CN107880427A - Rubber modified resin composition and preparation method thereof - Google Patents
Rubber modified resin composition and preparation method thereof Download PDFInfo
- Publication number
- CN107880427A CN107880427A CN201710793869.XA CN201710793869A CN107880427A CN 107880427 A CN107880427 A CN 107880427A CN 201710793869 A CN201710793869 A CN 201710793869A CN 107880427 A CN107880427 A CN 107880427A
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- Prior art keywords
- weight
- rubber
- acrylic ester
- modified resin
- meng
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 133
- 239000005060 rubber Substances 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011342 resin composition Substances 0.000 title claims abstract description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 49
- -1 acrylic ester Chemical class 0.000 claims description 125
- 229920005989 resin Polymers 0.000 claims description 83
- 239000011347 resin Substances 0.000 claims description 83
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 75
- 239000000470 constituent Substances 0.000 claims description 66
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 62
- 239000000178 monomer Substances 0.000 claims description 47
- 229920001577 copolymer Polymers 0.000 claims description 37
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 32
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 29
- 229920000126 latex Polymers 0.000 claims description 28
- 238000010559 graft polymerization reaction Methods 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 18
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 abstract 4
- 229930004008 p-menthane Natural products 0.000 abstract 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 239000003963 antioxidant agent Substances 0.000 description 16
- 235000006708 antioxidants Nutrition 0.000 description 16
- 230000003078 antioxidant effect Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 150000003440 styrenes Chemical class 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 4
- 241000894007 species Species 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- 235000010894 Artemisia argyi Nutrition 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 244000030166 artemisia Species 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000008301 phosphite esters Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 3
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 2
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical class CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- AMVCRKRPZIJXBV-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane;hexane Chemical compound CCCCCC.CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C AMVCRKRPZIJXBV-UHFFFAOYSA-N 0.000 description 2
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 2
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 2
- LIZVXGBYTGTTTI-UHFFFAOYSA-N 2-[(4-methylphenyl)sulfonylamino]-2-phenylacetic acid Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C(O)=O)C1=CC=CC=C1 LIZVXGBYTGTTTI-UHFFFAOYSA-N 0.000 description 2
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- GCFUAWRGEMQGAR-UHFFFAOYSA-N cyclopentane;hydrogen peroxide Chemical compound OO.C1CCCC1 GCFUAWRGEMQGAR-UHFFFAOYSA-N 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-UHFFFAOYSA-N 0.000 description 2
- XNTUJOTWIMFEQS-UHFFFAOYSA-N octadecanoyl octadecaneperoxoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCCCCCCCC XNTUJOTWIMFEQS-UHFFFAOYSA-N 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229930006728 pinane Natural products 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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- 150000003568 thioethers Chemical class 0.000 description 2
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- AAOADXIHXYIOMT-UHFFFAOYSA-N 1,1'-biphenyl;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=CC=C1C1=CC=CC=C1 AAOADXIHXYIOMT-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- IHWDIGHWDQPQMQ-UHFFFAOYSA-N 1-octadecylsulfanyloctadecane Chemical class CCCCCCCCCCCCCCCCCCSCCCCCCCCCCCCCCCCCC IHWDIGHWDQPQMQ-UHFFFAOYSA-N 0.000 description 1
- UBNPTJSGEYBDCQ-UHFFFAOYSA-N 1-phenylethanone Chemical compound CC(=O)C1=CC=CC=C1.CC(=O)C1=CC=CC=C1 UBNPTJSGEYBDCQ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 description 1
- HQWDILUMZXPFNW-UHFFFAOYSA-N 2-cyano-2-nitroacetamide Chemical compound NC(=O)C(C#N)[N+]([O-])=O HQWDILUMZXPFNW-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- HTCRKQHJUYBQTK-UHFFFAOYSA-N 2-ethylhexyl 2-methylbutan-2-yloxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)CC HTCRKQHJUYBQTK-UHFFFAOYSA-N 0.000 description 1
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 206010004966 Bite Diseases 0.000 description 1
- MOENVKIRNUAZQX-UHFFFAOYSA-N C(C)(C)(C)OOC1(CCC(CC1)C(C)(C)C1CCC(CC1)(OOC(C)(C)C)OOC(C)(C)C)OOC(C)(C)C.CCC Chemical compound C(C)(C)(C)OOC1(CCC(CC1)C(C)(C)C1CCC(CC1)(OOC(C)(C)C)OOC(C)(C)C)OOC(C)(C)C.CCC MOENVKIRNUAZQX-UHFFFAOYSA-N 0.000 description 1
- RONATMFPOIMNMR-UHFFFAOYSA-N C(C)C(CCC(C)(C)OO)CCCC Chemical compound C(C)C(CCC(C)(C)OO)CCCC RONATMFPOIMNMR-UHFFFAOYSA-N 0.000 description 1
- IZIRGRRMWGKLGO-UHFFFAOYSA-N C(CCCCCCCC)C1=C(C=CC=C1)P(O)(O)O Chemical class C(CCCCCCCC)C1=C(C=CC=C1)P(O)(O)O IZIRGRRMWGKLGO-UHFFFAOYSA-N 0.000 description 1
- VLMKZCPQJZCMIJ-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)C(C(=O)O)CSCCC(=O)O Chemical class C(CCCCCCCCCCCCCCC)C(C(=O)O)CSCCC(=O)O VLMKZCPQJZCMIJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- QKQSDLXVVTUQOB-UHFFFAOYSA-N OC(O)(O)CCC(=O)OC(C(=C)C)=O Chemical class OC(O)(O)CCC(=O)OC(C(=C)C)=O QKQSDLXVVTUQOB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- HAISMSJTPGJFIP-UHFFFAOYSA-N butyl 4-tert-butyl-4,5,5-trimethylhexaneperoxoate Chemical compound CCCCOOC(=O)CCC(C)(C(C)(C)C)C(C)(C)C HAISMSJTPGJFIP-UHFFFAOYSA-N 0.000 description 1
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 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
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010061 rubber shaping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
-
- 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
Abstract
The invention relates to a rubber modified resin composition and a preparation method thereof, the rubber modified resin composition comprises a continuous phase formed by a styrene-acrylonitrile copolymer (A), a dispersed phase formed by an acrylate rubber graft copolymer (B) and p-menthane, wherein the content of the p-menthane is more than 5ppm and less than 180ppm, and the rubber modified resin composition does not contain acetophenone. The rubber modified resin composition of the invention has no acetophenone residue, and has good impact resistance, heat resistance and surface gloss.
Description
Technical field
The present invention relates to a kind of resin combination, more particularly to a kind of rubber modified resin constituent and preparation method thereof.
