CN103980617A - Glass fiber reinforced flame retardant polypropylene material for household appliance products and preparation method thereof - Google Patents

Glass fiber reinforced flame retardant polypropylene material for household appliance products and preparation method thereof Download PDF

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Publication number
CN103980617A
CN103980617A CN201410171363.1A CN201410171363A CN103980617A CN 103980617 A CN103980617 A CN 103980617A CN 201410171363 A CN201410171363 A CN 201410171363A CN 103980617 A CN103980617 A CN 103980617A
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polypropylene
fire retardant
flame retardant
parts
polypropylene material
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CN103980617B (en
Inventor
沈旭渠
沈寒知
张翼翔
姚杏梅
陈锐彬
李玲玉
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GUANGDONG JUSHI CHEMICAL INDUSTRY Co Ltd
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GUANGDONG JUSHI CHEMICAL INDUSTRY Co Ltd
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/08—Organic materials containing halogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92009—Measured parameter
    • B29C2948/9218—Weight
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92609—Dimensions
    • B29C2948/92619—Diameter or circumference
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
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    • B29C2948/92704—Temperature
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
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    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract

The present invention relates to a glass fiber reinforced flame retardant polypropylene material for household appliance products, and belongs to the field of modified polypropylene plastic. The material comprises the following raw materials, by weight: a high-impact-resistance copolymer polypropylene resin, a bromine-based flame retardant agent, antimony trioxide, a flame retardant synergist, alkali-free continuous long glass fibers, a compatibility agent, a toughening agent, a lubricant, a UV absorber and an antioxidant. The present invention provides the glass fiber reinforced flame retardant polypropylene material with higher tensile strength, bending modulus and hardness as well as high impact-resistance, low molding shrinkage, aging resistance and the like. The glass fiber reinforced flame retardant polypropylene material has a high heat deformation temperature, good oxidation resistance at high temperature, and the flame retardant performance up to the level of UL94 V-2, and passes the glow wire test of GWIT: 700/3.0. The glass fiber reinforced flame retardant polypropylene material has a low cost and a light weight, and can be used instead of metal or plastic material to produce the household appliance products which need flame retardation and high temperature resistance.

Description

A kind of fiberglass reinforced fire retardant polypropylene material and preparation method thereof for household appliances
Technical field
The present invention relates to a kind of polypropylene flame redardant village material, relate in particular to a kind of household appliances fiberglass reinforced fire retardant polypropylene material and preparation method thereof.
Background technology
Polypropylene, owing to having the features such as good over-all properties, good chemical stability, good machine-shaping property and relative cheap price, is widely used in household electrical appliances and automobile-used field.But the polypropylene of non-modified exists tensile strength, modulus in flexure, hardness low, poor heat resistance, the shortcoming such as molding shrinkage is large, easily aging, inflammable, has had a strong impact on polyacrylic use range.
Reinforced Polypropylene is the mixture of polypropylene and glass fibre or mineral filler, glass fibre or mineral filler have improved polyacrylic tensile strength, flexural strength and modulus in flexure, increased substantially polyacrylic heat-drawn wire, fiberglass reinforced fire retardant polypropylene is wherein commonplace application.
In addition, polypropylene itself is very inflammable, after having added glass fibre, flame retardant resistance is poorer, and for the polypropylene of household appliances, not only to reach certain mechanical property, the stability of the work under flame retardant properties and hot conditions is also had to higher requirement, so to the polyacrylic flame-retardant modified very important using value that has of fiberglass reinforced fire retardant.
Traditional fire retardant is all generally to use bromine antimony synergistic fire-retardant, fire-retardant by the synergistic of bromine antimony, product flame is dripped go out or becomes carbon and reach fire-retardant effect, and the application of bromine antimony fire retardant is wide, and flame retardant properties is stablized.While replacing flame-proof ABS and flame-retardant PBT for household electrical appliances and automobile-used field with fiberglass reinforced fire retardant polypropylene, product cost significantly reduces, excellent performance.
Summary of the invention
The problem that the present invention need solve is the fiberglass reinforced fire retardant polypropylene material by providing a kind of household appliances to use, and it is good to make this material have higher tensile strength, modulus in flexure, hardness and its impact property, molding shrinkage is little, be difficult for aging, and the heat-drawn wire of this material is large, flame retardant resistance performance is up to standard.
