CN103183893A - Styrene resin composition, preparation method thereof and molded product prepared from styrene resin composition - Google Patents
Styrene resin composition, preparation method thereof and molded product prepared from styrene resin composition Download PDFInfo
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- CN103183893A CN103183893A CN2012101227367A CN201210122736A CN103183893A CN 103183893 A CN103183893 A CN 103183893A CN 2012101227367 A CN2012101227367 A CN 2012101227367A CN 201210122736 A CN201210122736 A CN 201210122736A CN 103183893 A CN103183893 A CN 103183893A
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- Prior art keywords
- styrene
- weight
- resin compositions
- reactor
- series resin
- Prior art date
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 239000011342 resin composition Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920001971 elastomer Polymers 0.000 claims abstract description 126
- 239000005060 rubber Substances 0.000 claims abstract description 124
- 239000002245 particle Substances 0.000 claims abstract description 100
- 229920001577 copolymer Polymers 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims description 62
- 239000002994 raw material Substances 0.000 claims description 49
- 239000011541 reaction mixture Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 25
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 230000008676 import Effects 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 abstract description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 description 31
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 17
- 229920002554 vinyl polymer Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 13
- 150000001993 dienes Chemical class 0.000 description 12
- 239000007858 starting material Substances 0.000 description 12
- 239000012986 chain transfer agent Substances 0.000 description 11
- -1 polysiloxane Polymers 0.000 description 11
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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 4
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 4
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 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
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-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
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 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
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 2
- 229960004419 dimethyl fumarate Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- DEDZSLCZHWTGOR-UHFFFAOYSA-N propylcyclohexane Chemical compound CCCC1CCCCC1 DEDZSLCZHWTGOR-UHFFFAOYSA-N 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- STGNLGBPLOVYMA-MAZDBSFSSA-N (E)-but-2-enedioic acid Chemical compound OC(=O)\C=C\C(O)=O.OC(=O)\C=C\C(O)=O STGNLGBPLOVYMA-MAZDBSFSSA-N 0.000 description 1
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-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
- 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
- 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
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-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
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- FFRUQSUMDFNBLG-UHFFFAOYSA-N 2-(2,4,5-trichlorophenoxy)ethyl 2,2,2-trichloroacetate Chemical compound ClC1=CC(Cl)=C(OCCOC(=O)C(Cl)(Cl)Cl)C=C1Cl FFRUQSUMDFNBLG-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- GIEGKXINITVUOO-UHFFFAOYSA-N 2-methylidenebutanedioic acid Chemical compound OC(=O)CC(=C)C(O)=O.OC(=O)CC(=C)C(O)=O GIEGKXINITVUOO-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
- GLZKPUOXHVXQSI-UHFFFAOYSA-N C(CCC)C(=C(C(=O)O)CC(=O)O)CCCC.C(C(=C)CC(=O)OCCCC)(=O)OCCCC Chemical compound C(CCC)C(=C(C(=O)O)CC(=O)O)CCCC.C(C(=C)CC(=O)OCCCC)(=O)OCCCC GLZKPUOXHVXQSI-UHFFFAOYSA-N 0.000 description 1
- JXXLYCXAOKJYRD-UHFFFAOYSA-N C(CCC)C=1C(=O)NC(C1)=O.[N] Chemical compound C(CCC)C=1C(=O)NC(C1)=O.[N] JXXLYCXAOKJYRD-UHFFFAOYSA-N 0.000 description 1
- BAOUTIJWHAKGRF-UHFFFAOYSA-N C(CCCCC)C=1C(=O)NC(C1)=O.[N] Chemical compound C(CCCCC)C=1C(=O)NC(C1)=O.[N] BAOUTIJWHAKGRF-UHFFFAOYSA-N 0.000 description 1
- NDZASJBVWYADBO-UHFFFAOYSA-N C(CCCCCCCCCCC)C=1C(=O)NC(C1)=O.[N] Chemical compound C(CCCCCCCCCCC)C=1C(=O)NC(C1)=O.[N] NDZASJBVWYADBO-UHFFFAOYSA-N 0.000 description 1
- GLQGUFRWCULBAH-UHFFFAOYSA-N C1(=CC=CC=C1)C(C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)C(C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C(C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)C(C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 GLQGUFRWCULBAH-UHFFFAOYSA-N 0.000 description 1
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- UXZXWJZUJXUNGP-UHFFFAOYSA-N C=C.BrC1=CC(=CC(=C1)Br)Br Chemical compound C=C.BrC1=CC(=CC(=C1)Br)Br UXZXWJZUJXUNGP-UHFFFAOYSA-N 0.000 description 1
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
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- 108700042658 GAP-43 Proteins 0.000 description 1
- PWGOWIIEVDAYTC-UHFFFAOYSA-N ICR-170 Chemical compound Cl.Cl.C1=C(OC)C=C2C(NCCCN(CCCl)CC)=C(C=CC(Cl)=C3)C3=NC2=C1 PWGOWIIEVDAYTC-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- WXEVUNJEJSDEBM-UHFFFAOYSA-N [N].C1(CCCCC1)C=1C(=O)NC(C1)=O Chemical compound [N].C1(CCCCC1)C=1C(=O)NC(C1)=O WXEVUNJEJSDEBM-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
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- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
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- VMRTVQZUEDMYNS-UHFFFAOYSA-N ditert-butyl nonanediperoxoate Chemical compound CC(C)(C)OOC(=O)CCCCCCCC(=O)OOC(C)(C)C VMRTVQZUEDMYNS-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
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- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
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- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
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- 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
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- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
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- IHVWIQJPVBMYOH-UHFFFAOYSA-N s-random Chemical compound O=C1NC(=O)C(C)=CN1C(OC1COP(O)(O)=O)CC1OP(O)(=S)OCC1OC(N2C(NC(=O)C(C)=C2)=O)CC1OP(O)(=S)OCC1OC(N2C(N=C(N)C=C2)=O)CC1OP(O)(=S)OCC1OC(N2C(NC(=O)C(C)=C2)=O)CC1OP(O)(=S)OCC1OC(N2C(NC(=O)C(C)=C2)=O)CC1OP(O)(=S)OCC1OC(N2C(NC(=O)C(C)=C2)=O)CC1OP(O)(=S)OCC1OC(N2C(N=C(N)C=C2)=O)CC1OP(O)(=S)OCC1OC(N2C(N=C(N)C=C2)=O)CC1OP(O)(=S)OCC1OC(N2C3=NC=NC(N)=C3N=C2)CC1OP(O)(=S)OCC1OC(N2C(NC(=O)C(C)=C2)=O)CC1OP(O)(=S)OCC1OC(N2C3=NC=NC(N)=C3N=C2)CC1OP(O)(=S)OCC(C(C1)OP(O)(=S)OCC2C(CC(O2)N2C(NC(=O)C(C)=C2)=O)OP(O)(=S)OCC2C(CC(O2)N2C3=C(C(NC(N)=N3)=O)N=C2)OP(O)(=S)OCC2C(CC(O2)N2C3=NC=NC(N)=C3N=C2)OP(S)(=O)OCC2C(CC(O2)N2C3=NC=NC(N)=C3N=C2)OP(O)(=S)OCC2C(CC(O2)N2C(NC(=O)C(C)=C2)=O)OP(O)(=S)OCC2C(CC(O2)N2C3=NC=NC(N)=C3N=C2)OP(O)(=S)OCC2C(CC(O2)N2C(NC(=O)C(C)=C2)=O)OP(O)(=S)OCC2C(CC(O2)N2C3=NC=NC(N)=C3N=C2)O)OC1N1C=C(C)C(=O)NC1=O IHVWIQJPVBMYOH-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention provides a styrene resin composition, a preparation method thereof and a molded product prepared from the styrene resin composition. The invention provides a method for preparing a styrene resin composition with high glossiness and high impact resistance, the styrene resin composition prepared by the method, and a specific styrene resin composition. The styrene resin composition comprises a copolymer as a continuous phase and rubber particles coated with the styrene copolymer as a dispersed phase. The range of C/B is less than 15% by collecting n rubber particles coated with a styrene copolymer having a particle diameter of more than 0.4 μm and calculating the particle diameter difference Ai between the styrene copolymer having the largest particle diameter and the styrene copolymer having the smallest particle diameter, the center value B of the particle diameter difference Ai, and the average value C of the difference between the particle diameter difference Ai and the center value B. The composition of the present invention has high gloss and high impact resistance.
