CN103183893B - 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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- CN103183893B CN103183893B CN201210122736.7A CN201210122736A CN103183893B CN 103183893 B CN103183893 B CN 103183893B CN 201210122736 A CN201210122736 A CN 201210122736A CN 103183893 B CN103183893 B CN 103183893B
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- styrene
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- 239000011342 resin composition Substances 0.000 title claims abstract description 89
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title abstract description 198
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920001971 elastomer Polymers 0.000 claims abstract description 119
- 239000005060 rubber Substances 0.000 claims abstract description 117
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims description 58
- 239000002994 raw material Substances 0.000 claims description 47
- 239000011541 reaction mixture Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 25
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 17
- 230000008676 import Effects 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 abstract description 92
- 229920001577 copolymer Polymers 0.000 abstract description 83
- 239000000203 mixture Substances 0.000 abstract description 14
- 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 14
- 230000000052 comparative effect Effects 0.000 description 13
- -1 polysiloxane Polymers 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000007858 starting material Substances 0.000 description 12
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 239000012986 chain transfer agent Substances 0.000 description 11
- 150000001993 dienes Chemical class 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
- 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
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 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
- 230000000996 additive effect Effects 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
- 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
- 230000001186 cumulative effect Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000126 substance Substances 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
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-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
- 238000007493 shaping process 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
- 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
- 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
- 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
- 238000000465 moulding Methods 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
- 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 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
- 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
- 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
- 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
- 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
- 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 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
- VNPPYKVXEQNADX-UHFFFAOYSA-N C(C)(C)C=1C(=O)NC(C1)=O.C[N]N1C(C=CC1=O)=O.[N] Chemical compound C(C)(C)C=1C(=O)NC(C1)=O.C[N]N1C(C=CC1=O)=O.[N] VNPPYKVXEQNADX-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
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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
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
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- 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
- 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
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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
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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 comprising the rubber particles of multipolymer and coated styrene based copolymer.
Background technology
Generally have the phenylethylene resin series of high-impact, because all there is good evaluation its processing forming, mechanicalness aspect, and the products formed formed by it has good appearance and glossiness, is then widely used on electronics, electrical appliance and auto parts.But for the phenylethylene resin series with high-impact, in order to be applied to widely on field, often to its glossiness and shock-resistance more very requirement.
Generally there is high impact styrene resin be made up of rubber particles and vinylbenzene main body, and this rubber particles can be divided into the rubber particles of the rubber particles of coated styrol copolymer and not coated styrol copolymer.In the styrene resin of rubber particles comprising not coated styrol copolymer, the weight average particle diameter of its rubber particles is less, makes phenylethylene resin series have higher gloss degree and the characteristic compared with high-impact.And comprising in the styrene resin of the rubber particles of coated styrol copolymer, the weight average particle diameter of its rubber particles is comparatively large and size distribution is uneven, makes the glossiness of phenylethylene resin series and shock-resistance not good, cannot meet the demand of user.
In addition, the styrene resin that current preparation comprises the rubber particles of not coated styrol copolymer mostly adopts the mode of emulsion polymerization, but 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 meet environmental protection requirement under, the method that preparation has the phenylethylene resin series of high-impact changes totally (bulk) polymerization methods or solution (solution) polymerization methods into by emulsion polymerization mode, but Bulk polymerization mode or the phenylethylene resin series obtained by solution polymerization mode are the above-mentioned styrene resin comprising the rubber particles of coated styrol copolymer, the product demand of industry is not met yet.
Therefore, how under the consideration based on environmental protection processing procedure, the phenylethylene resin series that development one has high glossiness and shock-resistance becomes the anxious problem for solving of affiliated art.
Summary of the invention
The first object of the present invention is to provide a kind of method preparing styrene-series resin compositions.
The present invention prepares the method for styrene-series resin compositions, comprises following steps:
The first starting raw material is made to carry out continuous solution polymerization reaction, form the first reaction mixture, and this first initial raw material packet is containing rubber components, the monomer component comprising styrenic monomers and solvent, and this rubber components comprises the first rubber components and the second rubber components;
Make the second starting raw material carry out continuous solution polymerization reaction, form the second reaction mixture, and this second starting raw material comprises the monomer component and solvent that comprise styrenic monomers; Then,
By the first reaction mixture and the second reaction mixture, and carry out continuous solution polymerization reaction, this styrene-series resin compositions can be obtained.
The present invention prepares the method for styrene-series resin compositions, and wherein this rubber components comprises first rubber components of 80 % by weight ~ 99 % by weight and second rubber components of 1 % by weight ~ 20 % by weight.
The present invention prepares the method for styrene-series resin compositions, and wherein this first starting raw material continuous print imports the first reactor R1 and carries out polyreaction, after reaction to be polymerized, forms the first reaction mixture, and imports the second reactor R2; Second starting raw material continuous print imports the 6th reactor R6, after reaction to be polymerized, forms the second reaction mixture, and imports this second reactor R2, and with this first reaction mixture, and this second reactor R2 produce Phase Inversion.
