CN103183880A - Styrene-acrylonitrile-diene copolymer composition and molded article using same - Google Patents
Styrene-acrylonitrile-diene copolymer composition and molded article using same Download PDFInfo
- Publication number
- CN103183880A CN103183880A CN2012100715096A CN201210071509A CN103183880A CN 103183880 A CN103183880 A CN 103183880A CN 2012100715096 A CN2012100715096 A CN 2012100715096A CN 201210071509 A CN201210071509 A CN 201210071509A CN 103183880 A CN103183880 A CN 103183880A
- Authority
- CN
- China
- Prior art keywords
- weight
- styrene
- copolymer
- copolymer component
- acrylonitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 187
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 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
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 150000002367 halogens Chemical class 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims description 88
- 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 61
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 61
- 239000002245 particle Substances 0.000 claims description 43
- 239000000126 substance Substances 0.000 claims description 33
- 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
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 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
- 238000000465 moulding Methods 0.000 claims description 11
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 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
- 239000003063 flame retardant Substances 0.000 abstract 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 17
- -1 polypropylene Polymers 0.000 description 17
- 239000012986 chain transfer agent Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000002360 preparation method Methods 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
- 238000000034 method Methods 0.000 description 14
- 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
- 229920000126 latex Polymers 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
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 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
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 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
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000012153 distilled water Substances 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
- 150000001875 compounds Chemical class 0.000 description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 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
- 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
- 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
- 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 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
- 229910052787 antimony Inorganic materials 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
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction 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
- QJQZEJFUIOWFMS-UHFFFAOYSA-N formaldehyde;sulfanediol Chemical compound O=C.OSO QJQZEJFUIOWFMS-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 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
- 239000002994 raw material Substances 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 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
- 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
- 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
- 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
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-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
- 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
- IFJPHKRPXHETAZ-UHFFFAOYSA-N C=C.ClC1=CC(=CC(=C1)Cl)Cl Chemical compound C=C.ClC1=CC(=CC(=C1)Cl)Cl IFJPHKRPXHETAZ-UHFFFAOYSA-N 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
- 208000006558 Dental Calculus Diseases 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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920003135 Eudragit® L 100-55 Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 239000004159 Potassium persulphate Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- 238000004458 analytical method Methods 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 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
- 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
- 239000011258 core-shell material Substances 0.000 description 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000010304 firing Methods 0.000 description 1
- 229940017705 formaldehyde sulfoxylate Drugs 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
- 239000007788 liquid Substances 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
- 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
- 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
- 238000012545 processing Methods 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
- 238000011084 recovery Methods 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
- 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
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 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 1
- 239000012745 toughening agent Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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 (B); 1 to 10 parts by weight ofAntimony-containing oxide ; 0.2 to 2.5 parts by weight of a dimethyltin maleate polymer (D); 0.2 to 1.5 parts by weight of an aluminum magnesium composite metal salt (E); and 60 to 95 parts by weight of a second styrene-acrylonitrile copolymer (F). The copolymer mixture (A) is prepared by mixing a first copolymer component (A)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 that is applicable to the plastic molded article of preparation electricmaterial, office equipment, trolley part, household supplies etc., particularly a kind of styrene-acrylonitrile-diene interpolymer constituent that contains tin methide maleate polymkeric substance and magnalium composite metal salt.It is a kind of by the formed moulding product of this constituent that the present invention also provides.
Background technology
The composition that the general plastic molded article that is used for electricmaterial or household supplies etc. contains mostly is rubber modified styrene series resin, polycarbonate resin (Polycarbonate Resin) etc.This rubber modified styrene series resin, as styrene-acrylonitrile-butadiene resin (Acrylonitrile-Butadiene-Styrene Resin, be called for short ABS), have high surface hardness, excellent in chemical resistance, electrical property is good and is easy to excellent specific properties such as moulding, and be widely used gradually to various plastic molded articles.
Yet, not good because of its flame retardancy matter when this rubber modified styrene series resin is used in the environment that need possess flame retardancy, can't reach difficult effect of firing.Though follow-up research promotes its flame retardancy by adding the halogen incombustible agent, but easily cause the thermostability of rubber modified styrene series resin not good, and can influence the physical properties (as low temperature impact strength) of rubber modified styrene series resin, make rubber modified styrene series resin use shortcomings such as easily producing embrittlement in low temperature environment.Therefore, though prior art can promote the flame resistivity of rubber modified styrene series resin, also can have influence on the original good physical properties of rubber modified styrene series resin simultaneously.
Be added at present in the chloride resin [for example polyvinyl chloride (PVC) RESINS (PVC) or acrylic resin (polypropylene)], the reagent that improves the thermostability of resin is dibutyl tin maleate polymkeric substance (polymer of dibutyltin maleate is called for short DBTM).But this dibutyl tin maleate polymkeric substance resolves into dibutyl tin (dibutylTin is called for short DBT) easily, and this dibutyl tin is for upsetting the biological internal secretion effect material of (endocrine disrupters is called for short Eds).Therefore, this dibutyl tin maleate polymkeric substance future can be limited the quantity of or even the forbidding control material, therefore look for the tool feature of environmental protection, and meet the standard of the relevant decree of carrying capacity of environment material control, and the thermo-stabilizer that does not damage the rubber modified styrene series resin physical properties is dealer's utmost point problem to be broken through.
In view of above-mentioned, except effectively keeping flame retardancy matter, still need develop a kind of rubber modified styrene series resin constituent, and it after forming the moulding product, following process can make these moulding product have preferable thermostability and low temperature impact strength, to meet the industry demand.