Description
Technical field
The present invention relates to a kind of phenylethylene resin series, particularly relate to a kind of styrene-series resin compositions that comprises multipolymer and coat the rubber particles of styrene based copolymer.
Background technology
The phenylethylene resin series that generally has high-impact because all there is good evaluation its processing forming, mechanicalness aspect, and has good appearance and glossiness by its formed moulding product, is widely used in then on electronics, electrical appliance and the auto parts.But for the phenylethylene resin series with high-impact, in order to be applied to widely on the field, often to its glossiness and more very requirement of shock-resistance.
Generally have the high impact styrene resin and formed by rubber particles and vinylbenzene main body, and this rubber particles can be divided into the rubber particles that coats styrol copolymer and not coat the rubber particles of styrol copolymer.In the styrene resin that comprises the rubber particles that does not coat styrol copolymer, the weight average particle diameter of its rubber particles is less, makes phenylethylene resin series have the higher gloss degree and than the characteristic of high-impact.And comprise in the styrene resin of the rubber particles that coats styrol copolymer, the weight average particle diameter of its rubber particles is big and size distribution is uneven, makes that the glossiness of phenylethylene resin series and shock-resistance are not good, can't satisfy user's demand.
In addition, prepare the mode that the styrene resin that comprises the rubber particles that does not coat styrol copolymer mostly adopts emulsion polymerization at present, but the emulsion polymerization mode can derive the problem of waste water and waste liquid, do not meet the economic benefit of industry, so in recent years for meeting under the environmental protection requirement, the method that preparation has the phenylethylene resin series of high-impact changes totally (bulk) polymerization methods or solution (solution) polymerization methods into by the emulsion polymerization mode, but overall polymerization methods or the prepared phenylethylene resin series of solution polymerization mode are the above-mentioned styrene resin that comprises the rubber particles that coats styrol copolymer, also do not meet the product demand of industry.
Therefore, how under the consideration based on the environmental protection processing procedure, the problem that the anxious desire of field personnel solved under development one phenylethylene resin series with high glossiness and shock-resistance became.
Summary of the invention
First purpose of the present invention provides a kind of method for preparing styrene-series resin compositions.
The present invention prepares the method for styrene-series resin compositions, comprises following steps:
Make first starting raw material carry out the continuous solution polymerization reaction, form first reaction mixture, and this first initial raw material packet contains rubber components, second rubber components, the monomer component that comprises styrenic monomers and solvent, and this rubber components comprises first rubber components and second rubber components;
Make second starting raw material carry out the continuous solution polymerization reaction, form second reaction mixture, and this second starting raw material comprises monomer component and the solvent that comprises styrenic monomers; Then,
With first reaction mixture and second reaction mixture, and carry out the continuous solution polymerization reaction, can obtain this styrene-series resin compositions.
The present invention prepares the method for styrene-series resin compositions, and wherein this rubber components comprises first rubber components of 80 weight %～99 weight % and second rubber components of 1 weight %～20 weight %.
The present invention prepares the method for styrene-series resin compositions, and wherein the continuous importing first reactor R1 of this first starting raw material carries out polyreaction, treat polyreaction after, form first reaction mixture, and import the second reactor R2; Importing the 6th reactor R6 that second starting raw material is continuous, treat polyreaction after, form second reaction mixture, and import this second reactor R2, and with this first reaction mixture, and produce the phase reversion phenomenon at this second reactor R2.
The present invention prepares the method for styrene-series resin compositions, and wherein the solids content scope of first reaction mixture behind this first initial raw material reaction is 10 weight %～30 weight %; This second starting raw material is 30 weight %～60 weight % in the solids content scope of reacted second reaction mixture of the 6th reactor R6.
The present invention prepares the method for styrene-series resin compositions, and wherein the first initial raw material packet contains rubber components, the 55 weight %～90 weight % of 5 weight %～20 weight % and comprises the monomer component of styrenic monomers, and the solvent of 5 weight %～25 weight %; Second starting raw material comprises 75 weight %～99 weight % and comprises the monomer component of styrenic monomers, and the solvent of 1 weight %～25 weight %.
Second purpose of the present invention is that a kind of styrene-series resin compositions is being provided.
Styrene-series resin compositions of the present invention is obtained by aforesaid method.
Especially, the present application people is by above-mentioned preparation method, active research and develop different styrene-series resin compositions helps to promote glossiness and the shock-resistance of styrene-series resin compositions, and can satisfy industry for the demand of styrene-series resin compositions.
The 3rd purpose of the present invention is that a kind of styrene-series resin compositions with preferable glossiness and shock-resistance is being provided, and comprises:
As the multipolymer of external phase, this multipolymer comprises the styrenic monomers unit; Reach the rubber particles as the coating styrene based copolymer of disperse phase;
Coat in the rubber particles of styrene based copolymer at this, collect n particle diameter greater than the rubber particles of the coating styrene based copolymer of 0.4 μ m, and be worth B and mean value C by following two formula computing centers:
This central value
Ai represents that in the rubber particles of i particle diameter greater than the coating styrene based copolymer of 0.4 μ m, the particle diameter of the styrene based copolymer of maximum particle diameter and the styrene based copolymer of minimum grain size is poor;
This mean value
And the scope of C/B is less than 15%.
Styrene-series resin compositions of the present invention, wherein the scope of C/B is less than 13%.
Styrene-series resin compositions of the present invention, wherein the scope of C/B is less than 11%.
Styrene-series resin compositions of the present invention, wherein the scope of this central value B is less than 0.29 μ m.
The 4th purpose of the present invention is that a kind of moulding product of styrene-series resin compositions are being provided.
The moulding product of styrene-series resin compositions of the present invention are formed by aforesaid styrene-series resin compositions.
Beneficial effect of the present invention is: by the particle diameter adjustment of the styrene based copolymer in the rubber particles that coats styrene based copolymer, make that the scope of C/B is less than 15%, make this styrene-series resin compositions have preferable glossiness and shock-resistance then.
Description of drawings
Fig. 1 is a synoptic diagram, illustrates that preferred embodiment styrene-series resin compositions enlargement ratio of the present invention is 25,000 times structure kenel;
Fig. 2 is a synoptic diagram, and the styrene-series resin compositions enlargement ratio that comparative example 1 of the present invention is described is 25,000 times structure kenel; And
Fig. 3 is a synoptic diagram, and the styrene-series resin compositions enlargement ratio that comparative example 2 of the present invention is described is 25,000 times structure kenel.