The present invention prepares the method for styrene-series resin compositions, and the solids content limits of the first reaction mixture wherein after this first initial raw material reaction is 10 % by weight ~ 30 % by weight; This second starting raw material in the solids content limits of reacted second reaction mixture of the 6th reactor R6 be 30 % by weight ~ 60 % by weight.
The present invention prepares the method for styrene-series resin compositions, wherein the first initial raw material packet containing 5 % by weight ~ 20 % by weight rubber components, 55 % by weight ~ 90 % by weight and comprise the monomer component of styrenic monomers, and the solvent of 5 % by weight ~ 25 % by weight; Second starting raw material comprises 75 % by weight ~ 99 % by weight and comprises the monomer component of styrenic monomers, and the solvent of 1 % by weight ~ 25 % by weight.
The second object of the present invention is providing a kind of styrene-series resin compositions.
Styrene-series resin compositions of the present invention is by obtained by method as above.
Especially, present inventor is by above-mentioned preparation method, active research and develop different styrene-series resin compositions, contributes to the glossiness and the shock-resistance that promote styrene-series resin compositions, and can meet the demand of industry for styrene-series resin compositions.
The third object of the present invention is providing a kind of styrene-series resin compositions with better glossiness and shock-resistance, comprises:
As the multipolymer of external phase, this multipolymer comprises styrenic monomer unit; And the rubber particles of coated styrene based copolymer as disperse phase;
In the rubber particles of this coated styrene based copolymer, collect the rubber particles that n particle diameter is greater than the coated styrene based copolymer of 0.4 μm, and by following two formulae discovery central value B and mean value C:
This central value
ai represents that i-th particle diameter is greater than in the rubber particles of coated styrene based copolymer of 0.4 μm, and 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 for being less than 15%.
Styrene-series resin compositions of the present invention, wherein the scope of C/B is for being less than 13%.
Styrene-series resin compositions of the present invention, wherein the scope of C/B is for being less than 11%.
Styrene-series resin compositions of the present invention, wherein the scope of this central value B is for being less than 0.29 μm.
The fourth object of the present invention is at the products formed providing a kind of styrene-series resin compositions.
The products formed of styrene-series resin compositions of the present invention formed by styrene-series resin compositions as above.
Beneficial effect of the present invention is: adjusted by the particle diameter of the styrene based copolymer in the rubber particles of coated styrene based copolymer, making the scope of C/B for being less than 15%, then making this styrene-series resin compositions have better glossiness and shock-resistance.
Accompanying drawing explanation
Fig. 1 is a schematic diagram, illustrates that present pre-ferred embodiments styrene-series resin compositions enlargement ratio is the structure kenel of 25,000 times;
Fig. 2 is a schematic diagram, illustrates that the styrene-series resin compositions enlargement ratio of comparative example 1 of the present invention is the structure kenel of 25,000 times; And
Fig. 3 is a schematic diagram, illustrates that the styrene-series resin compositions enlargement ratio of comparative example 2 of the present invention is the structure kenel of 25,000 times.
Embodiment
The preparation > of < styrene-series resin compositions
In 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:
The first starting raw material is made to carry out continuous solution polymerization reaction, form the first reaction mixture, and this first initial raw material packet is containing rubber components, the monomer component comprising styrenic monomers and solvent, and this rubber components comprises the first rubber components and the second rubber components;
Make the second starting raw material carry out continuous solution polymerization reaction, form the second reaction mixture, and this second starting raw material comprises the monomer component and solvent that comprise styrenic monomers; Then,
By the first reaction mixture and the second reaction mixture, and carry out continuous solution polymerization reaction, this styrene-series resin compositions can be obtained.
Carry out the reactor of this continuous solution polymerization reaction including but not limited to column flow reactor (plug flow reactor, be called for short PFR), complete mix flow (continuous stirred-tank reactor, be called for short CSTR), or contain the reactor (Static reactor) etc. of silent oscillation mixing tank.This reactor quantity can and with two or more, be preferably more than three or three.When using multiple reactor, these reactors can adopt the mode of serial or parallel connection, and are good in the mode that a reactor and other reactors are arranged in parallel.These reactors are good with column flow reactor.
Preferably, the reactor carrying out this continuous solution polymerization reaction comprises the first reactor R1 and the second reactor R2 that are sequentially connected in series, and in parallel with this first reactor R1 and there is the 6th reactor R6 of an outlet, the outlet of the 6th reactor R6 is connected to this second reactor R2.The temperature of reaction of these reactors is not particularly limited, and determines respectively according to the solids content of each reactor when the polyreaction.The range of reaction temperature of these reactors is 70 DEG C ~ 230 DEG C.
In detail, in the step that this continuous solution polymerization reacts, this first starting raw material continuous print imports the first reactor R1 and carries out polyreaction, after reaction to be polymerized, forms the first reaction mixture, and imports the second reactor R2; Second starting raw material continuous print imports the 6th reactor R6, after reaction to be polymerized, forms the second reaction mixture, and imports this second reactor R2, and with this first reaction mixture, and second reactor R2 produce Phase Inversion.Optionally further, react in the second reactor R2, form the 3rd reaction mixture, then import in the 3rd reactor R3, the 4th reactor R4 and the 5th reactor R5 and carry out polyreaction again.