Background technology
In general, mostly change for the composition contained by the plastic rubber shaping product of electrical product or household supplies etc. for rubber
Property phenylethylene resin series, polycarbonate resin (polycarbonate resin) or modified rubber methacrylate ester resin
Deng.Wherein, rubber modified styrene series resin is divided into butadiene rubber modified styrene resin and ACM changes
Property phenylethylene resin series.ACM modified styrene resin includes acrylonitrile, styrene and acrylate for one kind
The ternary graft copolymer of rubber composition.Compared with butadiene rubber modified styrene resin, ACM is modified benzene
Vinylite greatly improves weatherability because substituting butadiene rubber with the few acrylic ester rubber of double bond content,
That is it is not easy irradiation or heating and cracks.Furthermore, it is weather-proof due to ACM modified styrene resin
Property greatly improves than butadiene rubber modified styrene resin, therefore directly can use out of doors.ACM is modified
Phenylethylene resin series are commonly used to automotive field (such as the outdoor such as outer visor, radiator grid, afterbody plate washer, lampshade
Part)；Or applied to electric field (such as：The round-the-clock housing such as sewing machine, telephone set, cooking apparatus, satellite antenna)；
Or applied to building field etc..
However, just current existing preparation method, ACM modified styrene resin easily remain can produce it is smelly
The acetophenone (acetophenone) of taste, not only causes discomfort to human body, also limit the application of resin.Therefore, how to make
It is standby to go out to remain entirely without acetophenone and maintain the ACM modified styrene resin of physical property needed for industry processing,
The problem studied in a hurry as industry.
The content of the invention
The present invention provides a kind of rubber modified resin constituent and preparation method thereof, and it is remained entirely without acetophenone, and has
There are good impact resistance, heat resistance and surface gloss.
The present invention rubber modified resin constituent include styrene-acrylonitrile based copolymer (A) formed continuous phase,
Dispersed phase that acrylic ester rubber graft copolymer (B) is formed and to Meng's alkane, wherein being more than 5ppm to the content of Meng's alkane
And it is less than 180ppm, and rubber modified resin constituent is free of acetophenone, i.e. the content of acetophenone is less than 1ppm.
In one embodiment of the present invention, the above-mentioned content to Meng's alkane is more than 8ppm and is less than 150ppm.
In one embodiment of the present invention, with above-mentioned styrene-acrylonitrile based copolymer (A) and acrylic ester
The gross weight of rubber graft copolymer (B) is counted for 100 weight %, and the content of styrene-acrylonitrile based copolymer (A) is 40 weights
% to 90 weight % is measured, and the content of acrylic ester rubber graft copolymer (B) is 10 weight % to 60 weight %.
In one embodiment of the present invention, with above-mentioned styrene-acrylonitrile based copolymer (A) and acrylic ester
The gross weight of rubber graft copolymer (B) is counted for 100 weight %, and above-mentioned rubber modified resin constituent includes：15 weight %
Acrylic monomeric unit, 55 weight % to 25 weight % to 65 weight % styrenic monomer unit and 15 weight % extremely
25 weight % acrylic ester monomeric unit.
In one embodiment of the present invention, the weight average grain of above-mentioned acrylic ester rubber graft copolymer (B)
Footpath is divided in the unimodal formula distribution mode between 0.05 μm to 0.22 μm, in the unimodal formula between 0.26 μm to 0.55 μm
Mode for cloth or in the double-peak type distribution mode between 0.05 μm to 0.22 μm and between 0.26 μm to 0.55 μm.
The preparation method of the rubber modified resin constituent of the present invention comprises the following steps.Styrene-acrylonitrile system is provided
Copolymer (A) and acrylic ester rubber graft copolymer (B).By styrene-acrylonitrile based copolymer (A) and acrylic ester
Rubber graft copolymer (B) is kneaded, and wherein rubber modified resin constituent contains to Meng's alkane, and the content of Meng's alkane is more than
5ppm and it is less than 180ppm, and rubber modified resin constituent is free of acetophenone.
In one embodiment of the present invention, there is provided the method bag of above-mentioned acrylic ester rubber graft copolymer (B)
Include following steps.Acrylic ester monomer is set to carry out emulsion polymerization reaction, to form acrylic ester rubber latex.Make acrylic acid
Ester system rubber latex carries out graft polymerization reaction, and wherein graft polymerization reaction is used as to Meng's alkane including the use of hydrogen peroxide and triggered
Agent.
In one embodiment of the present invention, it is above-mentioned in terms of the dry weight of the acrylic ester rubber latex of 100 parts by weight
Hydrogen peroxide is less than 1.3 parts by weight to total usage amount of Meng's alkane and is more than 0.35 parts by weight.
In one embodiment of the present invention, the reaction of above-mentioned emulsion polymerization is used as including the use of hydrogen peroxide to Meng's alkane draws
Agent is sent out, wherein in emulsion polymerization reaction, in terms of the acrylic ester monomer of 100 parts by weight, hydrogen peroxide always makes to Meng's alkane
Dosage is less than 1 parts by weight and is more than 0.05 parts by weight.
Based on above-mentioned, of the invention rubber modified resin constituent by including styrene-acrylonitrile based copolymer (A),
Acrylic ester rubber graft copolymer (B) and with certain content scope to Meng's alkane, but do not contain acetophenone, whereby not only
Solve the problems, such as acetophenone residual and cause stink, and by, to Meng's alkane, also further changing containing one of perfume base
It has been apt to smell.Consequently, it is possible to the rubber modified resin constituent of the present invention has good application.In addition, by including benzene
Ethylene-propylene nitrile based copolymer (A), acrylic ester rubber graft copolymer (B) and with certain content scope to Meng's alkane,
Rubber modified resin constituent of the invention has good impact resistance, heat resistance and surface gloss simultaneously whereby.
For allow the present invention features described above and advantage can become apparent, embodiment cited below particularly elaborate as
Under.
Embodiment
Herein, the scope represented by " numerical value to another numerical value ", is that one kind avoids enumerating in the description
The summary representation of all numerical value in the scope.Therefore, the record of a certain special value scope, covers the number range
Interior any number and the relatively fractional value scope defined by any number in the number range, as bright in the description
Text writes out any number and is somebody's turn to do as compared with fractional value scope.
Herein, the construction unit that monomeric unit represents the aggregated reaction of monomer and formed.
The rubber modified resin constituent that one embodiment of the present invention provides includes styrene-acrylonitrile based copolymer
(A) dispersed phase that the continuous phase that is formed, acrylic ester rubber graft copolymer (B) are formed and to Meng's alkane, but be free of
There is acetophenone, wherein with the gross weight meter of rubber modified resin constituent, 5ppm is more than to the content of Meng's alkane and is less than 180ppm.
Consequently, it is possible to the rubber modified resin constituent of present embodiment not only solve acetophenone residual the problem of, and by containing
Have to Meng's alkane, also further improve smell, improve its application whereby.On the other hand, by including styrene-acrylonitrile
Based copolymer (A), acrylic ester rubber graft copolymer (B) and to Meng's alkane, and there is specific content model to Meng's alkane
Enclose, the rubber modified resin constituent of present embodiment has good impact resistance, heat resistance and surface gloss simultaneously.