Summary of the invention
First purpose of the present invention is for providing a kind of styrene-acrylonitrile-diene interpolymer constituent that has preferable thermostability and flame retardancy simultaneously.Styrene-acrylonitrile of the present invention-diene interpolymer constituent comprises:
The copolymer mixture (A) of 5 weight parts～40 weight parts is by comprising the first copolymer component (A
1), the second copolymer component (A
2) and the 3rd copolymer component (A
3) copolymer component mix form; The described first copolymer component (A
1) and the second copolymer component (A
2) obtained through the emulsion polymerization reaction by rubber components and monomer component respectively; Described the 3rd copolymer component (A
3) obtained through solution polymerization by rubber components and monomer component; Described rubber components comprises diene series rubber; Described monomer component comprises styrenic monomers and acrylic monomer;
The halogen incombustible agent (B) of 5 weight parts～30 weight parts;
1 weight part～10 weight parts contain sb oxide (C);
0.2 the tin methide maleate polymkeric substance (D) of weight part～2.5 weight parts;
0.2 the magnalium composite metal salt (E) of weight part～1.5 weight parts; And
Second styrene-acrylonitrile of 60 weight parts～95 weight parts is copolymerization (F).
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, total amount based on described copolymer mixture (A) and the described second styrene-acrylonitrile based copolymer (F) is 100 weight parts, and the content range of described tin methide maleate polymkeric substance (D) is 0.2 weight part～2.3 weight parts.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, total amount based on described copolymer mixture (A) and the 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 parts.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, described tin methide maleate polymkeric substance (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), through coupling agent modified [(4.5Mg) Al of vinyl-Trimethoxy silane
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 that the weight average particle diameter scope is the first copolymer component (A of 0.2 μ m～1.0 μ m
1), the weight average particle diameter scope is the second copolymer component (A of 0.05 μ m～0.2 μ m
2) and the weight average particle diameter scope be the 3rd copolymer component (A of 0.5 μ m～5 μ m
3) copolymer component mix form.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, described copolymer mixture (A) is by the first copolymer component (A that comprises 20 weight %～80 weight %
1), the second copolymer component (A of 15 weight %～75 weight %
2), and the 3rd copolymer component (A of 5 weight %～65 weight %
3) copolymer component mix form.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, described copolymer mixture (A) is by comprising that the weight average particle diameter scope is that 0.2 μ m～0.7 μ m and content range are the first copolymer component (A of 20 weight %～80 weight %
1), the weight average particle diameter scope is that 0.05 μ m～0.15 μ m and content range are the second copolymer component (A of 15 weight %～75 weight %
2), and the weight average particle diameter scope is that 0.5 μ m～5 μ m and content range are the 3rd copolymer component (A of 5 weight %～65 weight %
3) copolymer component mix form.
According to styrene-acrylonitrile of the present invention-diene interpolymer constituent, described copolymer mixture (A) is by comprising that the weight average particle diameter scope is that 0.2 μ m～0.7 μ m and content range are the first copolymer component (A of 30 weight %～70 weight %
1), the weight average particle diameter scope is that 0.05 μ m～0.15 μ m and content range are the second copolymer component (A of 25 weight %～65 weight %
2), and the weight average particle diameter scope is that 0.5 μ m～5 μ m and content range are the 3rd copolymer component (A of 5 weight %～45 weight %
3) copolymer component mix form.
Second purpose of the present invention is for providing a kind of moulding product with styrene-acrylonitrile-diene interpolymer constituent of preferable low temperature impact strength.The moulding product of styrene-acrylonitrile of the present invention-diene interpolymer constituent are formed by aforesaid styrene-acrylonitrile-diene interpolymer constituent.
Beneficial effect of the present invention is: by the interpolation of tin methide maleate polymkeric substance (D) and magnalium composite metal salt (E), can bring into play synergistic effect with containing sb oxide (C) with halogen incombustible agent (B), make this styrene-acrylonitrile-diene interpolymer constituent have preferable 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 parts～40 weight parts is by comprising the first copolymer component (A
1), the second copolymer component (A
2) and the 3rd copolymer component (A
3) copolymer component mix form; This first copolymer component (A
1) and the second copolymer component (A
2) obtained through the emulsion polymerization reaction by rubber components and monomer component respectively; The 3rd copolymer component (A
3) obtained through solution polymerization by rubber components and monomer component; This rubber components comprises diene series rubber; This monomer component comprises styrenic monomers and acrylic monomer;
The halogen incombustible agent (B) of 5 weight parts～30 weight parts;
1 weight part～10 weight parts contain sb oxide (C);
0.2 the tin methide maleate polymkeric substance (D) of weight part～2.5 weight parts;
0.2 the magnalium composite metal salt (E) of weight part～1.5 weight parts; And
The second styrene-acrylonitrile based copolymer (F) of 60 weight parts～95 weight parts.
Styrene-acrylonitrile of the present invention-diene interpolymer constituent uses tin methide maleate polymkeric substance (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 polymkeric substance (D), can make styrene-acrylonitrile of the present invention-diene interpolymer constituent have the feature of environmental protection, simultaneously, this magnalium composite metal salt (E) can be met the hydrogen halide effect that heat discharges with halogen incombustible agent (B), reduce hydrogen halide to the influence of styrene-acrylonitrile-diene interpolymer constituent thermostability, promote the thermostability of styrene-acrylonitrile-diene interpolymer constituent then.
Below will be elaborated to each composition in styrene-acrylonitrile-diene interpolymer constituent one by one:
[copolymer mixture (A)]
Preferably, this copolymer mixture (A) is by comprising that the weight average particle diameter scope is the first copolymer component (A of 0.2 μ m～1.0 μ m
1), the weight average particle diameter scope is the second copolymer component (A of 0.05 μ m～0.2 μ m
2) and the weight average particle diameter scope be the 3rd copolymer component (A of 0.5 μ m～5 μ m
3) copolymer component mix form.Employed copolymer component can make this styrene-acrylonitrile-diene interpolymer constituent have preferable low temperature impact strength in this copolymer mixture (A).
