CN103910960A - Rubber modified methacrylate resin composition - Google Patents
Rubber modified methacrylate resin composition Download PDFInfo
- Publication number
- CN103910960A CN103910960A CN201310282778.1A CN201310282778A CN103910960A CN 103910960 A CN103910960 A CN 103910960A CN 201310282778 A CN201310282778 A CN 201310282778A CN 103910960 A CN103910960 A CN 103910960A
- Authority
- CN
- China
- Prior art keywords
- weight
- styrene
- resin composition
- methacrylate ester
- based copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 95
- 239000011342 resin composition Substances 0.000 title claims abstract description 49
- 150000002734 metacrylic acid derivatives Chemical class 0.000 title abstract 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 71
- 239000002245 particle Substances 0.000 claims abstract description 43
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 30
- -1 modified methacrylate ester Chemical class 0.000 claims description 142
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 61
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 61
- 239000000178 monomer Substances 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 abstract 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 description 17
- 230000003078 antioxidant effect Effects 0.000 description 17
- 230000000704 physical effect Effects 0.000 description 17
- 229920000126 latex Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 238000010559 graft polymerization reaction Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000000470 constituent Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000005395 methacrylic acid group Chemical group 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 150000003440 styrenes Chemical class 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 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 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-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
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- IHWDIGHWDQPQMQ-UHFFFAOYSA-N 1-octadecylsulfanyloctadecane Chemical class CCCCCCCCCCCCCCCCCCSCCCCCCCCCCCCCCCCCC IHWDIGHWDQPQMQ-UHFFFAOYSA-N 0.000 description 1
- HSYSVFXBQIIBBJ-UHFFFAOYSA-N 1-tert-butyl-4-(2-hydroperoxypropan-2-yl)benzene Chemical compound CC(C)(C)C1=CC=C(C(C)(C)OO)C=C1 HSYSVFXBQIIBBJ-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
- 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 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- VHGGPTHBEBSSJW-UHFFFAOYSA-N 2,7-dimethylocta-2,6-dienedioic acid 2-(2-methylprop-2-enoyloxy)ethyl 2-methylprop-2-enoate Chemical compound C(CC=C(C(=O)O)C)C=C(C(=O)O)C.C(C(=C)C)(=O)OCCOC(C(=C)C)=O VHGGPTHBEBSSJW-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KHJWSKNOMFJTDN-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KHJWSKNOMFJTDN-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VXJHVLFCFWGXDD-UHFFFAOYSA-N 2-tert-butylbenzenecarboperoxoic acid (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound C(C)(C)(C)C1=C(C(=O)OO)C=CC=C1.C(C1=CC=CC=C1)(=O)OOOC(C)(C)C VXJHVLFCFWGXDD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 235000021357 Behenic acid Nutrition 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
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- FNEZKYFJDJFQSH-UHFFFAOYSA-N OO.CC(C)C1=CC=C(C(C)(C)C)C=C1 Chemical compound OO.CC(C)C1=CC=C(C(C)(C)C)C=C1 FNEZKYFJDJFQSH-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- BWBVNPNIHQQWIR-YAFCTCPESA-N [(e)-octadec-9-enoyl] (z)-octadec-9-eneperoxoate Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OOC(=O)CCCCCCC\C=C/CCCCCCCC BWBVNPNIHQQWIR-YAFCTCPESA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 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
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-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
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- GCFUAWRGEMQGAR-UHFFFAOYSA-N cyclopentane;hydrogen peroxide Chemical compound OO.C1CCCC1 GCFUAWRGEMQGAR-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- QZYRMODBFHTNHF-UHFFFAOYSA-N ditert-butyl benzene-1,2-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OOC(C)(C)C QZYRMODBFHTNHF-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 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
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- VGGFAUSJLGBJRZ-UHFFFAOYSA-N hydroperoxycyclopentane Chemical compound OOC1CCCC1 VGGFAUSJLGBJRZ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 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
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- LIXVMPBOGDCSRM-UHFFFAOYSA-N nonylbenzene Chemical compound CCCCCCCCCC1=CC=CC=C1 LIXVMPBOGDCSRM-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
- 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 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229930006728 pinane Natural products 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 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 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
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000010061 rubber shaping Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 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 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical class [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert-Butyl hydroperoxide Substances CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- YUMFXXAAFYXASW-UHFFFAOYSA-N tert-butyl ethaneperoxoate 3,3-dimethylbutaneperoxoic acid Chemical compound C(C)(C)(C)CC(=O)OO.C(C)(C)(C)OOC(C)=O YUMFXXAAFYXASW-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a rubber modified methacrylate resin composition. A rubber modified methacrylate resin composition comprises a continuous phase formed by a copolymer and a dispersed phase formed by rubber particles of an acrylate rubber graft copolymer (B). The copolymer contains 2 to 27% by weight of a first styrene-acrylonitrile copolymer based on 100% by weight of the total amount of the copolymer 1) 30 to 72% by weight of a methacrylate-based polymer (A)2) And 10 to 50% by weight of a second styrene-acrylonitrile copolymer (A)3). A first styrene-acrylonitrile copolymer (A)1) Comprises styrene monomer units and acrylonitrile monomer units with the weight percent of 26-35 percent; second phenyl ethylOlefin-acrylonitrile copolymer 3) Comprises styrene monomer units and 16-25 wt% of acrylonitrile monomer units.
