CN107815101A - A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composite material and preparation method thereof - Google Patents

A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composite material and preparation method thereof Download PDF

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CN107815101A
CN107815101A CN201711218577.XA CN201711218577A CN107815101A CN 107815101 A CN107815101 A CN 107815101A CN 201711218577 A CN201711218577 A CN 201711218577A CN 107815101 A CN107815101 A CN 107815101A
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weight
parts
halogen
fiberglass reinforced
free flameproof
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杨金波
陈旭东
杨军明
姚跃
许宏武
邓佳琪
其他发明人请求不公开姓名
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Guangdong Gunakai Material Technology Co Ltd
Guangdong Nanfang Fountain Plastic Technology Co Ltd
Guangdong New Material Research Institute Co Ltd
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Guangdong Gunakai Material Technology Co Ltd
Guangdong Nanfang Fountain Plastic Technology Co Ltd
Guangdong New Material Research Institute Co Ltd
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Priority to CN201711218577.XA priority Critical patent/CN107815101A/en
Publication of CN107815101A publication Critical patent/CN107815101A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions 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
    • C08L51/04Compositions 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 rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/08Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/24Crystallisation aids

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

The present invention provides a kind of halogen-free flameproof, fiberglass reinforced PA/ASA composite material, and the parts by weight of the halogen-free flameproof, the component of fiberglass reinforced PA/ASA composite material and component are as follows:Polyamide:20 ~ 65 parts by weight;Acrylate rubber like body and acrylonitrile, the graft copolymer of styrene:10 ~ 30 parts by weight;Fire retardant:10 ~ 25 parts by weight, compatilizer:2 ~ 5 parts by weight;Glass fibre:10 ~ 30 parts by weight;Toughener:3 ~ 8 parts by weight;Nucleator:0.1 ~ 1 parts by weight;Lubricant:0.1 ~ 1 parts by weight;Antioxidant:0.1 ~ 1 parts by weight.The present invention is blended using ASA and PA, be effectively improved PA water absorbing properties, reduce Material shrinkage performance, significantly improve dimensional stability while, impart the good weather resistance of material, ageing resistace.

Description

A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composite material and preparation method thereof
Technical field
The present invention relates to polymeric material field, specially a kind of halogen-free flameproof, fiberglass reinforced PA/ASA composite material and Its preparation method.
Background technology
Polyamide is due to excellent mechanical strength, corrosion resistance, wear-resisting and self-lubricating property, turning into most excellent five One of large-engineering plastics.Particularly through the modified product of fiberglass reinforced, it is widely used in electric tool, automobile industry, machine The fields such as tool industry, sports equipment, office equipment.But there is poor water absorption rate height, dimensional stability, low temperature and dry state toughness in it The defects of deficiency, inflammable heatproof deficiency and chance fire, it greatly limit its application in some fields.In recent years, ABS and PA is blended Alloy enjoys market to pay close attention to, and ABS addition can be effectively improved PA water absorbing properties and notch toughness, but due in ABS molecular structures The presence of unsaturated double-bond, the weather resistance that result in ABS/PA alloy materials is deteriorated, easily old under outdoor or solar radiation Change.
The content of the invention
In order to solve the above problems, the present invention provides a kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites and its system Preparation Method, it is blended using ASA and PA, is being effectively improved PA water absorbing properties, is reducing Material shrinkage performance, significantly improves While dimensional stability, the good weather resistance of material and ageing resistace are imparted.
The technical solution adopted by the present invention is:A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites are provided, it is described The component of halogen-free flameproof, fiberglass reinforced PA/ASA composites and the parts by weight of component are as follows:Polyamide:20 ~ 65 parts by weight; Acrylate rubber like body and acrylonitrile, the graft copolymer of styrene:10 ~ 30 parts by weight;Fire retardant:10 ~ 25 parts by weight, phase Hold agent:2 ~ 5 parts by weight;Glass fibre:10 ~ 30 parts by weight;Toughener:3 ~ 8 parts by weight;Nucleator:0.1 ~ 1 parts by weight;Lubrication Agent:0.1 ~ 1 parts by weight;Antioxidant:0.1 ~ 1 parts by weight.
