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 PDFInfo
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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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- 239000011152 fibreglass Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000003365 glass fiber Substances 0.000 claims abstract description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004952 Polyamide Substances 0.000 claims abstract description 30
- 229920002647 polyamide Polymers 0.000 claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 29
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 29
- 239000003063 flame retardant Substances 0.000 claims abstract description 25
- 239000000314 lubricant Substances 0.000 claims abstract description 25
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000012745 toughening agent Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims description 23
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000005453 pelletization Methods 0.000 claims description 13
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 12
- 238000013329 compounding Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- -1 nucleator Substances 0.000 claims description 7
- 230000003014 reinforcing effect Effects 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 6
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 5
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 5
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 5
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 4
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005461 lubrication Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims 3
- 239000001301 oxygen Substances 0.000 claims 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 5
- 230000008569 process Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical class C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 2
- 239000004605 External Lubricant Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910001125 Pa alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- 244000178289 Verbascum thapsus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- MEFUMNTZTUDUBG-UHFFFAOYSA-N oxalonitrile 1,3,5-triazine-2,4,6-triamine Chemical compound N#CC#N.N1=C(N)N=C(N)N=C1N MEFUMNTZTUDUBG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
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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
-
- 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
- C08L51/04—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 rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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
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.
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| CN112552635A (en) * | 2020-11-30 | 2021-03-26 | 金发科技股份有限公司 | Halogen-free flame-retardant ABS material special for storage battery and preparation method and application thereof |
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| CN116063845A (en) * | 2022-12-23 | 2023-05-05 | 金发科技股份有限公司 | Low-warpage polyamide composition and preparation method and application thereof |
| CN116063845B (en) * | 2022-12-23 | 2024-05-14 | 金发科技股份有限公司 | Low-warpage polyamide composition and preparation method and application thereof |
| JP2024137585A (en) * | 2023-03-25 | 2024-10-07 | 南亞塑膠工業股▲分▼有限公司 | Polyamide long glass fiber reinforced composite material and its manufacturing method |
| JP7637717B2 (en) | 2023-03-25 | 2025-02-28 | 南亞塑膠工業股▲分▼有限公司 | Polyamide long glass fiber reinforced composite material and its manufacturing method |
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