Embodiment
The preparation of＜styrene-series resin compositions 〉
Among the application, represent vinylformic acid and/or methacrylic acid with (methyl) vinylformic acid, similarly, represent acrylate and/or methacrylic ester with (methyl) acrylate.
The present invention prepares the method for styrene-series resin compositions, comprises following steps:
Make first starting raw material carry out the continuous solution polymerization reaction, form first reaction mixture, and this first initial raw material packet contains rubber components, comprises monomer component and the solvent of styrenic monomers, and this rubber components comprises first rubber components and second rubber components;
Make second starting raw material carry out the continuous solution polymerization reaction, form second reaction mixture, and this second starting raw material comprises monomer component and the solvent that comprises styrenic monomers; Then,
With first reaction mixture and second reaction mixture, and carry out the continuous solution polymerization reaction, can obtain this styrene-series resin compositions.
Carry out the reactor of this continuous solution polymerization reaction including but not limited to column flow reactor (plug flow reactor, abbreviation PFR), complete mixing reactor (continuous stirred-tank reactor, be called for short CSTR), perhaps contain the reactor (Static reactor) of silent oscillation mixing tank etc.This reactor quantity can and be used two or more, is preferably more than three or three.When using a plurality of reactor, these reactors can adopt the mode of serial or parallel connection, and the mode that is arranged in parallel with a reactor and other reactors is good.These reactors are good with the column flow reactor.
Preferably, the reactor that carries out this continuous solution polymerization reaction comprises the first reactor R1 and the second reactor R2 that is connected in series in regular turn, and in parallel with this first reactor R1 and have the 6th a reactor R6 who exports, the outlet of the 6th reactor R6 is connected to this second reactor R2.The temperature of reaction of these reactors and without particular limitation, respectively according to each reactor when the polyreaction solids content and decide.The range of reaction temperature of these reactors is 70 ℃～230 ℃.
In detail, in the step of this continuous solution polymerization reaction, the continuous importing first reactor R1 of this first starting raw material carries out polyreaction, treat polyreaction after, form first reaction mixture, and import the second reactor R2; Importing the 6th reactor R6 that second starting raw material is continuous, treat polyreaction after, form second reaction mixture, and import this second reactor R2, and with this first reaction mixture, and produce the phase reversion phenomenon at the second reactor R2.Optionally further, in the second reactor R2, react, form the 3rd reaction mixture, then import among the 3rd reactor R3, the 4th reactor R4 and the 5th reactor R5 and carry out polyreaction again.
In the concrete example of the present invention, the reactor that carries out this continuous solution polymerization reaction comprises the first reactor R1, the second reactor R2, the 3rd reactor R3, the 4th reactor R4 and the 5th reactor R5 that is connected in series in regular turn, and in parallel with this first reactor R1 and have the 6th a reactor R6 who exports, the outlet of the 6th reactor R6 is connected to this second reactor R2.
After treating that polyreaction in these reactors reaches required turnover ratio, again this reacted solution is taken out continuously by reactive system, and import a devolatilization device further, by this devolatilization device the volatile component of unreacted starting raw material and the generation of reaction back is removed, can obtain styrene-series resin compositions of the present invention, perhaps further give granulation again.
General devolatilization device can use decompression degassing vessel device, or extrudes de-gassing vessel.Unreacted starting raw material or the volatile component removed by this devolatilization device selectively reclaim with condenser again, after the moisture in the recovery liquid can being removed in case of necessity, use as starting raw material again.This devolatilization device for example can be single shaft with the forcing machine of devolatilization mouth, forcing machine, the thin-film evaporator (thin film) that twin shaft has the devolatilization mouth, or has the devolatilization groove of vaccum-pumping equipment.In the devolatilization process, can in forcing machine, add the devolatilization auxiliary agent according to need.This devolatilization auxiliary agent is including but not limited to water, hexanaphthene, carbonic acid gas etc.This devolatilization device also can be provided with according to need to be pinched confounding section (kneading zone) or pushes section (pumping zone) etc., and the screw speed scope is 120rpm～350rpm.For the present invention, this devolatilization device is good with twin shaft with the forcing machine of devolatilization mouth.Above-mentioned devolatilization device one or more use of can connecting, its temperature control is preferably 200 ℃～320 ℃ at 180 ℃～350 ℃, be more preferred from 220 ℃～300 ℃, and the vacuum degree control of devolatilization device is preferably below the 200Torr below 300Torr, is more preferred from below the 100Torr.
This first initial raw material packet contains rubber components, the 55 weight %～90 weight % of 5 weight %～20 weight % and comprises the monomer component of styrenic monomers, and the solvent of 5 weight %～25 weight %; This second starting raw material comprises 75 weight %～99 weight % and comprises the monomer component of styrenic monomers, and the solvent of 1 weight %～25 weight %.In this continuous solution polymerization reaction, optionally can in first starting raw material or second starting raw material, add polymerization starter or chain-transfer agent etc.
This rubber components is rubber including but not limited to diene series rubber, polyolerin elastomer, polyacrylic ester, or polysiloxane series rubber.This polyolerin elastomer is including but not limited to ethylene-propylene rubber.Preferably, this rubber components is diene series rubber.Preferably, this diene series rubber is obtained after polymerization by diene monomer (or diene monomer and other monomers), and its second-order transition temperature is below 0 ℃.This diene monomer can be used alone or as a mixture, and this diene monomer is including but not limited to 1,3-butadiene, methyl isophthalic acid, 3-divinyl, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, chloroprene etc.Preferably, this diene monomer is selected certainly in 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 1,3-pentadiene, chloroprene, or their combination.
This diene series rubber is including but not limited to divinyl rubber, synthetic polyisoprene, neoprene, ethylene-propylene-diolefin series ter-polymers rubber (ethylene propylene diene terpolymer is called for short EPDM), vinylbenzene-diene series rubber, vinyl cyanide-diene series rubber etc.This divinyl rubber is including but not limited to the divinyl rubber of high-cis (Hi-Cis) content and the divinyl rubber of low cis (Low-Cis) content.The typical weight of the cis in the divinyl rubber of this high-cis content (Cis)/vinyl (Vinyl) consists of (94～99wt%)/(0～5wt%), all the other compositions then are trans (Trans) structure, and mooney viscosity (mooney viscosity) is between 20～120, molecular weight ranges is with 100,000～800,000 is good.The typical weight compositing range of the cis/vinyl in the divinyl rubber of this low cis content (20～40wt%)/(6～20wt%), all the other are transconfiguration, and mooney viscosity is between 20～120, and molecular weight ranges is with 100,000～800, and 000 is good.
This vinylbenzene-diene series rubber is including but not limited to styrene butadiene rubbers, styrene isoprene rubber etc.The mooney viscosity of this vinylbenzene-diene series rubber is 20～80, and soltion viscosity is 3cps～200cps (styrene solution by concentration 5 weight % under 25 ℃ records).In this vinylbenzene-diene series rubber 1,2-vinyl (1,2-vinyl) content range of monomeric unit is 8 weight %～40 weight %, and be 100 weight % with vinylbenzene-diene series rubber total amount, the content range of this styrene monomer unit is 5 weight %～35 weight %, and the weight average molecular weight scope of this vinylbenzene-diene series rubber is 50,000～800,000.