Further, described polyamide is PA6 or PA66, and the relative viscosity scope of described polyamide is 2.0-3.5 P·S.Wherein, the relative viscosity scope of preferable polyamide is 2.45 ~ 2.8 PS.
Further, the melt index of described acrylate rubber like body and acrylonitrile, the graft copolymer of styrene For 5 ~ 30g/10min.Wherein, the melting of preferable acrylate rubber like body and acrylonitrile, the graft copolymer of styrene refers to Number is 15 ~ 20g/10min.
Further, described fire retardant is organic hypophosphites, hypo-aluminum orthophosphate and ammonium polyphosphate APP, melamine cyanogen The one or more of compoundings of lithate MCA form.
Further, described compatilizer is polystyrene-acrylonitrile-GMA copolymer SAG, ABS grafted maleic anhydrides One or more in ABS-g-MA, polystyrene-maleic anhydride copolymer SMA or polyethylene-methyl acrylate copolymer EMA Mixture.
Further, described glass fibre is by the silane coupler containing amido functional group or epoxy-functional The continuous fiber or chopped strand managed.Wherein, the line footpath of continuous long glass fiber is 13 ~ 17um, short glass fiber Line footpath is 7 ~ 13um.
Further, described toughener is POE grafted maleic anhydride POE-g-MAH, PE grafted maleic anhydrides PE-g- One or more of mixture in MAH, SEBS grafted maleic anhydride or MBS.
Further, described nucleator is talcum powder.Wherein, the particle diameter of preferable talcum powder is 5000 ~ 7000 mesh.
Further, described lubricant is OPE, polarity ethylene bis-fatty acid amides TAF or pentaerythrite One or more of mixtures in stearate PETS.
Further, it by mass ratio is 1 that described antioxidant, which is,:2 antioxidant 1010 or 1076 and irgasfos 168 compounding One or more of mixtures of rear antioxidant, antioxidant 1098 or antioxidant 412S.
Based on above-mentioned inventive concept, the present invention also provides a kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites Preparation method, comprise the following steps:
S1, according to described parts by weight weigh each component;
S2, by the polyamide, acrylate rubber like body and acrylonitrile, the graft copolymer of styrene, compatilizer, toughness reinforcing It is well mixed in agent, lubricant, nucleator, fire retardant and antioxidant input batch mixer, obtains compound;
S3, above-mentioned compound is fed into double screw extruder by main feeding hopper, within the temperature range of 220-270 DEG C Extruding pelletization;
S4, the glass fibre added from glass fiber opening or side spout, extruded machine melt blending, tie rod, pelletizing, and through dry Finished product is obtained after dry.
Compared with prior art, it is blended in the present invention using ASA and PA, is being effectively improved PA water absorbing properties, is reducing Material shrinkage performance, while significantly improve dimensional stability, impart the good weather resistance of material, ageing resistace. By adding suitable compatilizer in the present invention, matrix resin PA and ASA compatibility is improved;Meanwhile fire retardant use has What the one or more in machine hypophosphites, hypo-aluminum orthophosphate and ammonium polyphosphate APP, melamine cyanurate MCA compounded makes With, impart the excellent fire resistance of material, overcome using fire retardant such as RDP resorcinols double (diphenyl phosphates), BDP bisphenol-As double (diphenyl phosphates), TPP (triphenyl phosphate) and red phosphorus etc. to material thermal resistance energy and color outside The influence of sight;Appropriate glass fibre is added in its present invention and specific toughener is modified, it is good to impart material Mechanical property, mechanical performance and good toughness, the application of glass fiber reinforced nylon material has been expanded well.
Embodiment
For the ease of the understanding of those skilled in the art, present invention work is further retouched in detail below in conjunction with specific embodiment State.
