매 조성물 및 혼합용매의 존재 하에서 중합을 진행하여 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머를 제조하는 단계;Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent;
    상기 선상 터폴리머에서 남은 촉매 조성물을 용매로 제거하여 폴리케톤 수지를 수득하는 단계; 및Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And
    상기 폴리케톤 수지 50 내지 90중량%와 미네랄 보강재 10 내지 50중량%를 혼합한 블렌드 100중량%를 사출성형하여 폴리케톤 파이프 홀더를 제조하는 단계;Manufacturing a polyketone pipe holder by injection molding 100% by weight of the blend of 50 to 90% by weight of the polyketone resin and 10 to 50% by weight of the mineral reinforcing material;
    를 포함하는 폴리케톤 파이프 홀더의 제조방법.Method of producing a polyketone pipe holder comprising a.
  34. 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 50ppm이하 이고, 분자량 분포가 1.5 내지 2.5인 선상 교대 폴리케톤 폴리머 와 설폰아미드계 가소제, 폴리우레탄, ASA(Acrylic Styrene Acrylonitrile)를 포함하는 블렌드를 사출성형하여 제조되고, 상기 설폰아미드계 가소제, 폴리우레탄 및 ASA는 블렌드 전체 대비 각각 10 내지 20중량%, 15 내지 20중량% 및 1 내지 10중량% 인 것을 특징으로 하는 신발용 소재.Linear alternating polyketone polymer, sulfonamide plasticizer, polyurethane, ASA (Acrylic Styrene Acrylonitrile) consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon and having a residual amount of palladium catalyst of 50 ppm or less and a molecular weight distribution of 1.5 to 2.5 It is prepared by injection molding the blend, wherein the sulfonamide-based plasticizer, polyurethane and ASA is a shoe material, characterized in that 10 to 20% by weight, 15 to 20% by weight and 1 to 10% by weight, respectively, relative to the total blend .
  35. 제 34항에 있어서,The method of claim 34,
    상기 선상 교대 폴리케톤의 중합시 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 신발용 소재.The ligand of the catalyst composition in the polymerization of the linear alternating polyketone is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) force Pin) material for shoes.
  36. 제 34항에 있어서,The method of claim 34,
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.0 내지 2.0dl/g인 것을 특징으로 하는 신발용 소재.Shoe material, characterized in that the intrinsic viscosity of the linear alternating polyketone polymer is 1.0 to 2.0dl / g.
  37. 제 34항에 있어서,The method of claim 34,
    상기 신발용 소재는 굴곡탄성율이 7000 내지 8500MPa인 것을 특징으로 하는 신발용 소재.The shoe material is a shoe material, characterized in that the flexural modulus of 7000 to 8500 MPa.
  38. 하기 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어지고, y/x가 0.03 내지 0.3인 선상 교대 폴리케톤 터폴리머와 유리섬유를 포함하는 블렌드를 사출성형하여 제조되고, 이 때 50℃, 90%의 상대습도 조건에서의 흡습율이 1.0% 미만이고, 충격강도가 15kJ/m2 이상인 것을 특징으로 하는 폴리케톤 성형제품.It is made of a repeating unit represented by the following general formulas (1) and (2), prepared by injection molding a blend comprising a linear alternating polyketone terpolymer having a y / x of 0.03 to 0.3 and glass fibers, wherein 50 Polyketone molded article characterized in that the moisture absorption rate in the relative humidity conditions of 90%, ℃ less than 1.0%, the impact strength is 15kJ / m2 or more.
    -[-CH2CH2-CO]x- (1)-[-CH2CH2-CO] x- (1)
    -[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
    (x, y는 폴리케톤 터폴리머 중의 일반식 (1) 및 (2)의 각각의 몰%를 나타낸다.)(x, y represents the mole% of each of the general formulas (1) and (2) in the polyketone terpolymer.)
  39. 제 38항에 있어서,The method of claim 38,
    상기 폴리케톤 터폴리머의 고유점도는 1.0 내지 2.0 dl/g인 것을 특징으로 하는 폴리케톤 성형제품.Polyketone molded article, characterized in that the intrinsic viscosity of the polyketone terpolymer is 1.0 to 2.0 dl / g.
  40. 제 38항에 있어서,The method of claim 38,
    상기 폴리케톤 터폴리머의 함량은 50 내지 90 중량% 이고, 유리섬유의 함량은 10 내지 50 중량%인 것을 특징으로 하는 폴리케톤 성형제품.The content of the polyketone terpolymer is 50 to 90% by weight, the content of the glass fiber polyketone molded product, characterized in that 10 to 50% by weight.
  41. 제 38항에 있어서,The method of claim 38,
    상기 y/x은 0.03 내지 0.1인 것을 특징으로 하는 폴리케톤 성형제품.The y / x is polyketone molded product, characterized in that 0.03 to 0.1.
  42. 제 38항에 있어서,The method of claim 38,
    상기 폴리케톤 성형제품이 엑셀레이터 페달인 것을 특징으로 하는 폴리케톤 성형제품.The polyketone molded product, characterized in that the polyketone molded product is an accelerator pedal.
  43. 하기 일반식(1)과 (2)로 표시되는 반복단위로 이루어진 폴리케톤 공중합체로서, y/x가 0.03 내지 0.3인 폴리케톤 공중합체와 유리섬유를 포함하는 블렌드를 사출성형하고, 이 때 충격강도가 17kJ/m2이상인 것을 특징으로 하는 폴리케톤 변속기 브라켓.A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), wherein a blend containing a polyketone copolymer having y / x of 0.03 to 0.3 and glass fibers is injection molded, and at this time, impact Polyketone transmission bracket characterized in that the strength is 17kJ / m2 or more.
    -[-CH2CH2-CO-]x- (1)-[-CH2CH2-CO-] x- (1)
    -[-CH2-CH(CH3)-CO-]y- (2)-[-CH2-CH (CH3) -CO-] y- (2)
    (x, y는 폴리머 중의 일반식 (1) 및 (2) 각각의 몰%)(x, y are mole% of each of the general formulas (1) and (2) in the polymer)
  44. 제 43항에 있어서,The method of claim 43,
    상기 폴리케톤 공중합체의 고유점도는 1.0 내지 2.0dl/g 인 것을 특징으로 하는 폴리케톤 변속기 브라켓.Polyketone transmission bracket, characterized in that the intrinsic viscosity of the polyketone copolymer is 1.0 to 2.0dl / g.
