CN114573972A - Polycarbonate composite material and preparation method and application thereof - Google Patents
Polycarbonate composite material and preparation method and application thereof Download PDFInfo
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- CN114573972A CN114573972A CN202210331142.0A CN202210331142A CN114573972A CN 114573972 A CN114573972 A CN 114573972A CN 202210331142 A CN202210331142 A CN 202210331142A CN 114573972 A CN114573972 A CN 114573972A
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- copolymer
- styrene
- butadiene
- acrylonitrile
- polycarbonate composite
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 56
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 57
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 28
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229920007019 PC/ABS Polymers 0.000 claims abstract description 4
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 4
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 13
- -1 butylene-ethylene Chemical group 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 5
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 claims description 4
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 4
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical group C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 claims description 4
- 229920001038 ethylene copolymer Polymers 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 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 3
- 238000005303 weighing Methods 0.000 claims description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 2
- FLZYQMOKBVFXJS-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid Chemical compound CC1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O FLZYQMOKBVFXJS-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 2
- 230000002159 abnormal effect Effects 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- FGDAXMHZSNXUFJ-UHFFFAOYSA-N ethene;prop-1-ene;prop-2-enenitrile Chemical group C=C.CC=C.C=CC#N FGDAXMHZSNXUFJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- 230000002265 prevention Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- YJVBLROMQZEFPA-UHFFFAOYSA-L acid red 26 Chemical compound [Na+].[Na+].CC1=CC(C)=CC=C1N=NC1=C(O)C(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=CC=C12 YJVBLROMQZEFPA-UHFFFAOYSA-L 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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 description 1
- 230000005501 phase interface Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
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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 invention relates to a polycarbonate composite material and a preparation method and application thereof, belonging to the technical field of high polymer materials. The polycarbonate composite material comprises the following components in parts by weight: 40-90 parts of polycarbonate resin, 10-35 parts of acrylonitrile-butadiene-styrene resin, 2-25 parts of tearing resistance agent and 0.5-2 parts of auxiliary agent; the tearing-resistant agent is at least one of maleic anhydride copolymer, acrylate copolymer and vinyl copolymer; the acrylonitrile-butadiene-styrene resin contains 10-30 wt% of butadiene. According to the invention, a specific substance is compounded to serve as a tearing agent, so that the PC/ABS copolymer has good toughness and good high-temperature reciprocating tearing resistance, and the service life of an automobile door handle at high temperature can be prolonged.
Description
Technical Field
The invention relates to a polycarbonate composite material and a preparation method and application thereof, belonging to the technical field of high polymer materials.
Background
Since the German Karl Benz in the 19 th century invented the first gasoline internal combustion engine automobile, with the continuous development of automobile technology and production level, the global automobile yield reached 9686 thousands in 2017. In the modern society that the energy conservation and emission reduction problem also receives global attention, the light weight of the automobile is always the topic of continuous attention of the automobile industry. The rapid development of polymer material technology makes it possible to replace steel with plastic. Nowadays, large-sized parts such as automobile bumpers, spoilers, roof racks and the like are gradually "plasticized", which reduces the weight of the automobile body and can greatly reduce the fuel consumption of the automobile. According to the estimation of statistics in the industry, when the weight of the automobile is reduced by 10%, the fuel consumption can be reduced by 6-8%, and the emission can be reduced by 5-6%.