In following each embodiments, compatilizer refers to by means of intermolecular bonding force, promotes incompatible two kinds poly- Compound is incorporated in one, and then the auxiliary agent for the blend stablized, and applies in modifying plastics, can obtain performance well altogether Mixcibility material, the compatibility of composite and the dispersiveness of filler are greatly improved, so as to improve composite machinery intensity.Its In, maleic anhydride grafting compatilizer can improve inorganic filler and organic resin compatibility, improve stretching, the impact strength of product, High filling is realized, reduces resin demand, improves rheological performance, improves surface smoothness.
Glass fibre can improve the intensity and rigidity of plastics, improve heat resistance and heat distortion temperature, improve dimensionally stable Property, shrinkage factor is reduced, reduces buckling deformation, reduces creep, to fire resistance because candle wick effect, flame-retardant system can be disturbed, shadow Flame retardant effect is rung, reduces the glossiness on surface, increases hygroscopicity.Wherein, chopped strand has excellent dry state mobility, to even Continuous feeding is highly beneficial, glass fibre distributing very evenly in product.
Toughener is with the analog assistant for reducing composite fragility and raising composite shock resistance.In PA After ASA blending solidifications, the elongation of its bonded part is low, and fragility is larger, is easy to produce when external force is born in bonding site Crackle, and extend rapidly, cause glue-line to ftracture, not endurance, it is impossible to be used as structural bond.Therefore, it is necessary to try to reduce Fragility, increase toughness, improve bearing strength.Addition toughener is then a selection well.
Nucleator is by changing the crystallization behavior of resin, so as to accelerating crystalline rate, increasing crystal density and promoting crystal grain Size miniaturization, reach shorten molding cycle, improve the product transparency, lustrous surface, tensile strength, rigidity, heat distortion temperature, The physical and mechanical properties such as impact resistance, creep resistance.
Lubricant is divided into in-lubricant and external lubricant, and the effect of external lubricant mainly improves polymer melt and equipment Hot metal surface andfrictional conditions, plastic is easily stripped, it is poor with the compatibility of polymer, easily past from melt External migration, one layer of very thin barrier film can be formed between melt and mould in forming process, plastics is not stick to die surface; In-lubricant has good compatibility with polymer, the work of its cohesive force between polymeric inner plays and reduces polymer molecule With so as to improve the mobility of the interior frictional heat and melt of plastic melt.In-lubricant and the intermolecular knot of polymer long-chain Conjunction is not strong, and they are there may be the effect similar to rolling bearing, therefore its own can be arranged on melt flows direction, So as to slide over each other so that internal friction reduces, and here it is the mechanism of interior lubrication.Wherein, OPE is excellent new Type polar waxes, because OPE strand carries a certain amount of carbonyl and hydroxyl, so with filler, pigment, polarity tree The intermiscibility of fat just significantly improves;Polarity ethylene bis-fatty acid amides TAF not only has good external lubrication effect, and And with the effect of good internal lubrication so that molten mobility and release property every plastics is improved in plastics processing, so as to The yield of plastic processing is improved, reduces energy consumption, and product is obtained high surface smooth finish, flatness;Season penta Tetrol stearate PETS has good heat endurance and low volatility, the good demoulding and mobile performance at high temperature, right The plastics of partially crystallizable have fabulous nucleation, available for opaque products.The heat endurance that PETS is protruded, makes it can be used for this The process of class system, without worrying to degrade, and it can significantly improve transparency and surface smoothness.
Antioxidant can delay or suppress the progress of polymer oxidizing process, make so as to prevent the aging of polymer and extend it Use the life-span.Preferable antioxidant should possess following condition:There should be high oxidation resistance;It is good with the compatibility of resin, do not separate out; Processing characteristics is good, non-volatile under the processing temperature of high polymer, do not decompose;Resistance to extractable is good, in not soluble in water and oily;Itself Color is preferably colourless or light, not pollute product;It is nontoxic or less toxic;It is cheap.And in fact, any antioxidant Above-mentioned condition can not be all fully met, therefore, is typically used cooperatively using a variety of antioxidant, to produce cooperative effect.