  45. 제 43항에 있어서,The method of claim 43,
    상기 폴리케톤 공중합체의 분자량 분포는 1.5 내지 2.5 이며, 폴리케톤 중합시 사용되는 촉매 조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 폴리케톤 변속기 브라켓.The molecular weight distribution of the polyketone copolymer is 1.5 to 2.5, the ligand of the catalyst composition used in the polyketone polymerization is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) ) Bis (bis (2-methoxyphenyl) phosphine). Polyketone transmission bracket characterized by the above-mentioned.
  46. 제 43항에 있어서,The method of claim 43,
    상기 유리섬유는 전체 블렌드 100중량% 대비 5 내지 50 중량%인 것을 특징으로 하는 폴리케톤 변속기 브라켓.The glass fiber is a polyketone transmission bracket, characterized in that 5 to 50% by weight relative to the total blend 100% by weight.
  47. 제 43항에 있어서, The method of claim 43,
    상기 폴리케톤 변속기 브라켓의 흡습 후 인장강도 유지율이 80% 이상인 것을 특징으로 하는 폴리케톤 변속기 브라켓.Polyketone transmission bracket, characterized in that the tensile strength retention after the moisture absorption of the polyketone transmission bracket 80% or more.
  48. 일산화탄소와 적어도 일종의 올레핀계 불포화 탄화수소로 이루어진 선상 교대 폴리케톤과 폴리아미드6 및 고무를 포함하는 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 폴리케톤 범퍼 브라켓.A polyketone bumper bracket, which is produced by injection molding a blend comprising linear carbonaceous polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon, polyamide 6 and rubber.
  49. 제 48항에 있어서, The method of claim 48,
    상기 블렌드 전체 중량%에 대하여 폴리케톤은 40 내지 90중량%, 폴리아미드 6는 5 내지 40 중량% 및 고무는 5 내지 20중량%인 것을 특징으로 하는 폴리케톤 범퍼 브라켓.The polyketone bumper bracket, characterized in that the polyketone is 40 to 90% by weight, the polyamide 6 is 5 to 40% by weight and the rubber is 5 to 20% by weight relative to the total weight of the blend.
  50. 제 48항에 있어서, The method of claim 48,
    상기 폴리케톤은 70중량%, 폴리아미드 6는 22중량% 및 고무는 8중량%인 것을 특징으로 하는 폴리케톤 범퍼 브라켓.The polyketone is 70% by weight, polyamide 6 is 22% by weight and rubber is 8% by weight of the polyketone bumper bracket.
  51. 제 48항에 있어서,The method of claim 48,
    상기 폴리케톤 범퍼 브라켓의 충격강도는 75kJ/m2이상인 것을 특징으로 하는 폴리케톤 범퍼 브라켓.Impact strength of the polyketone bumper bracket is polyketone bumper bracket, characterized in that more than 75kJ / m2.
  52. 제 48항에 있어서,The method of claim 48,
    상기 폴리케톤 범퍼 브라켓은 염화칼슘 10% 수용액에서 인장강도 유지율이 75%이상인 것을 특징으로 하는 폴리케톤 범퍼 브라켓.The polyketone bumper bracket is a polyketone bumper bracket, characterized in that the tensile strength retention of 75% or more in 10% aqueous calcium chloride solution.
  53. 제 48항에 있어서,The method of claim 48,
    상기 고무는 에틸렌프로필렌 디엔모노머 고무인 것을 특징으로 하는 폴리케톤 범퍼 브라켓.The rubber is polyketone bumper bracket, characterized in that the ethylene propylene diene monomer rubber.
  54. 하기의 일반식(1)과(2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, y/x가 0.03 내지 0.3 인 폴리케톤 공중합체를 사출성형하여 제조되는 것을 특징으로 하는 자동차용 정션 박스.A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), wherein the junction box for automobiles is manufactured by injection molding a polyketone copolymer having y / x of 0.03 to 0.3 .
    -(CH2CH2-CO)x- (1)-(CH2CH2-CO) x- (1)
    -(CH2CH(CH3)-CO)y- (2)-(CH2CH (CH3) -CO) y- (2)
    (x, y는, 폴리머 중의 일반식(1) 및 (2) 각각의 몰%)(x, y are mole% of each of the general formulas (1) and (2) in the polymer)
  55. 제 54항에 있어서.55. The method of claim 54.
    상기 자동차용 정션 박스는 상온에서 충격강도가 12kJ/m2 이상인 것을 특징으로 하는 자동차용 정션 박스.The junction box for automobiles is an automobile junction box, characterized in that the impact strength at room temperature 12kJ / m2 or more.
  56. 제 54항에 있어서.55. The method of claim 54.
    상기 자동차용 정션 박스는 흡습 후 인장강도 유지율이 흡습 전 물성에 대하여 85%이상인 것을 특징으로 하는 자동차용 정션 박스.The junction box for automobiles is a junction box for automobiles, characterized in that the retention of tensile strength after moisture absorption is more than 85% of the physical properties before the moisture absorption.
  57. 제 54항에 있어서.55. The method of claim 54.
    상기 폴리케톤 공중합체의 고유점도는 1.0 내지 2.0 dl/g 인 것을 특징으로 하는 자동차용 정션 박스.Automotive junction box, characterized in that the intrinsic viscosity of the polyketone copolymer is 1.0 to 2.0 dl / g.
  58. 제 54항에 있어서.55. The method of claim 54.
    상기 폴리케톤 공중합체의 중합시 사용되는 촉매 조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 자동차용 정션 박스.The ligand of the catalyst composition used in the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl Junction box for cars characterized in that)).
  59. 자동차 휠의 림에 있어서,In the rim of the car wheel,
    상기 림은 하기의 일반식(1)과(2)로 표시되며 y/x가 0.03 내지 0.3 인 폴리케톤 공중합체와; 유리섬유와; 무기 충전제로 구성된 폴리케톤 수지 조성물로부터 제조되는 것을 특징으로 한 자동차 휠의 림.The rim is represented by the following general formulas (1) and (2) and a polyketone copolymer having y / x of 0.03 to 0.3; Glass fibers; A rim of an automobile wheel, which is made from a polyketone resin composition composed of an inorganic filler.
    -(CH2CH2-CO)x- (1)-(CH2CH2-CO) x- (1)
    -(CH2CH(CH3)-CO)y- (2)-(CH2CH (CH3) -CO) y- (2)
    (x, y는, 폴리머 중의 일반식(1) 및 (2) 각각의 몰%)(x, y are mole% of each of the general formulas (1) and (2) in the polymer)
  60. 제 59항에 있어서,The method of claim 59,
    상기 유리섬유와 무기 충전제는 폴리케톤 공중합체 100중량부 대비 각각 20~50중량부, 5.5~15.5 중량부만큼 포함되는 것을 특징으로 한 자동차 휠의 림.The rim of the automobile wheel, wherein the glass fiber and the inorganic filler are included in an amount of 20 to 50 parts by weight and 5.5 to 15.5 parts by weight, respectively, based on 100 parts by weight of the polyketone copolymer.