PC has the advantages of high strength, high toughness, high heat resistance, fatigue resistance and the like, but also has the defects of poor fluidity, large internal stress, poor solvent resistance and the like. ABS has the advantages of good fluidity, good low-temperature toughness, certain solvent resistance and the like, so that PC and ABS are prepared into alloy through a double-screw extruder, the defects of PC can be overcome, and the ABS can be used as a raw material for producing various plastic products. Along with the development requirements of diversification of appearance design of the automobile outer door handle and thinning of parts, the strength performance requirement of the material is gradually improved, the improvement of the PC content in the PC/ABS composite material is beneficial to improving the tear resistance, but the formability of the material is greatly reduced, and the space of structural design of the parts is limited. In addition to the requirement of good rigidity and toughness of materials, products such as door handles on vehicles have high requirements on the resistance of materials to repeated tearing. Particularly, under the long-term sun exposure in summer, the part cannot be broken after being drawn for thousands of times.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polycarbonate composite material, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a polycarbonate composite material comprises the following components in parts by weight: 40-90 parts of polycarbonate resin, 10-35 parts of acrylonitrile-butadiene-styrene resin, 2-25 parts of tearing resistance agent and 0.5-2 parts of auxiliary agent; the tearing-resistant agent is at least one of maleic anhydride copolymer, acrylate copolymer and vinyl copolymer; the acrylonitrile-butadiene-styrene resin contains 10-30 wt% of butadiene.
The polycarbonate resin (PC resin) has a melt flow rate of 3-22 g/10min (300 ℃ C., 1.2kg) and the acrylonitrile-butadiene-styrene resin (ABS resin) has a melt flow rate of 5-40 g/10min (220 ℃ C., 10 kg).
Research shows that the tearing-resistant agent is favorable for promoting the binding force between PC and ABS microscopic phase interfaces, and the promoting effect has good effect at high temperature. And the tearing-resistant agent has similar molecular group structures with PC and ABS respectively, and the promotion effect is more obvious. When the amount of the tearing agent of the present invention is less than 2 parts by weight, the tearing resistance is poor, and although the more the tearing agent is, the better the tearing resistance is, once the amount of the tearing agent is more than 25 parts by weight, the combination properties of the PC/ABS copolymer of the present invention, such as rigidity and toughness, are affected, and the use thereof is affected. The maleic anhydride copolymer is a substance containing a maleic anhydride group or a derivative group thereof in a molecular structure; the acrylate copolymer is a substance containing acrylate groups or derivative groups thereof in a molecular structure; the vinyl copolymer is a substance containing a vinyl group or a derivative group thereof in a molecular structure.
In a preferred embodiment of the polycarbonate composite material of the present invention, the tear resistance agent is 5 to 15 parts by weight. Research shows that when the tear-resistant agent is 5-15 parts by weight, the tear property of the polycarbonate composite material is better.
As a preferred embodiment of the polycarbonate composite material of the present invention, at least one of the following (a) to (c):
(a) the maleic anhydride copolymer is at least one of acrylonitrile-butadiene-styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer and styrene-hydrogenated ethylene-styrene-maleic anhydride copolymer;
(b) the acrylate copolymer is acrylonitrile-styrene-acrylate copolymer or butadiene-styrene-acrylate copolymer;
(c) the vinyl copolymer is at least one of propylene-ethylene copolymer, butylene-ethylene copolymer, octene-ethylene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer and acrylonitrile-ethylene propylene rubber-styrene copolymer; the acrylonitrile-butadiene-styrene copolymer contains 50-70 wt% of butadiene.
As a preferred embodiment of the polycarbonate composite of the present invention, the tear-resistant agent includes acrylonitrile-butadiene-styrene-maleic anhydride copolymer, butadiene-styrene-acrylate copolymer, and acrylonitrile-butadiene-styrene copolymer. Research shows that the selection of the tearing resistant agent has great influence on the tearing resistant performance of the polycarbonate composite material, when acrylonitrile-butadiene-styrene-maleic anhydride copolymer, butadiene-styrene-acrylate copolymer and acrylonitrile-butadiene-styrene copolymer are selected as the high temperature resistant tearing agents, the acrylonitrile-butadiene-styrene-maleic anhydride copolymer, the butadiene-styrene-acrylate copolymer and the acrylonitrile-butadiene-styrene copolymer are compounded, the butadiene-styrene-acrylate copolymer can increase the binding force effect between the acrylonitrile-butadiene-styrene-maleic anhydride copolymer and the acrylonitrile-butadiene-styrene copolymer, the C ═ O in the acrylate is more similar in structure to the C ═ O in the maleic anhydride than the C ═ C in the butadiene, and can optimize the high temperature tear resistance of the polycarbonate composite of the present invention.