Description
Technical field
The present invention relates to a kind of rubber modified methacrylate ester resin composition, particularly a kind of rubber modified methacrylate ester resin composition that comprises methacrylate ester polymkeric substance and contain the styrene-acrylonitrile based copolymer of low acrylic monomeric unit content.
Background technology
The contained composition of plastic rubber shaping product that is generally used for electricmaterial or household supplies etc. is mostly rubber modified styrene series resin, polycarbonate resin (polycarbonate resin) or rubber modified methacrylate ester resin etc.Wherein, this rubber modified methacrylate ester resin is the ternary graft copolymer that comprises vinyl cyanide, vinylbenzene and acrylic elastomer composition.This rubber modified methacrylate ester resin and rubber modified styrene series resin-phase ratio, the acrylic ester rubber few due to double bond content has replaced divinyl rubber, thereby weathering resistance has had essential improvement, exceed 10 times of left and right than rubber modified styrene series resin, can directly use out of doors, be typically applied in the outdoor parts such as automotive field for example outer visor, radiator grid, afterbody plate washer, lampshade; Or be applied to electric field, for example: the round-the-clock housings such as sewing machine, telephone set, galley equipment, satellite antenna; Or be applied to building field etc.But rubber modified methacrylate ester resin is poor compared to rubber modified styrene series resin for shock-resistance, and other performances of rubber modified methacrylate ester resin for example: the physical propertiess such as surface gloss and thermotolerance still cannot reach industry requirement.
Because above-mentioned, still need to develop one and there is the preferably rubber modified methacrylate ester resin compositions of physical properties such as better shock-resistance, surface gloss and thermotolerance, to meet industry demand.
Summary of the invention
The object of the present invention is to provide a kind of rubber modified methacrylate ester resin composition with balance of physical properties such as better shock-resistance, surface gloss and thermotolerances.The rubber modified methacrylate ester resin composition of the present invention, comprises:
The external phase that the multipolymer (A) of 68 % by weight to 90 % by weight forms, and the disperse phase that forms of the rubber particles of the acrylic ester rubber graft copolymer (B) of 10 % by weight to 32 % by weight, taking the total amount of multipolymer (A) as 100 % by weight, the first styrene-acrylonitrile based copolymer (A that this multipolymer (A) comprises 2 % by weight to 27 % by weight
1), the methacrylate ester polymkeric substance (A of 30 % by weight to 72 % by weight
2) and the second styrene-acrylonitrile based copolymer (A of 10 % by weight to 50 % by weight
3); The first styrene-acrylonitrile based copolymer (A
1) comprise the styrenic monomers unit of 65 % by weight to 74 % by weight and the acrylic monomeric unit of 26 % by weight to 35 % by weight; The second styrene-acrylonitrile based copolymer (A
3) comprise the styrenic monomers unit of 75 % by weight to 84 % by weight and the acrylic monomeric unit of 16 % by weight to 25 % by weight.
Preferably, rubber modified methacrylate ester resin composition of the present invention, wherein, taking the total amount of multipolymer (A) as 100 % by weight, the first styrene-acrylonitrile based copolymer (A that this multipolymer (A) comprises 5 % by weight to 20 % by weight
1), the methacrylate ester polymkeric substance (A of 35 % by weight to 70 % by weight
2) and the second styrene-acrylonitrile based copolymer (A of 12 % by weight to 45 % by weight
3).
Preferably, rubber modified methacrylate ester resin composition of the present invention, wherein, taking the total amount of multipolymer (A) as 100 % by weight, the first styrene-acrylonitrile based copolymer (A that this multipolymer (A) comprises 7 % by weight to 18 % by weight
1), the methacrylate ester polymkeric substance (A of 45 % by weight to 70 % by weight
2) and the second styrene-acrylonitrile based copolymer (A of 15 % by weight to 40 % by weight
3).
Preferably, rubber modified methacrylate ester resin composition of the present invention, wherein, this first styrene-acrylonitrile based copolymer (A
1) comprise the styrenic monomers unit of 68 % by weight to 73 % by weight and the acrylic monomeric unit of 27 % by weight to 32 % by weight.
Preferably, rubber modified methacrylate ester resin composition of the present invention, wherein, this second styrene-acrylonitrile based copolymer (A
3) comprise the styrenic monomers unit of 75 % by weight to 82 % by weight and the acrylic monomeric unit of 18 % by weight to 25 % by weight.
More preferably, rubber modified methacrylate ester resin composition of the present invention, wherein, this second styrene-acrylonitrile based copolymer (A
3) comprise the styrenic monomers unit of 76 % by weight to 80 % by weight and the acrylic monomeric unit of 20 % by weight to 24 % by weight.
Preferably, rubber modified methacrylate ester resin composition of the present invention, wherein, taking the total amount of this rubber modified methacrylate ester resin composition as 100 % by weight, the content range of this multipolymer (A) is 74 % by weight to 86 % by weight; The content range of acrylic ester rubber graft copolymer (B) is 14 % by weight to 26 % by weight.
Preferably, rubber modified methacrylate ester resin composition of the present invention, wherein, the weight average particle diameter scope of this rubber particles is 0.05 μ m to 1 μ m.
Preferably, rubber modified methacrylate ester resin composition of the present invention, wherein, the weight average particle diameter scope of this rubber particles is that 0.05 μ m to 0.22 μ m, weight average particle diameter scope are 0.26 μ m to 0.55 μ m, or aforementioned the two mix.