  61. 제 59항에 있어서,The method of claim 59,
    상기 무기 충전제는 탄산칼슘, 황산마그네슘, 실리콘 카바이드, 산화칼슘으로부터 선택되는 것을 특징으로 한 자동차 휠의 림.Wherein said inorganic filler is selected from calcium carbonate, magnesium sulfate, silicon carbide, calcium oxide.
  62. 제 59항에 있어서,The method of claim 59,
    상기 폴리케톤 공중합체는 고유점도가 1.0~2.0dl/g, 분자량 분포가 1.5~2.5 이며, 촉매 조성물을 구성하는 인의 2배위자 화합물로 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)을 사용하는 것을 특징으로 한 자동차 휠의 림.The polyketone copolymer has an intrinsic viscosity of 1.0 to 2.0 dl / g, a molecular weight distribution of 1.5 to 2.5, and is a double ligand compound of phosphorus constituting the catalyst composition ((2,2-dimethyl-1,3-dioxane-5) A rim of an automobile wheel characterized by using, 5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine).
  63. 일산화탄소와 적어도 1종의 에틸렌계 불포화 탄화수소로 이루어진 선상 교대 폴리케톤을 사출성형하여 제조되는 것을 특징으로 하는 전력선 결속용 브라켓.A power line binding bracket, which is manufactured by injection molding a linear alternating polyketone made of carbon monoxide and at least one ethylenically unsaturated hydrocarbon.
  64. 제 63항에 있어서,The method of claim 63, wherein
    상기 전력선 결속용 브라겟은 충격강도가 8kJ/m2 이상인 것을 특징으로 하는 전력선 결속용 브라켓.The power line binding bracket is a power line binding bracket, characterized in that the impact strength of 8kJ / m2 or more.
  65. 제 63항에 있어서,The method of claim 63, wherein
    상기 폴리케톤은 에틸렌과 프로필렌의 몰비%가 9 내지 24 : 1 인 것을 특징으로 하는 전력선 결속용 브라켓.The polyketone is a power line binding bracket, characterized in that the molar ratio of ethylene and propylene is 9 to 24: 1.
  66. 제 63항에 있어서,The method of claim 63, wherein
    상기 폴리케톤의 고유점도는 1.0 내지 2.0 dl/g 인 것을 특징으로 하는 전력선 결속용 브라켓.The inherent viscosity of the polyketone is a power line binding bracket, characterized in that 1.0 to 2.0 dl / g.
  67. 제 63항에 있어서,The method of claim 63, wherein
    상기 폴리케톤은 분자량 분포가 1.5 내지 2.5 인 것을 특징으로 하는 전력선 결속용 브라켓.The polyketone is a power line binding bracket, characterized in that the molecular weight distribution of 1.5 to 2.5.
  68. 제 63항에 있어서,The method of claim 63, wherein
    상기 폴리케톤의 중합시 사용되는 촉매 조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 전력선 결속용 브라켓.The ligand of the catalyst composition used in the polymerization of the polyketone is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) force Pin) pins for power line binding.
  69. 하기 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, y/x가 0.03~0.3인 선상 교대 폴리케톤과 유리섬유의 블렌드를 사출성형하여 제조되고, 충격강도는 8kJ/m2 이상인 것을 특징으로 하는 폴리케톤 전자기기 커버.A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), which is prepared by injection molding a blend of linear alternating polyketones and glass fibers having a y / x of 0.03 to 0.3, and the impact strength is Polyketone electronic device cover, characterized in that more than 8kJ / m2.
    -[-CH2CH2-CO]x- (1)-[-CH2CH2-CO] x- (1)
    -[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
    (x, y는 폴리머 중의 일반식 (1) 및 (2)의 각각의 몰%를 나타낸다.)(x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)
  70. 제 69항에 있어서, The method of claim 69,
    상기 블렌드 대비 유리섬유의 함량은 5 내지 50중량%인 것을 특징으로 하는 폴리케톤 전자기기 커버.Polyketone electronic device cover, characterized in that the content of the glass fiber relative to the blend is 5 to 50% by weight.
  71. 제 69항에 있어서, The method of claim 69,
    상기 전자기기 커버의 제품변형율이 0.1% 이하인 것을 특징으로 하는 폴리케톤 전자기기 커버.Polyketone electronic device cover, characterized in that the product strain of the electronic device cover is less than 0.1%.
  72. 제 69항에 있어서,The method of claim 69,
    상기 폴리케톤 공중합체의 고유점도는 1.0dl/g 내지 2.0dl/g 인 것을 특징으로 하는 폴리케톤 전자기기커버Polyketone electronic device cover, characterized in that the intrinsic viscosity of the polyketone copolymer is 1.0dl / g to 2.0dl / g
  73. 제 69항에 있어서,The method of claim 69,
    상기 전자기기 커버는 핸드폰 보호 커버인 것을 특징으로 하는 폴리케톤 전자기기 커버.The electronic device cover is a polyketone electronic device cover, characterized in that the mobile phone protective cover.
  74. 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 50ppm 이하 이고, 분자량 분포가 1.5 내지 2.5인 선상 교대 폴리케톤 폴리머 70 내지 85 중량%와 유리섬유 15 내지 30 중량%를 포함하는 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 전기전자제품용 뚜껑.Consists of carbon monoxide and at least one olefinically unsaturated hydrocarbon, the catalyst has a residual amount of palladium of 50 ppm or less, and includes 70 to 85 wt% of linear alternating polyketone polymer having a molecular weight distribution of 1.5 to 2.5 and 15 to 30 wt% of glass fibers. Lid for electrical and electronic products, characterized in that the blend is produced by injection molding.
  75. 제 74항에 있어서,The method of claim 74, wherein
    상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비가 9 내지 24:1 인 것을 특징으로 하는 전기전자제품용 뚜껑.The linear alternating polyketone is an electrical and electronic product lid, characterized in that the molar ratio of ethylene and propylene is 9 to 24: 1.
  76. 제 74항에 있어서,The method of claim 74, wherein
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.0 내지 2.0dl/g인 것을 특징으로 하는 전기전자제품용 뚜껑.Lid for electric and electronic products, characterized in that the intrinsic viscosity of the linear alternating polyketone polymer is 1.0 to 2.0dl / g.
  77. 제 74항에 있어서,The method of claim 74, wherein
    상기 전지전자제품용 뚜껑은 충격강도가 15kJ/m2 이상이고, The lid for a battery electronic product has an impact strength of 15 kJ / m 2 or more,
    50℃, 상대습도 90%RH에서 수분 흡습율이 1.5% 미만이며, Moisture absorption rate is less than 1.5% at 50 ℃ and 90% RH relative humidity.
