CN103183880B - Styrene-acrylonitrile-diene copolymer composition and molded article using same - Google Patents
Styrene-acrylonitrile-diene copolymer composition and molded article using same Download PDFInfo
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- CN103183880B CN103183880B CN201210071509.6A CN201210071509A CN103183880B CN 103183880 B CN103183880 B CN 103183880B CN 201210071509 A CN201210071509 A CN 201210071509A CN 103183880 B CN103183880 B CN 103183880B
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- styrene
- copolymer
- copolymer component
- acrylonitrile
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 187
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 150000002367 halogens Chemical class 0.000 claims abstract description 15
- 239000003063 flame retardant Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims description 84
- 239000000470 constituent Substances 0.000 claims description 77
- 229920001971 elastomer Polymers 0.000 claims description 66
- 239000005060 rubber Substances 0.000 claims description 66
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 55
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 55
- 239000002245 particle Substances 0.000 claims description 42
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 claims description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 27
- 229910001051 Magnalium Inorganic materials 0.000 claims description 23
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 23
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 17
- 150000001993 dienes Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 claims description 3
- QPMDWIOUHQWKHV-TYYBGVCCSA-M potassium;(e)-but-2-enedioate;hydron Chemical compound [H+].[K+].[O-]C(=O)\C=C\C([O-])=O QPMDWIOUHQWKHV-TYYBGVCCSA-M 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 2
- PKZGKWFUCLURJO-GRHBHMESSA-L (z)-but-2-enedioate;dimethyltin(2+) Chemical compound C[Sn+2]C.[O-]C(=O)\C=C/C([O-])=O PKZGKWFUCLURJO-GRHBHMESSA-L 0.000 abstract 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 abstract 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- -1 polypropylene Polymers 0.000 description 16
- 239000012986 chain transfer agent Substances 0.000 description 15
- 239000007858 starting material Substances 0.000 description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 15
- 229920002554 vinyl polymer Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 13
- 238000005054 agglomeration Methods 0.000 description 12
- 230000002776 aggregation Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 229920000126 latex Polymers 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 150000003440 styrenes Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- 229920000578 graft copolymer Polymers 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 5
- 238000010556 emulsion polymerization method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229940096992 potassium oleate Drugs 0.000 description 5
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 5
- 238000005185 salting out Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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 2
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-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
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 238000001816 cooling Methods 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
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229940017705 formaldehyde sulfoxylate Drugs 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WPZJSWWEEJJSIZ-UHFFFAOYSA-N tetrabromobisphenol-F Natural products C1=C(Br)C(O)=C(Br)C=C1CC1=CC(Br)=C(O)C(Br)=C1 WPZJSWWEEJJSIZ-UHFFFAOYSA-N 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- JGYYEVYMHYLGII-UHFFFAOYSA-N 1,1,2,2,3,3-hexabromocyclododecane Chemical compound BrC1(C(C(CCCCCCCCC1)(Br)Br)(Br)Br)Br.BrC1(C(C(CCCCCCCCC1)(Br)Br)(Br)Br)Br JGYYEVYMHYLGII-UHFFFAOYSA-N 0.000 description 1
- NDRKXFLZSRHAJE-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4-tribromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=CC=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br NDRKXFLZSRHAJE-UHFFFAOYSA-N 0.000 description 1
- LJDGJCNHVGGOFW-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2-bromophenoxy)benzene Chemical compound BrC1=CC=CC=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br LJDGJCNHVGGOFW-UHFFFAOYSA-N 0.000 description 1
- KTHDEQBOHFRRBF-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-ethoxybenzene Chemical compound CCOC1=C(Br)C(Br)=C(Br)C(Br)=C1Br KTHDEQBOHFRRBF-UHFFFAOYSA-N 0.000 description 1
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-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
- YUAPUIKGYCAHGM-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromopropoxy)propane Chemical compound BrCC(Br)COCC(Br)CBr YUAPUIKGYCAHGM-UHFFFAOYSA-N 0.000 description 1
- BJQFWAQRPATHTR-UHFFFAOYSA-N 1,2-dichloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1Cl BJQFWAQRPATHTR-UHFFFAOYSA-N 0.000 description 1
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- TXFONIGDXLPYOB-UHFFFAOYSA-N 1,3,5-trichloro-2-ethenylbenzene Chemical compound ClC1=CC(Cl)=C(C=C)C(Cl)=C1 TXFONIGDXLPYOB-UHFFFAOYSA-N 0.000 description 1
- IZMZREOTRMMCCB-UHFFFAOYSA-N 1,4-dichloro-2-ethenylbenzene Chemical compound ClC1=CC=C(Cl)C(C=C)=C1 IZMZREOTRMMCCB-UHFFFAOYSA-N 0.000 description 1
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- GOKUDEWVRNZXDZ-UHFFFAOYSA-N 1-bromo-3-(3-bromopropoxy)propane Chemical compound BrCCCOCCCBr GOKUDEWVRNZXDZ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 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
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-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
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- MSXBEWYXWRVJPB-UHFFFAOYSA-N CN(C)CCOC(=O)C(C)=C.CN(C)CCC=C(C)C(O)=O Chemical compound CN(C)CCOC(=O)C(C)=C.CN(C)CCC=C(C)C(O)=O MSXBEWYXWRVJPB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 239000001836 Dioctyl sodium sulphosuccinate Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920003135 Eudragit® L 100-55 Polymers 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- MAYCNCJAIFGQIH-UHFFFAOYSA-N buta-1,3-diene 5-phenylpenta-2,4-dienenitrile Chemical compound C=CC=C.N#CC=CC=CC1=CC=CC=C1 MAYCNCJAIFGQIH-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GDCRSXZBSIRSFR-UHFFFAOYSA-N ethyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCOC(=O)C=C GDCRSXZBSIRSFR-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- QJQZEJFUIOWFMS-UHFFFAOYSA-N formaldehyde;sulfanediol Chemical compound O=C.OSO QJQZEJFUIOWFMS-UHFFFAOYSA-N 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Abstract
The present invention provides a styrene-acrylonitrile-diene copolymer composition comprising: 5 to 40 parts by weight of a copolymer mixture ; 5 to 30 parts by weight of a halogen flame retardant ; 1 to 10 parts by weight of an antimony-containing oxide ; 0.2 to 2.5 parts by weight of a dimethyltin maleate polymer ; 0.2 to 1.5 parts by weight of an aluminum magnesium composite metal salt ; and 60 to 95 parts by weight of a second styrene-acrylonitrile copolymer . The copolymer mixture is prepared by mixing a first copolymer component 1) A second copolymer component (A)2) And a third copolymer component (A)3) Is mixed with the copolymer component (b). The styrene-acrylonitrile-diene copolymer composition has better thermal stability, low-temperature impact strength and flame retardancy.
Description
Technical field
The present invention relates to a kind of material being applicable to the plastic molded article preparing electricmaterial, office equipment, trolley part, household supplies etc., particularly a kind of styrene-acrylonitrile-diene interpolymer constituent containing tin methide maleate polymer and magnalium composite metal salt.The present invention also provides a kind of products formed formed by this constituent.
Background technology
The composition contained by plastic molded article being generally used for electricmaterial or household supplies etc. is mostly rubber modified styrene series resin, polycarbonate resin (PolycarbonateResin) etc.This rubber modified styrene series resin, as styrene-acrylonitrile-butadiene resin (Acrylonitrile-Butadiene-Styrene Resin, be called for short ABS), there is high surface hardness, excellent in chemical resistance, electrical property good and be easy to the excellent specific property such as shaping, and be widely used gradually on various plastic molded article.