Need the problem the present invention who solves to adopt following technical scheme according to above-mentioned:
A kind of household appliances fiberglass reinforced fire retardant polypropylene material, is made up of the following raw material of metering by weight:
40 ~ 60 parts of High Impact Polypropylene resins, 20 ~ 25 parts of alkali-free continuous long glass fibers, 6 ~ 15 parts of bromide fire retardants, 3 ~ 6 parts of antimonous oxides, 2 ~ 5 parts of fire retarding synergists, 3 ~ 8 parts of compatilizers, 0 ~ 5 part of toughner, 0.5 part of lubricant, 0.2 part of UV light absorber, 0.3 part, oxidation inhibitor; Wherein, described High Impact Polypropylene is that melting index is the Co-polypropylene that 3 ~ 15g/10min, socle girder notched Izod impact strength are greater than 400J/m.Described bromide fire retardant is any one or several combination of two (2, the 3-dibromopropyl) ether of tetrabromo-bisphenol, TDE, hexabromocyclododecane, three (2,3-dibromopropyl) isocyanuric acid ester.Described antimonous oxide is the antimonous oxide that purity is greater than 99.5%.Described fire retarding synergist is any one or several combination of magnesium hydroxide, aluminium hydroxide, zinc borate, MCA fire retardant, silicon-series five-retardant.
Other auxiliary agent also has, and described compatilizer is maleic anhydride inoculated polypropylene or acrylic acid-grafted polypropylene; Described toughner is any one or several combination in POE, EVA, EPR, SEBS and SBS; Described lubricant is any one or several combination in stearic acid, EBS, polyethylene wax, calcium stearate, Zinic stearas and silicone powder; Described UV light absorber is any one or several combination of UV light absorber UV-234, UV light absorber UV-328 and ultraviolet absorbent UV-531; Described antioxidant is any one or several combination in antioxidant 1010, irgasfos 168, oxidation inhibitor 1098, oxidation inhibitor 245 and antioxidant 1076.Described auxiliary agent be commercial product and in the industry by those of ordinary skill is known, thereby just do not enumerate at this.
The preparation method who the invention allows for above-mentioned household appliances fiberglass reinforced fire retardant polypropylene material, comprises the following steps:
1) after bromide fire retardant, antimonous oxide, fire retarding synergist, toughner, compatilizer, lubricant, UV light absorber and oxidation inhibitor are prepared by proportioning, pre-mixing 1min in low-speed mixer;
2) High Impact Polypropylene is added in low-speed mixer, and in low-speed mixer with mixing of materials 1min after step 1), then material is fed into twin screw extruder from main feed system;
3) alkali-free continuous long glass fiber is added twin screw extruder from the fibre mouthful that adds of twin screw extruder;
4) by the material after step 3) by screw diameter be in 30 ~ 75mm, the length-to-diameter ratio twin screw extruder that is 36 ~ 44:1, carry out mixing, twin screw extruder temperature the firstth district is that 120 ~ 135 DEG C, Second Region ~ Si district are that 180 ~ 185 DEG C, Wu district ~ Shi district are 185 ~ 195 DEG C, head temperature is 200 DEG C, simultaneously by tie rod, pelletizing after water cooling, isolate particle through vibratory screening apparatus, mix rear packaging, to obtain final product.
The present invention selects High Impact Polypropylene as resin base material, has given the basic shock resistance of material itself, makes modification finished product afterwards be unlikely too crisp, is applicable to produce the household appliances product that some need anti-impact; Wherein low flow energy, can ensure that under the prerequisite of the smooth injection moulding of product, shrinking percentage is slightly little, and modulus in flexure is slightly high.Described Co-polypropylene is random copolymers, and by adding different types of monomer molecule, modification---ethene is the most frequently used monomer to the basic structure of its macromolecular chain in addition, and it causes the change of polypropylene physical properties.Compared with PP homopolymer, random copolymers has improved optical property (increased transparency and reduced preformed casse), promote shock resistance, increase flexible, reduce temperature of fusion, thereby also reduced thermal welding temperature, and basic identical with homopolymer aspect chemical stability, water vapor isolation performance and organ sensation performance (low aroma and flavor).