In concrete example of the present invention, the reactor carrying 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 are sequentially connected in series, and in parallel with this first reactor R1 and there is the 6th reactor R6 of an outlet, the outlet of the 6th reactor R6 is connected to this second reactor R2.
After the turnover ratio that the polyreaction in these reactors reaches required, again this reacted solution is taken out continuously by reactive system, and import a Devolatilization device further, by the volatile component removing that this Devolatilization device will produce after unreacted starting raw material and reaction, styrene-series resin compositions of the present invention can be obtained, or give granulation more further.
General Devolatilization device can use decompression degassing vessel device, or extrudes de-gassing vessel.The unreacted starting raw material removed by this Devolatilization device or volatile component selectively reclaim with condenser again, by after the moisture removing in Ethylene recov, again can use as starting raw material if desired.This Devolatilization device such as can be single shaft with the forcing machine of devolatilization mouth, twin shaft with forcing machine, the thin-film evaporator (thin film) of devolatilization mouth, or with the devolatilization groove of vaccum-pumping equipment.Devolatilization auxiliary agent can be added according to need in forcing machine in devolatilization processes.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 screw speed scope is 120rpm ~ 350rpm.For the present invention, the forcing machine that this Devolatilization device has devolatilization mouth with twin shaft is good.Above-mentioned Devolatilization device can be connected one or more use, and its temperature controls, at 180 DEG C ~ 350 DEG C, to be preferably 200 DEG C ~ 320 DEG C, be more preferred from 220 DEG C ~ 300 DEG C, and the vacuum degree control of Devolatilization device is at below 300Torr, be preferably below 200Torr, be more preferred from below 100Torr.
This first initial raw material packet containing 5 % by weight ~ 20 % by weight rubber components, 55 % by weight ~ 90 % by weight and comprise the monomer component of styrenic monomers, and the solvent of 5 % by weight ~ 25 % by weight; This second starting raw material comprises 75 % by weight ~ 99 % by weight and comprises the monomer component of styrenic monomers, and the solvent of 1 % by weight ~ 25 % by weight.In the reaction of this continuous solution polymerization, optionally can add polymerization starter or chain-transfer agent etc. in the first starting raw material or the second starting raw material.
This rubber components is including but not limited to diene series rubber, polyolerin elastomer, polyacrylic ester system rubber, 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 by diene monomer (or diene monomer and other monomers) is after being polymerized, and its second-order transition temperature is below 0 DEG C.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 diene ter-polymers rubber (ethylene propylene diene terpolymer is called for short EPDM), styrenic-diene system rubber, vinyl cyanide-diene series rubber etc.The divinyl rubber of this divinyl rubber including but not limited to high-cis (Hi-Cis) content and the divinyl rubber of low cis (Low-Cis) content.The typical weight of the cis (Cis) in the divinyl rubber of this high cis-contents/vinyl (Vinyl) consists of (94 ~ 99wt%)/(0 ~ 5wt%), all the other compositions are then 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 is at (20 ~ 40wt%)/(6 ~ 20wt%), all the other are transconfiguration, and mooney viscosity is between 20 ~ 120, and molecular weight ranges is with 100,000 ~ 800,000 is good.
This styrenic-diene system rubber is including but not limited to styrene butadiene rubbers, styrene isoprene rubber etc.The mooney viscosity of this styrenic-diene system rubber is 20 ~ 80, and soltion viscosity is 3cps ~ 200cps (being recorded by the styrene solution of concentration 5 % by weight at 25 DEG C).In this styrenic-diene system rubber 1,2-vinyl (1,2-vinyl) content range of monomeric unit is 8 % by weight ~ 40 % by weight, and be 100 % by weight with styrenic-diene system rubber total amount, the content range of this styrenic monomer units is 5 % by weight ~ 35 % by weight, and the weight average molecular weight scope of this styrenic-diene system 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 construct (taper structure), aligned structure, difference structure, or the combination construction of these structures.Such as, the styrenic-diene system rubber of this homopolymer block structure is including but not limited to styrene-butadiene-styrene block (S-B-S).The styrenic-diene system 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).Cumulative or the styrenic-diene system rubber that decrescence constructs of this composition is cumulative or the decrescence cumulative or decrescence phenylethylene/butadiene-styrene block (B-taper S/B-S) of phenylethylene/butadiene-styrene block (S-taper S/B-S), divinyl-form including but not limited to vinylbenzene-form.
This styrenic monomers can be used alone or as a mixture, and this styrenic monomers is including but not limited to vinylbenzene, alpha-methyl styrene, p-methylstyrene, m-vinyl toluene, o-vinyl toluene, ethyl styrene, 2,4-dimethyl styrene, p-t-butyl styrene, Alpha-Methyl-p-methylstyrene, bromo-vinylbenzene, two bromo-vinylbenzene, 2,4,6-phenylstilbene bromide etc.
