KR20170050186A - Polyketone resin composition and method for preparing the same - Google Patents
Polyketone resin composition and method for preparing the same Download PDFInfo
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- KR20170050186A KR20170050186A KR1020150151405A KR20150151405A KR20170050186A KR 20170050186 A KR20170050186 A KR 20170050186A KR 1020150151405 A KR1020150151405 A KR 1020150151405A KR 20150151405 A KR20150151405 A KR 20150151405A KR 20170050186 A KR20170050186 A KR 20170050186A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
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- Manufacturing & Machinery (AREA)
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Abstract
The present invention relates to a polyketone resin composition and a process for producing the same. The polyketone resin composition of the present application is capable of achieving high mechanical strength, anti-freeze-resistance, anti-hygroscopicity, chemical resistance, and the like, thereby achieving various physical properties in a harmonious manner. For example).
Description
The present invention relates to a polyketone resin composition and a process for producing the same.
The radiator end tank for an automobile distributes a high temperature antifreeze received from an automobile engine to a radiator core for heat exchange and collects an antifreeze solution so that the heat exchanged antifreeze flows into the automobile engine again. At this time, the radiator end tank is always in contact with the antifreeze in the temperature range of about 100 ° C with a pressure of about 1 kg / cm 2. It also requires a high mechanical strength to provide a shape for mounting peripheral components and is complicated in shape.
Typical materials used in conventional automotive radiator end tanks include polyamide 66 (PA66) and glass fiber blends, and polyamide 6,12 / 66 blends (PA6, 12/66) and glass fiber blends.
However, PA66, PA6, 12/66 and the like have a problem that their physical properties and dimensions change after moisture absorption, and when they come into contact with calcium chloride (CaCl2) used as a winter seasoning agent due to low chemical resistance, There is a case where the antifreeze is leaked due to the crack of the radiator end tank due to the weakening of the bonding force by cutting off the hydrogen bond and thus the vehicle can not be operated.
Accordingly, there is a demand for development of new materials suitable for various materials, particularly automobile radiator end tanks, because of excellent chemical resistance, antifreeze resistance, durability and resistance to water absorption such as calcium chloride resistance as well as mechanical properties .
The present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide an automobile radiator end tank which is excellent in mechanical properties such as calcium chloride resistance as well as mechanical properties basically required for industrial materials, The present invention provides a polyketone resin composition and a process for producing the same.
In order to solve the above problems, the present application relates to a polyketone resin; Amorphous aromatic polyamides; And a silane coupling agent, and a molded article thereof (particularly, an automobile radiator end tank).
The present application also covers polyketone resin from 40 parts by weight to 60 parts by weight; 5 to 30 parts by weight of an amorphous aromatic polyamide; And 0.1 part by weight to 3 parts by weight of a silane coupling agent.
The polyketone resin composition of the present application is capable of achieving high mechanical strength, anti-freeze-resistance, anti-hygroscopicity, chemical resistance, and the like, thereby achieving various physical properties in a harmonious manner. For example).
The present application relates to a polyketone resin composition.
Exemplary polyketone resin compositions include polyketone resins; Amorphous aromatic polyamides; And a silane coupling agent.
The polyketone resin is a new resin which has recently been developed and is excellent in mechanical properties such as impact strength and molding properties and is a thermoplastic synthetic resin which is usefully applied to molded articles such as food containers and various parts. The mechanical properties of the polyketone resin belong to the category of high performance plastics. Polyketone resins having other desirable properties such as conductivity while retaining inherent physical properties such as mechanical properties and molding properties are widely used for various purposes.
The polyketone resin is a polymer material synthesized from carbon monoxide as a raw material, and has attracted great attention as an environmentally friendly material.
Generally, the polyketone resin is synthesized from carbon monoxide and olefins. For example, U.S. Patent No. 4,843,144 discloses line alternating polymers synthesized from olefins such as ethylene and propylene and carbon monoxide. The polyketone resin produced in this patent has been shown to have excellent impact resistance, high rebound resilience at room temperature and low temperature, and excellent creep properties.