If being more than or equal to 180ppm to the content of Meng's alkane, the mobility of rubber modified resin constituent is poor, by shadow
Ring following process shaping；It is the impact resistance of rubber modified resin constituent, resistance to if being less than or equal to 5ppm to the content of Meng's alkane
The physical property such as hot and surface gloss will be impacted, is unable to reach standard needed for industry.In one embodiment, Meng's alkane is contained
Amount is preferably more than 8ppm and is less than 150ppm, more preferably more than 10ppm and is less than 100ppm, is most preferably more than 10ppm and is less than
80ppm。
In the present embodiment, with styrene-acrylonitrile based copolymer (A) and acrylic ester rubber graft copolymer
(B) gross weight is counted for 100 weight %, and the content of styrene-acrylonitrile based copolymer (A) is 40 weight % to 90 weight %,
And the content of acrylic ester rubber graft copolymer (B) is 10 weight % to 60 weight %.For another viewpoint, with benzene second
The gross weight of alkene-acrylic copolymer (A) and acrylic ester rubber graft copolymer (B) is counted for 100 weight %, rubber
Modified resin constituent includes 15 weight % to 25 weight % acrylic monomeric unit, 55 weight % to 65 weight % benzene
The acrylic ester monomeric unit of vinyl monomer unit and 15 weight % to 25 weight %.Herein, the acrylic ester
Monomeric unit, styrenic monomer unit and acrylic monomeric unit, refer to acrylic ester monomer, styrenic monomers respectively
And acrylic monomer it is aggregated reaction and formed construction unit.
Specifically, in the present embodiment, styrene-acrylonitrile based copolymer (A) is by styrenic monomers and third
Alkene nitrile system monomer it is aggregated reaction and obtain.The composition of styrene-acrylonitrile based copolymer (A) includes 60 weight % to 85 weight %
Styrenic monomer unit and 15 weight % to 40 weight % acrylic monomeric unit, preferably 64 weight % to 78 weights
Measure % styrenic monomer unit and 22 weight % to 36 weight % acrylic monomeric unit.Aforementioned monomer unit refers to
Residue (i.e. relict structure) in polymer molecule obtained by after the aggregated reaction of monomer.The specific reality of the styrenic monomers
Example includes but is not limited to：Styrene, α-methylstyrene, p- t-butyl styrene, p-methylstyrene, ortho-methyl benzene
Ethene, m- methyl styrene, 2,4- dimethyl styrenes, ethyl styrene, Alpha-Methyl-p-methylstyrene or bromstyrol
Deng wherein being preferable using styrene or α-methylstyrene.The instantiation of the acrylic monomer includes but is not limited to：
Acrylonitrile or Alpha-Methyl acrylonitrile etc., wherein being preferable using acrylonitrile.
The polymerisation can be carried out using block polymerization, solution polymerization process, suspended polymerization or emulsion polymerization method,
It is preferable wherein using block polymerization or solution polymerization process.By taking solution polymerization as an example, styrene-acrylonitrile based copolymer
(A) preparation method is included in the presence of solvent, and styrenic monomers, acrylic monomer and polymerization initiator are carried out into solution
Polymerisation is completed, and wherein operating temperature range is preferably 70 DEG C to 140 DEG C, more preferably 90 DEG C to 130 DEG C.It is used molten
Agent is, for example, toluene, ethylbenzene or MEK etc..
The polymerization initiator includes but is not limited to：Hydrogen peroxide (hydroperoxide) class compound, such as：Uncle
Butylperoxide (tert-butyl hydroperoxide), hydrogen peroxide are to Meng's alkane (paramenthane
Hydroperoxide) etc.；Peroxy ketal (peroxyketal) class compound, such as：1,1- pairs-tert-butyl hydroperoxide -3,
3,5- trimethyl-cyclohexanes (1,1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane), 2,2- bis-
(4,4- bis- (tert-butyl hydroperoxide) cyclohexyl) propane (2,2-di (4,4-di (tert-butylperoxy) cyclohexyl)
Propane) etc.；Peroxyester (peroxyesters) class compound, such as：Tbutylperoxypivalate (t-butyl
Peroxypivalate), 2,5- dimethyl -2,5- two (2-Ethylhexyl Alcohol peroxidating) hexane (2,5-dimethyl-2,5-di
(2-ethylhexanoylperoxy) hexane) etc.；Ketal peroxide class compound, such as：The 4,4- diperoxies tert-butyl group-
Valeric acid-N-butyl (4,4-di-t-butyl peroxy valeric acid-n-butyl ester, abbreviation TX-17) etc.；Cross
Carbonic ester (peroxycarbonate) class compound is aoxidized, such as：2- ethylhexyl t-amyl peroxy carbonic esters (tert-
Amylperoxy 2-ethylhexyl carbonate), 2- ethylhexyl tert-butyl hydroperoxide carbonic esters (tert-
Butylperoxy 2-ethylhexyl carbonate) etc.；Or azo-compound with nitro and cyclohexanes etc..With benzene
The gross weight of vinyl monomer and acrylic monomer is 100 parts by weight meters, and the addition scope of polymerization initiator is 0.01 weight
Part is measured to 2.0 parts by weight, preferably 0.01 parts by weight to 1.0 parts by weight.
In addition, when preparing styrene-acrylonitrile based copolymer (A), except polymerization initiator can be added as mentioned before
Enter in reaction, can also use thermal polymerization mode.
In addition, reactor used in carrying out previous reaction may include (but not limited to)：It is thoroughly mixed flow reactor
(CSTR), the pipe reactor of column flow reactor (Plug flow reactor, PFR) or the hybrid element containing silent oscillation
Deng wherein being preferred with being thoroughly mixed flow reactor.The usage quantity of the reactor can be one, also can and with two or
Two or more.
In one embodiment, the molecular weight of styrene-acrylonitrile based copolymer (A) is 60,000 to 400,000.
In addition, in the present embodiment, the preparation method of acrylic ester rubber graft copolymer (B) includes：Make propylene
Acid esters system rubber latex carries out graft polymerization reaction.Specifically, the preparation method of acrylic ester rubber latex includes：Make third
Olefin(e) acid ester system monomer carries out emulsion polymerization reaction in the presence of initiator.The instantiation of the acrylic ester monomer includes
(but not limited to)：Methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate, methyl-prop
Olefin(e) acid pentyl ester, hexyl methacrylate, metering system heptyl heptylate, methacrylic acid -2- ethylhexyls, methyl acrylate, propylene
Acetoacetic ester, propyl acrylate, n-butyl acrylate, amyl acrylate, Hexyl 2-propenoate, heptylacrylate, acrylic acid-2-ethyl
Own ester, dodecylacrylate etc., wherein being preferred with n-butyl acrylate.