    50℃, 상대습도 90%RH에서 측정한 인장강도가 25℃, 상대습도 65%RH에서 측정한 인장강도 대비 85% 이상 수준을 유지하는 것을 특징으로 하는 전기전자제품용 뚜껑.Cap for electrical and electronic products, characterized in that the tensile strength measured at 50 ℃, relative humidity 90% RH is maintained at a level of 85% or more compared to the tensile strength measured at 25 ℃, 65% RH relative humidity.
  78. 제 74항에 있어서, The method of claim 74, wherein
    상기 뚜껑은 압력밥솥용인 것을 특징으로 하는 전기전자제품용 뚜껑.The lid is a lid for electrical and electronic products, characterized in that for pressure cooker.
  79. 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 60 내지 90중량%와 유리섬유 10 내지 40 중량%를 혼합한 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 폴리케톤 자동차 에어 인테이크 매니폴드.Composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon, a palladium catalyst residue of 5 to 50 ppm, a mixture of 60 to 90 wt% of linear alternating polyketone having a molecular weight distribution of 1.5 to 3.0 and 10 to 40 wt% of glass fiber Polyketone automotive air intake manifold, characterized in that the blend is manufactured by injection molding.
  80. 제 79항에 있어서,The method of claim 79,
    상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15 인 것을 특징으로 하는 폴리케톤 자동차 에어 인테이크 매니폴드.The linear alternating polyketone polyketone automotive air intake manifold, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15.
  81. 제 79항에 있어서,The method of claim 79,
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.2 내지 2.0dl/g인 것을 특징으로 하는 폴리케톤 자동차 에어 인테이크 매니폴드.Polyketone automotive air intake manifold, characterized in that the intrinsic viscosity of the linear alternating polyketone polymer is 1.2 to 2.0dl / g.
  82. 제 79항에 있어서,The method of claim 79,
    상기 폴리케톤 자동차 에어 인테이크 매니폴드는 충격강도가 8kJ/m2 이상이고, 120℃에서 300시간 처리 후 인장강도 유지율이 100% 이상인 것을 특징으로 하는 폴리케톤 자동차 에어 인테이크 매니폴드.The polyketone car air intake manifold is polyketone car air intake manifold, characterized in that the impact strength is more than 8kJ / m2, the tensile strength retention is 100% or more after 300 hours treatment at 120 ℃.
  83. 팔라듐 화합물, pKa값이 6 이하인 산, 및 인의 2배위자 화합물을 포함하는 촉매 조성물을 준비하는 단계; Preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bipolar compound of phosphorus;
    알코올(예컨대, 메탄올)과 물을 포함하는 혼합용매(중합용매)를 준비하는 단계; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water;
    상기 촉매 조성물 및 혼합용매의 존재 하에서 중합을 진행하여 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머를 제조하는 단계; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent;
    상기 선상 터폴리머에서 남은 촉매 조성물을 용매로 제거하여 폴리케톤 수지를 수득하는 단계; 및 Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And
    상기 폴리케톤 수지 60 내지 90중량%와 유리섬유 10 내지 40중량%를 혼합한 블렌드 100중량%를 사출성형하여 폴리케톤 자동차 에어 인테이크 매니폴드를 제조하는 단계;Manufacturing a polyketone automobile air intake manifold by injection molding 100% by weight of the blend containing 60 to 90% by weight of the polyketone resin and 10 to 40% by weight of glass fibers;
    를 포함하는 폴리케톤 자동차 에어 인테이크 매니폴드의 제조방법.Polyketone car air intake manifold manufacturing method comprising a.
  84. 일산화탄소와 적어도 1종의 올레핀계 탄화수소로 이루어진 선상 교대 폴리케톤 60 내지 90중량%와 유리섬유 10 내지 40 중량%를 혼합한 블렌드를 사출성형하여 자동차 프론트엔드모듈의 캐리어를 제조되는 것을 특징으로 하는 폴리케톤 자동차 프론트엔드모듈의 캐리어.A carrier of an automobile front end module is manufactured by injection molding a blend of 60 to 90 wt% of linear alternating polyketone and 10 to 40 wt% of glass fiber composed of carbon monoxide and at least one olefinic hydrocarbon. Carrier of the ketone car front end module.
  85. 제 84항에 있어서,85. The method of claim 84,
    상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15 인 것을 특징으로 하는 폴리케톤 자동차 프론트엔드모듈의 캐리어.The linear alternating polyketone is a carrier of a polyketone car front end module, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15.
  86. 제 84항에 있어서,85. The method of claim 84,
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.2 내지 2.0dl/g인 것을 특징으로 하는 폴리케톤 자동차 프론트엔드모듈의 캐리어.The intrinsic viscosity of the linear alternating polyketone polymer is a carrier of a polyketone automotive front end module, characterized in that 1.2 to 2.0dl / g.
  87. 제 84항에 있어서,85. The method of claim 84,
    상기 폴리케톤 자동차 프론트엔드모듈의 캐리어는 충격강도가 8kJ/m2 이상이고, 120℃에서 300시간 처리 후 인장강도 유지율이 100% 이상인 것을 특징으로 하는 폴리케톤 자동차 프론트엔드모듈의 캐리어.The carrier of the polyketone car front end module is a carrier of the polyketone car front end module, characterized in that the impact strength is more than 8kJ / m2, the tensile strength retention is 100% or more after processing at 120 ℃ 300 hours.
  88. 팔라듐 화합물, pKa값이 6 이하인 산, 및 인의 2배위자 화합물을 포함하는 촉매 조성물을 준비하는 단계; Preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bipolar compound of phosphorus;
    알코올(예컨대, 메탄올)과 물을 포함하는 혼합용매(중합용매)를 준비하는 단계; Preparing a mixed solvent (polymer solvent) including an alcohol (eg, methanol) and water;
    상기 촉매 조성물 및 혼합용매의 존재 하에서 중합을 진행하여 일산화탄소, 에틸렌 및 프로필렌의 선상 터폴리머를 제조하는 단계; Preparing a linear terpolymer of carbon monoxide, ethylene and propylene by polymerizing in the presence of the catalyst composition and the mixed solvent;
    상기 선상 터폴리머에서 남은 촉매 조성물을 용매로 제거하여 폴리케톤 수지를 수득하는 단계; 및 Removing the catalyst composition remaining in the linear terpolymer with a solvent to obtain a polyketone resin; And
    상기 폴리케톤 수지 60 내지 90중량%와 유리섬유 10 내지 40중량%를 혼합한 블렌드 100중량%를 사출성형하여 폴리케톤 자동차 프론트엔드모듈의 캐리어를 제조하는 단계;Manufacturing a carrier of a polyketone automobile front end module by injection molding 100 wt% of a blend of 60 to 90 wt% of the polyketone resin and 10 to 40 wt% of glass fibers;
    를 포함하는 폴리케톤 자동차 프론트엔드모듈의 캐리어의 제조방법.Method of manufacturing a carrier of a polyketone car front end module comprising a.