Beneficial effect of the present invention is: rubber modified acrylate resin composition of the present invention is by using this second styrene-acrylonitrile based copolymer (A of this methacrylate ester polymkeric substance and this low acrylic monomeric unit content
3), and regulate and control the content of described composition, can make this rubber modified methacrylate ester resin composition there is the physical propertiess such as better impact strength, surface gloss and thermotolerance, and reach the balance of physical properties of this resin combination.
Embodiment
The rubber modified methacrylate ester resin composition of the present invention, comprise: the external phase that the multipolymer (A) of 68 % by weight to 90 % by weight forms, and the disperse phase that forms of the rubber particles of the acrylic ester rubber graft copolymer (B) of 10 % by weight to 32 % by weight, taking the total amount of multipolymer (A) as 100 % by weight, the first styrene-acrylonitrile based copolymer (A that this multipolymer (A) comprises 2 % by weight to 27 % by weight
1), the methacrylate ester polymkeric substance (A of 30 % by weight to 72 % by weight
2) and the second styrene-acrylonitrile based copolymer (A of 10 % by weight to 50 % by weight
3); The first styrene-acrylonitrile based copolymer (A
1) comprise the styrenic monomers unit of 65 % by weight to 74 % by weight and the acrylic monomeric unit of 26 % by weight to 35 % by weight; The second styrene-acrylonitrile based copolymer (A
3) comprise the styrenic monomers unit of 75 % by weight to 84 % by weight and the acrylic monomeric unit of 16 % by weight to 25 % by weight.
This methacrylate ester polymkeric substance (A
2) and this second styrene-acrylonitrile based copolymer (A
3) content in the time of aforementioned range, can obtain the constituent of the balance of physical properties such as better impact strength, surface gloss and thermotolerance.
Preferably, taking the total amount of multipolymer (A) as 100 % by weight, the first styrene-acrylonitrile based copolymer (A that this multipolymer (A) comprises 5 % by weight to 20 % by weight
1), the methacrylate ester polymkeric substance (A of 35 % by weight to 70 % by weight
2) and the second styrene-acrylonitrile based copolymer (A of 12 % by weight to 45 % by weight
3).More preferably, taking the total amount of multipolymer (A) as 100 % by weight, the first styrene-acrylonitrile based copolymer (A that this multipolymer (A) comprises 7 % by weight to 18 % by weight
1), the methacrylate ester polymkeric substance (A of 45 % by weight to 70 % by weight
2) and the second styrene-acrylonitrile based copolymer (A of 15 % by weight to 40 % by weight
3).
Preferably, this first styrene-acrylonitrile based copolymer (A
1) comprise the styrenic monomers unit of 68 % by weight to 73 % by weight and the acrylic monomeric unit of 27 % by weight to 32 % by weight.More preferably, this first styrene-acrylonitrile based copolymer (A
1) comprise the styrenic monomers unit of 70 % by weight to 73 % by weight and the acrylic monomeric unit of 27 % by weight to 30 % by weight.
Preferably, this second styrene-acrylonitrile based copolymer (A
3) comprise the styrenic monomers unit of 75 % by weight to 82 % by weight and the acrylic monomeric unit of 18 % by weight to 25 % by weight.More preferably, this second styrene-acrylonitrile based copolymer (A
3) comprise the styrenic monomers unit of 76 % by weight to 80 % by weight and the acrylic monomeric unit of 20 % by weight to 24 % by weight.
Preferably, taking the total amount of this rubber modified methacrylate ester resin composition as 100 % by weight, the content range of this multipolymer (A) is 74 % by weight to 86 % by weight, and the content range of acrylic ester rubber graft copolymer (B) is 14 % by weight to 26 % by weight.
Preferably, the weight average particle diameter scope of this rubber particles is 0.05 μ m to 1 μ m.More preferably, the weight average particle diameter scope of this rubber particles is that 0.05 μ m to 0.22 μ m, weight average particle diameter are 0.26 μ m to 0.55 μ m, or aforementioned the two mix.
This first styrene-acrylonitrile based copolymer (A
1) and this acrylic ester rubber graft copolymer (B) formation graft copolymer blends, be described in detail as follows: this graft copolymer blends is carried out graft polymerization reaction and obtained by the monomer mixture of the acrylic monomer of the acrylic ester rubber latex of 100 weight parts (dry weight) and the styrenic monomers that comprises 60 % by weight to 74 % by weight of 20 weight part to 120 weight parts and 26 % by weight to 40 % by weight.
This acrylic ester rubber latex makes as good with emulsion polymerization method.It is that principal constituent is polymerized that this acrylic ester rubber latex comprises by acrylic ester monomer, aforesaid propylene acid esters is that the concrete example of monomer is as methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, ethyl acrylate, dodecylacrylate etc., wherein taking n-butyl acrylate as good.Aforesaid propylene acid esters is that the manufacture of rubber latex can add graft crosslinking agent to carry out polyreaction, this graft crosslinking agent concrete example is as diacrylate fourth diester, Vinylstyrene, butene diol dimethacrylate ester, dimethacrylate, trimethyol propane triacrylate, trihydroxy methyl propane trimethyl acrylate, allyl methacrylate(AMA), methacrylic diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl phthalate, methacrylic acid triallyl, triallyl cyanurate, isocyanuric acid triallyl, tricyclo decene alcohol acrylate, polyalkylene glycol diacrylate etc., these graft crosslinking agent can be used alone or two or more is also used.Preferably, taking the total amount of this acrylic ester monomer and this graft crosslinking agent with as 100 % by weight, the usage quantity scope of this graft crosslinking agent is 0.1 % by weight to 10 % by weight.