Embodiment 1
A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites are provided, the halogen-free flameproof, fiberglass reinforced PA/ASA are compound The component of material and the mass weight number of component are as follows:Polyamide:30 parts by weight;Acrylate rubber like body and acrylonitrile, The graft copolymer of styrene:18 parts by weight;Fire retardant:25 parts by weight;Compatilizer:4 parts by weight;Glass fibre:18 parts by weight; Toughener:5 parts by weight;Nucleator:0.1 parts by weight;Lubricant:0.1 parts by weight;Antioxidant:0.1 parts by weight.
Described polyamide is PA6, and the relative of described polyamide is 2.45.
Described ASA melt index is 15g/10min.
Described fire retardant is that organic hypophosphites and hypo-aluminum orthophosphate and ammonium polyphosphate APP compounding form.
Described compatilizer is polystyrene-acrylonitrile-GMA copolymer SAG and ABS grafted maleic anhydrides ABS-g- MAH mixture.
Described glass fibre is to pass through the silane coupler containing amido functional group or epoxy-functional treats, line Footpath is 13um continuous fiber.
Described toughener is the mixed of POE grafted maleic anhydride POE-g-MAH and PE grafted maleic anhydrides PE-g-MAH Compound.
Described nucleator is the talcum powder that particle diameter is 5000 mesh.
Described lubricant is OPE and polarity ethylene bis-fatty acid amides TAF mixture.
It by mass ratio is 1 that described antioxidant, which is,:Antioxygen after 2 antioxidant 1010 or 1076 and irgasfos 168 compounding Agent.
Based on above-mentioned inventive concept, the present invention also provides a kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites Preparation method, comprise the following steps:
S1, according to described parts by weight weigh each component;
S2, by the polyamide, acrylate rubber like body and acrylonitrile, the graft copolymer of styrene, compatilizer, toughness reinforcing It is well mixed in agent, lubricant, nucleator, fire retardant and antioxidant input batch mixer, obtains compound;
S3, above-mentioned compound is fed into double screw extruder by main feeding hopper, the extruding pelletization at a temperature of 220 DEG C;
S4, the glass fibre added from glass fiber opening or side spout, extruded machine melt blending, tie rod, pelletizing, and through dry Finished product is obtained after dry.
Embodiment 2
A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites are provided, the halogen-free flameproof, fiberglass reinforced PA/ASA are compound The component of material and the mass weight number of component are as follows:Polyamide:45 parts by weight;Acrylate rubber like body and acrylonitrile, The graft copolymer of styrene:20 parts by weight;Fire retardant:18 parts by weight;Compatilizer:3.5 parts by weight;Glass fibre:20 weight Part;Toughener:5 parts by weight;Nucleator:0.1 parts by weight;Lubricant:0.1 parts by weight;Antioxidant:0.1 parts by weight.
Described polyamide is PA66, and the relative viscosity of described polyamide is 2.8PS.
The melt index of described acrylate rubber like body and acrylonitrile, the graft copolymer of styrene is 20g/ 10min。
Described fire retardant is melamine cyanurate MCA.
Described compatilizer is polystyrene-maleic anhydride copolymer SMA and polyethylene-methyl acrylate copolymer EMA Mixture.
Described glass fibre is to pass through the silane coupler containing amido functional group or epoxy-functional treats, line Footpath is 13um chopped strand..
Described toughener is SEBS grafted maleic anhydrides and MBS mixture.
Described nucleator is the talcum powder that particle diameter is 7000 mesh.
Described lubricant is polarity ethylene bis-fatty acid amides TAF and pentaerythritol stearate PETS mixture.
Described antioxidant is antioxidant 1098 and antioxidant 412S mixture.