The present invention selects bromine antimony flame-retardant system, and bromine antimony fire retardant is to use to obtain the most general fire retardant, and addition is few, good flame retardation effect and stable.By utilizing the synergy of bromine antimony fire retardant, in the time that polypropylene is subject to high-temp combustion, generate SbBr 3, SbBr 3deng the higher volatile gases of boiling point, this gas relative density is higher, can rest on for a long time dilution inflammable gas in combustion zone, and isolated air, plays fire retardation; This gas can also be caught has combustible radical H, HO, CH 3deng, play inhibition flame interaction.In addition, SbBr 3can condense in the overhead of flame drop formula solia particle, its wall effect scattering amount of heat, slows down combustionvelocity or stops.Report in addition SbCl 3can further be reduced into metallic antimony, antimony reacts with the unsaturated compound forming after the de-HBr of polymkeric substance, forms cross-linked polymer, has improved the thermostability of material.Add fire retarding synergist, the expensive antimonous oxide of Substitute For Partial with bromine antimony fire retardant performance synergistic effect, has improved flame retardant properties in combustion processes, has reduced material cost.
Compatilizer self the band reactive pattern group that the present invention uses, can improve the consistency between glass fibre and acrylic resin, improves tensile strength, flexural strength and the surface smoothness of product.The interpolation of toughner, can, on original basis, improve the polyacrylic socle girder notched Izod impact strength of fiberglass reinforced fire retardant, makes injection moulding product out can meet complete machine fall down test and unlikely breaking; Toughner can determine according to demand and add and do not add, and not adding is exactly 0, and toughness can be not good enough.
In addition, the interpolation of lubricant of the present invention, UV light absorber and oxidation inhibitor, can further improve the processing characteristics of fiberglass reinforced fire retardant polypropylene material, improves thermotolerance and the ageing resistance of product, reduce product and be subject to ultraviolet broken ring, keep the physicals of product.
In a word, when the present invention gives tensile strength that fiberglass reinforced fire retardant polypropylene material is higher, modulus in flexure, hardness, also make it take into account that resistance to impact shock is good, molding shrinkage is little, be difficult for the features such as aging, meanwhile, the heat-drawn wire of this material is large, under hot conditions, oxidation-resistance is good, good flame resistance, glowing filament reaches GWIT:700/3.0, with low cost, lightweight, can replace metallic substance or engineering plastics for making small household electrical appliance.
Embodiment
Base case of the present invention has been to provide a kind of household appliances fiberglass reinforced fire retardant polypropylene material, is made up of the following raw material of metering by weight:
40 ~ 60 parts of High Impact Polypropylene resins, 20 ~ 25 parts of alkali-free continuous long glass fibers, 6 ~ 15 parts of bromide fire retardants, 3 ~ 6 parts of antimonous oxides, 2 ~ 5 parts of fire retarding synergists, 3 ~ 8 parts of compatilizers, 0 ~ 5 part of toughner, 0.5 part of lubricant, 0.2 part of UV light absorber, 0.3 part, oxidation inhibitor; Wherein, described High Impact Polypropylene is that melting index is the Co-polypropylene that 3 ~ 15g/10min, socle girder notched Izod impact strength are greater than 400J/m.Described bromide fire retardant is any one or several combination of two (2, the 3-dibromopropyl) ether of tetrabromo-bisphenol, TDE, hexabromocyclododecane, three (2,3-dibromopropyl) isocyanuric acid ester.Described antimonous oxide is the antimonous oxide that purity is greater than 99.5%.Described fire retarding synergist is any one or several combination of magnesium hydroxide, aluminium hydroxide, zinc borate, MCA fire retardant, silicon-series five-retardant.
Other auxiliary agent also has, and described compatilizer is maleic anhydride inoculated polypropylene or acrylic acid-grafted polypropylene; Described toughner is any one or several combination in POE, EVA, EPR, SEBS and SBS; Described lubricant is any one or several combination in stearic acid, EBS, polyethylene wax, calcium stearate, Zinic stearas and silicone powder; Described UV light absorber is any one or several combination of UV light absorber UV-234, UV light absorber UV-328 and ultraviolet absorbent UV-531; Described antioxidant is any one or several combination in antioxidant 1010, irgasfos 168, oxidation inhibitor 1098, oxidation inhibitor 245 and antioxidant 1076.Described auxiliary agent be commercial product and in the industry by those of ordinary skill is known, thereby only in embodiment, suitably select (being that the auxiliary agent that performance is identical and close can be replaced mutually according to practical situation), just do not enumerate at this.