The initiator can be except cumene hydrogen peroxide (cumene hydroperoxide, abbreviation CHP)
Various existing radical polymerization initiators in addition, and the addition manner of the initiator can be used and once added, or
It is continuously or incrementally to add etc..Specifically, the instantiation of initiator includes but is not limited to：Hydrogen peroxide is to Meng's alkane
(p-menthane hydroperoxide, abbreviation PMHP), tert-butyl peroxide (tert-butyl peroxide), 12
Alkanoyl peroxide (layroyl peroxide), octadecanoyl peroxide (oleyl peroxide), peracetic acid uncle
Butyl ester (tert-butyl peracetate), heavy carbonic isopropyl peroxide base ester (isopropyl peroxy
Dicarbonate), 2,5- dimethyl -2,5- two (tertiary peroxidating butyl) hexane (2,5-dimethyl-2,5-di (tert-
Butyl peroxy) hexane), TBHP (tert-butyl hydroperoxide), 2,5- dimethyl -2,5-
Two (tertiary peroxidating butyl)-hexyl -3- TBHPs (2,5-dimethyl-2,5-di (tert-butylperoxy)
Hexane-3-tert-butyl hydroperoxide), cyclopenta hydrogen peroxide (cyclopentane
Hydroperoxide), pinane hydrogen peroxide (pinane hydroperoxide), the mistakes of 2,5- dimethyl-hexyls -2,5- two
Hydrogen oxide (2,5-dimethyl-hexane-2,5-dihydroperoxide) or its mixture.In one embodiment, with third
The gross weight of olefin(e) acid ester system monomer is 100 parts by weight meters, and total usage amount of initiator is preferably 0.01 parts by weight to 2 parts by weight.
In addition, the preparation method of acrylic ester rubber latex can be additionally included in when carrying out polymerisation, by bridging agent plus
Enter.The bridging agent includes but is not limited to：Diacrylate second diester, butylene diacrylate, divinylbenzene, dimethyl propylene
Olefin(e) acid butylene glycol ester, dimethylacrylate, three (methyl) acrylic acid trihydroxymethylpropanyl esters, allyl methacrylate
(allyl methacrylate, AMA), diallyl methacrylate, diallyl maleate, diallyl fumarate, phthalein
Diallyl phthalate, methacrylic acid triallyl, TAC, fulminuric acid triallyl, tricyclo decene alcohol
Acrylate, the diacrylate etc. of ployalkylene glycol, wherein foregoing bridging agent can be used alone or two or more is used in combination.
In one embodiment, counted by 100 weight % of the gross weight of acrylic ester monomer and bridging agent, the usage amount of bridging agent is preferable
For 0.1 weight % to 10 weight %.
In addition, the average grain diameter of acrylic ester rubber latex can be controlled by by polymeric reaction condition, such as：Polymerization
Temperature；Initiator, emulsifying agent, the dosage and species of activator；Adding method of monomer etc. is controlled by.The emulsifying agent does not have
Special limitation, in order that the stability for carrying out emulsion during emulsion polymerization reaction is excellent, improves aggregate rate, with selected from butanedioic acid
The carboxylate of sodium, aliphatic acid potassium, sodium soap, alkenyl succinic acid dipotassium, roseolic acid soap etc., sulfuric acid alkyl ester, sodium alkyl benzene sulfonate
Deng sulfonate, and the anion system emulsifying agent of PEO nonyl benzene ether sodium sulfate etc. is preferable.The activator it is specific
Example includes but is not limited to：Ferrous sulfate, formaldehyde sodium sulfoxylate, EDTA sodium, tetrasodium pyrophosphate etc..
In addition, the weight average particle diameter of acrylic ester rubber latex can be in unimodal formula distribution mode or double-peak type distribution side
Formula.In one embodiment, the weight average particle diameter of acrylic ester rubber latex is in unimodal between 0.05 μm to 1 μm
Formula distribution mode.In another embodiment, the weight average particle diameter of acrylic ester rubber latex is between 0.05 μm to 0.2
Unimodal formula distribution mode between μm.In yet another embodiment, the weight average particle diameter of acrylic ester rubber latex is in Jie
Unimodal formula distribution mode between 0.26 μm to 0.5 μm.In a further embodiment, the weight of acrylic ester rubber latex
Average grain diameter is in the double-peak type distribution mode between 0.05 μm to 0.2 μm and between 0.26 μm to 0.5 μm.
Acrylic ester rubber latex is carried out graft polymerization reaction includes：In the presence of initiator, make 100 parts by weight
The acrylic ester rubber latex of (dry weight) carries out graft polymerization reaction with the monomer mixture of 50 parts by weight to 100 parts by weight,
Wherein monomer mixture includes 64 weight % to 78 weight % styrenic monomers and 22 weight % to 36 weight % propylene
Nitrile system monomer.The addition manner of aforementioned monomer mixture can use and once add, is added portionwise, is continuously added to or mix monomer
Various monomers segmentation in thing adds.In addition, as it was noted above, when the weight average particle diameter of acrylic ester rubber latex is in double
During peak formula distribution mode, two kinds of acrylic ester rubber latexs mix again after can separating progress graft polymerization reaction individually, or
It is that the state that two kinds of acrylic ester rubber latexs can mix carries out graft polymerization reaction.Specifically, in this embodiment party
In formula, the composition of acrylic ester rubber graft copolymer (B) includes 5 weight % to 25 weight % acrylic monomer list
The acrylic ester monomer list of member, 25 weight % to 45 weight % styrenic monomer unit and 40 weight % to 70 weight %
Member, preferably 5 weight % are to 20 weight % acrylic monomeric unit, 30 weight % to 40 weight % styrenic monomers
The acrylic ester monomeric unit of unit and 40 weight % to 60 weight %.
The instantiation of the styrenic monomers includes but is not limited to：Styrene, α-methylstyrene, p- tertiary fourth
Base styrene, p-methylstyrene, ortho-methyl styrene, m- methyl styrene, 2,4- dimethyl styrenes, ethylo benzene second
Alkene, Alpha-Methyl-p-methylstyrene or bromstyrol etc., wherein being preferable using styrene or α-methylstyrene.The propylene
The instantiation of nitrile system monomer includes but is not limited to：Acrylonitrile or Alpha-Methyl acrylonitrile etc., wherein being preferable using acrylonitrile.
The initiator can be each in addition to cumene hydrogen peroxide (cumene hydroperoxide)
The existing radical polymerization initiator of kind, and the addition manner of the initiator can be used and once added, or continuously
Or incrementally add etc..Specifically, the instantiation of initiator includes but is not limited to：Hydrogen peroxide is to Meng's alkane (p-
Menthane hydroperoxide), tert-butyl peroxide (tert-butyl peroxide), dodecane acyl group peroxidating
Thing (layroyl peroxide), octadecanoyl peroxide (oleyl peroxide), peracetic acid tertiary butyl ester (tert-
Butyl peracetate), heavy carbonic isopropyl peroxide base ester (isopropyl peroxy dicarbonate), 2,5- diformazans
Base -2,5- two (tertiary peroxidating butyl) hexane (2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane), uncle
Butylhydroperoxide (tert-butyl hydroperoxide), 2,5- dimethyl -2,5- two (tertiary peroxidating butyl)-hexyl -
3- TBHPs (2,5-dimethyl-2,5-di (tert-butylperoxy) hexane-3-tert-butyl
Hydroperoxide), cyclopenta hydrogen peroxide (cyclopentane hydroperoxide), pinane hydrogen peroxide
(pinane hydroperoxide), 2,5- dimethyl-hexyl -2,5- diperoxies hydrogen (2,5-dimethyl-hexane-2,
5-dihydroperoxide) or its mixture.In one embodiment, using the gross weight of monomer mixture as 100 parts by weight
Meter, total usage amount of initiator are preferably 0.01 parts by weight to 2 parts by weight.