In recent years, among polyketones, there is a growing interest in a series of alternating polyketones in which ketone groups and at least one ethylenically unsaturated hydrocarbon are alternately polymerized and improved in mechanical properties and molding characteristics. For example, U.S. Patent No. 4,880,903 discloses a polyketone terpolymer in which ketone groups, ethylene, and other olefinically unsaturated hydrocarbons (such as propylene) are alternately polymerized and formed.
The contents of the aforementioned U.S. Patent Nos. 4,843,144 and 4,880,903 are incorporated herein by reference.
Specifically, the linear alternating polyketone, which is the main component of the polyketone resin composition of the present application, is a linear alternating structure composed of a ketone group and at least one ethylenically unsaturated hydrocarbon, and substantially one carbon monoxide (or ketone And excellent physical properties, appearance characteristics and molding characteristics.
The polyketone resin may contain a repeating unit represented by the following formula (1).
[Chemical Formula 1]
- {- CO- (- CH2 --CH2 -) -} x- {CO- (G)
Wherein G is derived from monomers of at least three ethylenically unsaturated hydrocarbons polymerized through ethylenic unsaturation and x: y is at least 2: 1.
Ethylenically unsaturated hydrocarbons suitable for use as the precursor of the polyketone resin include ethyne having up to 20 carbon atoms, preferably up to 10 carbon atoms, alpha -olefins (e.g., propene, 1-butene aliphatic hydrocarbons such as isobutene, 1-hexene and 1-octene, or aryl aliphatic hydrocarbons in which aryl substituents are formed on aliphatic molecules, in particular ethylenically unsaturated carbon Is an aryl aliphatic hydrocarbon having an aryl substituent on the atom. Examples of the aryl aliphatic hydrocarbon in the ethylenic unsaturated hydrocarbon include styrene, p-methylstyrene, p-ethylstyrene, and m-isopropyl styrene.
Such ethylenically unsaturated hydrocarbons and ketone compounds are copolymerized to form a linear alternating polyketone. Among them, a linear alternating polyketone formed by copolymerization of ethene and a ketone compound, or a mixture of at least three Linear alternating polyketone formed by copolymerization of an ethylenically unsaturated hydrocarbon having a carbon atom is preferable in view of the fact that the copolymerization reaction is easy and the molecular weight of the copolymerized linear alternating polyketone is relatively uniform. In short, the preferred polyketone resin is a copolymer of carbon monoxide and ethene, more preferably a second ethylenically unsaturated hydrocarbon having carbon monoxide, ethene and at least three carbon atoms (especially propene) is a linear terpolymer with an a-olefin.
The polyketone resin preferably has an intrinsic viscosity (LVN) of 0.5 to 10 dl / g, more preferably 0.8 to 4 dl / g, and most preferably 1 to 1.5 dl / g. If the intrinsic viscosity of the polyketone resin is less than 0.5 dl / g, the mechanical properties may be deteriorated. If the intrinsic viscosity exceeds 10 dl / g, the workability may be deteriorated.
The polyketone resin has a number-average molecular weight, as measured by gel permeation chromatography, of preferably 100 to 200,000, more preferably 20,000 to 90,000. The physical properties of the polymer depend on the molecular weight, whether the polymer is a copolymer or a terpolymer, and in the case of a terpolymer, the physical properties of the second hydrocarbon moiety are determined.
The melting point of the polyketone resin is usually in the range of 175 ° C to 300 ° C, specifically 210 ° C to 270 ° C, but is not limited thereto.
The amorphous aromatic polyamide is aromatic nylon, and preferably contains an aromatic structure in the main chain.
When the amorphous aromatic polyamide is included, it is excellent in high strength, high rigidity, high heat resistance, low absorptivity and dimensional stability and is widely used in electric / electronic, automobile, industrial equipment, and aircraft.
The amorphous aromatic polyamide is not particularly limited, but may be, for example, polyhexamethyleneisophthalamide having an aromatic structure in the main chain.
The polyketone resin composition according to the present application may contain a silane coupling agent for improving the interfacial adhesion between the polyketone resin and the glass fiber described later.
As the silane coupling agent, aminosilane can be used. By coating the glass fiber with a glass fiber described later, compatibility of the glass fiber and the polyketone can be imparted to improve the interfacial adhesion.