The preparation method who the invention allows for above-mentioned household appliances fiberglass reinforced fire retardant polypropylene material, comprises the following steps:
1) after bromide fire retardant, antimonous oxide, fire retarding synergist, toughner, compatilizer, lubricant, UV light absorber and oxidation inhibitor are prepared by proportioning, pre-mixing 1min in low-speed mixer;
2) High Impact Polypropylene is added in low-speed mixer, and in low-speed mixer with mixing of materials 1min after step 1), then material is fed into twin screw extruder from main feed system;
3) alkali-free continuous long glass fiber is added twin screw extruder from the fibre mouthful that adds of twin screw extruder;
4) by the material after step 3) by screw diameter be in 30 ~ 75mm, the length-to-diameter ratio twin screw extruder that is 36 ~ 44:1, carry out mixing, twin screw extruder temperature the firstth district is that 120 ~ 135 DEG C, Second Region ~ Si district are that 180 ~ 185 DEG C, Wu district ~ Shi district are 185 ~ 195 DEG C, head temperature is 200 DEG C, simultaneously by tie rod, pelletizing after water cooling, isolate particle through vibratory screening apparatus, mix rear packaging, to obtain final product.
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The fiberglass reinforced fire retardant polypropylene material that the present embodiment household appliances are used is made up of the following raw material of metering by weight:
40 parts of High Impact Polypropylene resins, 20 parts of alkali-free continuous long glass fibers, 6 parts of bromide fire retardants, 3 parts of antimonous oxides, 2 parts of fire retarding synergists, 3 parts of compatilizers, 0 part of toughner, 0.5 part of lubricant, 0.2 part of UV light absorber, 0.3 part, oxidation inhibitor.
Embodiment 2
The fiberglass reinforced fire retardant polypropylene material that the present embodiment household appliances are used is made up of the following raw material of metering by weight:
43 parts of High Impact Polypropylene resins, 21 parts of alkali-free continuous long glass fibers, 8 parts of bromide fire retardants, 2.7 parts of antimonous oxides, 2.7 parts of fire retarding synergists, 4 parts of compatilizers, 1 part of toughner, 0.5 part of lubricant, 0.2 part of UV light absorber, 0.3 part, oxidation inhibitor.
Embodiment 3
The fiberglass reinforced fire retardant polypropylene material that the present embodiment household appliances are used is made up of the following raw material of metering by weight:
47 parts of High Impact Polypropylene resins, 22 parts of alkali-free continuous long glass fibers, 10 parts of bromide fire retardants, 3.5 parts of antimonous oxides, 3.5 parts of fire retarding synergists, 5 parts of compatilizers, 2 parts of toughner, 0.5 part of lubricant, 0.2 part of UV light absorber, 0.3 part, oxidation inhibitor.
Embodiment 4
The fiberglass reinforced fire retardant polypropylene material that the present embodiment household appliances are used is made up of the following raw material of metering by weight:
53 parts of High Impact Polypropylene resins, 23 parts of alkali-free continuous long glass fibers, 12 parts of bromide fire retardants, 4.2 parts of antimonous oxides, 4 parts of fire retarding synergists, 6 parts of compatilizers, 4 parts of toughner, 0.5 part of lubricant, 0.2 part of UV light absorber, 0.3 part, oxidation inhibitor.
Embodiment 5
The fiberglass reinforced fire retardant polypropylene material that the present embodiment household appliances are used is made up of the following raw material of metering by weight:
60 parts of High Impact Polypropylene resins, 25 parts of alkali-free continuous long glass fibers, 15 parts of bromide fire retardants, 6 parts of antimonous oxides, 5 parts of fire retarding synergists, 8 parts of compatilizers, 5 parts of toughner, 0.5 part of lubricant, 0.2 part of UV light absorber, 0.3 part, oxidation inhibitor.