The weight average particle diameter scope of this acrylic ester rubber latex is 0.05 μ m to 1 μ m, to be preferably weight average particle diameter scope be the acrylic ester rubber latex of 0.05 μ m to 0.2 μ m, for weight average particle size range is the acrylic ester rubber latex of 0.26 μ m to 0.5 μ m, or aforementioned the two mix.
It is to carry out graft polymerization reaction with the monomer mixture that comprises styrenic monomers and acrylic monomer under rubber latex exists that the graft polymerization reaction of this graft copolymer blends is included in aforesaid propylene acid esters, and the weight average particle diameter particle diameter of the rubber particles in gained graft copolymer blends can be unimodal formula distribution kenel or double-peak type distribution kenel.Preferably, the weight average particle diameter scope of this rubber particles is 0.05 μ m to 1 μ m.More preferably, weight average particle diameter scope is that 0.05 μ m to 0.22 μ m, weight average particle diameter scope are 0.26 μ m to 0.55 μ m, or aforementioned the two mix.
The graft polymerization reaction of above-mentioned graft copolymer blends comprises monomer mixture graft polymerization on this acrylic ester rubber; The ratio of adding according to monomer and the condition of polymerization, can obtain monomeric unit multipolymer and the monomer mixture that monomer mixture is grafted on this acrylic ester rubber simultaneously and not be grafted on the monomeric unit multipolymer on this acrylic ester rubber.The first styrene-acrylonitrile based copolymer (A of the present invention
1) for not being grafted on the monomeric unit multipolymer on this acrylic ester rubber; This acrylic ester rubber graft copolymer (B) by this acrylic ester rubber and the styrene-acrylonitrile that is grafted on this acrylic ester rubber be that monomeric unit is formed.
Aforesaid propylene acid esters is that the percentage of grafting of rubber graft copolymer (B) can be controlled by polymeric reaction condition, for example: consumption and the addition means etc. of the consumption of polymerization temperature, initiator, emulsifying agent, activator, chain-transfer agent and kind, monomer are controlled.Above-mentioned chain-transfer agent concrete example is as n-butyl mercaptan (n-butyl mercaptan), n-octyl mercaptan (n-octyl mercaptan), n-lauryl mercaptan (n-dodecyl mercaptan), uncle-lauryl mercaptan (tert-dodecyl mercaptan) etc.Mentioned emulsifier has no particular limits, when making emulsion polymerization the excellent in stability of emulsion, improve percent polymerization, to be selected from the various carboxylate salts of sodium succinate, lipid acid potassium, sodium soap, alkenyl succinic acid dipotassium, roseolic acid soap etc.; The various sulfonate of sulfuric acid alkane ester, sodium alkyl benzene sulfonate etc.; The negatively charged ion of polyethylene oxide nonyl benzene ether sodium sulfate etc. is that emulsifying agent is better.Above-mentioned activator concrete example is as ferrous sulfate, formaldehyde sodium sulfoxylate, ethylene dinitrilotetra-acetic acid sodium, tetrasodium pyrophosphate etc.
The molecular weight of above-mentioned graft copolymer blends also can be adjusted by the change of the polymerizing conditions such as the addition means of the kind of polymerization temperature, initiator and consumption, monomer, the temperature of reaction of its graft polymerization below 90 DEG C, especially between 25 DEG C to 40 DEG C for better.And grafting monomer can once add, also can add in batches, also can add continuously or by various monomer segmentation graft polymerizations.Aforementioned initiator can use various known Raolical polymerizable initiators, and the addition manner of this initiator can adopt once add continuously or increment add etc., the concrete example of above-mentioned initiator is as benzoyl peroxide (benzoyl peroxide), lauroyl superoxide (lauroyl peroxide), octadecanoyl superoxide (oleoyl peroxide), toluyl superoxide (toluyl peroxide), cumyl superoxide (dicumyl peroxide), tert-butyl peroxide (tert-butyl-peroxide), two cross the two tert-butyl esters (di-tert-butyl-diperphthalate) of phthalandione, peroxyacetic acid tertiary butyl ester (tert-butyl-peracetate), t-butylperoxyl benzoate (tert-butyl-perbenzoate), heavy carbonic sec.-propyl peroxy ester (isopropyl peroxy dicarbonate), 2,5-dimethyl-2,5-bis-(tert-butyl peroxide) hexane [2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane], 2,5-dimethyl-2,5-bis-(tert-butyl peroxide)-hexyl-3-tertbutyl peroxide [2,5-dimethyl-2,5-di (tert-butylperoxy) hexane-3-tert-butyl hydroperoxide], isopropyl benzene hydrogen peroxide (cumene hydroperoxide), the p-hydrogen peroxide that methylates (p-methane hydroperoxide), cyclopentyl hydrogen peroxide (cyclopentane hydroperoxide), diisopropyl benzene hydrogen peroxide (diisopropylbenzene hydroperoxide), p-tertiary butyl isopropyl benzene hydrogen peroxide (p-tert-butylcumene hydroperoxide), pinane hydrogen peroxide (pinane hydroperoxide), 2,5-dimethyl-hexyl-2,5-diperoxy hydrogen (2,5-dimethyl-hexane-2,5-dihydroperoxide) etc., or above mixture.Taking the total amount of monomer mixture as 100 weight parts, the usage quantity scope of this initiator is 0.01 weight part to 5 weight part.