What deserves to be explained is if using hydrogen peroxide to Meng's alkane as initiator in the reaction of foregoing emulsion polymerization,
It can draw in graft polymerization reaction equally using hydrogen peroxide to Meng's alkane as initiator or without using hydrogen peroxide to the conduct of Meng's alkane
Send out agent；And if foregoing emulsion polymerization reaction in be not used hydrogen peroxide to Meng's alkane as initiator, in graft polymerization reaction
In must use hydrogen peroxide to Meng's alkane as initiator.That is, in the present embodiment, preparing acrylic ester rubber
During graft copolymer (B), at least one of emulsion polymerization reaction and graft polymerization reaction are using hydrogen peroxide to Meng
Alkane is as initiator.Also, it is preferred that during acrylic ester rubber graft copolymer (B) is prepared, it is graft-polymerized anti-
Hydrogen peroxide should be used to Meng's alkane as initiator.
Specifically, in the present embodiment, in emulsion polymerization reaction, with the acrylic ester monomer of 100 parts by weight
Meter, the hydrogen peroxide as initiator are less than 1 parts by weight to total usage amount of Meng's alkane and are more than 0.05 parts by weight.In emulsion polymerization
In reaction, if hydrogen peroxide is more than or equal to 1 parts by weight to the usage amount of Meng's alkane, rubber modified resin constituent glossiness with
Heat resistance is poor；If hydrogen peroxide is less than or equal to 0.05 parts by weight to the usage amount of Meng's alkane, rubber modified resin composition
Impact resistance will obvious deficiency.In addition, in the present embodiment, in graft polymerization reaction, with the acrylate of 100 parts by weight
It is the dry weight meter of rubber latex, the hydrogen peroxide as initiator is less than 1.3 parts by weight to total usage amount of Meng's alkane and is more than
0.35 parts by weight.In graft polymerization reaction, if hydrogen peroxide is more than or equal to 1.3 parts by weight, rubber to the usage amount of Meng's alkane
The mobility of glue modified resin constituent will be too high；If hydrogen peroxide is less than or equal to 0.35 parts by weight to the usage amount of Meng's alkane,
Then the mobility of rubber modified resin constituent will be too low.
Furthermore, what rubber modified resin constituent was included be to Meng's alkane hydrogen peroxide initiator it is reacted after
Caused product, that is to say, that be to prepare the accessory substance during acrylic ester rubber graft copolymer (B) to Meng's alkane.
No matter in addition, as it was noted above, because in emulsion polymerization reaction or in graft polymerization reaction, initiator is all without being anti-
Ying Houhui produces the hydrogen peroxide initiator of acetophenone, therefore rubber modified resin constituent does not contain acetophenone.In addition, need to more it enter
What one step illustrated be in the present embodiment because used gas chromatograph is 1ppm for the detecting limit of acetophenone,
Therefore so-called rubber modified resin constituent does not contain acetophenone, refers to that the content of acetophenone is less than 1ppm.
In addition, the grafting rate of acrylic ester rubber graft copolymer (B) can be controlled by by polymeric reaction condition, example
Such as：Polymerization temperature；Initiator, emulsifying agent, activator, the dosage and species of chain transfer agent；The dosage of monomer and adding method etc.
It is controlled by.In one embodiment, the reaction temperature of graft polymerization reaction is below 90 DEG C, preferably between 25 DEG C to 40 DEG C.
The emulsifying agent has no particular limits, in order that the stability of emulsion is excellent when carrying out emulsion polymerization reaction, carries
High aggregate rate, with the carboxylic acid selected from sodium succinate, aliphatic acid potassium, sodium soap, alkenyl succinic acid dipotassium, roseolic acid soap etc.
The sulfonate of salt, sulfuric acid alkyl ester, sodium alkyl benzene sulfonate etc., and the anion system emulsification of PEO nonyl benzene ether sodium sulfate etc.
Agent is preferable.The instantiation of the activator includes but is not limited to：Ferrous sulfate, formaldehyde sodium sulfoxylate, ethylenediamine tetraacetic vinegar
Sour sodium, tetrasodium pyrophosphate etc..The specific embodiment of the chain transfer agent includes but is not limited to：N-butyl mercaptan (n-butyl
Mercaptan), n-octyl mercaptan (n-octyl mercaptan), n- lauryl mercaptan (n-dodecyl
Mercaptan), tert- lauryl mercaptan (tert-dodecyl mercaptan).In one embodiment, mixed with monomer
The gross weight of thing is 100 parts by weight meters, and the usage amount of chain transfer agent is preferably 0.01 parts by weight to 5 parts by weight.
In addition, the weight average particle diameter of acrylic ester rubber graft copolymer (B) can be in unimodal formula distribution mode or double
Peak formula distribution mode.In one embodiment, the weight average particle diameter of acrylic ester rubber graft copolymer (B) be between
Unimodal formula distribution mode between 0.05 μm to 0.22 μm.In another embodiment, the weight of acrylic ester rubber latex
Average grain diameter is in the unimodal formula distribution mode between 0.26 μm to 0.55 μm.In yet another embodiment, acrylic ester
The weight average particle diameter of rubber latex is in bimodal between 0.05 μm to 0.22 μm and between 0.26 μm to 0.55 μm
Formula distribution mode.
In addition, the rubber modified resin constituent of present embodiment can also include additive.The additive is selected from anti-
Oxidant, lubrication prescription, plasticizer, processing aid, ultraviolet stabilization agent, ultra-violet absorber, filler, hardening agent, colouring agent, band
Electric preventing agent, incombustible agent, fire retardant auxiliary agent, thermal stabilizer, coupling agent, or these combination.