Preferably, this copolymer mixture (A) is by the first copolymer component (A that comprises 20 weight %～80 weight %
1), the second copolymer component (A of 15 weight %～75 weight %
2), and the 3rd copolymer component (A of 5 weight %～65 weight %
3) copolymer component mix form.
More preferably, this copolymer mixture (A) is by comprising that the weight average particle diameter scope is that 0.2 μ m～0.7 μ m and content range are the first copolymer component (A of 20 weight %～80 weight %
1), the weight average particle diameter scope is that 0.05 μ m～0.15 μ m and content range are the second copolymer component (A of 15 weight %～75 weight %
2), and the weight average particle diameter scope is that 0.5 μ m～5 μ m and content range are the 3rd copolymer component (A of 5 weight %～65 weight %
3) copolymer component mix form.
Again more preferably, this copolymer mixture (A) is by comprising that the weight average particle diameter scope is that 0.2 μ m～0.7 μ m and content range are the first copolymer component (A of 30 weight %～70 weight %
1), the weight average particle diameter scope is that 0.05 μ m～0.15 μ m and content range are the second copolymer component (A of 25 weight %～65 weight %
2), and the weight average particle diameter scope is that 0.5 μ m～5 μ m and content range are the 3rd copolymer component (A of 5 weight %～45 weight %
3) copolymer component mix form.
The present invention first copolymer component (A
1) and the second copolymer component (A
2) the 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 first styrene-acrylonitrile-diene interpolymer (a-1-1), second styrene-acrylonitrile-diene interpolymer (a-1-2), or their combination.
This first styrene-acrylonitrile-diene interpolymer (a-1-1) is by comprising that one or more styrene based copolymers, first rubber body that coats styrene based copolymer and first graft copolymer that grafts on first rubber body are constituted; And this second styrene-acrylonitrile-diene interpolymer (a-1-2) is by comprising that second graft copolymer that second rubber body and this graft on second rubber body is constituted.This first rubber body and second rubber body can be identical or different, and this first graft copolymer and second graft copolymer can be identical or different.This styrene based copolymer, first graft copolymer or second graft copolymer are formed through polyreaction by the monomer component that comprises styrenic monomers and acrylic monomer respectively.This first rubber body or second rubber body are formed by rubber components respectively.
＜the first copolymer component (A
1) preparation
This first copolymer component (A
1) obtained through the emulsion polymerization reaction by first monomer component of first rubber latex (Gu composition) that comprises 40 weight %～90 weight % and 10 weight %～60 weight %.This first monomer component comprises the styrenic monomers (i-1) of 50 weight %～85 weight %, the acrylic monomer (i-2) of 15 weight %～50 weight %, and other copolymerizable vinyl monomer (i-3) of 0 weight %～35 weight %.In this emulsion polymerization reaction, optionally can add emulsifying agent, polymerization starter or chain-transfer agent etc.Optionally can be again after emulsion polymerization reaction via condense, dehydration, drying and other steps.
This first rubber latex is obtained through emulsion polymerization method by first rubber components, and further gives agglomeration (Agglomeration) processing again after the emulsion polymerization reaction, and optionally adds other copolymerizable monomer in the emulsion polymerization reaction.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 is 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, vinylbenzene-diene series rubber, acrylic-nitrile rubber etc.This divinyl rubber is including but not limited to the divinyl rubber of high-cis (Hi-Ci s) content and the divinyl rubber of low cis (Low-Cis) content.The typical weight of the cis in the divinyl rubber of this high-cis content (Cis)/vinyl (Vinyl) consists of (94～99 weight %)/(1～5 weight %), all the other compositions then are trans (Trans) structure, and mooney viscosity (mooney viscosity) is between 20～120, molecular weight ranges is with 100,000～800,000 is good.The typical weight compositing range of the cis/vinyl in the divinyl rubber of this low cis content is at (20～40 weight %)/(1～20 weight %), and all the other are transconfiguration, and mooney viscosity is between 20～120.
This vinylbenzene-diene series rubber is including but not limited to styrene butadiene rubbers (styrene-butadiene rubber is called for short SBR).The structure of this vinylbenzene-diene series rubber can be diblock (di-block) copolymerization, three blocks (tri-block) copolymerization, random (random) copolymerization or star formula copolymerization (star type).Preferably, the part by weight scope of styrene monomer unit and butadiene monomer unit is 5/95～80/20 in this styrene butadiene rubbers.Preferably, the molecular weight ranges of this vinylbenzene-diene series 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 is handled can adopt general freezing agglomeration technique, additive agglomeration technique or mechanical agglomeration technique etc.The additive that uses in this additive agglomeration technique comprises but is not limited to (1) acidic substance: acetic anhydride, hydrogenchloride, sulfuric acid etc.; (2) salt compounds: sodium-chlor, Repone K, calcium chloride etc.; (3) contain carboxylic acid group's polymer coagulant: (methyl) vinylformic acid-(methyl) acrylate copolymer [as methacrylic acid-butyl acrylate copolymer, EUDRAGIT L100-55] etc.
For instance, diene series rubber emulsion manufacture method can use diene monomer (for example divinyl) with the emulsion polymerization method polymerization, perhaps, monomers such as the vinylbenzene of the diene monomer of 50 weight %～100 weight % and 0 weight %～50 weight % and/or vinyl cyanide are reacted with emulsion polymerization method, after can obtaining weight average particle diameter and being the small particle size diene series rubber emulsion of 0.05 μ m～0.2 μ m, then give agglomeration and handle, this small particle size diene series rubber emulsion is agglomerated into the big particle diameter diene series rubber emulsion of weight average particle diameter 0.2 μ m～1.0 μ m.
This first copolymer component (A
1) comprise second styrene-acrylonitrile-diene interpolymer (a-1-2) and the first styrene-acrylonitrile based copolymer (a-2).