But, when this rubber modified styrene series resin is used in the environment needing to possess flame retardancy, because its flame retardancy matter is not good, the effect of difficult combustion cannot be reached.Although follow-up research promotes its flame retardancy by adding halogen fire retardant, but easily cause the thermostability of rubber modified styrene series resin not good, and the physical properties (as low temperature impact strength) of rubber modified styrene series resin can be affected, rubber modified styrene series resin is used in low temperature environment and easily produces the shortcomings such as brittle.Therefore, although prior art can promote the flame resistivity of rubber modified styrene series resin, also can have influence on the originally good physical properties of rubber modified styrene series resin simultaneously.
Be added in chloride resin [such as polyvinyl chloride (PVC) RESINS (PVC) or acrylic resin (polypropylene)] at present, the reagent improving the thermostability of resin is dibutyltin maleate polymkeric substance (polymer of dibutyltin maleate is called for short DBTM).But this dibutyltin maleate polymkeric substance easily resolves into dibutyl tin (dibutylTin is called for short DBT), and this dibutyl tin is for upsetting the material of biological internal secretion effect (endocrine disrupters is called for short Eds).Therefore, the material of control can be limited the quantity or even be forbidden to this dibutyltin maleate polymkeric substance in future, therefore the tool feature of environmental protection is looked for, and meet the specification of the relevant decree of carrying capacity of environment material control, and the thermo-stabilizer not damaging rubber modified styrene series resin physical properties is dealer pole problem to be broken through.
In view of above-mentioned, except effectively maintaining except flame retardancy matter, still need to develop a kind of rubber modified styrene series resin constituent, and it is after following process forms products formed, this products formed can be made to have better thermostability and low temperature impact strength, to meet industry demand.
Summary of the invention
The first object of the present invention is for providing a kind of styrene-acrylonitrile-diene interpolymer constituent simultaneously with preferably thermostability and flame retardancy.Styrene-acrylonitrile of the present invention-diene interpolymer constituent, comprises:
The copolymer mixture (A) of 5 weight part ~ 40 weight parts, by comprising the first copolymer component (A
1), the second copolymer component (A
2) and the 3rd copolymer component (A
3) copolymer component mixing formed; Described first copolymer component (A
1) and the second copolymer component (A
2) respectively obtained by rubber components and monomer component react through emulsion polymerization; Described 3rd copolymer component (A
3) by rubber components and monomer component obtained by the solution polymerization; Described rubber components comprises diene series rubber; Described monomer component comprises styrenic monomers and acrylic monomer;
The halogen fire retardant (B) of 5 weight part ~ 30 weight parts;
1 weight part ~ 10 weight part containing sb oxide (C);
The tin methide maleate polymer (D) of 0.2 weight part ~ 2.5 weight part;
The magnalium composite metal salt (E) of 0.2 weight part ~ 1.5 weight part; And
Second styrene-acrylonitrile system copolymerization (F) of 60 weight part ~ 95 weight parts.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, total amount based on described copolymer mixture (A) and described second styrene-acrylonitrile based copolymer (F) is 100 weight parts, and the content range of described tin methide maleate polymer (D) is 0.2 weight part ~ 2.3 weight part.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, total amount based on described copolymer mixture (A) and described second styrene-acrylonitrile based copolymer (F) is 100 weight parts, and the content range of described magnalium composite metal salt (E) is 0.3 weight part ~ 1.3 weight part.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, described tin methide maleate polymer (D) is selected from tin methide maleic acid potassium polymkeric substance, tin methide sodium maleate polymkeric substance, or their combination.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, described magnalium composite metal salt (E) is selected from [(Al
2o
3) (6MgO) (CO
2)] (12H
2o), [(4.5Mg) Al
2(OH)
13(CO
3)] (3.5H
2o), [(4MgO) Al
2o
3(CO
2)] (9H
2o), [(4MgO) Al
2o
3(CO
2)] (6H
2o), [(ZnO) (MgO) Al
2o
3(CO
2)] nH
2o (n=5 ~ 9), [(4.5Mg) Al through vinyl-trimethoxysilane coupling agent modification
2(OH)
13(CO
3)] (3.5H
2or their combination O).
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, described copolymer mixture (A) is by comprising the first copolymer component (A that weight average particle diameter scope is 0.2 μm ~ 1.0 μm
1), weight average particle diameter scope is the second copolymer component (A of 0.05 μm ~ 0.2 μm
2) and weight average particle diameter scope be the 3rd copolymer component (A of 0.5 μm ~ 5 μm
3) copolymer component mixing formed.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, described copolymer mixture (A) is by the first copolymer component (A comprising 20 % by weight ~ 80 % by weight
1), the second copolymer component (A of 15 % by weight ~ 75 % by weight
2), and the 3rd copolymer component (A of 5 % by weight ~ 65 % by weight
3) copolymer component mixing formed.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, described copolymer mixture (A) by comprise weight average particle diameter scope be 0.2 μm ~ 0.7 μm and content range be 20 % by weight ~ 80 % by weight the first copolymer component (A
1), weight average particle diameter scope be 0.05 μm ~ 0.15 μm and content range be 15 % by weight ~ 75 % by weight the second copolymer component (A
2), and weight average particle diameter scope be 0.5 μm ~ 5 μm and content range be 5 % by weight ~ 65 % by weight the 3rd copolymer component (A
3) copolymer component mixing formed.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, described copolymer mixture (A) by comprise weight average particle diameter scope be 0.2 μm ~ 0.7 μm and content range be 30 % by weight ~ 70 % by weight the first copolymer component (A
1), weight average particle diameter scope be 0.05 μm ~ 0.15 μm and content range be 25 % by weight ~ 65 % by weight the second copolymer component (A
2), and weight average particle diameter scope be 0.5 μm ~ 5 μm and content range be 5 % by weight ~ 45 % by weight the 3rd copolymer component (A
3) copolymer component mixing formed.
The second object of the present invention is for providing a kind of products formed with the styrene-acrylonitrile-diene interpolymer constituent of better low temperature impact strength.The products formed of styrene-acrylonitrile of the present invention-diene interpolymer constituent, formed by styrene-acrylonitrile as above-diene interpolymer constituent.
Beneficial effect of the present invention is: by the interpolation of tin methide maleate polymer (D) and magnalium composite metal salt (E), synergistic effect can be played with halogen fire retardant (B) with containing sb oxide (C), make this styrene-acrylonitrile-diene interpolymer constituent have preferably thermostability, low temperature impact strength and flame retardancy simultaneously.
Embodiment
Styrene-acrylonitrile of the present invention-diene interpolymer constituent comprises:
The copolymer mixture (A) of 5 weight part ~ 40 weight parts, by comprising the first copolymer component (A
1), the second copolymer component (A
2) and the 3rd copolymer component (A
3) copolymer component mixing formed; This first copolymer component (A
1) and the second copolymer component (A
2) respectively obtained by rubber components and monomer component react through emulsion polymerization; 3rd copolymer component (A
3) by rubber components and monomer component obtained by the solution polymerization; This rubber components comprises diene series rubber; This monomer component comprises styrenic monomers and acrylic monomer;
The halogen fire retardant (B) of 5 weight part ~ 30 weight parts;
1 weight part ~ 10 weight part containing sb oxide (C);
The tin methide maleate polymer (D) of 0.2 weight part ~ 2.5 weight part;
The magnalium composite metal salt (E) of 0.2 weight part ~ 1.5 weight part; And
Second styrene-acrylonitrile based copolymer (F) of 60 weight part ~ 95 weight parts.