Based on above-mentioned inventive concept, the present invention also provides a kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites Preparation method, comprise the following steps:
S1, according to described parts by weight weigh each component;
S2, by the polyamide, acrylate rubber like body and acrylonitrile, the graft copolymer of styrene, compatilizer, toughness reinforcing It is well mixed in agent, lubricant, nucleator, fire retardant and antioxidant input batch mixer, obtains compound;
S3, above-mentioned compound is fed into double screw extruder by main feeding hopper, the extruding pelletization at a temperature of 270 DEG C;
S4, the glass fibre added from glass fiber opening or side spout, extruded machine melt blending, tie rod, pelletizing, and through dry Finished product is obtained after dry.
Embodiment 3
A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites are provided, the halogen-free flameproof, fiberglass reinforced PA/ASA are compound The component of material and the mass weight number of component are as follows:Polyamide:20 parts by weight;Acrylate rubber like body and acrylonitrile, The graft copolymer of styrene:30 parts by weight;Fire retardant:15 parts by weight;Compatilizer:2 parts by weight;Glass fibre:30 parts by weight; Toughener:3 parts by weight;Nucleator:0.5 parts by weight;Lubricant:0.5 parts by weight;Antioxidant:0.5 parts by weight.
Described polyamide is PA66, and the relative viscosity scope of described polyamide is 2.6 PS.
The melt index of described acrylate rubber like body and acrylonitrile, the graft copolymer of styrene is 18g/ 10min。
Described fire retardant is that hypo-aluminum orthophosphate and ammonium polyphosphate APP and melamine cyanurate MCA compoundings form.
Described compatilizer is ABS grafted maleic anhydrides ABS-g-MAH's and polystyrene-maleic anhydride copolymer SMA Mixture.
Described glass fibre is to pass through the silane coupler containing amido functional group or epoxy-functional treats, line Footpath is 15 um continuous fiber.
Described toughener is PE grafted maleic anhydrides PE-g-MAH.
Described nucleator is the talcum powder that particle diameter is 6000 mesh.
Described lubricant is polarity ethylene bis-fatty acid amides TAF.
It by mass ratio is 1 that described antioxidant, which is,:Antioxygen after 2 antioxidant 1010 or 1076 and irgasfos 168 compounding Agent and the mixture of antioxidant 1098.
Based on above-mentioned inventive concept, the present invention also provides a kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites Preparation method, comprise the following steps:
S1, according to described parts by weight weigh each component;
S2, by the polyamide, acrylate rubber like body and acrylonitrile, the graft copolymer of styrene, compatilizer, toughness reinforcing It is well mixed in agent, lubricant, nucleator, fire retardant and antioxidant input batch mixer, obtains compound;
S3, above-mentioned compound is fed into double screw extruder by main feeding hopper, at a temperature of 230 DEG C within the temperature range of Extruding pelletization;
S4, the glass fibre added from glass fiber opening or side spout, extruded machine melt blending, tie rod, pelletizing, and through dry Finished product is obtained after dry.
Embodiment 4
A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites are provided, the halogen-free flameproof, fiberglass reinforced PA/ASA are compound The component of material and the mass weight number of component are as follows:Polyamide:50 parts by weight;Acrylate rubber like body and acrylonitrile, The graft copolymer of styrene:10 parts by weight;Fire retardant:20 parts by weight;Compatilizer:5 parts by weight;Glass fibre:10 parts by weight; Toughener:5 parts by weight;Nucleator:0.3 parts by weight;Lubricant:0.3 parts by weight;Antioxidant:0.3 parts by weight.
Described polyamide is PA66, and the relative viscosity of described polyamide is 2.0 PS.
The melt index of described acrylate rubber like body and acrylonitrile, the graft copolymer of styrene is 5g/ 10min。
Described fire retardant is that organic hypophosphites and melamine cyanurate MCA compoundings form.
Described compatilizer is polystyrene-acrylonitrile-GMA copolymer SAG, ABS grafted maleic anhydrides ABS-g-MAH With polystyrene-maleic anhydride copolymer SMA mixture.
Described glass fibre is to pass through the silane coupler containing amido functional group or epoxy-functional treats, line Footpath is 10um chopped strand.