This monomer component also comprises other copolymerizable monomer, and preferably, the usage quantity based on this monomer component is 100 % by weight, and the usage quantity scope of these other copolymerizable monomer is 5 % by weight ~ 50 % by 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, methacrylic monomers, acrylic ester monomer, methacrylate ester monomer, maleimide system monomer, Maleic Acid, Anhydrous (maleic acid), anhydrous methyl maleic acid (cis-methylbutenedioic acid), anhydrous methyl FUMARIC ACID TECH GRADE (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 methacrylic monomers is including but not limited to methacrylic acid etc.This methacrylate ester monomer is including but not limited to methyl methacrylate, β-dimethyl-aminoethylmethacrylate etc.This maleimide system monomer is including but not limited to maleimide, nitrogen-methylmaleimido, nitrogen-isopropylmaleimide, nitrogen-butyl maleimide, nitrogen-hexyl maleimide, nitrogen-octyl group maleimide, nitrogen-dodecyl maleimide, nitrogen-N-cyclohexylmaleimide, nitrogen-phenyl maleimide, bismaleimides system monomer etc.
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 concrete example of the present invention, this rubber components comprises first rubber components of 80 % by weight ~ 99 % by weight and second rubber components of 1 % by weight ~ 20 % by weight.
Preferably, this first rubber components comprises the aligned structure styrene butadiene rubbers of 5 % by weight ~ 20 % by weight and the difference structure styrene butadiene rubbers of 80 % by weight ~ 95 % by weight; This second rubber components comprises the aligned structure styrene butadiene rubbers of 50 % by weight ~ 70 % by weight and the difference structure styrene butadiene rubbers of 30 % by weight ~ 50 % by weight.
The mooney viscosity of the styrene butadiene rubbers in this first rubber components is 20 ~ 70, and soltion viscosity is 10cps ~ 50cps (being recorded by the styrene solution of concentration 5 % by weight at 25 DEG C).The content range of 1,2-vinyl monomer unit in this styrene butadiene rubbers is 8 % by weight ~ 30 % by 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 (being recorded by the styrene solution of concentration 5 % by weight at 25 DEG C).The content range of 1,2-vinyl monomer unit in this styrene butadiene rubbers is 8 % by weight ~ 25 % by weight, and the weight average molecular weight scope of this styrene butadiene rubbers is 400,000 ~ 800,000.
This first starting raw material in the solids content limits of reacted first reaction mixture of the first reactor R1 be 10 % by weight ~ 30 % by weight; Preferably, this solids content limits is 12 % by weight ~ 25 % by weight; More preferably, this solids content limits is 15 % by weight ~ 20 % by weight.
This second starting raw material in the solids content limits of reacted second reaction mixture of the 6th reactor R6 be 30 % by weight ~ 60 % by weight; Preferably, this solids content limits is 40 % by weight ~ 60 % by weight; More preferably, this solids content limits is 45 % by weight ~ 55 % by weight.
The solids content limits of the 3rd reaction mixture is 20 % by weight ~ 35 % by weight; Preferably, this solids content limits is 23 % by weight ~ 33 % by weight; More preferably, this solids content limits is 25 % by weight ~ 32 % by weight.
After the 5th reactor R5 mixes, carry out follow-up polyreaction, the solids content limits of its reacted reaction mixture is 25 % by weight ~ 55 % by weight; Preferably, this solids content limits is 30 % by weight ~ 50 % by weight; More preferably, this solids content limits is 35 % by weight ~ 45 % by weight.
This polymerization starter is selected certainly in mono-functional's polymerization starter, multi-functional polymerization starter, or their combination.This mono-functional's polymerization starter can be used alone or as a mixture, and this mono-functional's 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), t-butylperoxyisopropyl carbonic ether (tert-butyl peroxy isopropyl carbonate, be called for short BPIC), cyclohexanone peroxide (cyclohexanone peroxide), 2, 2 '-azo-bis--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-bis--2-methylbutyronitrile (2, 2 '-azo-bis-2-methyl butyronitrile) etc.Wherein better 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)-hexane [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-bis--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, such as U.S. ATOFINA Inc., trade(brand)name Luperox JWE B-50) etc.Preferably, the total amount based on starting raw material is 100 parts by weight, and 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 mono-functional's chain-transfer agent, multi-functional chain-transfer agent, or their combination.This mono-functional's chain-transfer agent can be used alone or as a mixture, and this mono-functional's chain-transfer agent is including but not limited to (1) mercaptan (mercaptan) class: methyl mercaptan, n-butyl mercaptan, cyclohexanethiol, n-lauryl mercaptan (n-dodecyl mercaptan, be called for short NDM), stearyl-mercaptan (stearyl mercaptan), uncle-lauryl mercaptan (t-dodecyl mercaptan, be called for short TDM), n-propyl group mercaptan, n-octyl mercaptan, uncle-octyl mercaptan, uncle-nonyl mercaptan etc.; (2) alkanamine (alkylamine s) class: MEA, diethylamide, triethylamine, single isopropylamine, diisopropylamine, monobutyl amine, di-n-butyl amine, three-n-butylamine etc.; (3) other; Pentaphenylethane (penta phenylethane), α-methylstyrenedimer (α-methylstyrene dimer), terpinolene (terpinolene) etc.Wherein better with n-lauryl mercaptan, uncle-lauryl mercaptan.