  89. 하기의 화학식(1)과(2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, y/x가 0.1 내지 0.3 인 폴리케톤 공중합체와 미네랄 필러의 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 폴리케톤 블렌드 자동차 헤드램프베젤.A polyketone copolymer composed of repeating units represented by the following formulas (1) and (2), characterized in that it is prepared by injection molding a blend of polyketone copolymer and mineral filler of y / x of 0.1 to 0.3 Polyketone blend car headlamp bezel.
    [화학식 1][Formula 1]
    -(CH2CH2-CO)x--(CH2CH2-CO) x-
    [화학식 2][Formula 2]
    -(CH2CH(CH3)-CO)y--(CH2CH (CH3) -CO) y-
    (x, y는, 폴리머 중의 화학식(1) 및 (2) 각각의 몰%)(x, y is the mole% of each of formulas (1) and (2) in the polymer)
  90. 제 89항에 있어서,91. The method of claim 89,
    상기 자동차 헤드램프베젤은 충격강도가 20kJ/m2 이상인 것을 특징으로 하는 폴리케톤 블렌드 자동차 헤드램프베젤.The car headlamp bezel is a polyketone blend car headlamp bezel, characterized in that the impact strength is 20kJ / m 2 or more.
  91. 제 89항에 있어서,The method of claim 89,
    상기 미네랄 필러는 탈크(Talc), 카오린(Kaolin), 마이카(Mica), 월라스토나이트(wollastonite), TiO2-코팅된 마이카 소형판 (TiO2-coated mica platelets), 실리카(silica), 알루미나(alumina), 붕규산염 (borosilicates) 및 산화물 (oxides)로 이루어진 군에서 선택된 어느 하나인 것을 특징으로 하는 자동차 헤드램프베젤.The mineral filler may include talc, kaolin, mica, mica, wollastonite, TiO2-coated mica platelets, silica, alumina, and alumina. The car headlamp bezel, characterized in that any one selected from the group consisting of borosilicates (oxides) and oxides (oxides).
  92. 제 89항에 있어서,The method of claim 89,
    상기 블렌드 전체 100 중량%를 기준으로, 상기 미네랄 필러는 5 내지 50 중량%인 것을 특징으로 하는 자동차 헤드램프베젤.Based on 100% by weight of the total blend, the mineral filler is an automobile headlamp bezel, characterized in that 5 to 50% by weight.
  93. 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 폴리머 60 내지 85 중량%와 유리섬유 15 내지 40 중량%를 포함하는 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 폴리케톤 블렌드를 포함하는 차량용 캐니스터.Consists of carbon monoxide and at least one olefinically unsaturated hydrocarbon, containing 5 to 50 ppm of palladium catalyst residue, 60 to 85 wt% of linear alternating polyketone polymer having a molecular weight distribution of 1.5 to 3.0, and 15 to 40 wt% of glass fibers. A vehicle canister comprising a polyketone blend, which is produced by injection molding the blend.
  94. 제 93항에 있어서,94. The method of claim 93,
    상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15 인 것을 특징으로 하는 폴리케톤 블렌드를 포함하는 차량용 캐니스터.The linear alternating polyketone is a vehicle canister comprising a polyketone blend, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15.
  95. 제 93항에 있어서,94. The method of claim 93,
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.2 내지 2.0dl/g인 것을 특징으로 하는 폴리케톤 블렌드를 포함하는 차량용 캐니스터.The intrinsic viscosity of the linear alternating polyketone polymer is a vehicle canister comprising a polyketone blend, characterized in that 1.2 to 2.0dl / g.
  96. 제 93항에 있어서,94. The method of claim 93,
    상기 캐니스터는 충격강도가 20kJ/m2 이상인 것을 특징으로 하는 폴리케톤 블렌드를 포함하는 차량용 캐니스터.The canister is a vehicle canister comprising a polyketone blend, characterized in that the impact strength is 20kJ / m 2 or more.
  97. 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 폴리머 60 내지 85 중량%와 유리섬유 15 내지 40 중량%를 포함하는 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 실내등 하우징.Consists of carbon monoxide and at least one olefinically unsaturated hydrocarbon, containing 5 to 50 ppm of palladium catalyst residue, 60 to 85 wt% of linear alternating polyketone polymer having a molecular weight distribution of 1.5 to 3.0, and 15 to 40 wt% of glass fibers. Interior lamp housing, characterized in that the blend is manufactured by injection molding.
  98. 제 97항에 있어서,97. The method of claim 97,
    상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15 인 것을 특징으로 하는 실내등 하우징.The linear alternating polyketone is a room lamp housing, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15.
  99. 제 97항에 있어서,97. The method of claim 97,
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.2 내지 2.0dl/g인 것을 특징으로 하는 실내등 하우징.Indoor light housing, characterized in that the intrinsic viscosity of the linear alternating polyketone polymer is 1.2 to 2.0dl / g.
  100. 제 97항에 있어서,97. The method of claim 97,
    상기 실내등 하우징은 충격강도가 20kJ/m2 이상인 것을 특징으로 하는 실내등 하우징.The indoor light housing is characterized in that the impact strength of 20kJ / m 2 or more.
  101. 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 폴리머 60 내지 90중량%와 유리섬유 10 내지 40 중량%를 포함하는 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 차량용 재떨이.Consists of carbon monoxide and at least one olefinically unsaturated hydrocarbon, containing 5 to 50 ppm of palladium catalyst residue, 60 to 90 wt% of linear alternating polyketone polymer having a molecular weight distribution of 1.5 to 3.0, and 10 to 40 wt% of glass fibers. The ashtray for a vehicle, which is manufactured by injection molding the blend.
  102. 제 101항에 있어서,102. The method of claim 101, wherein
    상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15 인 것을 특징으로 하는 차량용 재떨이.The linear alternating polyketone is an ashtray for a vehicle, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15.
  103. 제 101항에 있어서,102. The method of claim 101, wherein
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.2 내지 2.0dl/g인 것을 특징으로 하는 차량용 재떨이.The intrinsic viscosity of the linear alternating polyketone polymer is a vehicle ashtray, characterized in that 1.2 to 2.0dl / g.