Examples of the silane coupling agent include aminoethyltrimethoxysilane, aminoethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, methylaminopropyltrimethoxysilane, ethylaminopropyltrimethoxysilane, Aminopropyltripropoxysilane, aminoisobutyltrimethoxysilane, and aminobutyltriethoxysilane, but are not limited thereto.
The polyketone resin composition according to the present application comprises 40 to 60 parts by weight of a polyketone resin; 5 to 30 parts by weight of an amorphous aromatic polyamide; And 0.1 to 3 parts by weight of a silane coupling agent.
In the present specification, the unit " part by weight " may mean the ratio of the weight between each component.
More specifically, the polyketone resin composition according to the present application comprises 50 to 60 parts by weight of a polyketone resin; 5 parts by weight to 15 parts by weight of amorphous aromatic polyamide; And 0.1 part by weight to 1 part by weight of a silane coupling agent.
The polyketone resin composition according to the present invention has the above-mentioned constitution within the above-mentioned range, and it is possible to improve the calcium chloride resistance, anti-freeze property, hygroscopicity and chemical resistance, while achieving mechanical stiffness, Bar, and various industrial materials (particularly, materials for automobile radiator end tanks).
The polyketone resin composition according to the present application may further comprise glass fibers.
The glass fiber preferably has a particle diameter of 6 mu m to 3,000 mu m. If the particle diameter of the glass fiber is less than 6 mu m, the shape of the glass fiber may change and the mechanical properties may deteriorate. If the particle diameter exceeds 3,000 mu m, the glass fiber may protrude from the product surface.
The polyketone resin composition of the present application may further contain tribasic calcium phosphate as a processing stabilizer in order to alleviate poor workability due to an increase in viscosity of the extruder due to polyketone residues in the extruder and to maintain the viscosity.
The amount of the tribasic calcium phosphate is preferably 0.1 part by weight to 3 parts by weight or 0.1 part by weight to 1 part by weight in the polyketone resin composition of the present application. The content of tribasic calcium phosphate can be controlled within the above-mentioned range to maintain the mechanical rigidity and maintain the viscosity for securing workability.
The polyketone resin composition of the present application may include a pigment (plastic coloring agent) for realizing black when used as a material for parts to be mounted on automobile engine room or the like.
The pigment is preferably contained in the polyketone resin composition of the present application in an amount of 0.1 part by weight to 3 parts by weight or 0.1 part by weight to 1 part by weight. The pigment content can be adjusted to the above-mentioned range to maintain the mechanical rigidity and enable more effective color implementation.
The polyketone resin composition of the present application may additionally contain additives commonly used in the art within the scope not deviating from the object.
Illustratively, the polyketone resin composition of the present application may be added to the polyketone resin composition of the present application alone, or in combination of two or more, in addition to the components described above, antioxidants, heat stabilizers, lubricants, processing aids and weather stabilizers.
As the antioxidant, a phenolic oxamide antioxidant may be used, which has a deactivation effect of the metal catalyst used in the polymerization. The antioxidant is preferably contained in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the polyketone resin. If the content of the antioxidant is less than 0.1 parts by weight, the deactivation function of the metal catalyst may be deteriorated. If the amount is more than 0.5 parts by weight, the physical properties of the product may be deteriorated.
As the heat stabilizer, a phosphorus-based heat stabilizer, particularly a hydroxy apatite represented by M10 (PO4) 6 (OH) 2 (wherein M is barium, strontium or calcium), preferably calcium hydroxyapatite Which suppresses the problem of an increase in viscosity during processing. The heat-resistant stabilizer is preferably contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the polyketone resin. If the content of the heat-resistant stabilizer is less than 0.1 parts by weight, the viscosity-restraining function may be deteriorated. If the content is more than 2 parts by weight, the physical properties of the product may be deteriorated.
As the activator, an ethylene-methacrylic acid ester and / or a polyethylene-based synthetic lubricant such as ethylene bisstearamide, which is an acrylic lubricant, may be used. These lubricants are preferably contained in an amount of 0.1 to 1 part by weight per 100 parts by weight of the polyketone resin. If the content of the lubricant is less than 0.1 part by weight, the appearance quality may be deteriorated, and if it exceeds 1 part by weight, the mechanical properties may be deteriorated.