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), be called for short TMPT], three-(6-mercaptohexanoic acid) trishydroxymethyl propyl ester [trimethylol-propane tris (6-mercapto hexanate)] etc.Wherein better with three-(3-thiohydracrylic acid) trishydroxymethyl propyl ester.Preferably, the total amount based on starting raw material is 100 parts by weight, and 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 effect not undermining styrene-series resin compositions of the present invention, in preparation styrene-series resin compositions process of the present invention, various additive can be added if desired.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 respectively in the reaction of above-mentioned continuous solution polymerization or add after polyreaction.Above-mentioned additive can the ester system plasticizer of such as mineral oil, butyl stearate, Polyester plasticizer, organopolysiloxane (as polydimethylsiloxane), higher fatty acid and metal-salt, bulky amine system antioxidant (hindered amine), glass fibre etc.The total amount of styrene-based resin composition is 100 parts by weight, and the usage quantity scope of this Polyester plasticizer or mineral oil is respectively 0 weight part ~ 5 weight part.Preferably, the usage quantity scope of this Polyester plasticizer or mineral oil is respectively 0.05 weight part ~ 2 weight part.The total amount of styrene-based resin composition is 100 parts by weight, 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 effect not undermining styrene-series resin compositions of the present invention, in preparation styrene-series resin compositions process of the present invention, various polymkeric substance can be mixed if desired.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 copolymer, polystyrene-(methyl) acrylic ester-Maleimide copolymer, (methyl) acrylic ester-Maleimide copolymer, or through the aforementioned copolymer of diene series rubber upgrading (or grafting upgrading).Total amount based on this styrene-series resin compositions is 100 parts by weight, and the usage quantity scope of this polymkeric substance is below 200 weight parts.Its adjustable or the thermotolerance of this styrene-series resin compositions of improving, rigidity or flow processability.
Styrene-series resin compositions of the present invention, obtained by method as above.
Especially, present inventor is by above-mentioned preparation method, active research and develop different styrene-series resin compositions, contributes to the glossiness and the shock-resistance that promote styrene-series resin compositions, and can meet the demand for styrene-series resin compositions of industry.
< styrene-series resin compositions >
The rubber particles of the coated styrene based copolymer in this styrene-series resin compositions comprises one or more styrene based copolymers, the rubber body of coated styrene based copolymer and the graft copolymer that grafts in rubber body.This styrene based copolymer and graft copolymer formed through polyreaction by the monomer component comprising styrenic monomers respectively.This rubber body formed by rubber components.The rubber particles particle diameter of this coated styrene based copolymer is bimodal distribution, and a weight average particle diameter scope is at 0.4 μm ~ 1.2 μm, and another weight average particle diameter scope is at 4 μm ~ 9 μm.
Styrene-series resin compositions of the present invention comprises the multipolymer as external phase, and this multipolymer comprises styrenic monomer unit; And the rubber particles of coated styrene based copolymer as disperse phase;
In the rubber particles of this coated styrene based copolymer, collect the rubber particles that n particle diameter is greater than the coated styrene based copolymer of 0.4 μm, and by following two formulae discovery central value B and mean value C:
This central value
ai represents that i-th particle diameter is greater than in the rubber particles of coated styrene based copolymer of 0.4 μm, and 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 for being less than 15%.
When the scope of this C/B is more than 15%, represent the styrene based copolymer of greater particle size in the rubber particles of each coated styrene based copolymer with more compared with the styrene based copolymer of small particle size, namely the uniform particle sizes degree of styrene based copolymer is not good, and the size of this styrene based copolymer is more unequal, the glossiness of styrene-series resin compositions and shock-resistance can be made not good.When the scope of this C/B is for being less than 15%, represent the styrene based copolymer of greater particle size in the rubber particles of each coated styrene based copolymer with less compared with the styrene based copolymer of small particle size, namely the size of styrene based copolymer is more homogeneous, and styrene-series resin compositions can be made to have preferably glossiness and shock-resistance.Preferably, the scope of this C/B is for being less than 13%.More preferably, the scope of this C/B is for being less than 11%.
In styrene-series resin compositions of the present invention, particle diameter is greater than the measuring method of the rubber particles of the coated styrene based copolymer of 0.4 μm, is with perosmic anhydride (OsO
4) by after styrene-series resin compositions dyeing, take a picture with transmission electron microscope again, and amplify 25,000 times, in photograph the rubber particles of coated styrene based copolymer that shines carry out grain diameter measurement, the rubber particles that particle diameter is greater than the coated styrene based copolymer of 0.4 μm can be obtained.And in the rubber particles of coated styrene based copolymer greater particle size styrene based copolymer with compared with the measuring method of the poor Ai of the particle diameter of the styrene based copolymer of small particle size, by above-mentioned 25, the photograph of 000 multiplying power obtains the image of styrene based copolymer with image processing technique, then measures the size of styrene based copolymer with the Analy SIS software of Soft Imaging System company.