Styrene-acrylonitrile of the present invention-diene interpolymer constituent uses tin methide maleate polymer (D) and magnalium composite metal salt (E) simultaneously, thermostability for styrene-acrylonitrile of the present invention-diene interpolymer constituent has the effect of addition, and use tin methide maleate polymer (D), styrene-acrylonitrile of the present invention-diene interpolymer constituent can be made to have the feature of environmental protection, simultaneously, the hydrogen halide effect that this magnalium composite metal salt (E) can discharge with halogen fire retardant (B) heat, reduce hydrogen halide to the impact of styrene-acrylonitrile-diene interpolymer constituent thermostability, then the thermostability of styrene-acrylonitrile-diene interpolymer constituent is promoted.
One by one each composition in styrene-acrylonitrile-diene interpolymer constituent will be described in detail below:
[copolymer mixture (A)]
Preferably, this copolymer mixture (A) is by comprising the first copolymer component (A that weight average particle diameter scope is 0.2 μm ~ 1.0 μm
1), weight average particle diameter scope is the second copolymer component (A of 0.05 μm ~ 0.2 μm
2) and weight average particle diameter scope be the 3rd copolymer component (A of 0.5 μm ~ 5 μm
3) copolymer component mixing formed.The copolymer component used in this copolymer mixture (A) can make this styrene-acrylonitrile-diene interpolymer constituent have preferably low temperature impact strength.
Preferably, this copolymer mixture (A) is by the first copolymer component (A comprising 20 % by weight ~ 80 % by weight
1), the second copolymer component (A of 15 % by weight ~ 75 % by weight
2), and the 3rd copolymer component (A of 5 % by weight ~ 65 % by weight
3) copolymer component mixing formed.
More preferably, this copolymer mixture (A) by comprise weight average particle diameter scope be 0.2 μm ~ 0.7 μm and content range be 20 % by weight ~ 80 % by weight the first copolymer component (A
1), weight average particle diameter scope be 0.05 μm ~ 0.15 μm and content range be 15 % by weight ~ 75 % by weight the second copolymer component (A
2), and weight average particle diameter scope be 0.5 μm ~ 5 μm and content range be 5 % by weight ~ 65 % by weight the 3rd copolymer component (A
3) copolymer component mixing formed.
Again more preferably, this copolymer mixture (A) by comprise weight average particle diameter scope be 0.2 μm ~ 0.7 μm and content range be 30 % by weight ~ 70 % by weight the first copolymer component (A
1), weight average particle diameter scope be 0.05 μm ~ 0.15 μm and content range be 25 % by weight ~ 65 % by weight the second copolymer component (A
2), and weight average particle diameter scope be 0.5 μm ~ 5 μm and content range be 5 % by weight ~ 45 % by weight the 3rd copolymer component (A
3) copolymer component mixing formed.
The present invention first copolymer component (A
1) and the second copolymer component (A
2) weight ratio scope be 5/95 ~ 95/5.
This copolymer mixture (A) comprises styrene-acrylonitrile-diene interpolymer component (a-1) and the first styrene-acrylonitrile based copolymer (a-2).
This styrene-acrylonitrile-diene interpolymer component (a-1) is selected from the first styrene-acrylonitrile-diene interpolymer (a-1-1), the second styrene-acrylonitrile-diene interpolymer (a-1-2), or their combination.
This first styrene-acrylonitrile-diene interpolymer (a-1-1) formed by comprising one or more styrene based copolymers, the first rubber body of coated styrene based copolymer and the first graft copolymer grafted in the first rubber body; And this second styrene-acrylonitrile-diene interpolymer (a-1-2) is by comprising the second rubber body and this second graft copolymer grafted in the second rubber body formed.This first rubber body and the second rubber body can be identical or different, and this first graft copolymer and the second graft copolymer can be identical or different.This styrene based copolymer, the first graft copolymer or the second graft copolymer formed through polyreaction by the monomer component comprising styrenic monomers and acrylic monomer respectively.This first rubber body or the second rubber body formed by rubber components respectively.
< first copolymer component (A
1) preparation >
This first copolymer component (A
1) by comprising obtained by first rubber latex (Gu composition) of 40 % by weight ~ 90 % by weight and first monomer component of 10 % by weight ~ 60 % by weight react through emulsion polymerization.This first monomer component comprises the styrenic monomers (i-1) of 50 % by weight ~ 85 % by weight, the acrylic monomer (i-2) of 15 % by weight ~ 50 % by weight, and other copolymerizable vinyl monomer (i-3) of 0 % by weight ~ 35 % by weight.In the reaction of this emulsion polymerization, optionally can add emulsifying agent, polymerization starter or chain-transfer agent etc.Optionally can again via condensation, dehydration, drying and other steps after emulsion polymerization reaction.
This first rubber latex obtained through emulsion polymerization method by the first rubber components, and give agglomeration (Agglomeration) process more further after emulsion polymerization reaction, and optionally in emulsion polymerization reaction, add other copolymerizable monomer.This other copolymerizable monomer is including but not limited to vinylbenzene, vinyl cyanide, acrylate and methacrylic ester etc.This first rubber components is selected from diene series rubber, polyacrylic ester system rubber, or polysiloxane series rubber.
This diene series rubber can be used alone or as a mixture, and this diene series rubber is including but not limited to divinyl rubber, synthetic polyisoprene (isoprene rubber), neoprene, styrenic-diene system rubber, acrylic-nitrile rubber etc.The divinyl rubber of this divinyl rubber including but not limited to high-cis (Hi-Ci s) 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 ~ 99 % by weight)/(1 ~ 5 % by weight), 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 in (20 ~ 40 % by weight)/(1 ~ 20 % by weight), and all the other are transconfiguration, and mooney viscosity is between 20 ~ 120.
This styrenic-diene system rubber is including but not limited to styrene butadiene rubbers (styrene-butadiene rubber is called for short SBR).The structure of this styrenic-diene system rubber can be diblock (di-block) copolymerization, three blocks (tri-block) copolymerization, random (random) copolymerization or planetary copolymerization (star type).Preferably, in this styrene butadiene rubbers, the part by weight scope of styrenic monomer units and butadiene monomer unit is 5/95 ~ 80/20.Preferably, the molecular weight ranges of this styrenic-diene system rubber is 50,000 ~ 600,000.This first rubber components is selected from divinyl rubber, styrene butadiene rubbers, or their combination.Preferably, this first rubber components is styrene butadiene rubbers.
This agglomeration process can adopt general freezing agglomeration technique, additive agglomeration technique or mechanical agglomeration technique etc.The additive used in this additive agglomeration technique is including but not limited to (1) acidic substance: acetic anhydride, hydrogenchloride, sulfuric acid etc.; (2) salt compounds: sodium-chlor, Repone K, calcium chloride etc.; (3) containing the polymer coagulant of carboxylic acid group: (methyl) vinylformic acid-(methyl) acrylate copolymer [as methacrylic acid-acrylic acid acrylate copolymer, EUDRAGIT L100-55] etc.