As a preferable embodiment of the polycarbonate composite material, the weight ratio of the acrylonitrile-butadiene-styrene-maleic anhydride copolymer to the butadiene-styrene-acrylate copolymer in the tearing-resistant agent is 3: 5-5: 3. Research shows that the maleic anhydride copolymer has high binding force with Polycarbonate (PC), and the vinyl copolymer has good binding force with acrylonitrile-butadiene-styrene copolymer (ABS). The acrylonitrile-butadiene-styrene-maleic anhydride copolymer and the butadiene-styrene-acrylate copolymer have similar structures and good binding force, and when the ratio of the acrylonitrile-butadiene-styrene-maleic anhydride copolymer to the butadiene-styrene-acrylate copolymer is in a certain range, the binding force of PC and ABS can be effectively improved, so that the tear resistance of the integrated material is enhanced. In experiments, the inventor of the present application finds that the acrylonitrile-butadiene-styrene resin with a low butadiene content can provide the product with better fluidity, but because the molecular chain structure of acrylonitrile-styrene is rigid and the flexibility is insufficient, the defect of the flexibility is compensated by adding the tearing resistance agent acrylonitrile-butadiene-styrene copolymer with a high butadiene content.
As a preferred embodiment of the polycarbonate composite material, the additive is at least one of an antioxidant, a lubricant, a toner and an anti-abnormal noise additive. The study shows that the selection of the auxiliary agent can influence the performance of the polycarbonate composite material, and the skilled person can select the appropriate auxiliary agent according to the comprehensive performance of the polycarbonate composite material.
As a preferred embodiment of the polycarbonate composite material according to the invention, the antioxidant is at least one of an organic phosphate, an alkylated monophenol or polyphenol, tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane, an alkylated hydroquinone, a hydroxylated thiodiphenyl ether, an alkylidene bisphenol, a benzyl compound, an ester of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with a monohydric or polyhydric alcohol, an ester of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with a monohydric or polyhydric alcohol, an ester of a sulfanyl or thioaryl compound, an amide of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, in particular tris (nonylphenyl) phosphite, tris (nonylphenyl) phosphite, Tris (2, 4-di-t-butylphenyl) phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetrakis [ methylene (3, 5-di-t-butyl-4-hydroxyhydrocinnamate) ] methane, distearyl thiopropionate, dilauryl thiopropionate, ditridecyl thiopropionate, octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) ] propionate, and the like. The lubricant is at least one of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax, EVA wax, oleamide, erucamide, ethylene bis stearamide, an organic silicon lubricant and pentaerythritol stearate; the toner is pigment or dye additive, and can be selected from zinc oxide, titanium dioxide, iron oxide, zinc sulfide, carbon black, zinc ferrite, ultramarine blue, pigment brown 24, pigment red 101, pigment yellow 119, etc. The abnormal sound prevention auxiliary agent is styrene-hydrogenated ethylene-styrene copolymer.
The invention also provides a preparation method of the polycarbonate composite material, which comprises the following steps:
(1) weighing each component in the polycarbonate composite material according to a proportion, and uniformly mixing to obtain a premixed material;
(2) and (2) placing the premixed material obtained in the step (1) into a double-screw extruder, mixing, extruding and granulating at 200-260 ℃ and 300-1000 r/min to obtain the polycarbonate composite material.
The invention also provides application of the polycarbonate composite material in producing parts resistant to high-temperature reciprocating tearing.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a novel polycarbonate composite material, which improves the high-temperature tear resistance of the polycarbonate composite material and prolongs the service life of parts on an automobile with higher requirements on the high-temperature tear resistance by screening the content of each component and screening the type of a tear-resistant agent.