First copolymer component (the A
1) second styrene-acrylonitrile-diene interpolymer (a-1-2) in the percentage of grafting of rubber body can be controlled by polymeric reaction condition, for example: the addition means of the consumption of polymerization temperature, polymerization starter, emulsifying agent, chain transfer agent and kind, first monomer component etc. is controlled.And first monomer component can once add, and also can add in batches, also can add continuously or each monomer segmentation is added, and can obtain the first copolymer component (A of weight average particle diameter 0.2 μ m required for the present invention～1.0 μ m
1).First copolymer component (the A
1) 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 second graft copolymer in second styrene-acrylonitrile-diene interpolymer (a-1-2) is 40,000～120,000.
Preferably, this first copolymer component (A
1) the weight average particle diameter scope be 0.20 μ m～0.7 μ m.
This styrenic monomers (i-1) can be used alone or as a mixture, and this styrenic monomers (i-1) including but not limited to vinylbenzene, alpha-methyl styrene, α-chloro-styrene, right-t-butyl styrene, p-methylstyrene, neighbour-chloro-styrene, right-chloro-styrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-trichlorobenzene ethene, 2,5-Dowspray 9 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 monomer etc. including but not limited to acrylic monomer, metha crylic monomer, acrylic ester monomer, methacrylate ester monomer, maleimide.
This methacrylate ester monomer is including but not limited to methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, methacrylic acid dodecane ester, methacrylic acid 2-hydroxyl ethyl ester, glytidyl methacrylate, dimethylaminoethyl methacrylate (dimethylaminoethyl methacrylate) etc.Preferably, this methacrylate ester monomer is methyl methacrylate.
In this emulsion polymerization reaction, optionally can add polymerization starter.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), the two benzene sec.-propyls (dicumyl hydroperoxide) of hydrogen peroxide, tert-butyl peroxide (t-butyl peroxide), hydrogen phosphide cumene (cumene peroxide), Potassium Persulphate etc.Wherein preferable with the organic hydroperoxide class.
In this emulsion polymerization reaction, optionally can add chain-transfer agent.This chain-transfer agent can be used alone or as a mixture, and this chain-transfer agent including but not limited to just-lauryl mercaptan (n-dodecyl mercaptan, abbreviation NDM), uncle-lauryl mercaptan (t-dodecyl mercaptan is called for short TDM), n-butyl mercaptan, n-octyl mercaptan etc.
Preferably, the operating temperature range of this emulsion polymerization reaction is below 90 ℃; More preferably, the operating temperature range of this emulsion polymerization reaction is 30 ℃～80 ℃.
In this emulsion polymerization reaction, optionally can add salting-out agent.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, vitriolate of tartar, sodium bisulfite, Potassium hydrogen sulfite, ammonium bisulfite, pyrosulfite, pyrosulphate, hyposulfite (hydrosulfite), formaldehydesulfoxylate (formaldehyde sulfoxylate salt), formolation sulfoxylic acid hydrogen salt (formaldehyde sulfoxylate salt), thiosulphate, sulfoxylate.Preferably, these salting-out agent are selected from sodium bisulfite, Sodium Pyrosulfite, V-Brite B or formolation sodium hydrosulfite.Preferably, be 100 weight parts in the usage quantity summation of (i-1), (i-2), (i-3), the usage quantity scope of these salting-out agent is 10ppm～1,000ppm.
＜the second copolymer component (A
2) preparation
This second copolymer component (A
2) comprise second rubber latex (Gu composition) of 40 weight %～90 weight % and 10 weight %～60 weight % second monomer component obtained through the emulsion polymerization reaction.This second monomer component comprises the styrenic monomers of 50 weight %～85 weight %, the acrylic monomer of 15 weight %～50 weight %, and other copolymerizable vinyl monomer of 0 weight %～35 weight %.In this emulsion polymerization reaction, optionally can add emulsifying agent, polymerization starter or chain-transfer agent etc.Optionally can be again after emulsion polymerization reaction via condense, dehydration, drying and other steps.
This second rubber latex is obtained through emulsion polymerization method by second rubber components, and optionally adds other copolymerizable monomer in the emulsion polymerization reaction.This second rubber components is as the above-mentioned preparation first copolymer component (A
1) 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 handled without agglomeration.
The kind of the styrenic monomers in this second monomer component, acrylic monomer, other copolymerizable vinyl monomer, polymerization starter and chain-transfer agent is as the above-mentioned preparation first copolymer component (A
1) in the kind of styrenic monomers (i-1), acrylic monomer (i-2), other copolymerizable vinyl monomer (i-3), polymerization starter and chain-transfer agent, so repeat no more.The condition of this polyreaction is also with the above-mentioned preparation first copolymer component (A
1) polymeric reaction condition.
This second copolymer component (A
2) comprise second styrene-acrylonitrile-diene interpolymer (a-1-2) and the first styrene-acrylonitrile based copolymer (a-2).
Second copolymer component (the A
2) second styrene-acrylonitrile-diene interpolymer (a-1-2) in the percentage of grafting of rubber body can be controlled by polymeric reaction condition, for example: the addition means of the consumption of polymerization temperature, polymerization starter, emulsifying agent, chain transfer agent and kind, second monomer component etc. is controlled.And second monomer component can once add, and also can add in batches, also can add continuously or each monomer segmentation is added, and can obtain the second copolymer component (A of weight average particle diameter 0.05 μ m required for the present invention～0.2 μ m
2).Second copolymer component (the A
2) 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 second graft copolymer in second styrene-acrylonitrile-diene interpolymer (a-1-2) is 40,000～120,000.
Preferably, this second copolymer component (A
2) the weight average particle diameter scope be 0.05 μ m～0.15 μ m.