For example, diene series rubber emulsion making process can use diene monomer (such as divinyl) to be polymerized with emulsion polymerization method, or, the monomer such as vinylbenzene and/or vinyl cyanide of the diene monomer of 50 % by weight ~ 100 % by weight and 0 % by weight ~ 50 % by weight is reacted with emulsion polymerization method, can obtain weight average particle diameter is after the small particle size diene series rubber emulsion of 0.05 μm ~ 0.2 μm, then give agglomeration process, this small particle size diene series rubber emulsion is agglomerated into the Large stone diene series rubber emulsion of weight average particle diameter 0.2 μm ~ 1.0 μm.
This first copolymer component (A
1) comprise the second styrene-acrylonitrile-diene interpolymer (a-1-2) and the first styrene-acrylonitrile based copolymer (a-2).
First copolymer component (A
1) the second styrene-acrylonitrile-diene interpolymer (a-1-2) in the percentage of grafting of rubber body controlled by polymeric reaction condition, such as: the addition means etc. of the consumption of polymerization temperature, polymerization starter, emulsifying agent, chain transfer agent and kind, the first monomer component is controlled.And the first monomer component can once add, also can add in batches, also can add continuously or each monomer segmentation is added, the first copolymer component (A of weight average particle diameter required for the present invention 0.2 μm ~ 1.0 μm can be obtained
1).First copolymer component (A
1) the second styrene-acrylonitrile-diene interpolymer (a-1-2) in the percentage of grafting of rubber body be 10% ~ 40%, and the molecular weight ranges of the second graft copolymer in the second styrene-acrylonitrile-diene interpolymer (a-1-2) is 40,000 ~ 120,000.
Preferably, this first copolymer component (A
1) weight average particle diameter scope be 0.20 μm ~ 0.7 μm.
This styrenic monomers (i-1) can be used alone or as a mixture, and this styrenic monomers (i-1) is including but not limited to vinylbenzene, alpha-methyl styrene, α-chloro-styrene, p-t-butyl styrene, p-methylstyrene, o-chloro-styrene, p-chloro-styrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-trichlorostyrene, 2,5-Dowspray 9s etc.Preferably, this styrenic monomers (i-1) is selected from vinylbenzene, alpha-methyl styrene, or their combination.This acrylic monomer (i-2) can be used alone or as a mixture, and this acrylic monomer (i-2) is including but not limited to vinyl cyanide, Alpha-Methyl vinyl cyanide etc.
This other copolymerizable vinyl monomer (i-3) can be used alone or as a mixture, and this other copolymerizable vinyl monomer (i-3) is including but not limited to acrylic monomer, methacrylic monomers, acrylic ester monomer, methacrylate ester monomer, maleimide system monomer etc.
This methacrylate ester monomer is including but not limited to methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, N-Hexyl methacrylate, cyclohexyl methacrylate, lauryl ester, HEMA, glytidyl methacrylate, dimethylaminoethyl methacrylate (dimethylaminoethyl methacrylate) etc.Preferably, this methacrylate ester monomer is methyl methacrylate.
In the reaction of this emulsion polymerization, optionally polymerization starter can be added.This polymerization starter can be used alone or as a mixture, and this polymerization starter is including but not limited to dibenzoyl peroxide (benzoyl peroxide), hydrogen peroxide two benzene sec.-propyl (dicumylhydroperoxide), tert-butyl peroxide (t-butyl peroxide), hydrogen phosphide cumene (cumene peroxide), Potassium Persulphates etc.Wherein better with organic hydroperoxide class.
In the reaction of this emulsion polymerization, optionally chain-transfer agent can be added.This chain-transfer agent can be used alone or as a mixture, and this chain-transfer agent is including but not limited to n-lauryl mercaptan (n-dodecyl mercaptan, be called for short NDM), uncle-lauryl mercaptan (t-dodecyl mercaptan, be called for short TDM), n-butyl mercaptan, n-octyl mercaptan etc.
Preferably, the operating temperature range of this emulsion polymerization reaction is less than 90 DEG C; More preferably, the operating temperature range of this emulsion polymerization reaction is 30 DEG C ~ 80 DEG C.
In the reaction of this emulsion polymerization, optionally salting-out agent can be added.These salting-out agent can be used alone or as a mixture, and these salting-out agent are including but not limited to sodium sulfate, potassium sulfate, sodium bisulfite, Potassium hydrogen sulfite, ammonium bisulfite, pyrosulfite, pyrosulphate, hyposulfite (hydrosulfite), formaldehydesulfoxylate (formaldehydesulfoxylate salt), formolation sulfoxylic acid hydrogen salt (formaldehyde sulfoxylatesalt), thiosulphate, sulfoxylate.Preferably, these salting-out agent are selected from sodium bisulfite, Sodium Pyrosulfite, V-Brite B or white discharzereazent.Preferably, be 100 parts by weight with the usage quantity summation of (i-1), (i-2), (i-3), the usage quantity scope of these salting-out agent is 10ppm ~ 1,000ppm.
< second copolymer component (A
2) preparation >
This second copolymer component (A
2) comprise second rubber latex (Gu composition) of 40 % by weight ~ 90 % by weight and the second comonomer component of 10 % by weight ~ 60 % by weight obtained by the emulsion polymerization reaction.This second comonomer component comprises the styrenic monomers of 50 % by weight ~ 85 % by weight, the acrylic monomer of 15 % by weight ~ 50 % by weight, and other copolymerizable vinyl monomer of 0 % by weight ~ 35 % by weight.In the reaction of this emulsion polymerization, optionally can add emulsifying agent, polymerization starter or chain-transfer agent etc.Optionally can again via condensation, dehydration, drying and other steps after emulsion polymerization reaction.
This second rubber latex obtained through emulsion polymerization method by the second rubber components, and optionally in emulsion polymerization reaction, add other copolymerizable monomer.This second rubber components is as above-mentioned preparation first copolymer component (A
1) the first rubber components.This other copolymerizable monomer is including but not limited to vinylbenzene, vinyl cyanide, acrylate and methacrylic ester etc.This second rubber latex is without agglomeration process.
The kind of the styrenic monomers in this second comonomer component, acrylic monomer, other copolymerizable vinyl monomer, polymerization starter and chain-transfer agent is as above-mentioned preparation first copolymer component (A
1) in styrenic monomers (i-1), acrylic monomer (i-2), other copolymerizable vinyl monomer (i-3), polymerization starter and chain-transfer agent kind, so repeat no more.The condition of this polyreaction is also with above-mentioned preparation first copolymer component (A
1) polymeric reaction condition.
This second copolymer component (A
2) comprise the second styrene-acrylonitrile-diene interpolymer (a-1-2) and the first styrene-acrylonitrile based copolymer (a-2).
Second copolymer component (A
2) the second styrene-acrylonitrile-diene interpolymer (a-1-2) in the percentage of grafting of rubber body controlled by polymeric reaction condition, such as: the addition means etc. of the consumption of polymerization temperature, polymerization starter, emulsifying agent, chain transfer agent and kind, second comonomer component is controlled.And second comonomer component can once add, also can add in batches, also can add continuously or each monomer segmentation is added, the second copolymer component (A of weight average particle diameter required for the present invention 0.05 μm ~ 0.2 μm can be obtained
2).Second copolymer component (A
2) the second styrene-acrylonitrile-diene interpolymer (a-1-2) in the percentage of grafting of rubber body be 10% ~ 40%, and the molecular weight ranges of the second graft copolymer in the second styrene-acrylonitrile-diene interpolymer (a-1-2) is 40,000 ~ 120,000.