As the processing aid, ethylene methacrylic acid may be used. As the weather stabilizer, a benzotriazole-based material, a triazine-based material, a hindered amine-based material, and the like may be used, but the present invention is not limited thereto.
By containing the polyketone resin composition according to the present application in the content ratio between the above-described components and the above-mentioned components, the mechanical strength can be secured and the calcium chloride resistance, anti-antifreeze property, moisture absorption resistance and chemical resistance can be greatly improved, And can be suitably used as various industrial materials (particularly, a material for an automobile radiator end tank).
Regarding the above mechanical stiffness, the polyketone resin composition of the present application can satisfy the following formulas (1) and (2).
[Equation 1]
X ≥ 1,800 Kgf / cm2
[Equation 2]
Y? 2,300 Kgf / cm2
In the above formula (1), X represents the tensile strength of the polyketone resin composition measured by a commonly known ASTM D638, and Y represents the flexural strength of the polyketone resin composition measured by a commonly known ASTM D790.
The lower limit of the range of X is not particularly limited, but may be 1,820 Kgf / cm2 or more, 1,840 Kgf / cm2 or more, or 1,860 Kgf / cm2 or more, for example.
The lower limit of the range of Y is not particularly limited, but may be, for example, 2,350 Kgf / cm2 or more, 2,400 Kgf / cm2 or more, or 2,450 Kgf / cm2 or more.
The present application also relates to a method for producing the above polyketone resin composition.
Illustratively, the present application relates to a process for the preparation of polyolefin resins comprising: 40 to 60 parts by weight of a polyketone resin; 5 to 30 parts by weight of an amorphous aromatic polyamide; And 0.1 part by weight to 3 parts by weight of a silane coupling agent.
The polyketone resin, the amorphous aromatic polyamide and the silane coupling agent are as described above.
The polyketone resin composition of the present application can be molded into various various products by molding by a conventional method such as extrusion and injection.
Specifically, the polyketone resin composition of the present application is injection-molded or extruded to obtain a sheet, a film, a plate, an OA device, an electric / electronic part, a housing part, an automobile part, a machine part, Various industrial materials can be produced, and such industrial materials can have excellent mechanical properties and molding properties.
The present application also relates to a molded article of the polyketone resin composition.
Particularly, the polyketone resin composition of the present application is excellent in mechanical strength and durability, as well as in calcium chloride resistance, anti-antifreeze property, hygroscopicity and chemical resistance, and is a material for molding an automobile radiator end tank It is very suitable.
Hereinafter, the polyketone resin composition will be described in detail by way of examples and comparative examples, but the scope of the polyketone resin composition is not limited by the following examples and comparative examples.
In the following Examples, the physical properties were measured in the following manner.
1. Specific gravity
The specific gravity of specimens for automobile radiator end tanks manufactured in Examples and Comparative Examples was measured according to ASTM D792 and is shown in Table 1 below.
2. Ash content
Blends of test specimens for automobile radiator end tanks prepared in Examples and Comparative Examples were measured according to ASTM D5630 and are shown in Table 1 below.
3. Tensile Strength and Elongation at Break
Tensile strength and elongation at break of specimens for automobile radiator end tanks prepared in Examples and Comparative Examples were measured according to ASTM D638 and are shown in Table 2 below.
4. Flexural Strength and Flexural Modulus
The flexural strength and flexural modulus of specimens for automobile radiator end tanks prepared in Examples and Comparative Examples were measured according to ASTM D790 and are shown in Table 2 below.
5. Izod impact strength
The Izod impact strengths of the specimens for automobile radiator end tanks prepared in Examples and Comparative Examples were measured according to ASTM D256 and are shown in Table 2 below.
Example 1
Preparation of polyketone resin composition
57 parts by weight of "PK 230" as a polyketone resin, 10 parts by weight of "PA 6I" as an amorphous aromatic polyamide and "SCA11WT (molecular weight 221.33, specific gravity 0.946 g / cm 3, Struktol Co.) , 33 parts by weight of "435TM (length x diameter = 3 mm x 10 m, Taishan Fiberglass Co., Ltd.)" as the glass fiber, "TCP (tricalcium phosphate, density 3.14 g / cm3, melting point (Tm) , 0.3 parts by weight of "NB9089 (carbon black: polyethylene = 50:50, density 1.7 to 2.1 g / cm 3, melting point (Tm) 3,550 ° C)" as a pigment were uniformly mixed to obtain a polyketone resin A composition was prepared.