The preparation of＜the three copolymer component (A3) 〉
The 3rd copolymer component (A
3) be that to comprise the 3rd monomer component of the 3rd rubber components of 3 weight parts～15 weight parts and 100 weight parts obtained through body or solution polymerization.The 3rd monomer component comprises the styrenic monomers of 50 weight %～80 weight %, the acrylic monomer of 15 weight %～50 weight %, and other copolymerizable vinyl monomer of 0 weight %～35 weight %.In this body or the solution polymerization, optionally can add solvent, polymerization starter or chain-transfer agent etc.
The 3rd rubber components is as the above-mentioned preparation first copolymer component (A
1) first rubber components.
The 3rd copolymer component (A
3) manufacture method be that the 3rd rubber components is dissolved in the 3rd monomer component and/or the solvent in advance, import reactive tank again and carry out graft polymerization reaction.This reactive tank can be combined by a plurality of, generally can utilize with the still type reactive tank of machine,massing or the piston-type reactive tank of tower.
The kind of this styrenic monomers, acrylic monomer, other copolymerizable vinyl monomer, polymerization starter and chain-transfer agent is as the above-mentioned preparation first copolymer component (A
1) in the kind of styrenic monomers (i-1), acrylic monomer (i-2), other copolymerizable vinyl monomer (i-3), polymerization starter and chain-transfer agent, so repeat no more.
The 3rd copolymer component (A
3) comprise first styrene-acrylonitrile-diene interpolymer (a-1-1) and the first styrene-acrylonitrile based copolymer (a-2).
Preferably, the 3rd copolymer component (A
3) the weight average particle diameter scope be 0.5 μ m～5 μ m.More preferably, the 3rd copolymer component (A
3) the weight average particle diameter scope be 0.5 μ m～3 μ m.
[halogen incombustible agent (B)]
This halogen incombustible agent (B) can be used alone or as a mixture, preferably, this halogen incombustible agent (B) is selected from tetrabromo-bisphenol (tetrabromobisphenol A, be called for short TBBA), tetrabromo-bisphenol s (tetrabromo bisphenol S), tetrabromobisphenol F (tetrabromo bi sphenol F), tetrabromo-bisphenol two (2, the 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, be 100 weight parts based on the total amount of this copolymer mixture (A) and this second styrene-acrylonitrile based copolymer (F), the content range of this halogen incombustible agent (B) is 10 weight parts～27 weight parts.
[containing sb oxide (C)]
This contains sb oxide (C) and can be used alone or as a mixture, and preferably, this contains, and sb oxide (C) is selected from ANTIMONY TRIOXIDE SB 203 99.8 PCT, (antimony trioxide is called for short Sb to antimonous oxide
2O
3), antimony tetroxide, antimony peroxide, or these combination.Preferably, be 100 weight parts based on the total amount of this copolymer mixture (A) and this second styrene-acrylonitrile based copolymer (F), this content range that contains sb oxide (C) is 3 weight parts～8 weight parts.Preferably, the content of halogen in this halogen incombustible agent (B) and this part by weight scope that contains the antimony content in the sb oxide (C) are 1～10.
[tin methide maleate polymkeric substance (D)]
Preferably, this tin methide maleate polymkeric substance (polymer ofdimethyltin maleate is called for short DMTM) (D) is selected from tin methide maleic acid potassium polymkeric substance, tin methide sodium maleate polymkeric substance or their combination.When the content of tin methide maleate polymkeric substance (D) during less than 0.2 weight part or greater than 2.5 weight parts, the thermostability extreme difference of styrene-acrylonitrile-diene interpolymer constituent then.Preferably, be 100 weight parts based on the total amount of this copolymer mixture (A) and this second styrene-acrylonitrile based copolymer (F), the content range of this tin methide maleate polymkeric substance (D) is 0.2 weight part～2.3 weight parts.
[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), through coupling agent modified [(4.5Mg) Al of vinyl-Trimethoxy silane
2(OH)
13(CO
3)] (3.5H
2O), or they one the combination.
When the content of magnalium composite metal salt (E) during less than 0.2 weight part or greater than 1.5 weight parts, the thermostability extreme difference of styrene-acrylonitrile-diene interpolymer constituent then.Preferably, be 100 weight parts based on the total amount of this copolymer mixture (A) and this second styrene-acrylonitrile based copolymer (F), the content range of this magnalium composite metal salt (E) is 0.3 weight part～1.3 weight parts.
[the second styrene-acrylonitrile based copolymer (F)]
This second styrene-acrylonitrile based copolymer (F) is by the acrylic monomer of the styrenic monomers that comprises 50 weight %～80 weight %, 20 weight %～50 weight %, and the 4th monomer component that optionally adds other copolymerizable vinyl monomer is obtained through 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 preferable 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 the above-mentioned preparation first copolymer component (A
1) in the kind of styrenic monomers (i-1), acrylic monomer (i-2), other copolymerizable vinyl monomer (i-3), polymerization starter and chain-transfer agent of first monomer component, so repeat no more.
[additive (G)]
In styrene-acrylonitrile of the present invention-diene interpolymer constituent, can add various additives (G) in case of necessity, for example: 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 be respectively at the preparation first copolymer component (A
1), the preparation the second copolymer component (A
2), the preparation the 3rd copolymer component (A
3) polyreaction in, after the polyreaction, condense preceding or the preparation styrene-acrylonitrile-diene interpolymer constituent process in add.Preferably, be 100 weight parts based on the total amount of this copolymer mixture (A) and this second styrene-acrylonitrile based copolymer (F), 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 parts.
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 that for example weight average molecular weight is at the nucleocapsid more than 50,000 (core-shell) type processing aid including but not limited to methyl methacrylate.This UV light absorber is including but not limited to benzotriazole based compound, benzophenone based compound or cyanogen acrylic acid series compound 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, with copolymer mixture (A), halogen incombustible agent (B), contain sb oxide (C), tin methide maleate polymkeric substance (D), magnalium composite metal salt (E) and the second styrene-acrylonitrile based copolymer (F), be positioned in the agitator and stir, make its even mixing, additive (G) can be added in case of necessity, styrene-acrylonitrile of the present invention-diene interpolymer constituent can be obtained.