Described toughener is POE grafted maleic anhydride POE-g-MAH, PE grafted maleic anhydrides PE-g-MAH, SEBS The mixture of grafted maleic anhydride and MBS.
Described nucleator is the talcum powder that particle diameter is 5500 mesh.
Described lubricant is OPE, polarity ethylene bis-fatty acid amides TAF and pentaerythritol stearate PETS mixture.
It by mass ratio is 1 that described antioxidant, which is,:Antioxygen after 2 antioxidant 1010 or 1076 and irgasfos 168 compounding Agent and antioxidant 412S mixture.
Based on above-mentioned inventive concept, the present invention also provides a kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites Preparation method, comprise the following steps:
S1, according to described parts by weight weigh each component;
S2, by the polyamide, acrylate rubber like body and acrylonitrile, the graft copolymer of styrene, compatilizer, toughness reinforcing It is well mixed in agent, lubricant, nucleator, fire retardant and antioxidant input batch mixer, obtains compound;
S3, above-mentioned compound is fed into double screw extruder by main feeding hopper, at a temperature of 240 DEG C in the range of squeeze Go out to be granulated;
S4, the glass fibre added from glass fiber opening or side spout, extruded machine melt blending, tie rod, pelletizing, and through dry Finished product is obtained after dry.
Embodiment 5
A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites are provided, the halogen-free flameproof, fiberglass reinforced PA/ASA are compound The component of material and the mass weight number of component are as follows:Polyamide:45 parts by weight;Acrylate rubber like body and acrylonitrile, The graft copolymer of styrene:10 parts by weight;Fire retardant:30 parts by weight;Compatilizer:2 parts by weight;Glass fibre:10 parts by weight; Toughener:.3 parts by weight;Nucleator:0.8 parts by weight;Lubricant:0.8 parts by weight;Antioxidant:0.8 parts by weight.
Described polyamide is PA6, and the relative viscosity of described polyamide is 3.5 PS.
The melt index of described acrylate rubber like body and acrylonitrile, the graft copolymer of styrene is 30g/ 10min。
Described fire retardant is organic hypophosphites, hypo-aluminum orthophosphate and APP(APP)And melamine cyanurate MCA compoundings form.
Described compatilizer is polystyrene-acrylonitrile-GMA copolymers SAG and polyethylene-methyl acrylate copolymer EMA mixture.
Described glass fibre is to pass through the silane coupler containing amido functional group or epoxy-functional treats, line Footpath is 16um continuous fiber.
Described toughener is POE grafted maleic anhydride POE-g-MAH, SEBS grafted maleic anhydrides and MBS mixing Thing.
Described nucleator is the talcum powder that particle diameter is 6500 mesh.
Described lubricant is OPE and pentaerythritol stearate PETS mixture.
It by mass ratio is 1 that described antioxidant, which is,:Antioxygen after 2 antioxidant 1010 or 1076 and irgasfos 168 compounding Agent.
Based on above-mentioned inventive concept, the present invention also provides a kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites Preparation method, comprise the following steps:
S1, according to described parts by weight weigh each component;
S2, by the polyamide, acrylate rubber like body and acrylonitrile, the graft copolymer of styrene, compatilizer, toughness reinforcing It is well mixed in agent, lubricant, nucleator, fire retardant and antioxidant input batch mixer, obtains compound;
S3, above-mentioned compound is fed into double screw extruder by main feeding hopper, the extruding pelletization at a temperature of 250 DEG C;
S4, the glass fibre added from glass fiber opening or side spout, extruded machine melt blending, tie rod, pelletizing, and through dry Finished product is obtained after dry.
Embodiment 1-5 test result such as table 1.
Table 1:
Above-described embodiment is the preferable implementation of the present invention, is not limited to the present invention, is not departing from structure of the present invention It is any obviously to replace within protection scope of the present invention on the premise of think of.