Preferably, this second copolymer component (A
2) weight average particle diameter scope be 0.05 μm ~ 0.15 μm.
The preparation > of < the 3rd copolymer component (A3)
3rd copolymer component (A
3) be comprise the 3rd rubber components of 3 weight part ~ 15 weight parts and the Third monomer component of 100 weight parts obtained by the body or solution polymerization.This Third monomer component comprises the styrenic monomers of 50 % by weight ~ 80 % by weight, the acrylic monomer of 15 % by weight ~ 50 % by weight, and other copolymerizable vinyl monomer of 0 % by weight ~ 35 % by weight.In this body or solution polymerization, optionally can add solvent, polymerization starter or chain-transfer agent etc.
3rd rubber components is as above-mentioned preparation first copolymer component (A
1) the first rubber components.
3rd copolymer component (A
3) manufacture method be that the 3rd rubber components is dissolved in Third monomer component and/or solvent in advance, then import reactive tank and carry out graft polymerization reaction.This reactive tank can be combined by multiple, generally can utilize the piston-type reactive tank of still type reactive tank with machine,massing or tower.
The kind of this styrenic monomers, acrylic monomer, other copolymerizable vinyl monomer, polymerization starter and chain-transfer agent is as above-mentioned preparation first copolymer component (A
1) in styrenic monomers (i-1), acrylic monomer (i-2), other copolymerizable vinyl monomer (i-3), polymerization starter and chain-transfer agent kind, so repeat no more.
3rd copolymer component (A
3) comprise the first styrene-acrylonitrile-diene interpolymer (a-1-1) and the first styrene-acrylonitrile based copolymer (a-2).
Preferably, the 3rd copolymer component (A
3) weight average particle diameter scope be 0.5 μm ~ 5 μm.More preferably, the 3rd copolymer component (A
3) weight average particle diameter scope be 0.5 μm ~ 3 μm.
[halogen fire retardant (B)]
This halogen fire retardant (B) can be used alone or as a mixture, preferably, this halogen fire retardant (B) is selected from tetrabromo-bisphenol (tetrabromobisphenol A, be called for short TBBA), tetrabromo-bisphenol s (tetrabromo bisphenol S), tetrabromobisphenol F (tetrabromobi sphenol F), tetrabromo-bisphenol two (2, 3-dibromopropyl) ether [tetrabromobisphenol A bis (di bromopropyl ether)], decabrominated dipheny base ether (decabromo diphenyl ether), brominated Polystyrene oligomerization zoarium (brominated poly styrene, be called for short BP S), hexabromocyclododecane (hexabromocyclo dodecane), octabromodiphenyl base ether (octabromo diphenylether, be called for short OBDPE), hexabromo diphenyl ether (hexabromobiphenyl ether), 1, two (pentabromo-phenoxy group) ethane [1 of 2-, 2-bis (pentabromophenoxy) ethane, be called for short BPBPE], chlorinatedpolyethylene (chlorinated poly ethylene), or their combination.Preferably, the total amount based on this copolymer mixture (A) and this second styrene-acrylonitrile based copolymer (F) is 100 weight parts, and the content range of this halogen fire retardant (B) is 10 weight part ~ 27 weight parts.
[containing sb oxide (C)]
Should can be used alone or as a mixture containing sb oxide (C), preferably, ANTIMONY TRIOXIDE SB 203 99.8 PCT should be selected from containing sb oxide (C), (antimony trioxide is called for short Sb to antimonous oxide
2o
3), antimony tetroxide, antimony peroxide, or these combination.Preferably, the total amount based on this copolymer mixture (A) and this second styrene-acrylonitrile based copolymer (F) is 100 weight parts, should be 3 weight part ~ 8 weight parts containing the content range of sb oxide (C).Preferably, the content of halogen in this halogen fire retardant (B) be 1 ~ 10 with the part by weight scope of the antimony content that should contain in sb oxide (C).
[tin methide maleate polymer (D)]
Preferably, (D) is selected from tin methide maleic acid potassium polymkeric substance, tin methide sodium maleate polymkeric substance to this tin methide maleate polymer (polymer ofdimethyltin maleate is called for short DMTM), or their combination.When the content of tin methide maleate polymer (D) is less than 0.2 weight part or is greater than 2.5 weight part, then the thermostability extreme difference of styrene-acrylonitrile-diene interpolymer constituent.Preferably, total amount based on this copolymer mixture (A) and this second styrene-acrylonitrile based copolymer (F) is 100 weight parts, and the content range of this tin methide maleate polymer (D) is 0.2 weight part ~ 2.3 weight part.
[magnalium composite metal salt (composite metal salt) (E)]
Preferably, this magnalium composite metal salt (E) is selected from [(Al
2o
3) (6MgO) (CO
2)] (12H
2o), [(4.5Mg) Al
2(OH)
13(CO
3)] (3.5H
2o), [(4MgO) Al
2o
3(CO
2)] (9H
2o), [(4MgO) Al
2o
3(CO
2)] (6H
2o), [(ZnO) (MgO) Al
2o
3(CO
2)] nH
2o (n=5 ~ 9), [(4.5Mg) Al through vinyl-trimethoxysilane coupling agent modification
2(OH)
13(CO
3)] (3.5H
2or their combination O).
When the content of magnalium composite metal salt (E) is less than 0.2 weight part or is greater than 1.5 weight part, then the thermostability extreme difference of styrene-acrylonitrile-diene interpolymer constituent.Preferably, the total amount based on this copolymer mixture (A) and this second styrene-acrylonitrile based copolymer (F) is 100 weight parts, and the content range of this magnalium composite metal salt (E) is 0.3 weight part ~ 1.3 weight part.
[the second styrene-acrylonitrile based copolymer (F)]
This second styrene-acrylonitrile based copolymer (F) is by comprising the styrenic monomers of 50 % by weight ~ 80 % by weight, the acrylic monomer of 20 % by weight ~ 50 % by weight, and the 4th monomer component optionally adding other copolymerizable vinyl monomer is obtained by the polyreaction, and in this polyreaction, optionally can add polymerization starter or chain-transfer agent etc.The preparation method of this second styrene-acrylonitrile based copolymer (F) can adopt mass polymerization, solution polymerization process, suspension polymerization or emulsion polymerization method.Be better with mass polymerization or solution polymerization process.The molecular weight ranges of this second styrene-acrylonitrile based copolymer (F) is 60,000 ~ 400,000.Preferably, the molecular weight ranges of this second styrene-acrylonitrile based copolymer (F) is 80,000 ~ 300,000.
The kind of the styrenic monomers in the 4th monomer component, acrylic monomer, other copolymerizable vinyl monomer, polymerization starter and chain-transfer agent is as above-mentioned preparation first copolymer component (A
1) in the styrenic monomers (i-1) of the first monomer component, acrylic monomer (i-2), other copolymerizable vinyl monomer (i-3), polymerization starter and chain-transfer agent kind, so repeat no more.
[additive (G)]
In styrene-acrylonitrile of the present invention-diene interpolymer constituent, various additive (G) can be added if desired, such as: softening agent, processing aid, ultra-violet stabilizer, UV light absorber, weighting agent, toughener, tinting material, lubricant, static inhibitor, coupling agent etc.Above-mentioned additive (G) can respectively at preparation first copolymer component (A
1), prepare the second copolymer component (A
2), preparation the 3rd copolymer component (A
3) polyreaction in, add after polyreaction, before condensation or in the process preparing styrene-acrylonitrile-diene interpolymer constituent.Preferably, the total amount based on this copolymer mixture (A) and this second styrene-acrylonitrile based copolymer (F) is 100 weight parts, and the content range of this additive (G) is below 6 weight parts.Preferably, the content range of this additive (G) is 0.02 weight part ~ 2 weight part.