Comparative example is on the basis of embodiment 1, to remove each fire retardant composition, and comparative example 2 is to remove glass fibre on the basis of embodiment 1.The fiberglass reinforced fire retardant polypropylene material that the household appliances of embodiment 1 ~ 5 and comparative example 1 ~ 2 gained are used is all to adopt following methods to prepare, and the method comprises following concrete steps:
1) after bromide fire retardant, antimonous oxide, fire retarding synergist, toughner, compatilizer, lubricant, UV light absorber and oxidation inhibitor are prepared by proportioning, pre-mixing 1min in low-speed mixer;
2) High Impact Polypropylene is added in low-speed mixer, and in low-speed mixer with mixing of materials 1min after step 1), then material is fed into twin screw extruder from main feed system;
3) alkali-free continuous long glass fiber is added twin screw extruder from the fibre mouthful that adds of twin screw extruder;
4) by the material after step 3) by screw diameter be in 30 ~ 75mm, the length-to-diameter ratio twin screw extruder that is 36 ~ 44:1, carry out mixing, twin screw extruder temperature is: the firstth district is 120 ~ 135 DEG C, Second Region ~ Si district is 180 ~ 185 DEG C, Wu district ~ Shi district is 185 ~ 195 DEG C, head temperature is 200 DEG C, by tie rod, pelletizing after water cooling, isolates particle through vibratory screening apparatus simultaneously, mix rear packaging, obtain the fiberglass reinforced fire retardant polypropylene material that a kind of household appliances are used.
Wherein, the temperature in twin screw extruder granulation process Shi Ge district is as shown in table 1:
The temperature in table 1 twin screw extruder granulation process Shi Ge district
The performance of the fiberglass reinforced fire retardant polypropylene material that the household appliances of embodiment 1 ~ 5 and comparative example 1 ~ 2 gained are used is tested, and adopt CG110E horizontal injection machine injection molding standard test specimen, molding technological condition: 170/175/185/180 DEG C of injection temperature (charging opening) (nozzle); Injection pressure 60MPa, dwell time 8s; Cooling time 8s.The testing method of properties is as follows:
Tensile strength: test according to ASTM D-638 standard;
Flexural strength and modulus in flexure: test according to ASTM D-790 standard;
Notch shock performance: test according to ASTM D-256 standard;
Heat-drawn wire: test by ASTM D-648 standard;
Flame retardant test: test by UL 94 standards;
Glowing filament test: test by IEC 60695-2-12/IEC 60695-2-13 standard;
Test result is as shown in table 2:
Table 2: the performance of fiberglass reinforced fire retardant acrylic plastering
　 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2
High Impact Polypropylene resin 40 43 47 53 60 69 73
Alkali-free continuous long glass fiber 20 21 22 23 25 20 0
Bromide fire retardant 6 8 10 12 15 0 10
Antimonous oxide 3 2.7 3.5 4.2 6 0 3
Fire retarding synergist 2 2.7 3.5 4 5 0 3
Compatilizer 3 4 5 5 8 5 5
Toughner 0 1 2 4 5 5 5
Lubricant 0.5 0.5 0.5 0.5 0.5 0.5 0.5
UV light absorber 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Oxidation inhibitor 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Tensile strength (MPa) 52 61 53 63 52 50 32
Flexural strength (MPa) 70 81 75 84 72 67 35
Modulus in flexure (MPa) 3123 3574 3356 3711 3256 3205 1236
Socle girder notched Izod impact strength (J/m) 132 126 88 96 135 148 181
Heat-drawn wire (0.46MPa)/DEG C 151 163 154 164 153 147 95
UL 94 V-2（0.8mm） Qualified Qualified Qualified Qualified Qualified Defective Qualified
UL 94 V-2（3.2mm） Qualified Defective Qualified Defective Qualified Defective Qualified
Glowing filament (GWIT:700/3.0) Qualified Qualified Qualified Qualified Qualified Defective Defective
Glowing filament (GWFI:850/3.0) Qualified Qualified Qualified Qualified Qualified Defective Qualified
As shown in Table 2, the tensile strength of the fiberglass reinforced fire retardant polypropylene material that household appliances of the present invention are used improves 1～3 times than acrylic resin, modulus in flexure improves 2～4 times, after adding toughner, shock strength improves 0.5～1.5 times, heat-drawn wire also significantly rises, but also has given the flame retardant resistance of Reinforced Polypropylene.In addition, the dimensional stability of product, resistance to deflection is good, can replace metallic substance or engineering plastics to apply in the material in the electric equipment products fields such as household appliances.