The antioxidant can be used alone or as a mixture, and antioxidant includes but is not limited to：Phenol antioxidant, sulphur
Ether system antioxidant, or phosphorous antioxidant etc..The phenol antioxidant can be used alone or as a mixture, and phenol antioxidant
Instantiation include but is not limited to：Double (1,1- the dimethyl ethyls) -4- hydroxy-phenylpropionic acid stearyls (3,5- of 3,5-
Bis (1,1-dimethylethyl) -4-hydroxybenzenepropanoic acid octadecyl ester, Xing ︰ resist
Oxidant IX-1076), triethylene glycol double [3- (the 3- tert-butyl group -5- methyl -4- hydroxyphenyls) propionic ester], four [methylene base -3- (3,
5- dual-tert-butyl -4- hydroxyphenyls) propionic ester] methane, the 2- tert-butyl groups -6- (the 3- tert-butyl group -2- hydroxyl -6- methylbenzyls) -4-
Aminomethyl phenyl acrylate, 2,2'- methylenes base-bis- (4- methyl-6-tert butyl phenol) (2,2'-methylene-bis (4-
Methyl-6-tert-butylphenol), type ︰ antioxidants 2246), 2,2'- sulphur double (4- methyl-6-tert butyl phenol), 2,
Thio-diethyl the support groups-of 2'- are bis- [3- (3,5- dual-tert-butyl -4- hydroxyphenyls) propionic ester], or 2,2'- oxalamide-bis- [ethyl -
3- (3,5- pairs-tert-butyl group -4- hydroxyphenyls) propionic ester] etc..The thioether antioxidant can be used alone or as a mixture, and thioether
It is that the instantiation of antioxidant includes but is not limited to：It is distearyl thiodipropionic acid ester, two palmityl thiodipropionic acid esters, five red
Moss alcohol-four-(β-ten dimethyl-sulphur propionic ester), or double octadecyl thioethers etc..The phosphorous antioxidant can individually or mixing
Use, and phosphorous antioxidant includes but is not limited to：The phosphorus system of phosphorous antioxidant or phosphate ester-containing containing phosphite ester resists
Oxidant.The instantiation of the phosphorous antioxidant containing phosphite ester includes but is not limited to：Three (nonyl phenyl) phosphorous
Acid esters, dodecyl phosphite ester, 4,4' butylidene biss (3- methyl-6-terts butyl phenyl-double tridecyl phosphite ester) or
Three (2,4- tert-butyl-phenyls) phosphite esters etc..The instantiation of the phosphorous antioxidant of the phosphate ester-containing includes (but unlimited
In)：Four (2,4- tert-butyl-phenyl) -4,4'- stretch biphenyl phosphate, or the support of 9,10- dihydro-9-oxy -10- phosphoric acid phenanthrene -10- oxygen
Deng.
The lubrication prescription can be used alone or as a mixture, and the instantiation of lubrication prescription includes but is not limited to：Calcium stearate, tristearin
It is the metallic soaps of sour magnesium, lithium stearate etc., ethylene distearyl acid amides (ethylene bis-stearamide, abbreviation EBA), hard
It is the ester of resin acid isoamyl four (pentaerythritol stearate, abbreviation PETS), methylene distearyl acid amides, palmitamide, hard
Resin acid butyl ester, stearic acid palm ester, the fatty acid ester of pentaerythrite four, poly- propionic acid alcohol tristearate, behenic acid, tristearin
Compound, Tissuemat E, octocosoic acid wax, Brazil wax (carnauba wax) or pertroleum wax of acid etc. etc..
In one embodiment, counted by 100 parts by weight of the gross weight of rubber modified resin constituent, the content of additive
Scope is 0.01 parts by weight to 20 parts by weight.
The preparation method for the rubber modified resin constituent that another embodiment of the present invention provides includes：There is provided any
After styrene-acrylonitrile based copolymer (A) and acrylic ester rubber graft copolymer (B) in aforementioned embodiments, by benzene
Ethylene-propylene nitrile based copolymer (A) is kneaded with acrylic ester rubber graft copolymer (B), to form modified rubber tree
Fat composition.Rubber modified resin constituent, styrene-acrylonitrile based copolymer (A) and the copolymerization of acrylic ester grafting rubbers
The associated description of thing (B) is at large illustrated in above-mentioned embodiment, therefore is repeated no more in this.
In the present embodiment, by styrene-acrylonitrile based copolymer (A) and acrylic ester rubber graft copolymer
(B) method being kneaded is not particularly limited, and can use any kneading having in field well known to usually intellectual
Method.In one embodiment, styrene-acrylonitrile based copolymer (A) and acrylic ester rubber graft copolymer (B) are entered
The method that row is kneaded includes：With the Han Xieer mixers typically used it is dry-mixed after, then with such as extrusion mixer, kneader or class
The mixer melting mixing of the vertical muller of uncle etc..
In addition, the additive that rubber modified resin constituent can be included can also prepare styrene-acrylonitrile based copolymer
(A) before, in the polymerisation of acrylic ester rubber graft copolymer (B), after polymerisation, condensing, or by styrene-
Acrylic copolymer (A) adds during being kneaded with acrylic ester rubber graft copolymer (B).
What deserves to be explained is as it was noted above, during acrylic ester rubber graft copolymer (B) is prepared, by
Use hydrogen peroxide to Meng's alkane as initiator at least one of emulsion polymerization reaction and graft polymerization reaction, therefore final production
Accessory substance can be contained in thing to Meng's alkane, be whereby copolymerized styrene-acrylonitrile based copolymer (A) and acrylic ester grafting rubbers
Thing (B), which be kneaded, is able to be formed the rubber modified resin constituent to Meng's alkane containing certain content.On the other hand, preparing
During acrylic ester rubber graft copolymer (B), no matter due in emulsion polymerization reaction or anti-being graft-polymerized
Ying Zhong, initiator is all without being that the cumene hydrogen peroxide of acetophenone can be produced after reaction, therefore by styrene-acrylonitrile system
Copolymer (A) with acrylic ester rubber graft copolymer (B) be kneaded and is able to form the rubber for being entirely free of acetophenone
Modified resin constituent.
Consequently, it is possible to the rubber modified resin obtained by the preparation method of the rubber modified resin constituent of present embodiment
Constituent not only solves the problem of acetophenone residual, by containing to Meng's alkane, also further improving smell.On the other hand,
By including styrene-acrylonitrile based copolymer (A), acrylic ester rubber graft copolymer (B) and to Meng's alkane, and it is right
Meng's alkane has specific content range, and the rubber obtained by the preparation method of the rubber modified resin constituent of present embodiment changes
Property resin combination simultaneously there is good impact resistance, heat resistance and surface gloss.
Below in reference to embodiment 1~8 and comparative example 1~4, feature of the invention is more specifically described.Although describe
Example 1 below~8, but in the case of insurmountability scope, can suitably change material therefor, its amount and ratio
Rate, processing details and handling process etc..Therefore, restricting property of the present invention should not be solved by embodiments described just below
Release.
Synthesis example 1
The preparation of styrene-acrylonitrile based copolymer (A)
By the 1,1- of the styrene of 76 parts by weight, the acrylonitrile of 24 parts by weight, the ethylbenzene of 8 parts by weight, 0.01 parts by weight it is double-
The raw material of the tert- lauryl mercaptan of tert-butyl hydroperoxide -3,3,5- trimethyl-cyclohexanes and 0.15 parts by weight is mixed, and
Two tandems are continuously supplied into speed 35kg/hr to be thoroughly mixed in flow reactor, wherein the volume of reactor is all
For 40 liters, the interior temperature of 2 reactors keeps 110 DEG C and 115 DEG C respectively, and the pressure of reactor all keeps 4kg/cm2, it is overall to turn
The rate of changing is about 50%.