The concrete example of the styrenic monomers that the graft polymerization reaction of aforementioned graft copolymer blends uses is as vinylbenzene, alpha-methyl styrene, p-t-butyl styrene, p-methylstyrene, o-vinyl toluene, m-vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, Alpha-Methyl-p-methylstyrene, or bromstyrol etc., wherein with vinylbenzene or alpha-methyl styrene for better.The concrete example of aforesaid acrylic monomer is as vinyl cyanide, Alpha-Methyl vinyl cyanide etc., wherein with vinyl cyanide for better.
[methacrylate ester polymkeric substance (A
2)]
Methacrylate ester polymkeric substance (A of the present invention
2) be selected from methacrylate ester homopolymer, methacrylic ester-acrylate based copolymer, or their combination.This methacrylate ester polymkeric substance (A
2) weight average molecular weight scope be 50,000 to 450,000, be preferably 70,000 to 200,000, the best is 70,000 to 150,000.
Preferably, this methacrylic ester-acrylate based copolymer comprises the methacrylate ester monomeric unit of 80 % by weight to 99.8 % by weight and the acrylic ester monomeric unit of 0.2 % by weight to 20 % by weight.More preferably, this methacrylic ester-acrylate based copolymer comprises the methacrylate ester monomeric unit of 85 % by weight to 98 % by weight and the acrylic ester monomeric unit of 2 % by weight to 15 % by weight.
Above-mentioned methacrylic ester-acrylate based copolymer is obtained through polyreaction by the component that comprises methacrylate ester monomer and acrylic ester monomer.This polyreaction can adopt body, solution, suspension or emulsion polymerization method to make, and preferably, the operating temperature range of this polyreaction is 50 DEG C to 160 DEG C.
Above-mentioned methacrylate ester monomer can be used alone or as a mixture, and this methacrylate ester monomer is such as but not limited to methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, methacrylic acid dodecane ester, HEMA, glytidyl methacrylate, dimethylaminoethyl methacrylate, ethylene dimethacrylate (ethylene dimethacrylate), or dimethacrylate peopentyl ester (neopentyl dimethacrylate) etc.Preferably, this methacrylate ester monomer is selected from methyl methacrylate, butyl methacrylate, or their combination.
This acrylic ester monomer can be used alone or as a mixture, and this acrylic ester monomer is such as but not limited to methyl acrylate, ethyl propenoate, isopropyl acrylate, butyl acrylate, or polyethyleneglycol diacrylate etc.Preferably, this acrylic ester monomer is butyl acrylate.
[the second styrene-acrylonitrile based copolymer (A
3)]
The second styrene-acrylonitrile based copolymer (A of the present invention
3) obtained through polyreaction by the component that comprises the styrenic monomers of 76 % by weight to 90 % by weight and the acrylic monomer of 10 % by weight to 24 % by weight.This polyreaction can be body, solution, suspension or emulsion polymerization method, wherein again with body or solution polymerization process for better, the monomer explanation that the explanation of the concrete example of above-mentioned styrenic monomers, acrylic monomer is used with the graft polymerization of aforementioned graft copolymer blends is identical, does not repeat them here.
The second styrene-acrylonitrile based copolymer (A of the present invention
3) better preparation method, can complete by the reactor of continous way body or solution polymerization, above-mentioned reactor comprises: column flow reactor, completely hybrid (CSTR) reactor, or contain the reactor of silent oscillation hybrid element etc., wherein taking complete mixing reactor as good, above-mentioned reactor quantity can be one, also can be also with two or more; Manufacturing the present invention the second styrene-acrylonitrile based copolymer (A
3) time, can thermopolymerization mode or polymerization initiator is added in reaction, this polymerization initiator is such as but not limited to acyl peroxide class, peroxyesters, ketal peroxide class, peroxycarbonates class, or has azo-compound of nitro and cyclohexanes etc.Taking monomer total amount as 100 weight parts, the addition scope of aforementioned polymerization initiator is 0 weight part to 1.0 weight part, is preferably 0.01 weight part to 0.5 weight part.The temperature of reaction of above-mentioned reactor is to be controlled at 20 DEG C to 300 DEG C, be preferably controlled in the scope of 60 DEG C to 250 DEG C, and the pressure of reactor is to be controlled at 1kg/cm
2to 10kg/cm
2between, the time being trapped in reactor as for material solution should, at 0.5 hour to 15 hours, be preferably 1 hour to 10 hours; In order to control the molecular weight of polymkeric substance, can use the such as chain-transfer agent of n-lauryl mercaptan, uncle-lauryl mercaptan, terpinolene etc.Taking monomer total amount as 100 weight parts, the addition scope of aforementioned chain-transfer agent is 0 weight part to 2 weight part, is preferably 0.001 weight part to 1 weight part.Arrive after 40 % by weight to 80 % by weight at polymer monomer transformation efficiency, normally the copolymer solution of gained is heated to the highest temperature with preheater, and then remove unreacted monomer and volatile matter with devolatilization step, general devolatilization step can be used the device of decompression degassing vessel, or forcing machine de-gassing vessel devolatilization, then with condenser, volatile matter is collected as reclaiming liquid, and after the moisture in recovery liquid is removed, again used as material solution; And after devolatilization step is processed the polymerization melts of gained, its extrusion granulator can be obtained to the second styrene-acrylonitrile based copolymer (A of the present invention
3).