The structure of this diene series rubber can be homopolymer block structure (homopolymer block structure), random structure (random structure), forms cumulative or decrescence constructs (taper structure), aligned structure, difference structure, or the combination construction of these structures.For example, the vinylbenzene-diene series rubber of this homopolymer block structure is including but not limited to styrene-butadiene-styrene block (S-B-S).Vinylbenzene-the diene series rubber of this random structure is including but not limited to vinylbenzene-irregular phenylethylene/butadiene-styrene block (S-random S/B-S), irregular phenylethylene/butadiene block (random S/B), divinyl-irregular phenylethylene/divinyl-butadiene block (B-random S/B-B), divinyl-irregular phenylethylene/butadiene block (B-random S/B).This form vinylbenzene-diene series rubber cumulative or decrescence structure including but not limited to vinylbenzene-composition cumulative or decrescence phenylethylene/butadiene-styrene block (S-taper S/B-S), divinyl-composition is cumulative or phenylethylene/butadiene-styrene block (B-taper S/B-S) decrescence.
This styrenic monomers can be used alone or as a mixture, and this styrenic monomers including but not limited to vinylbenzene, alpha-methyl styrene, p-methylstyrene ,-vinyl toluene, neighbour-vinyl toluene, ethyl styrene, 2,4-dimethyl styrene, right-t-butyl styrene, Alpha-Methyl-p-methylstyrene, bromo-vinylbenzene, two bromo-vinylbenzene, 2,4,6-tribromo-benzene ethene etc.
This monomer component also comprises other copolymerizable monomer, preferably, is 100 weight % based on the usage quantity of this monomer component, and the usage quantity scope of these other copolymerizable monomer is 5 weight %～50 weight %.These other copolymerizable monomer can be used alone or as a mixture, and this other copolymerizable monomer is including but not limited to ethylbenzene, acrylic monomer, the metha crylic monomer, the acrylic ester monomer, the methacrylate ester monomer, maleimide is monomer, Maleic Acid, Anhydrous (maleic acid), anhydrous methyl-maleic acid (cis-methylbutenedioic acid), anhydrous methylfumaric acid (trans-methylbutene dioic acid), fumaric acid (fumaric acid), methylene-succinic acid (itaconic acid), dimethyl fumarate (dimethylfumarate), dibutyl itaconate (dibutyl itaconate) etc.This acrylic monomer is including but not limited to vinylformic acid etc.This metha crylic monomer is including but not limited to methacrylic acid etc.This methacrylate ester monomer is including but not limited to methyl methacrylate, Jia Jibingxisuanyizhi etc.This maleimide is that monomer is monomer etc. including but not limited to maleimide, nitrogen-methyl maleimide, nitrogen-sec.-propyl maleimide, nitrogen-butyl maleimide, nitrogen-hexyl maleimide, nitrogen-octyl group maleimide, nitrogen-dodecyl maleimide, nitrogen-cyclohexyl maleimide, nitrogen-phenyl maleimide, bismaleimides.
This solvent can be used alone or as a mixture, and this solvent is including but not limited to (1) aromatic hydrocarbons: toluene, ethylbenzene, dimethylbenzene etc.; (2) aliphatic hydrocarbon: hexane, heptane, hexanaphthene; (3) ketone: methylethylketone, acetone and methyl butyl ketone; (4) ester class.
In the concrete example of the present invention, this rubber components comprises first rubber components of 80 weight %～99 weight % and second rubber components of 1 weight %～20 weight %.
Preferably, this first rubber components comprises the aligned structure styrene butadiene rubbers of 5 weight %～20 weight % and the difference structure styrene butadiene rubbers of 80 weight %～95 weight %; This second rubber components comprises the aligned structure styrene butadiene rubbers of 50 weight %～70 weight % and the difference structure styrene butadiene rubbers of 30 weight %～50 weight %.
The mooney viscosity of the styrene butadiene rubbers in this first rubber components is 20～70, and soltion viscosity is 10cps～50cps (styrene solution by concentration 5 weight % under 25 ℃ records).In this styrene butadiene rubbers 1, the content range of 2-vinyl monomer unit are 8 weight %～30 weight %, and the weight average molecular weight scope of this styrene butadiene rubbers is 200,000～500,000.
The mooney viscosity of the styrene butadiene rubbers in this second rubber components is 30～80, and soltion viscosity is 100cps～200cps (styrene solution by concentration 5 weight % under 25 ℃ records).In this styrene butadiene rubbers 1, the content range of 2-vinyl monomer unit are 8 weight %～25 weight %, and the weight average molecular weight scope of this styrene butadiene rubbers is 400,000～800,000.
This first starting raw material is 10 weight %～30 weight % in the solids content scope of reacted first reaction mixture of the first reactor R1; Preferably, this solids content scope is 12 weight %～25 weight %; More preferably, this solids content scope is 15 weight %～20 weight %.
This second starting raw material is 30 weight %～60 weight % in the solids content scope of reacted second reaction mixture of the 6th reactor R6; Preferably, this solids content scope is 40 weight %～60 weight %; More preferably, this solids content scope is 45 weight %～55 weight %.
The solids content scope of the 3rd reaction mixture is 20 weight %～35 weight %; Preferably, this solids content scope is 23 weight %～33 weight %; More preferably, this solids content scope is 25 weight %～32 weight %.
Carry out follow-up polyreaction after the 5th reactor R5 mixes, the solids content scope of its reacted reaction mixture is 25 weight %～55 weight %; Preferably, this solids content scope is 30 weight %～50 weight %; More preferably, this solids content scope is 35 weight %～45 weight %.
This polymerization starter is selected certainly in simple function polymerization starter, multi-functional polymerization starter, or their combination.This simple function polymerization starter can be used alone or as a mixture, and this simple function polymerization starter is including but not limited to benzoyl peroxide (benzoyl peroxide), dicumyl peroxide (dicumyl peroxide), tert-butyl peroxide (t-butyl peroxide), tert-butyl hydroperoxide (t-butyl hydroperoxide), hydrogen phosphide cumene (cumene hydroperoxide), tert butyl peroxy benzoate (t-butyl-peroxy benzoate), two-2-ethylhexyl peroxy dicarbonate (bis-2-ethylhexyl peroxy dicarbonate), tert-butyl hydroperoxide sec.-propyl carbonic ether (tert-butyl peroxy isopropyl carbonate, be called for short BPIC), cyclohexanone peroxide (cyclohexanone peroxide), 2,2 '-azo-two-isopropyl cyanide (2,2 '-azo-bis-isobutyronit rile, be called for short ANBN), 1,1 '-azo bis cyclohexane-1-nitrile (1,1 '-azo-biscy clohexane-1-carbonit rile), 2,2 '-azo-two-2-methylbutyronitrile (2,2 '-azo-bis-2-methyl butyronitrile) etc.Wherein preferable with dibenzoyl peroxide, dicumyl peroxide.