This lubricant is including but not limited to calcium stearate, Magnesium Stearate, lithium stearate, ethylene distearyl acid amides, methylene distearyl acid amides, palmitic amide, butyl stearate, stearic acid palm ester, poly-propionic acid alcohol tristearate, behenic acid, stearic acid, polyethylene wax, octocosoic acid wax, carnauba wax (carnauba wax) or petroleum wax etc.This processing aid is including but not limited to methyl methacrylate system, and such as weight average molecular weight is 50, nucleocapsid (core-shell) the type processing aid of more than 000.This UV light absorber is including but not limited to benzotriazole based compound, benzophenone based compound or cyanogen acrylic compounds etc.This ultra-violet stabilizer is including but not limited to bulky amine based compound (hindered amine).
The method for making of this styrene-acrylonitrile-diene interpolymer constituent can adopt general hybrid mode, by copolymer mixture (A), halogen fire retardant (B), containing sb oxide (C), tin methide maleate polymer (D), magnalium composite metal salt (E) and the second styrene-acrylonitrile based copolymer (F), be positioned in agitator and stir, make its Homogeneous phase mixing, additive (G) can be added if desired, styrene-acrylonitrile of the present invention-diene interpolymer constituent can be obtained.
The products formed of styrene-acrylonitrile of the present invention-diene interpolymer constituent, formed by styrene-acrylonitrile as above-diene interpolymer constituent.This formation method can be adopted with mixing mode, machine-shaping mode, or their combination.This mixing mode and machine-shaping mode can adopt in the past known mode, so repeat no more.
The present invention will be described further with regard to following examples, but it is to be understood that described embodiment is only and illustrates use, and should not be interpreted as restriction of the invention process.
< embodiment >
[synthesis example 1] first copolymer component (A
1)
By 1 of 95.0 weight parts, uncle-the lauryl mercaptan of the trisodium phosphate of the vinyl cyanide of 3-divinyl, 5.0 weight parts, the potassium persulfate solution of 15.0 weight parts, 3.0 weight parts, the potassium oleate of 1.5 weight parts, the distilled water of 140.0 weight parts and 0.2 weight part reacts 12 hours under 65 DEG C of temperature of reaction, obtain transformation efficiency 94%, solids content is about 40%, and weight average particle diameter is the rubber latex of 0.1 μm.
The distilled water of the dioctyl sodium sulphosuccinate of the uncle-lauryl mercaptan of the ethyl propenoate of 85.0 weight parts, the vinylformic acid of 15.0 weight parts, 0.3 weight part, the potassium oleate of 2.0 weight parts, 1.0 weight parts, the cumine hydroperoxide of 0.4 weight part, the white discharzereazent of 0.3 weight part and 200.0 weight parts reacts 5 hours under 75 DEG C of temperature of reaction, can obtain the polymer coagulant containing carboxylic acid group of transformation efficiency 95%, pH value 6.0.
Then, the polymer coagulant (dry weight) containing carboxylic acid group utilizing 3 weight parts above-mentioned carrys out the above-mentioned rubber latex (dry weight) of agglomeration 100 weight part, and the pH value of the agglomeration rubber latex of gained is 8.5, and weight average particle diameter is 0.30 μm.
Then, the white discharzereazent solution (concentration 10 % by weight) of the copperas solution (concentration 0.2 % by weight) of the hydrogen phosphide cumene of the uncle-lauryl mercaptan of the potassium oleate of the vinyl cyanide of the vinylbenzene of the above-mentioned agglomeration rubber latex (dry weight) of 100.0 weight parts, 25.0 weight parts, 8.3 weight parts, 1.2 weight parts, 0.2 weight part, 0.5 weight part, 3.0 weight parts, 3.0 weight parts, the edta solution (concentration 0.25 % by weight) of 20.0 weight parts and the distilled water of 200.0 weight parts are mixed and reacts.This vinylbenzene and vinyl cyanide added in reactive system with continuous addition manner and are polymerized in 5 hours, then, with calcium chloride (CaCl
2) condensation, after dehydration, then be dried to water content less than 2%, just can obtain the present invention first copolymer component (A
1).
[synthesis example 2] second copolymer component (A
2)
By 1 of 95.0 weight parts, uncle-the lauryl mercaptan of the trisodium phosphate of the vinyl cyanide of 3-divinyl, 5.0 weight parts, the potassium persulfate solution of 15.0 weight parts, 3.0 weight parts, the potassium oleate of 1.5 weight parts, the distilled water of 140.0 weight parts and 0.2 weight part reacts 12 hours under 65 DEG C of temperature of reaction, obtain transformation efficiency 94%, solids content is about 40%, and weight average particle diameter is the rubber latex of 0.1 μm.
By the above-mentioned rubber latex (dry weight) of 100.0 weight parts, the vinylbenzene of 75.0 weight parts, the vinyl cyanide of 25.0 weight parts, the potassium oleate of 2.0 weight parts, uncle-the lauryl mercaptan of 0.6 weight part, the hydrogen phosphide cumene of 1.4 weight parts, the copperas solution (concentration 0.2 % by weight) of 8.6 weight parts, the white discharzereazent solution (concentration 10 % by weight) of 8.6 weight parts, the edta solution (concentration 0.25 % by weight) of 57.0 weight parts and the distilled water of 200.0 weight parts mix and react.This vinylbenzene and vinyl cyanide added in reactive system with continuous addition manner and are polymerized in 5 hours, then, with calcium chloride (CaCl
2) condensation, after dehydration, then be dried to moisture content less than 2%, just can obtain the present invention second copolymer component (A
2).
[synthesis example 3] the 3rd copolymer component (A
3)
The benzoyl peroxide of the vinylbenzene of the polyhutadiene (Asahi Kasei Corporation's system, trade(brand)name: Asadedne55AS) of 6.6 weight parts, 74.4 weight parts, the ethylbenzene of 30 weight parts, the vinyl cyanide of 25.6 weight parts and 0.08 weight part is mixed to form mixture.
Be supplied to continuously by said mixture in the first reactor (volume 45 liters) and react, temperature of reaction is 100 DEG C.In this first reactor, configuration is provided with the screw mixer of refrigeration cycle pipe, and its stir speed (S.S.) is 150rpm.When in question response, monomer conversion is 15%, reaction mixture after the first reactor reaction is taken out continuously, and sequentially import in the second reactor, the 3rd reactor, the 4th reactor, in the 3rd reactor, add the uncle-lauryl mercaptan of 0.1 weight part simultaneously, Phase Inversion produces in the second reactor, the device of above-mentioned second reactor, the 3rd reactor, the 4th reactor is identical with the first reactor, but temperature of reaction is sequentially 105 DEG C, 110 DEG C, 125 DEG C, and stir speed (S.S.) is sequentially 270rpm, 150rpm and 110rpm.
When the transformation efficiency of the reaction mixture in the 4th reactor reaches 60%, reaction mixture is taken out and imports in devolatilizer, remove unreacted monomer and volatile matter, just can obtain the present invention the 3rd copolymer component (A
3), or further by its extrusion granulator.