After polymerization ends, the copolymer solution of gained is heated with preheater.Then, removed with depressurizing deaerating tank devolatilization
After unreacted monomer and other fugitive constituents, its extrusion is granulated to the styrene-acrylonitrile based copolymer that can obtain synthesis example 1
(A)。
Synthesis example 2
The preparation of acrylic ester rubber graft copolymer (B)
First, by the n-butyl acrylate of 99.0 parts by weight, the allyl methacrylate of 1.0 parts by weight, 0.1 parts by weight
Hydrogen peroxide to Meng's alkane, the copperas solution (concentration 0.2wt%) of 3.0 parts by weight, 3.0 parts by weight formolation sulphoxylic acid
It is small that sodium solution (concentration 10wt%) and the distilled water of 4000.0 parts by weight carry out emulsion polymerization reaction 7 under 60 DEG C of reaction temperature
When, to obtain weight average particle diameter as 0.1 μm of acrylic ester rubber latex (solids content about 38%).
Secondly, by the n-butyl acrylate of 99.0 parts by weight, the allyl methacrylate of 1.0 parts by weight, 0.1 parts by weight
Hydrogen peroxide to Meng's alkane, the copperas solution (concentration 0.2wt%) of 3.0 parts by weight, 3.0 parts by weight formolation sulphoxylic acid
It is small that sodium solution (concentration 10wt%) and the distilled water of 4000.0 parts by weight carry out emulsion polymerization reaction 7 under 65 DEG C of reaction temperature
When, to obtain weight average particle diameter as 0.4 μm of acrylic ester rubber latex (solids content about 38%).
Then, it is 0.4 μm of acrylic ester rubber latex (dry weight) by the above-mentioned weight average particle diameter of 30.0 parts by weight
And 70.0 parts by weight above-mentioned weight average particle diameter be 0.1 μm acrylic ester rubber latex (dry weight), 70.0 parts by weight
Styrene, the acrylonitrile of 30.0 parts by weight, the hydrogen peroxide of 0.86 parts by weight are to Meng's alkane, the copperas solution of 3.0 parts by weight
The formaldehyde sodium sulfoxylate solution (concentration 10wt%) of (concentration 0.2wt%), 3.0 parts by weight and the distilled water of 3000.0 parts by weight
Mix and carry out graft polymerization reaction.After the completion of graft polymerization reaction, acrylic ester grafting rubbers emulsion can be obtained.
Finally, by the acrylic ester grafting rubbers emulsion of gained with calcium chloride (CaCl2) condense, after dehydration, re-dry
To water content below 2%, you can the acrylic ester rubber graft copolymer of synthesis example 2 is made, its weight average particle diameter is
0.12 μm and 0.45 μm of double-peak type distribution mode.
Synthesis example 3-12
The preparation of acrylic ester rubber graft copolymer (B)
Made according to the preparation procedure similar to synthesis example 1, and according to the species and dosage of initiator shown by table 1
Standby synthesis example 3-12 acrylic ester rubber graft copolymer.
Illustrate the abbreviation in table 1 below：
Compound representated by abbreviation
BHP TBHPs
CHP cumene hydrogen peroxide
PMHP hydrogen peroxide is to Meng's alkane
Embodiment 1
The preparation of rubber modified resin constituent
In the state of drying, with twin shaft extruder (model：ZPT-25, manufacturer：Ze Ji Industrial Co., Ltd) by 54.1
The acrylic ester rubber of the styrene-acrylonitrile based copolymer (A) of weight % synthesis example 1,45.9 weight % synthesis example 2
The lubrication prescription of graft copolymer (B) and 2.0 weight % is kneaded in the case where being kneaded 220 DEG C of temperature.Then, with twin shaft extruder extrusion
Afterwards, you can obtain the rubber modified resin constituent of embodiment 1.
Embodiment 2-8 and comparative example 1-4
The preparation of rubber modified resin constituent
Prepared according to preparation procedure similar to Example 1, and according to the species and dosage of raw material shown by table 2
Embodiment 2-8 and comparative example 1-4 rubber modified resin constituent.In addition, (the weight %) in table 2 is with styrene-propene
The gross weight meter of nitrile based copolymer (A) and the acrylic ester rubber graft copolymer (B).
Afterwards, embodiment 1-8 and comparative example 1-4 rubber modified resin constituent is carried out respectively：The content of acetophenone
Measure, the assay to Meng's alkane, the measurement of fusing coefficient (melt index, MI), softening point temperature (vicat
Softening temperature) measurement, Chinese mugwort formula impact strength (Izod) measurement and surface gloss (gloss)
Measure.Foregoing every is described as follows, and measurement result is shown in table 3.In addition, the nd in table 3 represents that undetermined goes out, because
Gas chromatograph is 1ppm for the detecting limit of acetophenone, therefore nd represents that undetermined goes out to refer to that the content of acetophenone is less than
1ppm。
The assay ＞ of ＜ acetophenones
Instrument：Gas chromatograph (gas chromatography, GC) (model：Agilent 6890GC/FID)
Tubing string model：HP-5 30M*0.32mm*0.25um.
Pre-treatment：1 gram of sample (i.e. embodiment 1-8 and comparative example 1-4 rubber modified resin constituent) is taken to be dissolved in 5 milliliters
Dichloromethane after, then with 10 milliliters of methanol extraction.Afterwards, take quantitative in clarified solution injection GC.
Elevated Temperature Conditions：300 DEG C are warming up to by 60 DEG C 10 DEG C per minute to be detained 11 minutes.
Assay ＞s of the ＜ to Meng's alkane
With the assay of above-mentioned acetophenone.
The measurement ＞ of ＜ fusing coefficients
Measured according to ASTM D-1238 regulations, measuring condition is 220 DEG C, loading 10Kg, and unit is：g/10min.
In the field of ordinary rubber modified resin constituent, MI standard is at least greater than 5g/10min and is less than 12g/10min, and number
Value is higher, and expression mobility is better, that is, represents that the mouldability of rubber modified resin constituent is better.
The measurement ＞ of ＜ softening point temperatures
Provide to carry out the measurement of softening point temperature according to ASTM D-1525, unit is：℃.In general, softening point temperature is got over
Height represents that heat resistance is better.
The measurement ＞ of ＜ Chinese mugwort formula impact strengths
With ejaculator (model：SM-150, manufacturer：Limited company of Zhen Xiong machinery plants) respectively by embodiment 1-8 and ratio
The attached thickness jaggy of rubber modified resin constituent ejection formation compared with example 1-4 is the test piece of 1/8 English inch, and according to ASTM D-
256 regulations are measured.Unit is：Kg cm/cm.In the field of ordinary rubber modified resin constituent, Izod standard is extremely
It is greater than 10Kg cm/cm less, and the higher expression impact resistance of numerical value is better.
The measurement ＞ of ＜ surface glosses
With ejaculator (model：SM-150, manufacturer：Limited company of Zhen Xiong machinery plants) respectively by embodiment 1-8 and ratio
The disk test piece of a diameter of 5.5cm of rubber modified resin constituent ejection formation compared with example 1-4, and according to ASTM D-523 provide into
Row measures, and unit is：%.