The moulding product of styrene-acrylonitrile of the present invention-diene interpolymer constituent are formed by aforesaid styrene-acrylonitrile-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 known in the past mode, so repeat no more.
The present invention will be described further with regard to following examples, but will be appreciated that, described embodiment is only for illustrating usefulness, and should not be interpreted as restriction of the invention process.
＜embodiment 〉
[synthesis example 1] first copolymer component (A
1)
With 1 of 95.0 weight parts, uncle-the lauryl mercaptan of the distilled water of the potassium oleate of the trisodium phosphate of the potassium persulfate solution of the vinyl cyanide of 3-divinyl, 5.0 weight parts, 15.0 weight parts, 3.0 weight parts, 1.5 weight parts, 140.0 weight parts and 0.2 weight part reacted 12 hours under 65 ℃ 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 μ m.
85.0 the formolation sodium hydrosulfite of the dioctyl sodium sulphosuccinate of the uncle-lauryl mercaptan of parts by weight of acrylic ethyl ester, 15.0 parts by weight of acrylic, 0.3 weight part, the potassium oleate of 2.0 weight parts, 1.0 weight parts, the isopropyl benzene hydrogen peroxide of 0.4 weight part, 0.3 weight part and the distilled water of 200.0 weight parts reacted 5 hours under 75 ℃ of temperature of reaction, can make the polymer coagulant that contains the carboxylic acid group of transformation efficiency 95%, pH value 6.0.
Then, utilize the above-mentioned polymer coagulant that contains the carboxylic acid group (dry weight) of 3 weight parts to come the above-mentioned rubber latex (dry weight) of agglomeration 100 weight parts, the pH value of the agglomeration rubber latex of gained is 8.5, and weight average particle diameter is 0.30 μ m.
Then, the distilled water of the edta solution (concentration 0.25 weight %) of the formolation bisulphite sodium solution (concentration 10 weight %) of the copperas solution (concentration 0.2 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, 20.0 weight parts and 200.0 weight parts is mixed and react.This vinylbenzene and vinyl cyanide added polymerization in the reactive system with continuous addition manner in 5 hours, then, and with calcium chloride (CaCl
2) condense, dewater after, be dried to water content again below 2%, just can make the present invention first copolymer component (A
1).
[synthesis example 2] second copolymer component (A
2)
With 1 of 95.0 weight parts, uncle-the lauryl mercaptan of the distilled water of the potassium oleate of the trisodium phosphate of the potassium persulfate solution of the vinyl cyanide of 3-divinyl, 5.0 weight parts, 15.0 weight parts, 3.0 weight parts, 1.5 weight parts, 140.0 weight parts and 0.2 weight part reacted 12 hours under 65 ℃ 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 μ m.
Above-mentioned rubber latex (dry weight) with 100.0 weight parts, 75.0 the vinylbenzene of weight part, 25.0 the vinyl cyanide of weight part, 2.0 the potassium oleate of weight part, 0.6 the uncle-lauryl mercaptan of weight part, 1.4 the hydrogen phosphide cumene of weight part, 8.6 the copperas solution of weight part (concentration 0.2 weight %), 8.6 the formolation bisulphite sodium solution of weight part (concentration 10 weight %), 57.0 the distilled water of the edta solution of weight part (concentration 0.25 weight %) and 200.0 weight parts mixes and reacts.This vinylbenzene and vinyl cyanide added polymerization in the reactive system with continuous addition manner in 5 hours, then, and with calcium chloride (CaCl
2) condense, dewater after, be dried to moisture content again below 2%, just can make the present invention second copolymer component (A
2).
[synthesis example 3] the 3rd copolymer component (A
3)
With the polyhutadiene of 6.6 weight parts (Asahi Chemical Industry's corporate system, trade(brand)name: Asadedne55AS), the benzoyl peroxide of the vinyl cyanide of the ethylbenzene of the vinylbenzene of 74.4 weight parts, 30 weight parts, 25.6 weight parts and 0.08 weight part mixes and form mixture.
Said mixture is supplied in first reactor (45 liters of volumes) continuously reacts, temperature of reaction is 100 ℃.Configuration is provided with the screw mixer of refrigeration cycle pipe in this first reactor, and its stir speed (S.S.) is 150rpm.Monomer conversion is 15% o'clock in the question response, reaction mixture behind first reactor reaction is taken out continuously, and import in regular turn in second reactor, the 3rd reactor, the 4th reactor, uncle-the lauryl mercaptan that in the 3rd reactor, adds 0.1 weight part simultaneously, the phase reversion phenomenon produces in second reactor, the device of above-mentioned second reactor, the 3rd reactor, the 4th reactor is identical with first reactor, but temperature of reaction is 105 ℃, 110 ℃, 125 ℃ in regular turn, and stir speed (S.S.) is 270rpm, 150rpm and 110rpm in regular turn.
Treat to reach at 60% o'clock in the transformation efficiency of the reaction mixture of the 4th reactor, reaction mixture is taken out import in the devolatilization device, remove unreacted monomer and volatile matter, just can make the present invention the 3rd copolymer component (A
3), or further with its extrusion granulator.
[synthesis example 4] second styrene-acrylonitrile based copolymer (F)
To remain on 108 ℃ and capacity be 45 liters the continous way still type reactor with agitator to temperature in the speed of 12kg/hr the vinyl cyanide of the vinylbenzene of 68 weight % and 32 weight % being placed, mix and react, speed with 3.0g/hr is added into uncle-lauryl mercaptan in the reaction again, and make the toluene ratio in the reaction solution remain on 15%, percent polymerization remains on 55%.After the reaction, this reaction solution removed volatile component by the devolatilization device after, can obtain acrylonitrile content is the particle of the second styrene-acrylonitrile based copolymer (F) of 28 weight %.