This multi-functional polymerization starter can be used alone or as a mixture, and this multi-functional polymerization starter is including but not limited to 1,1-pair-tert-butyl hydroperoxide hexanaphthene (1,1-bis-t-butyl peroxy cyclohexane, be called for short TX-22), 1,1-pair-tert-butyl hydroperoxide-3,3,5-trimethyl-cyclohexane (1,1-bi s-t-butylperoxy-3,3,5-trimethyl cyclohexane, be called for short TX-29A), 2,5-dimethyl-2,5-pair-(2-ethyl peroxidation hexanoyl) hexane [2,5-dimethyl-2,5-bis-(2-ethylhexanoxy peroxy) hexane], 4-(tert-butyl hydroperoxide carbonyl)-3-hexyl-6-[7-(tert-butyl hydroperoxide carbonyl) heptyl] hexanaphthene 4-(t-butyl peroxy carbonyl)-3-hexyl-6-[7-(t-butyl peroxy carbonyl) heptyl] cyclohexane}, two-tertiary butyl diperoxy azelate (di-t-butyl-diperoxyazelate), 2,5-dimethyl-2, two (benzoyl the peroxidation)-hexanes [2 of 5-, 5-dimethyl-2,5-bis-(benzoyl peroxy) hexane], two-tert-butyl hydroperoxide-six hydrogen-terephthalate (di-t-butyl peroxy-hexahydro-terephthalate, be called for short BPHTH), 2,2-two (4,4-two-tert-butyl hydroperoxide) cyclohexyl propane [2,2-bi s-(4,4-di-t-butyl peroxy) cyclohexyl propane, be called for short PX-12], multi-functional single peroxycarbonates (multifunctional monoperoxycarbonate, U.S. ATOFINA corporate system for example, trade(brand)name Luperox JWE B-50) etc.Preferably, be 100 weight part meters based on the total amount of starting raw material, the usage quantity scope of this polymerization starter is 0ppm～10,000ppm; More preferably, the usage quantity scope of this polymerization starter is 10ppm～7,000ppm.
This chain-transfer agent is selected certainly in simple function chain-transfer agent, multi-functional chain-transfer agent, or their combination.This simple function chain-transfer agent can be used alone or as a mixture, and this simple function chain-transfer agent is including but not limited to (1) mercaptan (mercaptan) class: methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, just-lauryl mercaptan (n-dodecyl mercaptan, be called for short NDM), stearyl-mercaptan (stearyl mercaptan), uncle-lauryl mercaptan (t-dodecyl mercaptan is called for short TDM), just-propyl group mercaptan, n-octyl mercaptan, uncle-octyl mercaptan, uncle-nonyl mercaptan etc.; (2) alkanamine (alkylamine s) class: single ethylamine, diethylamide, triethylamine, single isopropylamine, diisopropylamine, monobutyl amine, di-n-butyl amine, three-n-butylamine etc.; (3) other; Pentaphenylethane (penta phenylethane), α-Jia Jibenyixierjuwu (α-methylstyrene dimer), terpinolene (terpinolene) etc.Wherein with just-lauryl mercaptan, uncle-lauryl mercaptan are preferable.
This multi-functional chain-transfer agent can be used alone or as a mixture, and this multi-functional chain-transfer agent is including but not limited to tetramethylolmethane four (3-mercaptopropionic acid ester) [pentaerythritol tetrakis (3-mercapto pro pionate)], tetramethylolmethane four (2-mercaptoacetate) [pentaerythritol tetrakis (2-mercapto acetate)], three-(2-Thiovanic acid) trishydroxymethyl propyl ester [trimethylolpropane tris (2-mercapto acetate)], three-(3-thiohydracrylic acid) trishydroxymethyl propyl ester [trimethylolpropane tris (3-mercapto propionate) is called for short TMPT], three-(6-mercaptohexanoic acid) trishydroxymethyl propyl ester [trimethylol-propane tris (6-mercapto hexanate)] etc.Wherein preferable with three-(3-thiohydracrylic acid) trishydroxymethyl propyl ester.Preferably, be 100 weight part meters based on the total amount of starting raw material, the usage quantity scope of this chain-transfer agent is 0ppm～10,000ppm; More preferably, the usage quantity scope of this chain-transfer agent is 10ppm～7,000ppm.
In the scope of the effect that does not undermine styrene-series resin compositions of the present invention, in preparation styrene-series resin compositions process of the present invention, can add various additives in case of necessity.This additive can be used alone or as a mixture, and this additive is selected certainly in antioxidant, conductive agent, charged preventor, plasticizer, weighting agent, tinting material, lubricant, charged preventor, incombustible agent, difficult combustion auxiliary agent, photostabilizer, thermo-stabilizer, parting agent, tackifier, coupler, or their combination.Above-mentioned additive can be respectively in above-mentioned continuous solution polymerization reaction or add after the polyreaction.The above-mentioned additive for example ester of mineral oil, butyl stearate is that plasticizer, polyester are that plasticizer, organopolysiloxane (as polydimethylsiloxane), higher fatty acid and metal-salt thereof, bulky amine are antioxidant (hindered amine), glass fibre etc.The total amount of styrene-based resin composition is 100 weight part meters, and this polyester is that the usage quantity scope of plasticizer or mineral oil is respectively 0 weight part～5 weight parts.Preferably, this polyester is that the usage quantity scope of plasticizer or mineral oil is respectively 0.05 weight part～2 weight parts.The total amount of styrene-based resin composition is 100 weight part meters, and the usage quantity scope of this organopolysiloxane is 0 weight part～0.5 weight part.Preferably, the usage quantity scope of this organopolysiloxane is 0.002 weight part～0.2 weight part.
In the scope of the effect that does not undermine styrene-series resin compositions of the present invention, in preparation styrene-series resin compositions process of the present invention, can mix various polymkeric substance in case of necessity.This polymkeric substance can be used alone or as a mixture, and this polymkeric substance is including but not limited to polystyrene-(methyl) acrylic ester-acrylic copolymer, polystyrene-(methyl) acrylate based copolymer, polystyrene-(methyl) acrylic ester-acrylic-maleimide based copolymer, polystyrene-(methyl) acrylic ester-maleimide based copolymer, (methyl) acrylic ester-maleimide based copolymer, or through the aforementioned multipolymer of diene series rubber upgrading (or grafting upgrading).Total amount based on this styrene-series resin compositions is 100 weight part meters, and the usage quantity scope of this polymkeric substance is below 200 weight parts.It can adjust or improve thermotolerance, rigidity or the flow processability of this styrene-series resin compositions.
Styrene-series resin compositions of the present invention, obtained by aforesaid method.
Especially, the present application people is by above-mentioned preparation method, active research and develop different styrene-series resin compositions helps to promote glossiness and the shock-resistance of styrene-series resin compositions, and can satisfy the demand for styrene-series resin compositions of industry.
＜styrene-series resin compositions 〉
The rubber particles of the coating styrene based copolymer in this styrene-series resin compositions is to comprise one or more styrene based copolymers, coat the rubber body of styrene based copolymer and graft on graft copolymer on the rubber body.This styrene based copolymer and graft copolymer are formed through polyreaction by the monomer component that comprises styrenic monomers respectively.This rubber body is formed by rubber components.The rubber particles particle diameter of this coating styrene based copolymer is bimodal distribution, and a weight average particle diameter scope is at 0.4 μ m～1.2 μ m, and another weight average particle diameter scope is at 4 μ m～9 μ m.
Styrene-series resin compositions of the present invention comprises the multipolymer as external phase, and this multipolymer comprises the styrenic monomers unit; Reach the rubber particles as the coating styrene based copolymer of disperse phase;
Coat in the rubber particles of styrene based copolymer at this, collect n particle diameter greater than the rubber particles of the coating styrene based copolymer of 0.4 μ m, and be worth B and mean value C by following two formula computing centers:
This central value
Ai represents that in the rubber particles of i particle diameter greater than the coating styrene based copolymer of 0.4 μ m, the particle diameter of the styrene based copolymer of maximum particle diameter and the styrene based copolymer of minimum grain size is poor;
This mean value
And wherein, the scope of C/B is less than 15%.