Claims (10)

1. a kind of halogen-free flameproof, fiberglass reinforced PA/ASA composites, it is characterised in that:The halogen-free flameproof, fiberglass reinforced The component of PA/ASA composites and the parts by weight of component are as follows:Polyamide:20 ~ 65 parts by weight;Acrylate rubber like body with The graft copolymer of acrylonitrile, styrene:10 ~ 30 parts by weight;Fire retardant:10 ~ 25 parts by weight, compatilizer:2 ~ 5 parts by weight;Glass Glass fiber:10 ~ 30 parts by weight;Toughener:3 ~ 8 parts by weight;Nucleator:0.1 ~ 1 parts by weight;Lubricant:0.1 ~ 1 parts by weight;It is anti- Oxygen agent:0.1 ~ 1 parts by weight.
2. halogen-free flameproof according to claim 1, fiberglass reinforced PA/ASA composites, it is characterised in that:Described is poly- Acid amides is PA6 or PA66, and the relative viscosity scope of described polyamide is 2.0-3.5 PS.
3. halogen-free flameproof according to claim 1, fiberglass reinforced PA/ASA composites, it is characterised in that:Described third The melt index of olefin(e) acid ester rubber body and acrylonitrile, the graft copolymer of styrene is 5 ~ 30g/10min.
4. halogen-free flameproof according to claim 1, fiberglass reinforced PA/ASA composites, it is characterised in that:Described resistance It is the one or more in organic hypophosphites, hypo-aluminum orthophosphate and ammonium polyphosphate APP or melamine cyanurate MCA to fire agent Compounding forms.
5. halogen-free flameproof according to claim 1, fiberglass reinforced PA/ASA composite material, it is characterised in that:Described phase Appearance agent is polystyrene-acrylonitrile-GMA copolymer SAG, ABS grafted maleic anhydrides ABS-g-MAH, polystyrene-Malaysia One or more of mixtures in acid anhydride copolymer SMA or polyethylene-methyl acrylate copolymer EMA.
6. halogen-free flameproof according to claim 1, fiberglass reinforced PA/ASA composites, it is characterised in that:Described glass Glass fiber is the continuous fiber treated by the silane coupler containing amido functional group or epoxy-functional or the fibre that is chopped Dimension.
7. halogen-free flameproof according to claim 1, fiberglass reinforced PA/ASA composite material, it is characterised in that:Described increasing Tough dose be POE grafted maleic anhydride POE-g-MAH, PE grafted maleic anhydride PE-g-MAH, SEBS grafted maleic anhydrides or One or more of mixture in MBS.
8. halogen-free flameproof according to claim 1, fiberglass reinforced PA/ASA composites, it is characterised in that:Described profit Lubrication prescription be OPE, polarity ethylene bis-fatty acid amides TAF or one kind in pentaerythritol stearate PETS or Several mixtures.
9. halogen-free flameproof according to claim 1, fiberglass reinforced PA/ASA composite material, it is characterised in that:Described is anti- It by mass ratio is 1 that oxygen agent, which is,:Antioxidant, antioxidant 1098 or anti-after 2 antioxidant 1010 or 1076 and irgasfos 168 compounding Oxygen agent 412S one or more of mixtures.
A kind of 10. preparation of halogen-free flameproof, fiberglass reinforced PA/ASA composite material according to described in claim any one of 1-9 Method, it is characterised in that:Comprise the following steps:
S1, according to described parts by weight weigh each component;
S2, by the polyamide, acrylate rubber like body and acrylonitrile, the graft copolymer of styrene, compatilizer, toughness reinforcing It is well mixed in agent, lubricant, nucleator, fire retardant and antioxidant input batch mixer, obtains compound;
S3, above-mentioned compound is fed into double screw extruder by main feeding hopper, within the temperature range of 220-270 DEG C Extruding pelletization;
S4, the glass fibre added from glass fiber opening or side spout, extruded machine melt blending, tie rod, pelletizing, and through dry Finished product is obtained after dry.
CN201711218577.XA 2017-11-28 2017-11-28 A kind of halogen-free flameproof, fiberglass reinforced PA/ASA composite material and preparation method thereof Pending CN107815101A (en)

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