  104. 제 101항에 있어서,102. The method of claim 101, wherein
    상기 차량용 재떨이는 충격강도가 8kJ/m2 이상이고, 50℃, 상대습도 90%RH에서 측정한 충격강도가 25℃, 상대습도 65%RH에서 측정한 충격강도 대비 90% 이상 수준을 유지하는 것을 특징으로 하는 차량용 재떨이.The ashtray for the vehicle has an impact strength of 8 kJ / m 2 or more, and the impact strength measured at 50 ° C. and a relative humidity of 90% RH is maintained at a level of 90% or more compared to the impact strength measured at 25 ° C. and a relative humidity of 65% RH. A vehicular ashtray.
  105. 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 폴리머 60 내지 90중량%와 유리섬유 10 내지 40 중량%를 포함하는 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 자동차용 멀티펑션 스위치.Consists of carbon monoxide and at least one olefinically unsaturated hydrocarbon, containing 5 to 50 ppm of palladium catalyst residue, 60 to 90 wt% of linear alternating polyketone polymer having a molecular weight distribution of 1.5 to 3.0, and 10 to 40 wt% of glass fibers. Multi-function switch for automobiles, characterized in that the blend is manufactured by injection molding.
  106. 제 105항에 있어서,105. The method of claim 105,
    상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15 인 것을 특징으로 하는 자동차용 멀티펑션 스위치.The linear alternating polyketone has a molar ratio of ethylene and propylene of 99: 1 to 85:15.
  107. 제 105항에 있어서,105. The method of claim 105,
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.2 내지 2.0dl/g인 것을 특징으로 하는 자동차용 멀티펑션 스위치.The intrinsic viscosity of the linear alternating polyketone polymer is 1.2 to 2.0 dl / g automotive multi-function switch.
  108. 제 105항에 있어서,105. The method of claim 105,
    상기 자동차용 멀티펑션 스위치는 충격강도가 8kJ/m2 이상이고, 물성유지율이 90% 이상인 것을 특징으로 하는 자동차용 멀티펑션 스위치.The automotive multi-function switch has an impact strength of 8 kJ / m 2 or more, the physical property maintenance rate of the vehicle multi-function switch, characterized in that more than 90%.
  109. 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 폴리머를 사출성형하여 제조되는 것을 특징으로 하는 자동차용 스피커 그릴.An automobile speaker grill, comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon, and having a palladium catalyst residue of 5 to 50 ppm and a linear alternating polyketone polymer having a molecular weight distribution of 1.5 to 3.0.
  110. 제 109항에 있어서,109. The method of claim 109,
    상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15 인 것을 특징으로 하는 자동차용 스피커 그릴.The linear alternating polyketone is an automobile speaker grill, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15.
  111. 제 109항에 있어서,109. The method of claim 109,
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.2 내지 2.0dl/g인 것을 특징으로 하는 자동차용 스피커 그릴.The intrinsic viscosity of the linear alternating polyketone polymer is 1.2 to 2.0 dl / g car speaker grill, characterized in that.
  112. 제 109항에 있어서,109. The method of claim 109,
    상기 자동차용 스피커 그릴은 충격강도가 15kJ/m2 이상인 것을 특징으로 하는 자동차용 스피커 그릴.The vehicle speaker grill is an automobile speaker grill, characterized in that the impact strength is more than 15kJ / m 2 .
  113. 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 폴리머를 사출성형하여 제조되는 것을 특징으로 하는 자동차용 헤드레스트 가이드.An automotive headrest guide comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon, injection molding a linear alternating polyketone polymer having a palladium catalyst residual of 5 to 50 ppm and a molecular weight distribution of 1.5 to 3.0. .
  114. 제 113항에 있어서,113. The method of claim 113,
    상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15 인 것을 특징으로 하는 자동차용 헤드레스트 가이드.The linear alternating polyketone has a molar ratio of ethylene and propylene of 99: 1 to 85:15.
  115. 제 113항에 있어서,113. The method of claim 113,
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.2 내지 2.0dl/g인 것을 특징으로 하는 자동차용 헤드레스트 가이드.The intrinsic viscosity of the linear alternating polyketone polymer is 1.2 to 2.0 dl / g vehicle headrest guide, characterized in that.
  116. 제 113항에 있어서,113. The method of claim 113,
    상기 자동차용 헤드레스트 가이드는 충격강도가 20kJ/m2 이상인 것을 특징으로 하는 자동차용 헤드레스트 가이드.The headrest guide for a car headrest guide for cars, characterized in that the impact strength is 20kJ / m 2 or more.
  117. 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 폴리머를 사출성형하여 제조되는 것을 특징으로 하는 자동차용 내비게이션 받침대.A vehicle navigation stand comprising a carbon monoxide and at least one olefinically unsaturated hydrocarbon, a palladium catalyst balance of 5 to 50 ppm, and a linear alternating polyketone polymer having a molecular weight distribution of 1.5 to 3.0.
  118. 제 117항에 있어서,118. The method of claim 117,
    상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15 인 것을 특징으로 하는 자동차용 내비게이션 받침대.The linear alternating polyketone has a molar ratio of ethylene and propylene in the range of 99: 1 to 85:15.
  119. 제 117항에 있어서,118. The method of claim 117,
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.2 내지 2.0dl/g인 것을 특징으로 하는 자동차용 내비게이션 받침대.The intrinsic viscosity of the linear alternating polyketone polymer is 1.2 to 2.0 dl / g, the navigation support for automobiles.
  120. 제 117항에 있어서,118. The method of claim 117,
    상기 자동차용 내비게이션 받침대는 충격강도가 15kJ/m2 이상인 것을 특징으로 하는 자동차용 내비게이션 받침대.The vehicle navigation pedestal is a vehicle navigation pedestal, characterized in that the impact strength is more than 15kJ / m 2 .
  121. 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 5 내지 50ppm이고, 분자량 분포가 1.5 내지 3.0인 선상 교대 폴리케톤 폴리머를 사출성형하여 제조되는 것을 특징으로 하는 자동차용 사이드 몰딩.An automobile side molding comprising a carbon monoxide and at least one olefinically unsaturated hydrocarbon, and having a palladium catalyst residue of 5 to 50 ppm and a linear alternating polyketone polymer having a molecular weight distribution of 1.5 to 3.0.
  122. 제 121항에 있어서,128. The method of claim 121, wherein
    상기 선상 교대 폴리케톤은 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15 인 것을 특징으로 하는 자동차용 사이드 몰딩.The linear alternating polyketone is an automobile side molding, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15.
  123. 제 121항에 있어서,128. The method of claim 121, wherein
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.2 내지 2.0dl/g인 것을 특징으로 하는 자동차용 사이드 몰딩.The intrinsic viscosity of the linear alternating polyketone polymer is 1.2 to 2.0 dl / g for automobile side molding.