When the scope of this C/B is 15% when above, represent the styrene based copolymer of greater particle size in the rubber particles of each coating styrene based copolymer with more than the styrene based copolymer of small particle size, the particle diameter uniformity coefficient that is styrene based copolymer is not good, and the size of this styrene based copolymer is more unequal, can make that the glossiness of styrene-series resin compositions and shock-resistance are not good.When the scope of this C/B is less than 15% the time, represent the styrene based copolymer of greater particle size in the rubber particles of each coating styrene based copolymer with less than the styrene based copolymer of small particle size, be the size of styrene based copolymer than homogeneous, can make styrene-series resin compositions have preferable glossiness and shock-resistance.Preferably, the scope of this C/B is less than 13%.More preferably, the scope of this C/B is less than 11%.
Particle diameter is with perosmic anhydride (OsO greater than the measuring method of the rubber particles of the coating styrene based copolymer of 0.4 μ m in the styrene-series resin compositions of the present invention
4) with after the styrene-series resin compositions dyeing, take a picture with transmission electron microscope again, and amplify 25,000 times, the rubber particles of the coating styrene based copolymer that shines in photograph carries out grain diameter measurement, can obtain particle diameter greater than the rubber particles of the coating styrene based copolymer of 0.4 μ m.And the styrene based copolymer that coats greater particle size in the rubber particles of styrene based copolymer and measuring method than the particle diameter difference Ai of the styrene based copolymer of small particle size, be with above-mentioned 25, the photograph of 000 multiplying power obtains the image of styrene based copolymer with image processing technique, measures the size of styrene based copolymer again with the Analy SIS software of Soft Imaging System company.
This central value B or mean value C are bigger, it is more unequal that expression coats the size of the styrene based copolymer in the rubber particles of styrene based copolymer, and to coat the size of the styrene based copolymer in the rubber particles of styrene based copolymer more average in little expression and this central value B or mean value C are healed.For making styrene-series resin compositions have preferable glossiness and shock-resistance, preferably, the scope of this central value B is less than 0.29 μ m; More preferably, the scope of this central value B is less than 0.28 μ m.
The central value B of styrene-series resin compositions of the present invention, the arrangement mode of a plurality of reactors when the ratio of mean value C and this central value B can be by polymerization, the reactor mixing speed, reactor size and other polymerizing conditions are reached, other polymerizing conditions are for example: polymeric reaction temperature, use kind and the content of polymerization starter, the solids content of the reaction mixture behind each reactor reaction, and the kind of rubber components waits to adjust in the starting raw material, and reactor arrangement particularly, the kind of rubber components more easily influences the ratio of mean value C and this central value B in the size of reactor and the starting raw material.
The weight average molecular weight of the multipolymer in the styrene-series resin compositions of the present invention is also without particular limitation, and preferably, the weight average molecular weight scope of this multipolymer is 50,000～300,000.More preferably, the weight average molecular weight scope of this multipolymer is 100,000～200,000.
Preferably, this styrene-series resin compositions comprises the multipolymer of 60 weight %～95 weight %; And the rubber particles of the coating styrene based copolymer of 5 weight %～40 weight %.More preferably, this styrene-series resin compositions comprises the multipolymer of 70 weight %～90 weight %; And the rubber particles of the coating styrene based copolymer of 10 weight %～30 weight %.Again more preferably, this styrene-series resin compositions comprises the multipolymer of 75 weight %～88 weight %; And the rubber particles of the coating styrene based copolymer of 12 weight %～25 weight %.
The moulding product of styrene-series resin compositions of the present invention are formed by aforesaid styrene-series resin compositions.Its formation method can adopt the mode of mixing, machine-shaping mode, or their combination.
This mode of mixing can be passed through Bradley Bender plastometer, Ban Baili muller, kneading-mixing machine, roller press or single shaft or biaxial extruder.Usually after mixing by these forcing machines, again the extrudate that signature is made cooled off, granulation.The operating temperature range of this mode of mixing is 160 ℃～280 ℃, and preferably, operating temperature range is 180 ℃～250 ℃.This machine-shaping mode can be used ejection formation, compressed moulding, extrusion moulding, blow and prolong moulding, thermoforming, vacuum forming and slush molding.
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are only for illustrating usefulness, and should not be interpreted as restriction of the invention process.
＜embodiment 〉
During the invention process, the array mode of reactor is for to be connected in series the first reactor R1 (30 liters of volumes), the second reactor R2 (10 liters of volumes), the 3rd reactor R3 (30 liters of volumes), the 4th reactor R4 (100 liters of volumes) and the 5th reactor R5 (100 liters of volumes) among the embodiment 1～3, and the six reactor R6 (volume 100 liter) in parallel with this first reactor R1, and the outlet of the 6th reactor R6 is connected to the top of this second reactor R2.These reactors are all the column flow reactor.The temperature of reaction of these reactors is the mean value of each reactor inlet zone and exit region.＜embodiment 1〉styrene-series resin compositions
The first reactor R1, the second reactor R2, the 3rd reactor R3, the 4th reactor R4, the temperature of reaction of the 5th reactor R5 and the 6th reactor R6 is respectively 96 ℃, 102 ℃, 102 ℃, 100 ℃, 100 ℃ and 120 ℃.The first reactor R1, the second reactor R2, the 3rd reactor R3, the 4th reactor R4, the stir speed (S.S.) of the 5th reactor R5 and the 6th reactor R6 is respectively 40rpm, 200rpm, 120rpm, 25rpm, 20rpm and 40rpm.
This first initial raw material packet contain vinylbenzene, the 13 weight % of rubber components, the 76.5 weight % of 10.5 weight % ethylbenzene, 900ppm 1,1-is two-tert-butyl hydroperoxide hexanaphthene and 1000ppm just-lauryl mercaptan.This rubber components comprises first rubber components and 5 weight %, second rubber components of 95 weight %.This second starting raw material comprises the styrenic monomers of 87 weight % and the ethylbenzene of 13 weight %.
This first rubber components comprises the aligned structure styrene butadiene rubbers of 13 weight % and the difference structure styrene butadiene rubbers of 87 weight %.The mooney viscosity of this styrene butadiene rubbers is 45, and soltion viscosity is 35cps (styrene solution by concentration 5 weight % under 25 ℃ records).In this styrene butadiene rubbers 1, the content range of 2-vinyl monomer unit are 18 weight %, and the weight average molecular weight scope of this styrene butadiene rubbers is 350,000.
This second rubber components comprises the aligned structure styrene butadiene rubbers of 58 weight % and the difference structure styrene butadiene rubbers of 42 weight %.The mooney viscosity of this styrene butadiene rubbers is 55, and soltion viscosity is 170cps (styrene solution by concentration 5 weight % under 25 ℃ records).In this styrene butadiene rubbers 1, the content range of 2-vinyl monomer unit are 12 weight %, and the weight average molecular weight scope of this styrene butadiene rubbers is 660,000.
First starting raw material is imported the first reactor R1 continuously with 38 liters/hour flow carry out polyreaction, after treating polyreaction, form first reaction mixture, and import the second reactor R2, and the solids content of this first reaction mixture is 16.6 weight %.