When obtaining the particle of this second styrene-acrylonitrile based copolymer (F), can the volatile component of removing is condensing as recovery liquid with condenser, and be added in the reaction continuously and re-use.
[embodiment 1] styrene-acrylonitrile-diene interpolymer constituent
The synthesis example 1 of 45 weight %, the synthesis example 2 of 35 weight % and the synthesis example 3 of 20 weight % are mixed, form copolymer mixture (A), then, the copolymer mixture (A) that takes 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; Shenzhen Jeff industrial corporation), (label: standing grain gathers company for the tin methide maleate polymkeric substance of 1.0 weight parts model: FR-1524), the antimonous oxide of 5.5 weight parts (label:; Model: HS3721) and the magnalium composite metal salt of 1.0 weight parts mix, can obtain styrene-acrylonitrile of the present invention-diene interpolymer constituent, its analysis and physical properties evaluation result see Table 1.This magnalium composite metal salt is through coupling agent modified [(4.5Mg) Al of vinyl-Trimethoxy silane
2(OH)
13(CO
3)] (3.5H
2O); Should [(4.5Mg) Al
2(OH)
13(CO
3)] (3.5H
2O) be DHT-4A-2 by Ky owa Chem. corporate system and model, and the weight ratio of this vinyl-Trimethoxy silane coupling agent and DHT-4A-2 is 3/17.
[embodiment 2～6 and comparative example 1～7]
Embodiment 2～6 and comparative example 1～7th prepare this styrene-acrylonitrile-diene interpolymer constituent with the step identical with embodiment 1, and different places are: change raw material type and usage quantity.This raw material type, usage quantity and evaluation result see Table 1.
[test item]
1. low temperature impact strength evaluation (Izod) is measured:
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 place-20 ℃ of refrigeration chambers after freezing 24 hours; to use instrument Dynatup 8250; stipulate according to AS TM-3763; 23.64 kilograms of the weight of dropping hammer, 0.56 meter of height of the fall, impact velocity 3.34m/sec tests; measurement makes the described test piece required energy that breaks, 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 carry out granulation; then; (Taiwan shakes male mechanical society system, and model: 4OZ is SM-90) at 200 ℃ of disks of injecting diameter 55mm and thickness 3.2mm with injection moulding machine respectively.
After treating described disk cooling, with spectrometer (model: Gretoawacbeth color-eye 3100) survey its yellowness index YI
1Value.Then, place the rotating disc type baking oven after 1 hour, after cooling, to measure its yellowness index YI again with 200 ℃ of high bakes respectively in described disk
2Value calculates yellowness index difference Δ YI, can judge its thermostability.
ΔYI＝YI
2-YI
1
◎: expression Δ YI＜2.0;
Zero: expression 2.0≤Δ YI≤3.0;
*: expression Δ YI＞3.0.
This styrene-acrylonitrile of the more little expression of Δ YI value-thermostability of diene interpolymer constituent in aerobic environment is more good.
3. flame retardancy is measured:
Styrene-acrylonitrile-diene interpolymer the constituent of embodiment 1～6 and comparative example 1～7 is measured standard according to the vertical flame of U.S. Underwriter Laboratory (UL) defined (UL 94 standards), and test thickness is 1.5mm.V-0 represents to measure by burning; V-1 represents that flame retardancy is poor slightly; V-2 represents not measure by burning.
As shown in Table 1, the styrene-acrylonitrile of embodiment 1～6-diene interpolymer constituent adds tin methide maleate polymkeric substance (D) and magnalium composite metal salt (E) simultaneously, and content range is respectively 0.3 weight part～2.0 weight parts and 0.5 weight part～1.0 weight parts, makes this styrene-acrylonitrile-diene interpolymer constituent have preferable 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 preferable low temperature impact strength, when being illustrated in the following process moulding, described constituent also can be operated under low temperature, and can be used under low temperature environment by the formed moulding product of described constituent.
Compare down, when not adding tin methide maleate polymkeric substance (D) and magnalium composite metal salt (E) in the styrene-acrylonitrile of comparative example 1-diene interpolymer constituent, then the thermostability utmost point of styrene-acrylonitrile-diene interpolymer constituent is not good.
When adding excessive tin methide maleate polymer poly compound (D) (3.0 weight part) in the styrene-acrylonitrile of comparative example 2-diene interpolymer constituent, then the thermostability of styrene-acrylonitrile-diene interpolymer constituent is not good.
(model: in the time of TM-600P), then the thermostability of this constituent descends, and does not have a feature of environmental protection, and can ban use of future to add the dibutyl tin maleate in the styrene-acrylonitrile of comparative example 3-diene interpolymer constituent.
The styrene-acrylonitrile of comparative example 4-diene interpolymer constituent only uses the 3rd copolymer component (A
3), and do not contain 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 add dibutyl tin maleate (D) in this constituent, then the thermostability of this constituent descends, and does not have a feature of environmental protection, and can ban use of future.
When not adding magnalium composite metal salt (E) in the styrene-acrylonitrile of comparative example 5-diene interpolymer constituent, then the thermostability of styrene-acrylonitrile-diene interpolymer constituent is not good.
When adding a spot of tin methide maleate polymkeric substance (D) (0.1 weight part) and excessive magnalium composite metal salt (E) (2.0 weight part) in the styrene-acrylonitrile of comparative example 6-diene interpolymer constituent, then the thermostability of styrene-acrylonitrile-diene interpolymer constituent is not good.