The second styrene-acrylonitrile based copolymer (A of the present invention
3) comprise the styrenic monomers unit of 75 % by weight to 84 % by weight and the acrylic monomeric unit of 16 % by weight to 25 % by weight.Preferably, this second styrene-acrylonitrile based copolymer (A
3) comprise 75 % by weight to 82 % by weight styrenic monomers unit, and the acrylic monomeric unit of 18 % by weight to 25 % by weight.More preferably, this second styrene-acrylonitrile based copolymer (A
3) comprise the styrenic monomers unit of 76 % by weight to 80 % by weight and the acrylic monomeric unit of 20 % by weight to 24 % by weight.Above-mentioned the second styrene-acrylonitrile based copolymer (A
3) weight average molecular weight scope between 60,000 to 400,000, be preferably between 80,000 to 300,000.
The preparation method of rubber modified methacrylate ester resin composition of the present invention is not particularly limited, and can adopt general blending means, for example, will comprise the first styrene-acrylonitrile based copolymer (A
1) and this acrylic ester rubber graft copolymer (B) graft copolymer blends, the methacrylate ester polymkeric substance (A that form
2), with the second styrene-acrylonitrile based copolymer (A
3) evenly mix, optionally add further additive; For obtaining rubber modified methacrylate ester resin composition of the present invention, its blending means is representative: after being dry mixed with the Han Xieer mixing machine generally using again with the mixing machine melting mixing such as extruding mixing machine, kneader or Ban Baili mixing roll etc.
Rubber modified methacrylate ester resin composition of the present invention also comprises additive, and this additive is selected from antioxidant, plasticizer, processing aid, ultra-violet stabilizer, UV light absorber, weighting agent, reinforcer, tinting material, lubrication prescription, charged preventor, incombustible agent, difficult combustion auxiliary agent, thermo-stabilizer, coupling agent, or their combination.This additive can be respectively at above-mentioned graft copolymer blends, methacrylate ester polymkeric substance (A
2) or the second styrene-acrylonitrile based copolymer (A
3) polyreaction in, after polyreaction, condense before, or preparation rubber modified methacrylate ester resin composition process in add.With this above-mentioned graft copolymer blends, methacrylate ester polymkeric substance (A
2) and the second styrene-acrylonitrile based copolymer (A
3) total amount be 100 weight part meters, the content range of this additive is 0.01 weight part to 20 weight part.
This antioxidant can be used alone or as a mixture, and this antioxidant is that antioxidant, thioether are antioxidant such as but not limited to phenol, or phosphorous antioxidant etc.
This phenol is that antioxidant can be used alone or as a mixture, and this phenol is that antioxidant is such as but not limited to 3, 5-two (1, 1-dimethyl ethyl)-4-hydroxy-phenylpropionic acid stearyl [3, 5-bis (1, 1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester, Xing ︰ antioxidant IX-1076], triethylene glycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester], four [methylene base-3-(3, 5-dual-tert-butyl-4-hydroxyphenyl) propionic ester] methane, the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxyl-6-methylbenzene methyl)-4-aminomethyl phenyl acrylate, 2, 2'-methylene base-bis-(4-methyl-6-tert butyl phenol) [2, 2'-methylenebis (4-methyl-6-tert-butylphenol), Xing ︰ antioxidant 2246], 2, 2'-sulphur two (4-methyl-6-tert butyl phenol), 2, 2'-sulfo--diethyl support group-bis-[3-(3, 5-dual-tert-butyl-4-hydroxyphenyl) propionic ester], or 2, 2'-oxalamide-bis-[ethyl-3-(3, 5-pair-tertiary butyl-4-hydroxyphenyl) propionic ester] etc.
This thioether is that antioxidant can be used alone or as a mixture, and this thioether be antioxidant such as but not limited to distearyl thiodipropionic acid ester, two palmityl thiodipropionic acid esters, five tetrahydroxybutane-tetra--(β-ten dimethyl-sulphur propionic ester), or two octadecyl thioethers etc.
This phosphorous antioxidant can be used alone or as a mixture, and this phosphorous antioxidant is selected from containing the phosphorous antioxidant of phosphorous acid ester or the phosphorous antioxidant of phosphate ester-containing.Should be containing the phosphorous antioxidant of phosphorous acid ester such as but not limited to three (nonyl phenyl) phosphorous acid ester, dodecyl phosphorous acid ester, 4,4'-butylidene two (3-methyl-6-tert butyl phenyl-double tridecyl phosphorous acid ester) or three (2,4-tert-butyl-phenyl) phosphorous acid ester etc.The phosphorous antioxidant of this phosphate ester-containing is such as but not limited to four (2,4-tert-butyl-phenyls)-4,4'-biphenylene phosphoric acid ester, or the support of 9,10-dihydro-9-oxy-10-phosphoric acid phenanthrene-10-oxygen etc.