Second starting raw material is imported the 6th reactor R6 continuously with 18 liters/hour flow carry out polyreaction, after treating polyreaction, form second reaction mixture, and import this second reactor R2, and the solids content of this second reaction mixture is 48 weight %.
First reaction mixture is mixed in the second reactor R2 with this second reaction mixture and proceed polyreaction, then import behind the question response among the 3rd reactor R3, the 4th reactor R4 and the 5th reactor R5 and carry out polyreaction again.Solids content in the reacted reaction mixture of the second reactor R2 is 30 weight %, and is 40.5 weight % in the solids content of the reacted reaction mixture of the 5th reactor R5.Through the devolatilization device low volatiles such as unreacted monomer, solvent are removed, can make styrene-series resin compositions of the present invention.This starting raw material kind, usage quantity and polymerizing condition see Table 1, and evaluation result sees Table 2.
In addition according to the particle diameter of the 15th page in specification sheets of the present invention measuring method greater than the rubber particles of the coating styrene based copolymer of 0.4 μ m, the structure kenel as Fig. 1 be can obtain, particle diameter difference Ai, central value B and mean value C calculated simultaneously, result such as table 2.
[embodiment 2～3]
Embodiment 2～3rd, prepare this styrene-series resin compositions with the step identical with embodiment 1, and different places are: change starting raw material kind, usage quantity and polymerizing condition.This starting raw material kind, usage quantity and polymerizing condition see Table 1, and evaluation result sees Table 2.
[comparative example 1]
The array mode of these reactors is with the first reactor R1 (100 liters of volumes), the second reactor R2 (100 liters of volumes), the 3rd reactor R3 (100 liters of volumes) and the 4th reactor R4 (100 liters of volumes) series connection.These reactors are all the column flow reactor.The temperature of reaction of these reactors is the mean value of each reactor inlet zone and exit region.
The temperature of reaction of the first reactor R1, the second reactor R2, the 3rd reactor R3 and the 4th reactor R4 is respectively 97 ℃, 105 ℃, 115 ℃ and 125 ℃.The stir speed (S.S.) of the first reactor R1, the second reactor R2, the 3rd reactor R3 and the 4th reactor R4 is respectively 40rpm, 200rpm, 60rpm and 25rpm.
This first initial raw material packet contain vinylbenzene, the 6 weight % of rubber components, the 87 weight % of 7 weight % ethylbenzene, 1000ppm 1,1-is two-tert-butyl hydroperoxide hexanaphthene and 500ppm just-lauryl mercaptan.This rubber components comprises first rubber components and 6 weight %, second rubber components of 94 weight %.
This first rubber components comprises the aligned structure styrene butadiene rubbers of 13 weight % and the difference structure styrene butadiene rubbers of 87 weight %.The mooney viscosity of this styrene butadiene rubbers is 45, and soltion viscosity is 35cps (styrene solution by concentration 5 weight % under 25 ℃ records).In this styrene butadiene rubbers 1, the content range of 2-vinyl monomer unit are 18 weight %, and the weight average molecular weight scope of this styrene butadiene rubbers is 350,000.
This second rubber components comprises the aligned structure styrene butadiene rubbers of 58 weight % and the difference structure styrene butadiene rubbers of 42 weight %.The mooney viscosity of this styrene butadiene rubbers is 55, and soltion viscosity is 170cps (styrene solution by concentration 5 weight % under 25 ℃ records).In this styrene butadiene rubbers 1, the content range of 2-vinyl monomer unit are 12 weight %, and the weight average molecular weight scope of this styrene butadiene rubbers is 660,000.
This first starting raw material is imported the first reactor R1 continuously with 53 liters/hour flow carry out polyreaction, after treating polyreaction, form first reaction mixture, and import the second reactor R2, the 3rd reactor R3 and the 4th reactor R4 in regular turn, wherein, the solids content of this first reaction mixture is 18 weight %, be 37 weight % in the solids content of the reacted reaction mixture of the second reactor R2, and be 35 weight % in the solids content of the reacted reaction mixture of the 4th reactor R4.Through the devolatilization device low volatiles such as unreacted monomer, solvent are removed, can make styrene-series resin compositions of the present invention.This starting raw material kind, usage quantity and polymerizing condition see Table 1, and evaluation result sees Table 2.
In addition according to the particle diameter of the 15th page in specification sheets of the present invention measuring method greater than the rubber particles of the coating styrene based copolymer of 0.4 μ m, the structure kenel as Fig. 2 be can obtain, particle diameter difference Ai, central value B and mean value C calculated simultaneously, result such as table 2.
[comparative example 2]
Styrene-series resin compositions is by Japanese Asahi Chemical Industry corporate system, model 403R.Its preparation method adopts the continuous solution polymerization reaction to make, and its evaluation result sees Table 2.
In addition according to the particle diameter of the 15th page in specification sheets of the present invention measuring method greater than the rubber particles of the coating styrene based copolymer of 0.4 μ m, the structure kenel as Fig. 3 be can obtain, particle diameter difference Ai, central value B and mean value C calculated simultaneously, result such as table 2.
[test item]
1. shock strength (Izod) evaluating and measuring:
The styrene-series resin compositions of embodiment 1～3 and comparative example 1～2 is penetrated, and according to (23 ℃ of the standard methods of ASTM D-256,1/4 inch thick test film with breach) preparation standard test piece is then tested unit: Kg-cm/cm according to the regulation of ASTM D-256.
2. the assay of external phase and disperse phase in the styrene-series resin compositions:
With the styrene-series resin compositions of embodiment 1～3 and comparative example 1～2 with tetrahydrofuran (THF) (tetra hydrofuran) dissolving after, behind membrane with fourier-transform infrared line spectrometer (Fourier Transform Infrared Spectrometer, the Nicolet corporate system, model Nexus 470) test, unit: weight %.
3. (expression is mobile, melt index, 200 ℃, 5kg for fusing coefficient; Be called for short MI) evaluating and measuring:
The styrene-series resin compositions of embodiment 1～3 and comparative example 1～2 is tested unit according to ASTM standard D-1238 method: g/10 minute.
4. tensile strength (Tsy) evaluating and measuring:
The styrene-series resin compositions of embodiment 1～3 and comparative example 1～2 is tested according to AS TM D-638 regulation, and with the 6mm/min velocity determination, unit is kg/cm
2
5. glossiness evaluating and measuring:
The styrene-series resin compositions of embodiment 1～3 and comparative example 1～2 is penetrated into thickness 1/8 at 220 ℃ " (3.17mm); the disk test piece of diameter 5.5cm; and analyze with BYK Micro-TRI (60 degree angle), and record unit according to ASTM D-2457 method: %.
Table 1
"--" expression is not added or is not used.Polymerization starter: 1,1-pair-the tert-butyl hydroperoxide hexanaphthene; Chain-transfer agent: just-lauryl mercaptan.
Table 2
Learnt by comparative example 1, in the rubber particles of the coating styrene based copolymer of styrene-series resin compositions, the central value B of the particle diameter difference of the styrene based copolymer of maximum particle diameter and the styrene based copolymer of minimum grain size is 0.370 μ m, and mean value C is 0.103 μ m, and this C/B is 27.8%, the styrene based copolymer of greater particle size and more than the styrene based copolymer of small particle size in the rubber particles of each coating styrene based copolymer in the expression comparative example 1, the size uniformity coefficient that is styrene based copolymer is not good, causes the glossiness of styrene-series resin compositions and shock-resistance not good.