  124. 제 121항에 있어서,128. The method of claim 121, wherein
    상기 자동차용 사이드 몰딩은 충격강도가 15kJ/m2 이상인 것을 특징으로 하는 자동차용 사이드 몰딩.The vehicle side molding is an automobile side molding, characterized in that the impact strength is more than 15kJ / m 2 .
  125. 하기의 일반식(1)과(2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, y/x가 0.03 내지 0.3 인 폴리케톤 공중합체를 사출성형하여 제조되고, 영하 30℃에서의 저온 충격강도가 4kJ/m2 이상인 것을 특징으로 하는 폴리케톤 호스 커넥터.A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), which is prepared by injection molding a polyketone copolymer having y / x of 0.03 to 0.3, and a low temperature impact at -30 ° C. Polyketone hose connector characterized in that the strength is more than 4kJ / m2.
    [일반식 1][Formula 1]
    -(CH2CH2-CO)x--(CH2CH2-CO) x-
    [일반식 2][Formula 2]
    -(CH2CH(CH3)-CO)y--(CH2CH (CH3) -CO) y-
    (x, y는, 폴리머 중의 일반식(1) 및 (2) 각각의 몰%)(x, y are mole% of each of the general formulas (1) and (2) in the polymer)
  126. 제 125항에 있어서, 126. The method of claim 125,
    상기 폴리케톤 공중합체는 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15인 것을 특징으로 하는 폴리케톤 호스 커넥터.The polyketone copolymer is a polyketone hose connector, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15.
  127. 제 125항에 있어서,126. The method of claim 125,
    상기 폴리케톤 공중합체의 고유 점도가 1.0 내지 2.0dl/g 인 것을 특징으로 하는 폴리케톤 호스 커넥터.Polyketone hose connector, characterized in that the intrinsic viscosity of the polyketone copolymer is 1.0 to 2.0dl / g.
  128. 제 125항에 있어서,126. The method of claim 125,
    상기 폴리케톤 공중합체의 중합에 사용되는 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 폴리케톤 호스 커넥터.The ligand of the catalyst composition used for the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl Phosphine) polyketone hose connector.
  129. 하기의 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, y/x가 0.03 내지 0.3 인 폴리케톤 공중합체를 사출성형하여 제조되는 것을 특징으로 하는 폴리케톤 에어컨용 스템 볼트.Polyketone copolymer comprising a repeating unit represented by the following general formula (1) and (2), for polyketone air conditioner, characterized in that produced by injection molding a polyketone copolymer having y / x of 0.03 to 0.3 Stem bolts.
    [일반식 1][Formula 1]
    -(CH2CH2-CO)x--(CH2CH2-CO) x-
    [일반식 2][Formula 2]
    -(CH2CH(CH3)-CO)y--(CH2CH (CH3) -CO) y-
    (x, y는, 폴리머 중의 일반식(1) 및 (2) 각각의 몰%)(x, y are mole% of each of the general formulas (1) and (2) in the polymer)
  130. 제 129항에 있어서, 129. The method of claim 129,
    상기 폴리케톤 에어컨용 스템 볼트는 파단신율이 100% 이상이고, 충격강도가 10kJ/m2 이상인 것을 특징으로 하는 폴리케톤 에어컨용 스템 볼트.The stem bolt for polyketone air conditioner has an elongation at break of 100% or more, the impact bolt is a polyketone air conditioning stem bolt, characterized in that more than 10kJ / m2.
  131. 제 129항에 있어서, 129. The method of claim 129,
    상기 폴리케톤 공중합체는 에틸렌과 프로필렌의 몰비%가 99:1 내지 85:15인 것을 특징으로 하는 폴리케톤 에어컨용 스템 볼트.The polyketone copolymer is a stem bolt for polyketone air conditioner, characterized in that the molar ratio of ethylene and propylene is 99: 1 to 85:15.
  132. 제 129항에 있어서,129. The method of claim 129,
    상기 폴리케톤 공중합체의 고유 점도가 1.0 내지 2.0dl/g 인 것을 특징으로 하는 폴리케톤 에어컨용 스템 볼트.Stem bolt for polyketone air conditioning, characterized in that the intrinsic viscosity of the polyketone copolymer is 1.0 to 2.0dl / g.
  133. 제 129항에 있어서,129. The method of claim 129,
    상기 폴리케톤 공중합체의 중합에 사용되는 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 폴리케톤 에어컨용 스템 볼트.The ligand of the catalyst composition used for the polymerization of the polyketone copolymer is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl Stem bolt for polyketone air conditioner characterized in that)).
  134. 하기 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, 분자량이 20,000 내지 200,000이며, 분자량 분포가 1.5 내지 2.5이고, y/x가 0.03 내지 0.3인 선상 교대 폴리케톤과 비정질 반방향족 폴리아미드를 포함하며, 상기 폴리케톤과 비정질 반방향족 폴리아미드의 중량비가 60:40 내지 95:5 인 것을 특징으로 하는 폴리케톤 조성물.A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), having a molecular weight of 20,000 to 200,000, a molecular weight distribution of 1.5 to 2.5, and a linear alternating polyketone having y / x of 0.03 to 0.3 And an amorphous semiaromatic polyamide, wherein the weight ratio of the polyketone and the amorphous semiaromatic polyamide is 60:40 to 95: 5.
    -[-CH2CH2-CO]x- (1)-[-CH2CH2-CO] x- (1)
    -[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
    (x, y는 폴리머 중의 일반식 (1) 및 (2)의 각각의 몰%를 나타낸다.)(x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)
  135. 제 134항에 있어서,135. The method of claim 134,
    상기 비정질 반방향족 폴리아미드는 폴리 헥사메틸렌이소프탈아미드인 것을 특징으로 하는 폴리케톤 조성물.Wherein said amorphous semiaromatic polyamide is poly hexamethyleneisophthalamide.
  136. 제 134항에 있어서,135. The method of claim 134,
    상기 폴리케톤 조성물의 굴곡강도는 65 내지 90MPa 인 것을 특징으로 하는 폴리케톤 조성물.Flexural strength of the polyketone composition is a polyketone composition, characterized in that 65 to 90MPa.
  137. 제 134항에 있어서,135. The method of claim 134,
    상기 폴리케톤 조성물의 굴곡탄성률은 1,700MPa 이상인 것을 특징으로 하는 폴리케톤 조성물.Flexural modulus of the polyketone composition is a polyketone composition, characterized in that 1,700MPa or more.