[synthesis example 4] the second styrene-acrylonitrile based copolymer (F)
With the speed of 12kg/hr by the vinylbenzene of 68 % by weight and 32 % by weight vinyl cyanide be placed in interior temperature temperature remain on 108 DEG C and capacity be 45 liters with the continous way still type reactor of agitator, carry out mixing and reacting, with the speed of 3.0g/hr, uncle-lauryl mercaptan is added in reaction again, and making the toluene ratio in reaction solution remain on 15%, percent polymerization remains on 55%.After reaction, by this reaction solution by after devolatilizer removing volatile component, the particle that acrylonitrile content is the second styrene-acrylonitrile based copolymer (F) of 28 % by weight can be obtained.
While the particle obtaining this second styrene-acrylonitrile based copolymer (F), can be condensing as Ethylene recov using condenser by removed volatile component, and be added in reaction continuously and re-use.
[embodiment 1] styrene-acrylonitrile-diene interpolymer constituent
The synthesis example 3 of the synthesis example 2 and 20 % by weight of the synthesis example 1,35 % by weight by 45 % by weight mixes, form copolymer mixture (A), then, the copolymer mixture (A) taking out 20 weight parts mixes with the synthesis example 4 of 80 weight parts, and the tetrabromo-bisphenol (label: Dead Sea company of interpolation and 15 weight parts; Model: FR-1524), the antimonous oxide (label: Shenzhen Jeff industrial corporation) of 5.5 weight parts, the tin methide maleate polymer (label: He Ju company of 1.0 weight parts; Model: HS3721) and 1.0 weight parts magnalium composite metal salt mixing, styrene-acrylonitrile of the present invention-diene interpolymer constituent can be obtained, its analyze and evaluation of physical properties the results are shown in Table 1.This magnalium composite metal salt is [(4.5Mg) Al through vinyl-trimethoxysilane coupling agent modification
2(OH)
13(CO
3)] (3.5H
2o); Should [(4.5Mg) Al
2(OH)
13(CO
3)] (3.5H
2o) by Ky owa Chem. Inc. and model is DHT-4A-2, and the weight ratio of this vinyl-trimethoxysilane coupling agent and DHT-4A-2 is 3/17.
[embodiment 2 ~ 6 and comparative example 1 ~ 7]
Embodiment 2 ~ 6 and comparative example 1 ~ 7 are that different places is: feed change kind and usage quantity with the step identical with embodiment 1 to prepare this styrene-acrylonitrile-diene interpolymer constituent.This raw material type, usage quantity and evaluation result are in table 1.
[test item]
1. low temperature impact strength evaluation (Izod) measures:
Styrene-acrylonitrile-diene interpolymer the constituent of embodiment 1 ~ 6 and comparative example 1 ~ 7 is made into 107mm × 107mm × 1/8 respectively " testing plate; and be placed in-20 DEG C of refrigeration chambers after freezing 24 hours; use instrument Dynatup 8250; specify according to AS TM-3763; weight of dropping hammer 23.64 kilograms, height of the fall 0.56 meter, impact velocity 3.34m/sec tests; measurement makes described test piece break required energy, unit: Kg-cm/cm.
2. thermal stability determination:
Styrene-acrylonitrile-diene interpolymer the constituent of embodiment 1 ~ 6 and comparative example 1 ~ 7 is put into tablets press and carries out granulation; then; diameter 55mm are injected and the disk of thickness 3.2mm at 200 DEG C respectively with injection moulding machine (Taiwan shake male mechanical society system, model: 4OZ, SM-90).
After described disk cooling, survey its yellowness index YI with spectrometer (model: Gretoawacbethcolor-eye 3100)
1value.Then, described disk is placed in respectively rotating disc type baking oven with 200 DEG C of high bakes after 1 hour, after cooling, then measures its yellowness index YI
2value, calculates yellowness index difference Δ YI, can judge its thermostability.
ΔYI＝YI
2-YI
1
◎: represent Δ YI < 2.0;
Zero: represent 2.0≤Δ YI≤3.0;
×: represent Δ YI > 3.0.
The less expression of Δ YI value this styrene-acrylonitrile-thermostability of diene interpolymer constituent in aerobic environment is better.
3. flame retardancy measures:
Styrene-acrylonitrile-diene interpolymer the constituent of embodiment 1 ~ 6 and comparative example 1 ~ 7 is measured specification according to the Vertical Flame of U.S.'s Underwriter Laboratory (UL) defined (UL 94 specification), and test thickness is 1.5mm.V-0 represents by burning mensuration; V-1 represents that flame retardancy is slightly poor; V-2 represents not by burning mensuration.
As shown in Table 1, styrene-acrylonitrile-diene interpolymer the constituent of embodiment 1 ~ 6 adds tin methide maleate polymer (D) and magnalium composite metal salt (E) simultaneously, and content range is respectively 0.3 weight part ~ 2.0 weight part and 0.5 weight part ~ 1.0 weight part, make this styrene-acrylonitrile-diene interpolymer constituent have preferably thermostability and flame retardancy simultaneously.And the styrene-acrylonitrile of embodiment 1 ~ 6-diene interpolymer constituent all comprises the first copolymer component (A
1), the second copolymer component (A
2) and the 3rd copolymer component (A
3), make described constituent have preferably low temperature impact strength, represent when following process is shaping, described constituent also can operate under low temperature, and the products formed formed by described constituent can use under low temperature environment.
Compare down, when not adding tin methide maleate polymer (D) and magnalium composite metal salt (E) in the styrene-acrylonitrile-diene interpolymer constituent of comparative example 1, then the thermostability pole of styrene-acrylonitrile-diene interpolymer constituent is not good.
When adding excessive tin methide maleate polymer polymkeric substance (D) (3.0 weight part) in the styrene-acrylonitrile-diene interpolymer constituent of comparative example 2, then the thermostability of styrene-acrylonitrile-diene interpolymer constituent is not good.
When adding dibutyltin maleate (model: TM-600P) in the styrene-acrylonitrile-diene interpolymer constituent of comparative example 3, then the thermostability of this constituent declines, and does not have a feature of environmental protection, and future can prohibit the use.
Styrene-acrylonitrile-diene interpolymer the constituent of comparative example 4 only uses the 3rd copolymer component (A
3), and not containing the first copolymer component (A
1) and the second copolymer component (A
2) time, then the low temperature impact strength of this styrene-acrylonitrile-diene interpolymer constituent is not good.And in this constituent, add dibutyltin maleate (D), then the thermostability of this constituent declines, and does not have a feature of environmental protection, and future can prohibit the use.
When not adding magnalium composite metal salt (E) in the styrene-acrylonitrile-diene interpolymer constituent of comparative example 5, then the thermostability of styrene-acrylonitrile-diene interpolymer constituent is not good.
When adding a small amount of tin methide maleate polymer (D) (0.1 weight part) and excessive magnalium composite metal salt (E) (2.0 weight part) in the styrene-acrylonitrile-diene interpolymer constituent of comparative example 6, then the thermostability of styrene-acrylonitrile-diene interpolymer constituent is not good.
Styrene-acrylonitrile-diene interpolymer the constituent of comparative example 7 only uses the first copolymer component (A
1), and not containing the second copolymer component (A
2) and the 3rd copolymer component (A
3) time, then the low temperature impact strength of this styrene-acrylonitrile-diene interpolymer constituent is not good.