The measurement ＞ of ＜ stinks
Take resin made of 50 grams to be placed in glass sample bottle to seal one day, be then turned on through the direct smelling of human body.
Odorless and tool armaticity：◎
Odorless：○
Stink slightly：Δ
Strong odor：X
From above-mentioned table 3, embodiment 1-8 rubber modified resin constituent does not all contain acetophenone, and all containing pair
Meng's alkane, its content range is between 19ppm~68ppm；On the contrary, comparative example 1-4 rubber modified resin constituent all contains
Acetophenone, easily cause the stink for making us uncomfortable.Therefore, compared with comparative example 1-4 rubber modified resin constituent, embodiment 1-
8 rubber modified resin constituent does not have the problem of producing stink because of acetophenone residual not only, and by containing to Meng
Alkane, also further improves smell, human body is caused when avoiding application whereby uncomfortable and has good application.
In addition, from above-mentioned table 3, embodiment 1-8 rubber modified resin constituent is in softening point temperature, Chinese mugwort formula impact
There is excellent performance in terms of intensity and surface gloss.This is as a result, it was confirmed that embodiment 1-8 rubber modified resin constituent
Not only remained without acetophenone, also maintain the physical property for having needed for industry processing.
In addition, from above-mentioned table 3, embodiment 1-6 rubber modified resin constituent has excellent in terms of fusing coefficient
Performance.This result represents, during acrylic ester rubber graft copolymer (B) is prepared, by using less than 1.3 weights
Measure part and the hydrogen peroxide more than 0.35 parts by weight carries out graft polymerization reaction to Meng's alkane as initiator, modified rubber can be made
Resin combination reaches good mobility.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
- A kind of 1. rubber modified resin constituent, it is characterised in that including：The continuous phase that styrene-acrylonitrile based copolymer (A) is formed；The dispersed phase that acrylic ester rubber graft copolymer (B) is formed；AndTo Meng's alkane, wherein the content to Meng's alkane is more than 5ppm and is less than 180ppm, and rubber modified resin composition Thing is free of acetophenone.
- 2. rubber modified resin constituent according to claim 1, it is characterised in that the content to Meng's alkane is more than 8ppm and it is less than 150ppm.
- 3. rubber modified resin constituent according to claim 1, it is characterised in that with the styrene-acrylonitrile system The gross weight of copolymer (A) and the acrylic ester rubber graft copolymer (B) is counted for 100 weight %, and the styrene- The content of acrylic copolymer (A) is 40 weight % to 90 weight %, and the acrylic ester rubber graft copolymer (B) Content be 10 weight % to 60 weight %.
- 4. rubber modified resin constituent according to claim 1, it is characterised in that with the styrene-acrylonitrile system The gross weight of copolymer (A) and the acrylic ester rubber graft copolymer (B) is counted for 100 weight %, and the rubber changes Property resin combination includes：15 weight % to 25 weight % acrylic monomeric unit, 55 weight % to 65 weight % benzene The acrylic ester monomeric unit of vinyl monomer unit and 15 weight % to 25 weight %.
- 5. rubber modified resin constituent according to claim 1, it is characterised in that the acrylic ester grafting rubbers The weight average particle diameter of copolymer (B) between 0.05 μm to 0.22 μm unimodal formula distribution mode, between 0.26 μm Unimodal formula distribution mode between to 0.55 μm or between 0.05 μm to 0.22 μm and between 0.26 μm to 0.55 μm it Between double-peak type distribution mode.
- A kind of 6. preparation method of rubber modified resin constituent, it is characterised in that including：Styrene-acrylonitrile based copolymer (A) and acrylic ester rubber graft copolymer (B) are provided；AndThe styrene-acrylonitrile based copolymer (A) and the acrylic ester rubber graft copolymer (B) are kneaded, Wherein described rubber modified resin constituent contains to Meng's alkane, and the content to Meng's alkane is more than 5ppm and is less than 180ppm, And the rubber modified resin constituent is free of acetophenone.
- 7. the preparation method of rubber modified resin constituent according to claim 6, it is characterised in that the propylene is provided The method of acid esters system rubber graft copolymer (B) includes：Acrylic ester monomer is set to carry out emulsion polymerization reaction, to form acrylic ester rubber latex；AndThe acrylic ester rubber latex is set to carry out graft polymerization reaction, wherein the graft polymerization reaction is including the use of peroxide Change hydrogen to Meng's alkane as initiator.
- 8. the preparation method of rubber modified resin constituent according to claim 7, it is characterised in that with 100 parts by weight The acrylic ester rubber latex dry weight meter, the hydrogen peroxide total usage amount of Meng's alkane is less than 1.3 parts by weight and More than 0.35 parts by weight.
- 9. the preparation method of rubber modified resin constituent according to claim 7, it is characterised in that the emulsion polymerization Reaction is including the use of the hydrogen peroxide to Meng's alkane as initiator.
- 10. the preparation method of rubber modified resin constituent according to claim 9, it is characterised in that in the emulsification In polymerisation, in terms of the acrylic ester monomer of 100 parts by weight, the hydrogen peroxide is less than to total usage amount of Meng's alkane 1 parts by weight and it is more than 0.05 parts by weight, and in the graft polymerization reaction, with the acrylic ester of 100 parts by weight The dry weight meter of rubber latex, the hydrogen peroxide are less than 1.3 parts by weight to total usage amount of Meng's alkane and are more than 0.35 parts by weight.
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| WO1998047961A1 (en) * | 1997-04-24 | 1998-10-29 | Kaneka Corporation | Impact-resistant thermoplastic resin composition |
| EP1149866A3 (en) * | 2000-04-27 | 2003-04-23 | JSR Corporation | Rubber mixtures based on crosslinked rubber particles and non-crosslinked rubbers |
| JP5066449B2 (en) * | 2004-11-22 | 2012-11-07 | アーケマ・インコーポレイテッド | Reinforced thermoplastic resin composition |
| TWI509014B (en) * | 2013-12-27 | 2015-11-21 | Chi Mei Corp | Thermoplastic resin composition and molding product |
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| CN102282209A (en) * | 2009-01-16 | 2011-12-14 | 电气化学工业株式会社 | Rubber-modified thermoplastic resin composition, injection molded article comprising the same, and washing machine lid using the same |
| CN101857701A (en) * | 2010-03-10 | 2010-10-13 | 上海锦湖日丽塑料有限公司 | Acrylonitrile-acrylate-styrene resin composite and preparation method thereof |
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| CN103910960A (en) * | 2012-12-28 | 2014-07-09 | 奇美实业股份有限公司 | Rubber modified methacrylate resin composition |
| CN103910957A (en) * | 2012-12-28 | 2014-07-09 | 奇美实业股份有限公司 | Rubber modified methacrylate resin composition |
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| Publication number | Publication date |
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| TWI604008B (en) | 2017-11-01 |
| CN107880427B (en) | 2020-04-14 |
| TW201811902A (en) | 2018-04-01 |
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