  138. 제 134항에 있어서,135. The method of claim 134,
    상기 폴리케톤 조성물의 충격강도는 7kJ/m2 이상인 것을 특징으로 하는 폴리케톤 조성물.Impact strength of the polyketone composition is a polyketone composition, characterized in that more than 7kJ / m2.
  139. 제 134항 내지 제 138항 중 어느 한 항에 기재된 폴리케톤 조성물로 제조된 폴리케톤 성형품.A polyketone molded article made of the polyketone composition according to any one of claims 134 to 138.
  140. 하기 일반식 (1)과 (2)로 표시되는 반복 단위로 이루어진 폴리케톤 공중합체로서, y/x가 0.03 내지 0.3인 선상 교대 폴리케톤과 폴리에스테르를 포함하고, 상기 폴리에스테르는 조성물 전체중량 대비 10 내지 90 중량%인 것을 특징으로 하는 폴리케톤 조성물.A polyketone copolymer composed of repeating units represented by the following general formulas (1) and (2), the linear alternating polyketone having y / x of 0.03 to 0.3 and polyester, wherein the polyester is compared to the total weight of the composition Polyketone composition, characterized in that 10 to 90% by weight.
    -[-CH2CH2-CO]x- (1)-[-CH2CH2-CO] x- (1)
    -[-CH2-CH(CH3)-CO]y- (2)-[-CH2-CH (CH3) -CO] y- (2)
    (x, y는 폴리머 중의 일반식 (1) 및 (2)의 각각의 몰%를 나타낸다.)(x, y represents the mole% of each of the general formulas (1) and (2) in the polymer.)
  141. 제 140항에 있어서,141. The method of claim 140,
    상기 폴리케톤은 고유점도가 1.0 내지 2.0 dl/g인 것을 특징으로 하는 폴리케톤 조성물. The polyketone polyketone composition, characterized in that the intrinsic viscosity is 1.0 to 2.0 dl / g.
  142. 제 140항에 있어서,141. The method of claim 140,
    상기 폴리케톤 조성물은 ASTM D-638에 의해 300℃에서 2시간 열처리하여, 상기 처리전후의 폴리케톤 조성물 시편의 사출방향부분 및 직각방향의 폭을 슬라이드캘리퍼에 의해 측정 시, 각각 2.0%이하 및 0.5%이하인 것을 특징으로 하는 폴리케톤 조성물.The polyketone composition was heat-treated at 300 ° C. for 2 hours by ASTM D-638, and the width of the injection direction portion and the right-angle direction of the polyketone composition specimens before and after the treatment were measured by a slide caliper, respectively, less than 2.0% and 0.5, respectively. Polyketone composition, characterized in that less than or equal to.
  143. 제 140항 내지 제 142항 중 어느 한 항의 폴리케톤 조성물을 포함하는 자동차 연료 용기용 폴리케톤 성형품.145. A polyketone molded article for an automotive fuel container comprising the polyketone composition of any one of claims 140-142.
  144. 폴리케톤 조성물 중 일산화탄소와 적어도 1종의 올레핀계 불포화 탄화수소로 이루어지고, 팔라듐 촉매잔량이 50ppm이하 이고, 분자량 분포가 1.5 내지 2.5인 선상 교대 폴리케톤 폴리머 53 내지 71중량%와, 유리섬유 25 내지 35중량%와, 인계 난연제 2 내지 12중량%와, 나일론 6I 2 내지 8중량%를 포함하는 블렌드를 사출성형하여 제조되는 것을 특징으로 하는 폴리케톤 노트북 하단 하우징.53-71 wt% of linear alternating polyketone polymers comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon in the polyketone composition, having a residual amount of palladium catalyst of 50 ppm or less, and a molecular weight distribution of 1.5-2.5, and glass fibers 25-35 A polyketone notebook bottom housing, comprising: injection molding a blend comprising a weight percent, 2-12 weight percent phosphorus-based flame retardant, and 2-8 weight percent nylon 6I.
  145. 제 144항에 있어서,145. The method of claim 144,
    상기 선상 교대 폴리케톤의 중합시 촉매조성물의 리간드는 ((2,2-디메틸-1,3-디옥산-5,5-디일)비스(메틸렌))비스(비스(2-메톡시페닐)포스핀)인 것을 특징으로 하는 폴리케톤 노트북 하단 하우징.The ligand of the catalyst composition in the polymerization of the linear alternating polyketone is ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) force Pin) the polyketone notebook bottom housing.
  146. 제 144항에 있어서,145. The method of claim 144,
    상기 선상 교대 폴리케톤 폴리머의 고유점도는 1.0 내지 2.0dl/g인 것을 특징으로 하는 폴리케톤 노트북 하단 하우징.The polyketone notebook bottom housing, characterized in that the intrinsic viscosity of the linear alternating polyketone polymer is 1.0 to 2.0dl / g.
  147. 제 144항에 있어서,145. The method of claim 144,
    상기 폴리케톤 노트북 하단 하우징의 굴곡 탄성율이 8,000MPa 이상이고, 저온 충격강도가 11.0kJ/m2 이상인 것을 특징으로 하는 폴리케톤 노트북 하단 하우징.Flexural modulus of the polyketone notebook lower housing is more than 8,000MPa, low-temperature impact strength polyketone notebook lower housing, characterized in that more than 11.0kJ / m 2 .
PCT/KR2015/011027 2014-11-07 2015-10-19 Polyketone resin composition with excellent impact resistance WO2016072642A2 (en)

Applications Claiming Priority (62)

Application Number Priority Date Filing Date Title
KR10-2014-0154613 2014-11-07
KR10-2014-0154626 2014-11-07
KR10-2014-0154617 2014-11-07
KR1020140154613A KR101664264B1 (en) 2014-11-07 2014-11-07 Polyketone glasses frame
KR1020140154624A KR101646033B1 (en) 2014-11-07 2014-11-07 Polyketone cable box
KR1020140154626A KR101664260B1 (en) 2014-11-07 2014-11-07 Polyketone molded article with excellent impact resistance
KR1020140154617A KR101611578B1 (en) 2014-11-07 2014-11-07 Polyketone high impact mask
KR10-2014-0154620 2014-11-07
KR1020140154620A KR101664219B1 (en) 2014-11-07 2014-11-07 Polyketone electronic device cover
KR10-2014-0154624 2014-11-07
KR10-2014-0161977 2014-11-19
KR1020140161992A KR101664919B1 (en) 2014-11-19 2014-11-19 Polyketone composition comprising polyurethane resin
KR1020140161978A KR101655336B1 (en) 2014-11-19 2014-11-19 Polyketone bumper bracket
KR1020140162006A KR101706052B1 (en) 2014-11-19 2014-11-19 Polyketone composition comprising polycarbonate
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