This central value B or mean value C is larger, represent that the size of the styrene based copolymer in the rubber particles of coated styrene based copolymer is more unequal, and the size of styrene based copolymer in the rubber particles of the coated styrene based copolymer of the less expression of this central value B or mean value C is average.For styrene-series resin compositions can be made to have preferably glossiness and shock-resistance, preferably, the scope of this central value B is for being less than 0.29 μm; More preferably, the scope of this central value B is for being less than 0.28 μm.
The central value B of styrene-series resin compositions of the present invention, mean value C can by the arrangement mode of reactor multiple when being polymerized with the ratio of this central value B, reactor mixing speed, reactor size and other polymerizing conditions are reached, other polymerizing conditions are such as: polymeric reaction temperature, the use contamination of polymerization starter, the solids content of the reaction mixture after each reactor reaction, and the kind etc. of rubber components adjusts in starting raw material, and particularly reactor arrangement, in the size of reactor and starting raw material, the kind of rubber components more easily affects the ratio of mean value C and this central value B.
The weight average molecular weight of the multipolymer in styrene-series resin compositions of the present invention is not particularly limited, 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 % by weight ~ 95 % by weight; And the rubber particles of the coated styrene based copolymer of 5 % by weight ~ 40 % by weight.More preferably, this styrene-series resin compositions comprises the multipolymer of 70 % by weight ~ 90 % by weight; And the rubber particles of the coated styrene based copolymer of 10 % by weight ~ 30 % by weight.Again more preferably, this styrene-series resin compositions comprises the multipolymer of 75 % by weight ~ 88 % by weight; And the rubber particles of the coated styrene based copolymer of 12 % by weight ~ 25 % by weight.
The products formed of styrene-series resin compositions of the present invention, formed by styrene-series resin compositions as above.Its formation method can adopt the mode of mixing, machine-shaping mode, or their combination.
This mode of mixing is by Brabender plastograph, Ban Baili muller, kneading-mixing machine, roller press or single shaft or biaxial extruder.Usually after being mixed by these forcing machines, then cooled giving as security the extrudate made, be granulated.The operating temperature range of this mode of mixing is 160 DEG C ~ 280 DEG C, and preferably, operating temperature range is 180 DEG C ~ 250 DEG C.This machine-shaping mode can use ejection formation, compressed moulding, extrusion moulding, blow and prolong shaping, thermoforming, vacuum forming and slush molding.
The present invention will be described further with regard to following examples, but it is to be understood that these embodiments are only and illustrate use, and should not be interpreted as restriction of the invention process.
< embodiment >
During the invention process, in embodiment 1 ~ 3, the array mode of reactor is for be connected in series the first reactor R1 (volume 30 liters), the second reactor R2 (volume 10 liters), the 3rd reactor R3 (volume 30 liters), the 4th reactor R4 (volume 100 liters) and the 5th reactor R5 (volume 100 liters), and the six reactor R6 in parallel with this first reactor R1 (volume 100 liters), and the outlet of the 6th reactor R6 is connected to the top of this second reactor R2.These reactors are all column flow reactor.The temperature of reaction of these reactors is the mean value of each reactor inlet region and exit region.< embodiment 1> styrene-series resin compositions
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 DEG C, 102 DEG C, 102 DEG C, 100 DEG C, 100 DEG C and 120 DEG C.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 containing 10.5 % by weight rubber components, 76.5 % by weight vinylbenzene, 13 % by weight ethylbenzene, 900ppm 1,1-two-the n-lauryl mercaptan of tert-butyl hydroperoxide hexanaphthene and 1000ppm.This rubber components comprises the first rubber components and 5 % by weight the second rubber components of 95 % by weight.This second starting raw material comprises the styrenic monomers of 87 % by weight and the ethylbenzene of 13 % by weight.
This first rubber components comprises the aligned structure styrene butadiene rubbers of 13 % by weight and the difference structure styrene butadiene rubbers of 87 % by weight.The mooney viscosity of this styrene butadiene rubbers is 45, and soltion viscosity is 35cps (being recorded by the styrene solution of concentration 5 % by weight at 25 DEG C).The content range of 1,2-vinyl monomer unit in this styrene butadiene rubbers is 18 % by 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 % by weight and the difference structure styrene butadiene rubbers of 42 % by weight.The mooney viscosity of this styrene butadiene rubbers is 55, and soltion viscosity is 170cps (being recorded by the styrene solution of concentration 5 % by weight at 25 DEG C).The content range of 1,2-vinyl monomer unit in this styrene butadiene rubbers is 12 % by 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 the flow of 38 public ls/h and carries out polyreaction, after reaction to be polymerized, form the first reaction mixture, and import the second reactor R2, and the solids content of this first reaction mixture is 16.6 % by weight.