This lubrication prescription can be used alone or as a mixture, and this lubrication prescription is such as but not limited to the metallic soaps of calcium stearate, Magnesium Stearate, lithium stearate etc.; The compound of ethylene distearyl acid amides (ethylene bis-stearamide is called for short EBA), methylene distearyl acid amides, palmitic amide, butyl stearate, stearic acid palm ester, tetramethylolmethane four fatty acid esters, poly-propionic acid alcohol tristearate, behenic acid, stearic acid etc.; Polyethylene wax, octocosoic acid wax, carnauba wax (carnauba wax) or petroleum wax etc.
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are only for illustrating use, and should not be interpreted as restriction of the invention process.
[preparation example 1] graft copolymer blends
The first styrene-acrylonitrile based copolymer (A
1) and acrylic ester rubber graft copolymer (B) formation graft copolymer blends, this graft copolymer blends manufacture method is as follows:
(1) first, the acrylic ester rubber latex of weight average particle diameter 0.1 μ m is by the n-butyl acrylate of 99.0 % by weight and the allyl methacrylate(AMA) polymerization of 1.0 % by weight and obtain, and solids content is about 38%, weight average particle diameter 0.1 μ m.
(2) secondly, the acrylic ester rubber latex of weight average particle diameter 0.4 μ m by
N-butyl acrylate 99.0
Allyl methacrylate(AMA) 1.0
Polymerization and obtaining, solids content is about 38%, weight average particle diameter 0.4 μ m.
(3) last, then by the acrylic ester rubber latex of the above-mentioned weight average particle diameter 0.4 μ m of the acrylic ester rubber latex of the above-mentioned weight average particle diameter of 70 % by weight 0.1 μ m and 30 % by weight, carry out graft polymerization reaction according to following formula.
After polymerization in 5 hours, with calcium chloride (CaCl
2) condense, dewater after, then be dried to moisture content below 2%, just can make graft copolymer blends, the weight average particle diameter of its rubber particles is the double-peak type distributional pattern of 0.12 μ m, 0.45 μ m.The first styrene-acrylonitrile based copolymer (A in above-mentioned graft copolymer blends
1) acrylonitrile monemer unit content be 28 % by weight.
[preparation example 2]
Methacrylate ester polymkeric substance (A
2) be Methylacrylate-Acrylate Copolymer, use Qi Mei company system, product type Acryrex CM-211.
[preparation example 3] second styrene-acrylonitrile based copolymer (A
3)
Speed with 12kg/hr is mixed the raw material of vinylbenzene 76 % by weight, vinyl cyanide 24 % by weight, again with ethylene distearyl acid amides 3.0g/hr, benzoyl peroxide, uncle-lauryl mercaptan, and aftermentioned is reacted the recovery liquid that the volatile matter removed forms after condensation and is merged as feeding feeding, remain on the continous way still type reactor with agitator of 45 liters of 108 DEG C and volumes to be fed into interior temperature, and make the toluene ratio in reaction solution remain on 15%, percent polymerization remains on 55%.
Remove after volatile component by devolatilization device when reaction solution, can obtain acrylonitrile unit content is the second styrene-acrylonitrile based copolymer (A of 23.8 % by weight
3).
[embodiment 1]
Under dry state, by the graft copolymer blends (B+A of [preparation example 1] of 34.9 % by weight
1), the second styrene-acrylonitrile based copolymer (A of [preparation example 3] of methacrylic ester-acrylate based copolymer of [preparation example 2] of 42.3 % by weight, 22.8 % by weight
3) with biaxial extruder after 220 DEG C of melting temperatures are mixing, after mixing and extrude with forcing machine, can obtain rubber modified methacrylate ester resin composition of the present invention, measure its physical properties as table 2.
[embodiment 2 to 6 and comparative example 1 to 4]
Embodiment 2 to 6 and comparative example 1 to 4 are prepared this rubber modified methacrylate ester resin composition with the mixing extrusion method identical with embodiment 1, different places are: the kind and the usage quantity that change each raw material, in table 1, its analysis and physical properties evaluation result are in table 2.
[test item]
1. fusing coefficient (represent mobility, melt index, is called for short MI) is measured:
The rubber modified methacrylate ester resin composition of embodiment 1 to 6 and comparative example 1 to 4 is specified according to D-1238, with 220 DEG C × 10kg test, unit: g/10min.
2. softening point temperature (Vicat softening temp.) is measured:
The rubber modified methacrylate ester resin composition of embodiment 1 to 6 and comparative example 1 to 4 is measured to softening point temperature according to ASTM D-1525 regulation, and unit is DEG C.
3. shock-resistance (Izod) is measured:
By the rubber modified methacrylate ester resin composition of embodiment 1 to 6 and comparative example 1 to 4 according to the standard method of ASTM D-256 (23 DEG C, attached jaggy 1/8 cun thick) preparation standard test piece tests, unit: Kg-cm/cm.
4. surface gloss (Gloss) is measured:
By the rubber modified methacrylate ester resin composition injection molding test film (diameter 5.5cm disk) of embodiment 1 to 6 and comparative example 1 to 4, and according to ASTM D-523 testing method regulation, unit: %.
5. the weight average particle diameter of the rubber particles of rubber modified methacrylate ester resin composition is measured:
The rubber modified methacrylate ester resin composition of embodiment 1 to 6 and comparative example 1 to 4 is taken pictures and is calculated and obtained by following formula with the ultrathin sectioning of electron microscope respectively, minimumly in photo contain 300 above particles:
Wherein ni represents the particle diameter of rubber particles; Di represents the number of rubber particles.