Manufacture of Specimen for Car Radiator End Tank
The polyketone resin composition pellets prepared above were molded (injection molded) into specimens for automobile radiator end tanks.
Comparative Example 1
Preparation of polyketone resin composition
52 parts by weight of "PK 230" as a polyketone resin, 15 parts by weight of "PA 6I" as amorphous aromatic polyamide, and 435 parts by weight of "435 TM (length × diameter = 3 mm × 10 μm, Taishan Fiberglass" 0.5 parts by weight of "TCP (tricalcium phosphate, density 3.14 g / cm3, melting point (Tm) 1,391 ° C, Budenheim Co.)" as a tribasic calcium phosphate and "NB9089 (carbon black: polyethylene = 50:50, density 1.7 To 2.1 g / cm < 3 >, melting point (Tm) 3,550 DEG C) " were uniformly mixed to prepare a polyketone resin composition.
Manufacture of Specimen for Car Radiator End Tank
The polyketone resin composition pellets prepared above were molded (injection molded) into specimens for automobile radiator end tanks.
Comparative Example 2
Preparation of polyketone resin composition
, 67 parts by weight of "PK 230" as a polyketone resin, 0.5 parts by weight of "SCA11WT (molecular weight 221.33, specific gravity 0.946 g / cm3, Struktol Co.)" as a silane coupling agent, "435 TM (length × diameter = 33 parts by weight of tungsten phosphate glass (Taishan Fiberglass Co., Ltd.), 0.5 parts by weight of "TCP (tricalcium phosphate, density 3.14 g / cm3, melting point (Tm) 1,391 ° C, Budenheim Co.)" as tribasic calcium phosphate and "NB9089 0.3 parts by weight of black: polyethylene = 50: 50, density: 1.7 to 2.1 g / cm3, melting point (Tm): 3,550 DEG C) were uniformly mixed to prepare a polyketone resin composition.
Manufacture of Specimen for Car Radiator End Tank
The polyketone resin composition pellets prepared above were molded (injection molded) into specimens for automobile radiator end tanks.
Comparative Example 3
Preparation of polyketone resin composition
67 parts by weight of "PK 230" as a polyketone resin, 33 parts by weight of "435TM (length × diameter = 3 mm × 10 μm, Taishan Fiberglass Co.)" as glass fibers, "TCP (tricalcium phosphate, density 3.14 g (carbon black: polyethylene = 50: 50, density: 1.7 to 2.1 g / cm3, melting point (Tm): 3,550 占 폚) as a pigment 0.3 parts by weight were uniformly mixed to prepare a polyketone resin composition.
Manufacture of Specimen for Car Radiator End Tank
The polyketone resin composition pellets prepared above were molded (injection molded) into specimens for automobile radiator end tanks.
Physical properties and mechanical properties measured for each of the above Examples and Comparative Examples are shown in Tables 1 and 2, respectively.
As can be seen from Tables 1 and 2, the polyketone resin composition of the present application has improved physical properties such as calcium chloride resistance, anti-freeze property, hygroscopicity and chemical resistance while securing physical properties and mechanical rigidity. And can be suitably used as various industrial materials (particularly, a material for an automobile radiator end tank).
Claims (12)
Amorphous aromatic polyamides; And a silane coupling agent.
[Equation 1]
X ≥ 1,800 Kgf / cm2
[Equation 2]
Y? 2,300 Kgf / cm2
X is the tensile strength of the polyketone resin composition measured by ASTM D638, and Y is the flexural strength of the polyketone resin composition measured by ASTM D790.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190103734A (en) * | 2018-02-28 | 2019-09-05 | 한국엔지니어링플라스틱 주식회사 | Polyketone composition with excellent appearance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190103734A (en) * | 2018-02-28 | 2019-09-05 | 한국엔지니어링플라스틱 주식회사 | Polyketone composition with excellent appearance |
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