In sum, by the interpolation of tin methide maleate polymer (D) and magnalium composite metal salt (E), synergistic effect can be played with containing sb oxide (C) with halogen fire retardant (B), make this styrene-acrylonitrile-diene interpolymer constituent have preferably thermostability and flame retardancy, and this styrene-acrylonitrile-diene interpolymer constituent comprise the first copolymer component (A simultaneously
1), the second copolymer component (A
2) and the 3rd copolymer component (A
3) time, this constituent can be made to have preferably low temperature impact strength, so really object of the present invention can be reached.
Claims (10)
1. styrene-acrylonitrile-diene interpolymer constituent, is characterized in that comprising:
The copolymer mixture (A) of 5 weight part ~ 40 weight parts, by comprising the first copolymer component (A
1), the second copolymer component (A
2) and the 3rd copolymer component (A
3) copolymer component mixing formed; Described first copolymer component (A
1) and the second copolymer component (A
2) respectively obtained by rubber components and monomer component react through emulsion polymerization; Described 3rd copolymer component (A
3) by rubber components and monomer component obtained by the solution polymerization; Described rubber components comprises diene series rubber; Described monomer component comprises styrenic monomers and acrylic monomer;
The halogen fire retardant (B) of 5 weight part ~ 30 weight parts;
1 weight part ~ 10 weight part containing sb oxide (C);
The tin methide maleate polymer (D) of 0.2 weight part ~ 2.5 weight part;
The magnalium composite metal salt (E) of 0.2 weight part ~ 1.5 weight part; And
The styrene-acrylonitrile based copolymer (F) of 60 weight part ~ 95 weight parts.
2. styrene-acrylonitrile according to claim 1-diene interpolymer constituent, it is characterized in that, total amount based on described copolymer mixture (A) and described styrene-acrylonitrile based copolymer (F) is 100 weight parts, and the content range of described tin methide maleate polymer (D) is 0.2 weight part ~ 2.3 weight part.
3. styrene-acrylonitrile according to claim 1-diene interpolymer constituent, it is characterized in that, total amount based on described copolymer mixture (A) and described styrene-acrylonitrile based copolymer (F) is 100 weight parts, and the content range of described magnalium composite metal salt (E) is 0.3 weight part ~ 1.3 weight part.
4. styrene-acrylonitrile according to claim 1-diene interpolymer constituent, it is characterized in that, described tin methide maleate polymer (D) is selected from tin methide maleic acid potassium polymkeric substance, tin methide sodium maleate polymkeric substance, or their combination.
5. styrene-acrylonitrile according to claim 1-diene interpolymer constituent, is characterized in that, described magnalium composite metal salt (E) is selected from [(Al
2o
3) (6MgO) (CO
2)] (12H
2o), [(4.5Mg) Al
2(OH)
13(CO
3)] (3.5H
2o), [(4MgO) Al
2o
3(CO
2)] (9H
2o), [(4MgO) Al
2o
3(CO
2)] (6H
2o), [(ZnO) (MgO) Al
2o
3(CO
2)] nH
2o (n=5 ~ 9), [(4.5Mg) Al through vinyl-trimethoxysilane coupling agent modification
2(OH)
13(CO
3)] (3.5H
2or their combination O).
6. styrene-acrylonitrile according to claim 1-diene interpolymer constituent, is characterized in that, described copolymer mixture (A) is by comprising the first copolymer component (A that weight average particle diameter scope is 0.2 μm ~ 1.0 μm
1), weight average particle diameter scope is the second copolymer component (A of 0.05 μm ~ 0.2 μm
2) and weight average particle diameter scope be the 3rd copolymer component (A of 0.5 μm ~ 5 μm
3) copolymer component mixing formed.
7. styrene-acrylonitrile according to claim 6-diene interpolymer constituent, is characterized in that, described copolymer mixture (A) is by the first copolymer component (A comprising 20 % by weight ~ 80 % by weight
1), the second copolymer component (A of 15 % by weight ~ 75 % by weight
2), and the 3rd copolymer component (A of 5 % by weight ~ 65 % by weight
3) copolymer component mixing formed.
8. styrene-acrylonitrile according to claim 6-diene interpolymer constituent, it is characterized in that, described copolymer mixture (A) by comprise weight average particle diameter scope be 0.2 μm ~ 0.7 μm and content range be 20 % by weight ~ 80 % by weight the first copolymer component (A
1), weight average particle diameter scope be 0.05 μm ~ 0.15 μm and content range be 15 % by weight ~ 75 % by weight the second copolymer component (A
2), and weight average particle diameter scope be 0.5 μm ~ 5 μm and content range be 5 % by weight ~ 65 % by weight the 3rd copolymer component (A
3) copolymer component mixing formed.
9. styrene-acrylonitrile according to claim 6-diene interpolymer constituent, it is characterized in that, described copolymer mixture (A) by comprise weight average particle diameter scope be 0.2 μm ~ 0.7 μm and content range be 30 % by weight ~ 70 % by weight the first copolymer component (A
1), weight average particle diameter scope be 0.05 μm ~ 0.15 μm and content range be 25 % by weight ~ 65 % by weight the second copolymer component (A
2), and weight average particle diameter scope be 0.5 μm ~ 5 μm and content range be 5 % by weight ~ 45 % by weight the 3rd copolymer component (A
3) copolymer component mixing formed.
10. a products formed for styrene-acrylonitrile-diene interpolymer constituent, is characterized in that, formed by the styrene-acrylonitrile according to any one of claim 1 to 9-diene interpolymer constituent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100149828A TWI440666B (en) | 2011-12-30 | 2011-12-30 | Styrene-acrylonitrile-diene-based copolmer composition and products made from said styrene-acrylonitrile-diene-based copolmer composition |
| TW100149828 | 2011-12-30 |
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| CN103183880A CN103183880A (en) | 2013-07-03 |
| CN103183880B true CN103183880B (en) | 2015-06-10 |
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Citations (4)
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|---|---|---|---|---|
| CN1053075A (en) * | 1990-01-02 | 1991-07-17 | 陶氏化学公司 | Have the three peak distribution ABS compositions that good gloss and gloss susceptibility reduce |
| CN1148609A (en) * | 1996-08-23 | 1997-04-30 | 奇美实业股份有限公司 | Styrene series resin composition |
| CN1152000A (en) * | 1995-12-14 | 1997-06-18 | 奇美实业股份有限公司 | Fireproof styrene resin composite |
| CN1894323A (en) * | 2003-11-12 | 2007-01-10 | 科聚亚公司 | Liquid microemulsion stabilizer composition for halogen-containing polymers |
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2011
- 2011-12-30 TW TW100149828A patent/TWI440666B/en active
-
2012
- 2012-03-16 CN CN201210071509.6A patent/CN103183880B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053075A (en) * | 1990-01-02 | 1991-07-17 | 陶氏化学公司 | Have the three peak distribution ABS compositions that good gloss and gloss susceptibility reduce |
| CN1152000A (en) * | 1995-12-14 | 1997-06-18 | 奇美实业股份有限公司 | Fireproof styrene resin composite |
| CN1148609A (en) * | 1996-08-23 | 1997-04-30 | 奇美实业股份有限公司 | Styrene series resin composition |
| CN1894323A (en) * | 2003-11-12 | 2007-01-10 | 科聚亚公司 | Liquid microemulsion stabilizer composition for halogen-containing polymers |
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| Publication number | Publication date |
|---|---|
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| CN103183880A (en) | 2013-07-03 |
| TWI440666B (en) | 2014-06-11 |
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