Table 1
"---": represent not add.
From the experimental result in table 2, the rubber modified methacrylate ester resin composition of comparative example 1 does not use the second styrene-acrylonitrile based copolymer (A
3), make the physical properties such as shock-resistance and glossiness of its constituent poor, cannot obtain the constituent of balance of physical properties.
The rubber modified methacrylate ester resin composition of comparative example 2 does not use methacrylate ester polymkeric substance (A
2), the physical properties such as shock-resistance extreme difference and thermotolerance of constituent is poor, cannot obtain the constituent of balance of physical properties.
Methacrylate ester polymkeric substance (A in the rubber modified methacrylate ester resin composition of comparative example 3
2) content is too many, makes the physical properties such as shock-resistance and glossiness of its constituent poor.
The second styrene-acrylonitrile based copolymer (A in the rubber modified methacrylate ester resin composition of comparative example 4
3) content not in the framework of the present definition, the physical properties such as shock-resistance extreme difference and thermotolerance of its constituent is poor, cannot obtain the constituent of balance of physical properties.
In sum, the rubber modified methacrylate ester resin composition of the present invention is by using methacrylate ester polymkeric substance (A
2) and the second styrene-acrylonitrile based copolymer (A
3), and regulate and control the content of described composition, can make this rubber modified methacrylate ester resin composition there is the preferably physical properties such as shock-resistance, surface gloss and thermotolerance, and reach the balance of physical properties of this resin combination, so really can reach object of the present invention.
Claims (9)
1. a rubber modified methacrylate ester resin composition, is characterized in that comprising:
The external phase that the multipolymer (A) of 68 % by weight to 90 % by weight forms, and the disperse phase that forms of the rubber particles of the acrylic ester rubber graft copolymer (B) of 10 % by weight to 32 % by weight, taking the total amount of described multipolymer (A) as 100 % by weight, the first styrene-acrylonitrile based copolymer (A that described multipolymer (A) comprises 2 % by weight to 27 % by weight
1), the methacrylate ester polymkeric substance (A of 30 % by weight to 72 % by weight
2) and the second styrene-acrylonitrile based copolymer (A of 10 % by weight to 50 % by weight
3); Described the first styrene-acrylonitrile based copolymer (A
1) comprise the styrenic monomers unit of 65 % by weight to 74 % by weight and the acrylic monomeric unit of 26 % by weight to 35 % by weight; Described the second styrene-acrylonitrile based copolymer (A
3) comprise the styrenic monomers unit of 75 % by weight to 84 % by weight and the acrylic monomeric unit of 16 % by weight to 25 % by weight.
2. rubber modified methacrylate ester resin composition according to claim 1, it is characterized in that, taking the total amount of described multipolymer (A) as 100 % by weight, described the first styrene-acrylonitrile based copolymer (A that described multipolymer (A) comprises 5 % by weight to 20 % by weight
1), the described methacrylate ester polymkeric substance (A of 35 % by weight to 70 % by weight
2) and the described second styrene-acrylonitrile based copolymer (A of 12 % by weight to 45 % by weight
3).
3. rubber modified methacrylate ester resin composition according to claim 2, it is characterized in that, taking the total amount of described multipolymer (A) as 100 % by weight, described multipolymer (A) comprises described the first styrene-acrylonitrile based copolymer (A that comprises 7 % by weight to 18 % by weight
1), the described methacrylate ester polymkeric substance (A of 45 % by weight to 70 % by weight
2) and the described second styrene-acrylonitrile based copolymer (A of 15 % by weight to 40 % by weight
3).
4. rubber modified methacrylate ester resin composition according to claim 1, is characterized in that, described the first styrene-acrylonitrile based copolymer (A
1) comprise the styrenic monomers unit of 68 % by weight to 73 % by weight and the acrylic monomeric unit of 27 % by weight to 32 % by weight.
5. rubber modified methacrylate ester resin composition according to claim 1, is characterized in that, described the second styrene-acrylonitrile based copolymer (A
3) comprise the styrenic monomers unit of 75 % by weight to 82 % by weight and the acrylic monomeric unit of 18 % by weight to 25 % by weight.
6. rubber modified methacrylate ester resin composition according to claim 5, is characterized in that, described the second styrene-acrylonitrile based copolymer (A
3) comprise the described styrenic monomers unit of 76 % by weight to 80 % by weight and the described acrylic monomeric unit of 20 % by weight to 24 % by weight.
7. rubber modified methacrylate ester resin composition according to claim 1, it is characterized in that, taking the total amount of described rubber modified methacrylate ester resin composition as 100 % by weight, the content range of described multipolymer (A) is 74 % by weight to 86 % by weight; The content range of described acrylic ester rubber graft copolymer (B) is 14 % by weight to 26 % by weight.
8. rubber modified methacrylate ester resin composition according to claim 1, is characterized in that, the weight average particle diameter scope of described rubber particles is 0.05 μ m to 1 μ m.
9. rubber modified methacrylate ester resin composition according to claim 8, it is characterized in that, the weight average particle diameter scope of described rubber particles is that 0.05 μ m to 0.22 μ m, weight average particle diameter scope are 0.26 μ m to 0.55 μ m, or aforementioned the two mix.
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| TW201425436A (en) | 2014-07-01 |
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