Second starting raw material is imported the 6th reactor R6 continuously with the flow of 18 public ls/h and carries out polyreaction, after reaction to be polymerized, form the second reaction mixture, and import this second reactor R2, and the solids content of this second reaction mixture is 48 % by weight.
First reaction mixture mixed with this second reaction mixture in the second reactor R2 and proceeds polyreaction, then importing after question response in 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 % by weight, and in the solids content of the reacted reaction mixture of the 5th reactor R5 be 40.5 % by weight.Through Devolatilization device, the low volatiles such as unreacted monomer, solvent are removed, styrene-series resin compositions of the present invention can be obtained.This starting raw material kind, usage quantity and polymerizing condition are in table 1, and evaluation result is in table 2.
The another particle diameter according to 15th page, specification sheets of the present invention is greater than the measuring method of the rubber particles of the coated styrene based copolymer of 0.4 μm, can obtain the structure kenel as Fig. 1, and calculate particle diameter difference Ai, central value B and mean value C, result is as table 2 simultaneously.
[embodiment 2 ~ 3]
Embodiment 2 ~ 3 is that different places is with the step identical with embodiment 1 to prepare this styrene-series resin compositions: change starting raw material kind, usage quantity and polymerizing condition.This starting raw material kind, usage quantity and polymerizing condition are in table 1, and evaluation result is in table 2.
[comparative example 1]
The array mode of these reactors is the first reactor R1 (volume 100 liters), the second reactor R2 (volume 100 liters), the 3rd reactor R3 (volume 100 liters) and the 4th reactor R4 (volume 100 liters) are connected.These reactors are all column flow reactor.The temperature of reaction of these reactors is the mean value of each reactor inlet region 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 DEG C, 105 DEG C, 115 DEG C and 125 DEG C.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 containing 7 % by weight rubber components, 87 % by weight vinylbenzene, 6 % by weight ethylbenzene, 1000ppm 1,1-two-the n-lauryl mercaptan of tert-butyl hydroperoxide hexanaphthene and 500ppm.This rubber components comprises the first rubber components and 6 % by weight the second rubber components of 94 % by weight.
This first rubber components comprises the aligned structure styrene butadiene rubbers of 13 % by weight and the difference structure styrene butadiene rubbers of 87 % by weight.The mooney viscosity of this styrene butadiene rubbers is 45, and soltion viscosity is 35cps (being recorded by the styrene solution of concentration 5 % by weight at 25 DEG C).The content range of 1,2-vinyl monomer unit in this styrene butadiene rubbers is 18 % by 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 % by weight and the difference structure styrene butadiene rubbers of 42 % by weight.The mooney viscosity of this styrene butadiene rubbers is 55, and soltion viscosity is 170cps (being recorded by the styrene solution of concentration 5 % by weight at 25 DEG C).The content range of 1,2-vinyl monomer unit in this styrene butadiene rubbers is 12 % by 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 the flow of 53 public ls/h and carries out polyreaction, after reaction to be polymerized, form the first reaction mixture, and sequentially import the second reactor R2, the 3rd reactor R3 and the 4th reactor R4, wherein, the solids content of this first reaction mixture is 18 % by weight, in the solids content of the reacted reaction mixture of the second reactor R2 be 37 % by weight, and in the solids content of the reacted reaction mixture of the 4th reactor R4 be 35 % by weight.Through Devolatilization device, the low volatiles such as unreacted monomer, solvent are removed, styrene-series resin compositions of the present invention can be obtained.This starting raw material kind, usage quantity and polymerizing condition are in table 1, and evaluation result is in table 2.
The another particle diameter according to 15th page, specification sheets of the present invention is greater than the measuring method of the rubber particles of the coated styrene based copolymer of 0.4 μm, can obtain the structure kenel as Fig. 2, and calculate particle diameter difference Ai, central value B and mean value C, result is as table 2 simultaneously.
[comparative example 2]
Styrene-series resin compositions by Japanese Asahi Kasei Corporation system, model 403R.Its preparation method adopts continuous solution polymerization reaction obtained, and its evaluation result is in table 2.
The another particle diameter according to 15th page, specification sheets of the present invention is greater than the measuring method of the rubber particles of the coated styrene based copolymer of 0.4 μm, can obtain the structure kenel as Fig. 3, and calculate particle diameter difference Ai, central value B and mean value C, result is as table 2 simultaneously.
[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 the standard method (23 DEG C of foundation ASTM D-256, attached 1/4 inch test film jaggy) preparation standard test piece, then the regulation according to ASTM D-256 is tested, unit: Kg-cm/cm.
2. the assay of external phase and disperse phase in styrene-series resin compositions:
After the styrene-series resin compositions of embodiment 1 ~ 3 and comparative example 1 ~ 2 is dissolved with tetrahydrofuran (THF) (tetra hydrofuran), with fourier-transform infrared line spectrometer (Fourier Transform Infrared Spectrometer after membrane, Nicolet Inc., model Nexus 470) test, unit: % by weight.