Drawings
FIG. 1 is a schematic diagram of a high temperature reciprocal tensile property test.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The raw materials used in the examples and comparative examples of the present invention are described below, but are not limited to these materials:
PC resin: mitsubishi IR-2200 with melt flow rate of 10g/10min at 300 deg.C and 1.2 kg;
ABS resin: qimei 757, melt flow rate of 20g/10min at 220 deg.C and 10kg, wherein butadiene content is 12-15 wt%, and acrylonitrile-styrene copolymer content is 85-88 wt%;
acrylonitrile-butadiene-styrene-maleic anhydride copolymer: ketong KT-2;
styrene-ethylene-styrene copolymer: zhongpetrochemical YH-802;
butadiene-styrene-acrylate copolymer: brillouin M-521;
acrylonitrile-styrene-acrylate copolymer: UMG a 600N;
acrylonitrile-butadiene-styrene copolymer: the Korea lake petrochemical HR181 contains butadiene 58-62 wt% and acrylonitrile-styrene copolymer 38-42 wt%;
propylene-ethylene copolymer: VITAMAXX, dow;
antioxidant: tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane, commercially available, the same in the other examples and comparative examples;
lubricant: pentaerythritol stearate, commercially available, the same in the other examples and comparative examples;
toner: carbon black, commercially available, the same in the other examples and comparative examples.
Examples 1 to 21 and comparative examples 1 to 2
The compositions of the polycarbonate composite materials of examples 1 to 21 and comparative examples 1 to 2 of the present invention are shown in table 1 below.
In table 1, a1 is an acrylonitrile-butadiene-styrene-maleic anhydride copolymer, B1 is a butadiene-styrene-acrylate copolymer, C1 is an acrylonitrile-butadiene-styrene copolymer (chinhu petrochemical HR181), a2 is an ethylene-maleic anhydride copolymer, B2 is an acrylonitrile-styrene-acrylate copolymer, and C2 is a propylene-ethylene copolymer.
The preparation method of the polycarbonate composite material of the embodiment 1-21 and the comparative example 1-2 comprises the following steps:
(1) weighing each component in the polycarbonate composite material according to a proportion, and uniformly mixing to obtain a premixed material;
(2) and (2) placing the premixed material obtained in the step (1) in a double-screw extruder, mixing, extruding and granulating at 200-260 ℃ and 300-1000 r/min to obtain the polycarbonate composite material.
TABLE 1 EXAMPLES 1 TO 21 COMPARATIVE EXAMPLES 1 TO 2 COMPOSITION RATIO (in parts by weight)
Performance testing
The polycarbonate composite materials of examples 1-21 and comparative examples 1-2 were tested for high temperature tear resistance, and the test results are shown in tables 2 and 3.
High-temperature reciprocal tensile failure times: the test method is shown in fig. 1. And (3) performing injection molding on the polycarbonate composite material by using an injection molding machine to obtain an ISO dumbbell type 1eA sample bar. The sample specimens were tested after being placed in an environmental chamber at 90 ℃ for more than 4 hours. The above-mentioned sample specimens were mounted on a reciprocating tensile testing machine as shown in FIG. 1 for testing. And (3) testing conditions are as follows: the environmental temperature is 90 ℃, the tensile load is 20MPa, and the tensile frequency is 10 HZ. The apparatus automatically measures the number of draw reciprocations and records the reciprocations when the sample strip breaks. The larger the reciprocating times, the better the high temperature resistance and the reciprocating tearing resistance of the material.