Learnt by comparative example 2, in the rubber particles of the coating styrene based copolymer of styrene-series resin compositions, the central value B of the particle diameter difference of the styrene based copolymer of maximum particle diameter and the styrene based copolymer of minimum grain size is 0.300 μ m, and mean value C is 0.050 μ m, and this C/B is 18%, the styrene based copolymer of greater particle size and more than the styrene based copolymer of small particle size in the rubber particles of each coating styrene based copolymer in the expression comparative example 2, the size uniformity coefficient that is styrene based copolymer is not good, causes the glossiness of styrene-series resin compositions and shock-resistance not good.
And learnt by embodiment 1～3, in the rubber particles of the coating styrene based copolymer of styrene-series resin compositions of the present invention, this C/B is 10.5%～12.1%, the styrene based copolymer of greater particle size and less than the styrene based copolymer of small particle size in each rubber particles among the expression embodiment 1～3, the size uniformity coefficient that is styrene based copolymer is good, makes styrene-series resin compositions have preferable glossiness and shock-resistance.By The above results, prove that more method for making of the present invention can effectively make the styrene-series resin compositions that has good glossiness and shock-resistance concurrently.
In sum, particle diameter adjustment by the styrene based copolymer in the rubber particles that coats styrene based copolymer, make that the scope of C/B is less than 15%, make this styrene-series resin compositions have high glossiness and high-impact then, so can reach purpose of the present invention really.
Claims (11)
1. method for preparing styrene-series resin compositions is characterized in that comprising following steps:
Make first starting raw material carry out the continuous solution polymerization reaction, form first reaction mixture, and this first initial raw material packet contains rubber components, second rubber components, the monomer component that comprises styrenic monomers and solvent, and this rubber components comprises first rubber components and second rubber components;
Make second starting raw material carry out the continuous solution polymerization reaction, form second reaction mixture, and this second starting raw material comprises monomer component and the solvent that comprises styrenic monomers; Then,
With this first reaction mixture and this second reaction mixture, and carry out the continuous solution polymerization reaction, can obtain this styrene-series resin compositions.
2. the method for preparing styrene-series resin compositions according to claim 1 is characterized in that, this rubber components comprises first rubber components of 80 weight %～99 weight % and second rubber components of 1 weight %～20 weight %.
3. the method for preparing styrene-series resin compositions according to claim 1, it is characterized in that the continuous importing first reactor R 1 of this first starting raw material carries out polyreaction, treat polyreaction after, form first reaction mixture, and import the second reactor R2; Importing the 6th reactor R6 that second starting raw material is continuous, treat polyreaction after, form second reaction mixture, and import this second reactor R2, and with this first reaction mixture, and produce the phase reversion phenomenon at this second reactor R2.
4. the method for preparing styrene-series resin compositions according to claim 1 is characterized in that, the solids content scope of first reaction mixture behind this first initial raw material reaction is 10 weight %～30 weight %; This second starting raw material is 30 weight %～60 weight % in the solids content scope of reacted second reaction mixture of the 6th reactor R6.
5. the method for preparing styrene-series resin compositions according to claim 1, it is characterized in that, the first initial raw material packet contains rubber components, the 55 weight %～90 weight % of 5 weight %～20 weight % and comprises the monomer component of styrenic monomers, and the solvent of 5 weight %～25 weight %; Second starting raw material comprises 75 weight %～99 weight % and comprises the monomer component of styrenic monomers, and the solvent of 1 weight %～25 weight %.
6. a styrene-series resin compositions is characterized in that, by obtained according to each described method in the claim 1 to 5.
7. styrene-series resin compositions is characterized in that comprising:
As the multipolymer of external phase, this multipolymer comprises the styrenic monomers unit; Reach the rubber particles as the coating styrene based copolymer of disperse phase;
Coat in the rubber particles of styrene based copolymer at this, collect n particle diameter greater than the rubber particles of the coating styrene based copolymer of 0.4 μ m, and be worth B and mean value C by following two formula computing centers:
This central value
Ai represents that in the rubber particles of i particle diameter greater than the coating styrene based copolymer of 0.4 μ m, the particle diameter of the styrene based copolymer of maximum particle diameter and the styrene based copolymer of minimum grain size is poor; This mean value
And the scope of C/B is less than 15%.
8. styrene-series resin compositions according to claim 7 is characterized in that, the scope of C/B is less than 13%.
9. styrene-series resin compositions according to claim 8 is characterized in that, the scope of C/B is less than 11%.
10. styrene-series resin compositions according to claim 7 is characterized in that, the scope of this central value B is less than 0.29 μ m.
11. the moulding product of a styrene-series resin compositions is characterized in that, by being formed according to each described styrene-series resin compositions in the claim 7 to 10.
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| CN201510011235.5A Active CN104610694B (en) | 2011-12-30 | 2012-04-24 | Styrene resin composition and molded article obtained therefrom |
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| CN114409839A (en) * | 2022-01-27 | 2022-04-29 | 万华化学集团股份有限公司 | SAN resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI580720B (en) * | 2015-12-10 | 2017-05-01 | 奇美實業股份有限公司 | Thermoplastic resin composition and molding product made therefrom |
| TWI580721B (en) * | 2015-12-11 | 2017-05-01 | 奇美實業股份有限公司 | Thermoplastic resin composition and molding product made therefrom |
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| US4146589A (en) * | 1978-05-19 | 1979-03-27 | Monsanto Company | Method for preparing a monoalkenyl aromatic polyblend having a dispersed rubber phase as particles with a bimodal particle size distribution |
| JP2001089620A (en) * | 1999-09-21 | 2001-04-03 | Denki Kagaku Kogyo Kk | Rubber modified aromatic vinyl resin composition |
| CN1911971A (en) * | 2005-04-15 | 2007-02-14 | 切弗朗菲利浦化学公司 | Process for making high impact strength polystyrene and related compositions |
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| ES2321402T3 (en) * | 2003-02-05 | 2009-06-05 | Dow Global Technologies Inc. | AROMATIC POLYMERS OF MOVILINILIDENO MODIFIED WITH RUBBER, WITH HIGH BRIGHTNESS PRODUCED BY A MASS POLYMERIZATION PROCESS. |
| CN101205274B (en) * | 2006-12-18 | 2011-06-01 | 奇美实业股份有限公司 | Rubber modified styrene series resin composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146589A (en) * | 1978-05-19 | 1979-03-27 | Monsanto Company | Method for preparing a monoalkenyl aromatic polyblend having a dispersed rubber phase as particles with a bimodal particle size distribution |
| JP2001089620A (en) * | 1999-09-21 | 2001-04-03 | Denki Kagaku Kogyo Kk | Rubber modified aromatic vinyl resin composition |
| CN1911971A (en) * | 2005-04-15 | 2007-02-14 | 切弗朗菲利浦化学公司 | Process for making high impact strength polystyrene and related compositions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409839A (en) * | 2022-01-27 | 2022-04-29 | 万华化学集团股份有限公司 | SAN resin and preparation method thereof |
| CN114409839B (en) * | 2022-01-27 | 2023-12-19 | 万华化学集团股份有限公司 | SAN resin and preparation method thereof |
Also Published As
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| CN104610694B (en) | 2017-10-10 |
| CN103183893B (en) | 2015-03-18 |
| TW201326218A (en) | 2013-07-01 |
| CN104610694A (en) | 2015-05-13 |
| TWI432461B (en) | 2014-04-01 |
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