3. fusing coefficient (represents mobility, melt index, 200 DEG C, 5kg; Be called for short MI) evaluating and measuring:
The styrene-series resin compositions of embodiment 1 ~ 3 and comparative example 1 ~ 2 is tested according to ASTM standard D-1238 method, unit: g/10 minute.
4. tensile strength (Tsy) evaluating and measuring:
Tested according to AS TM D-638 regulation by the styrene-series resin compositions of embodiment 1 ~ 3 and comparative example 1 ~ 2, with 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 DEG C " (3.17mm); the disk test piece of diameter 5.5cm; and analyze with BYK Micro-TRI (60 degree of angles); and record according to ASTM D-2457 method, unit: %.
Table 1
"--" expression is not added or does not use.Polymerization starter: 1,1-pair-tert-butyl hydroperoxide hexanaphthene; Chain-transfer agent: n-lauryl mercaptan.
Table 2
Learnt by comparative example 1, in the rubber particles of the coated 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 μm, and mean value C is 0.103 μm, and this C/B is 27.8%, represent that the styrene based copolymer of greater particle size in the rubber particles of each coated styrene based copolymer in comparative example 1 is with more compared with the styrene based copolymer of small particle size, namely the size uniformity coefficient of styrene based copolymer is not good, cause the glossiness of styrene-series resin compositions and shock-resistance not good.
Learnt by comparative example 2, in the rubber particles of the coated 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 μm, and mean value C is 0.050 μm, and this C/B is 18%, represent that the styrene based copolymer of greater particle size in the rubber particles of each coated styrene based copolymer in comparative example 2 is with more compared with the styrene based copolymer of small particle size, namely the size uniformity coefficient of styrene based copolymer is not good, cause the glossiness of styrene-series resin compositions and shock-resistance not good.
And learnt by embodiment 1 ~ 3, in the rubber particles of the coated styrene based copolymer of styrene-series resin compositions of the present invention, this C/B is 10.5% ~ 12.1%, represent that the styrene based copolymer of greater particle size in each rubber particles in embodiment 1 ~ 3 is with less compared with the styrene based copolymer of small particle size, namely the size uniformity coefficient of styrene based copolymer is good, makes styrene-series resin compositions have preferably glossiness and shock-resistance.By the above results, more prove that method for making of the present invention can effectively obtain the styrene-series resin compositions having good glossiness and shock-resistance concurrently.
In sum, adjusted by the particle diameter of the styrene based copolymer in the rubber particles of coated styrene based copolymer, making the scope of C/B for being less than 15%, then making this styrene-series resin compositions have high glossiness and high-impact, so really object of the present invention can be reached.
Claims (5)
1. prepare a method for styrene-series resin compositions, it is characterized in that comprising following steps:
The first starting raw material is made to carry out continuous solution polymerization reaction, form the first reaction mixture, and this first initial raw material packet is containing the rubber components, 55 % by weight ~ 90 % by weight and comprise the monomer component of styrenic monomers and the solvent of 5 % by weight ~ 25 % by weight of 5 % by weight ~ 20 % by weight, and this rubber components comprises the first rubber components and the second rubber components;
Make the second starting raw material carry out continuous solution polymerization reaction, form the second reaction mixture, and this second starting raw material comprises 75 % by weight ~ 99 % by weight and comprises the monomer component of styrenic monomers and the solvent of 1 % by weight ~ 25 % by weight; Then,
By this first reaction mixture and this second reaction mixture, and carry out continuous solution polymerization reaction, this styrene-series resin compositions can be obtained.
2. the method preparing styrene-series resin compositions according to claim 1, is characterized in that, this rubber components comprises first rubber components of 80 % by weight ~ 99 % by weight and second rubber components of 1 % by weight ~ 20 % by weight.
3. the method preparing styrene-series resin compositions according to claim 1, it is characterized in that, this first starting raw material continuous print imports the first reactor R1 and carries out polyreaction, after reaction to be polymerized, form the first reaction mixture, and import the second reactor R2; Second starting raw material continuous print import the 6th reactor R6, after reaction to be polymerized, form the second reaction mixture, and import this second reactor R2, and with this first reaction mixture, and this second reactor R2 produce Phase Inversion.
4. the method preparing styrene-series resin compositions according to claim 1, is characterized in that, the solids content limits of the first reaction mixture after this first initial raw material reaction is 10 % by weight ~ 30 % by weight; This second starting raw material in the solids content limits of reacted second reaction mixture of the 6th reactor R6 be 30 % by weight ~ 60 % by weight.
5. a styrene-series resin compositions, is characterized in that, obtained by the method according to any one of Claims 1-4 item.
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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 |
| 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 |
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 |
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| KR101027307B1 (en) * | 2003-02-05 | 2011-04-06 | 다우 글로벌 테크놀로지스 엘엘씨 | High gloss rubber modified monovinylidene aromatic polymers 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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| 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 |
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| CN104610694A (en) | 2015-05-13 |
| CN103183893A (en) | 2013-07-03 |
| CN104610694B (en) | 2017-10-10 |
| TWI432461B (en) | 2014-04-01 |
| TW201326218A (en) | 2013-07-01 |
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