TABLE 2
TABLE 3
As can be seen from tables 1 to 3, when the content of the tearing agent in the polycarbonate composite material is 2 to 25 parts by weight, the high temperature tearing resistance of the polycarbonate composite material is better, when the content of the tearing agent is lower than the weight range, the high temperature tearing resistance of the polycarbonate composite material is poorer, and when the content of the tearing agent is higher than the weight range, the high temperature tearing resistance is not improved. As can be seen from comparison of examples 3, 6 to 7, and 13 to 14, when the weight ratio of the acrylonitrile-butadiene-styrene-maleic anhydride copolymer to the butadiene-styrene-acrylate copolymer in the tearing agent of the polycarbonate composite material is 3: 5-5: 3, the high temperature tear resistance is better, especially when the weight ratio of the acrylonitrile-butadiene-styrene-maleic anhydride copolymer to the butadiene-styrene-acrylate copolymer is 1: 1, the high temperature tear resistance is best. Comparing the embodiment 3 with the embodiments 8-10, it can be seen that when the high temperature resistant tearing agent is selected from maleic anhydride copolymer, acrylate copolymer and vinyl copolymer, the maleic anhydride copolymer, acrylate copolymer and vinyl copolymer are compounded, so that the high temperature resistant tearing performance of the polycarbonate composite material is better.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The polycarbonate composite material is characterized by comprising the following components in parts by weight: 40-90 parts of polycarbonate resin, 10-35 parts of acrylonitrile-butadiene-styrene resin, 2-25 parts of tearing resistance agent and 0.5-2 parts of auxiliary agent; the tearing-resistant agent is at least one of maleic anhydride copolymer, acrylate copolymer and vinyl copolymer; the acrylonitrile-butadiene-styrene resin contains 10-30 wt% of butadiene.
2. The polycarbonate composite of claim 1, wherein the tear resistance agent is 5 to 15 parts by weight.
3. The polycarbonate composite of claim 1, wherein the tear resistance agent is at least two of a maleic anhydride copolymer, an acrylate copolymer, and a vinyl copolymer.
4. The polycarbonate composite of claim 1, wherein at least one of the following (a) to (c):
(a) the maleic anhydride copolymer is at least one of acrylonitrile-butadiene-styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer and styrene-hydrogenated ethylene-styrene-maleic anhydride copolymer;
(b) the acrylate copolymer is acrylonitrile-styrene-acrylate copolymer and/or butadiene-styrene-acrylate copolymer;
(c) the vinyl copolymer is at least one of propylene-ethylene copolymer, butylene-ethylene copolymer, octene-ethylene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer and acrylonitrile-ethylene propylene rubber-styrene copolymer; the acrylonitrile-butadiene-styrene copolymer contains 50-70 wt% of butadiene.
5. The polycarbonate composite of claim 4, wherein the tear resistant agent comprises an acrylonitrile-butadiene-styrene-maleic anhydride copolymer, a butadiene-styrene-acrylate copolymer, and an acrylonitrile-butadiene-styrene copolymer.
6. The polycarbonate composite of claim 5, wherein the weight ratio of the acrylonitrile-butadiene-styrene-maleic anhydride copolymer to the butadiene-styrene-acrylate copolymer in the tear resistance agent is 3:5 to 5: 3.
7. The polycarbonate composite of claim 1, wherein the additive is at least one of an antioxidant, a lubricant, a toner, and an anti-squeal additive.
8. The polycarbonate composite of claim 1, the antioxidant is at least one of an organophosphate, an alkylated monophenol or polyphenol, tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane, an alkylated hydroquinone, a hydroxylated thiodiphenyl ether, an alkylidene bisphenol, a benzyl compound, an ester of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with a monohydric or polyhydric alcohol, an ester of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with a monohydric or polyhydric alcohol, an ester of a sulfanyl or thioaryl compound, an amide of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid; the lubricant is at least one of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax, EVA wax, oleamide, erucamide, ethylene bis stearamide, an organic silicon lubricant and pentaerythritol stearate; the toner is a pigment or dye additive; the abnormal sound prevention auxiliary agent is styrene-hydrogenated ethylene-styrene copolymer.
9. The method for preparing a polycarbonate composite material according to any one of claims 1 to 8, comprising the steps of:
(1) weighing each component in the PC/ABS copolymer according to a proportion, and uniformly mixing to obtain a premixed material;
(2) and (2) placing the premixed material obtained in the step (1) into a double-screw extruder, mixing, extruding and granulating at 200-260 ℃ and 300-1000 r/min to obtain the polycarbonate composite material.
10. Use of the polycarbonate composite material as defined in any one of claims 1 to 8 for the production of parts resistant to high temperature repeated tearing.
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