According to the elaboration in above specification sheets, those skilled in the art in the invention can also carry out suitable change and amendment to above-mentioned embodiment.Therefore, the content of mentioning in above-described embodiment is not limitation of the invention, is not departing under the prerequisite of inventive concept of the present invention, and any apparent replacement is all within protection scope of the present invention.

Claims (6)

1. a household appliances fiberglass reinforced fire retardant polypropylene material, is made up of the following raw material of metering by weight:
40 ~ 60 parts of High Impact Polypropylene resins, 20 ~ 25 parts of alkali-free continuous long glass fibers, 6 ~ 15 parts of bromide fire retardants, 3 ~ 6 parts of antimonous oxides, 2 ~ 5 parts of fire retarding synergists, 3 ~ 8 parts of compatilizers, 0 ~ 5 part of toughner, 0.5 part of lubricant, 0.2 part of UV light absorber, 0.3 part, oxidation inhibitor;
Wherein, described High Impact Polypropylene is that melting index is the Co-polypropylene that 3 ~ 15g/10min, socle girder notched Izod impact strength are greater than 400J/m.
2. household appliances according to claim 1 fiberglass reinforced fire retardant polypropylene material, it is characterized in that, described bromide fire retardant is tetrabromo-bisphenol two (2,3-dibromopropyl) any one or several combination of ether, TDE, hexabromocyclododecane, three (2,3-dibromopropyl) isocyanuric acid ester.
3. household appliances according to claim 1 fiberglass reinforced fire retardant polypropylene material, is characterized in that, described antimonous oxide is the antimonous oxide that purity is greater than 99.5%.
4. household appliances according to claim 1 fiberglass reinforced fire retardant polypropylene material, is characterized in that, described fire retarding synergist is any one or several combination of magnesium hydroxide, aluminium hydroxide, zinc borate, MCA fire retardant, silicon-series five-retardant.
5. household appliances according to claim 1 fiberglass reinforced fire retardant polypropylene material, is characterized in that, described compatilizer is maleic anhydride inoculated polypropylene or acrylic acid-grafted polypropylene;
Described toughner is any one or several combination in POE, EVA, EPR, SEBS and SBS;
Described lubricant is any one or several combination in stearic acid, EBS, polyethylene wax, calcium stearate, Zinic stearas and silicone powder;
Described UV light absorber is any one or several combination of UV light absorber UV-234, UV light absorber UV-328 and ultraviolet absorbent UV-531;
Described antioxidant is any one or several combination in antioxidant 1010, irgasfos 168, oxidation inhibitor 1098, oxidation inhibitor 245 and antioxidant 1076.
6. the preparation method with fiberglass reinforced fire retardant polypropylene material according to the household appliances described in any one in claim 1 to 5, the method comprises the following steps:
1) after bromide fire retardant, antimonous oxide, fire retarding synergist, toughner, compatilizer, lubricant, UV light absorber and oxidation inhibitor are prepared by proportioning, pre-mixing 1min in low-speed mixer;
2) High Impact Polypropylene is added in low-speed mixer, and in low-speed mixer with mixing of materials 1min after step 1), then material is fed into twin screw extruder from main feed system;
3) alkali-free continuous long glass fiber is added twin screw extruder from the fibre mouthful that adds of twin screw extruder;
4) by the material after step 3) by screw diameter be in 30 ~ 75mm, the length-to-diameter ratio twin screw extruder that is 36 ~ 44:1, carry out mixing, twin screw extruder temperature the firstth district is that 120 ~ 135 DEG C, Second Region ~ Si district are that 180 ~ 185 DEG C, Wu district ~ Shi district are 185 ~ 195 DEG C, head temperature is 200 DEG C, simultaneously by tie rod, pelletizing after water cooling, isolate particle through vibratory screening apparatus, mix rear packaging, to obtain final product.
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