The styrene-acrylonitrile of comparative example 7-diene interpolymer constituent only uses the first copolymer component (A
1), and do not contain 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, interpolation by tin methide maleate polymkeric substance (D) and magnalium composite metal salt (E), can and contain sb oxide (C) performance synergistic effect with halogen incombustible agent (B), make this styrene-acrylonitrile-diene interpolymer constituent have preferable thermostability and flame retardancy simultaneously, and this styrene-acrylonitrile-diene interpolymer constituent comprise the first copolymer component (A
1), the second copolymer component (A
2) and the 3rd copolymer component (A
3) time, can make this constituent have preferable low temperature impact strength, so can reach purpose of the present invention really.
Claims (10)
1. styrene-acrylonitrile-diene interpolymer constituent is characterized in that comprising:
The copolymer mixture (A) of 5 weight parts～40 weight parts is by comprising the first copolymer component (A
1), the second copolymer component (A
2) and the 3rd copolymer component (A
3) copolymer component mix form; The described first copolymer component (A
1) and the second copolymer component (A
2) obtained through the emulsion polymerization reaction by rubber components and monomer component respectively; Described the 3rd copolymer component (A
3) obtained through solution polymerization by rubber components and monomer component; Described rubber components comprises diene series rubber; Described monomer component comprises styrenic monomers and acrylic monomer;
The halogen incombustible agent (B) of 5 weight parts～30 weight parts;
1 weight part～10 weight parts contain sb oxide (C);
0.2 the tin methide maleate polymkeric substance (D) of weight part～2.5 weight parts;
0.2 the magnalium composite metal salt (E) of weight part～1.5 weight parts; And
The second styrene-acrylonitrile based copolymer (F) of 60 weight parts～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 the described second styrene-acrylonitrile based copolymer (F) is 100 weight parts, and the content range of described tin methide maleate polymkeric substance (D) is 0.2 weight part～2.3 weight parts.
3. styrene-acrylonitrile according to claim 1-diene interpolymer constituent, it is characterized in that, total amount based on described copolymer mixture (A) and the 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 parts.
4. styrene-acrylonitrile according to claim 1-diene interpolymer constituent, it is characterized in that, described tin methide maleate polymkeric substance (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), through coupling agent modified [(4.5Mg) Al of vinyl-Trimethoxy silane
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 that the weight average particle diameter scope is the first copolymer component (A of 0.2 μ m～1.0 μ m
1), the weight average particle diameter scope is the second copolymer component (A of 0.05 μ m～0.2 μ m
2) and the weight average particle diameter scope be the 3rd copolymer component (A of 0.5 μ m～5 μ m
3) copolymer component mix form.
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 that comprises 20 weight %～80 weight %
1), the second copolymer component (A of 15 weight %～75 weight %
2), and the 3rd copolymer component (A of 5 weight %～65 weight %
3) copolymer component mix form.
8. styrene-acrylonitrile according to claim 6-diene interpolymer constituent, it is characterized in that described copolymer mixture (A) is by comprising that the weight average particle diameter scope is that 0.2 μ m～0.7 μ m and content range are the first copolymer component (A of 20 weight %～80 weight %
1), the weight average particle diameter scope is that 0.05 μ m～0.15 μ m and content range are the second copolymer component (A of 15 weight %～75 weight %
2), and the weight average particle diameter scope is that 0.5 μ m～5 μ m and content range are the 3rd copolymer component (A of 5 weight %～65 weight %
3) copolymer component mix form.
9. styrene-acrylonitrile according to claim 6-diene interpolymer constituent, it is characterized in that described copolymer mixture (A) is by comprising that the weight average particle diameter scope is that 0.2 μ m～0.7 μ m and content range are the first copolymer component (A of 30 weight %～70 weight %
1), the weight average particle diameter scope is that 0.05 μ m～0.15 μ m and content range are the second copolymer component (A of 25 weight %～65 weight %
2), and the weight average particle diameter scope is that 0.5 μ m～5 μ m and content range are the 3rd copolymer component (A of 5 weight %～45 weight %
3) copolymer component mix form.
10. the moulding product of styrene-acrylonitrile-diene interpolymer constituent is characterized in that, by being formed according to each described styrene-acrylonitrile-diene interpolymer constituent of claim 1 to 9.
Applications Claiming Priority (2)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103183880A true CN103183880A (en) | 2013-07-03 |
| CN103183880B CN103183880B (en) | 2015-06-10 |
Family
ID=48675341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210071509.6A Active CN103183880B (en) | 2011-12-30 | 2012-03-16 | Styrene-acrylonitrile-diene copolymer composition and molded article using same |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103183880B (en) |
| TW (1) | TWI440666B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106459449A (en) * | 2015-04-14 | 2017-02-22 | 电化株式会社 | Styrene-based biaxially-stretched sheet, biaxially-stretched sheet with antifogging agent layer, packaging container, and cooking method |
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 |
| 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 |
-
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 |
Non-Patent Citations (1)
| Title |
|---|
| 张莉: "镁铝水滑石为基础的复合稳定体系在PVC热稳定性中的应用研究", 《中国优秀硕士学位论文全文数据库（工程科技I辑）》, no. 11, 15 November 2006 (2006-11-15), pages 016 - 97 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106459449A (en) * | 2015-04-14 | 2017-02-22 | 电化株式会社 | Styrene-based biaxially-stretched sheet, biaxially-stretched sheet with antifogging agent layer, packaging container, and cooking method |
| CN106459449B (en) * | 2015-04-14 | 2021-04-27 | 电化株式会社 | Styrene-based biaxially stretched sheet, biaxially stretched sheet with antifogging agent layer, packaging container, and heat cooking method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103183880B (en) | 2015-06-10 |
| TW201326293A (en) | 2013-07-01 |
| TWI440666B (en) | 2014-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI297348B (en) | Flame retardant polycarbonate resin composition | |
| JP2010509427A (en) | Thermoplastic resin with uniform composition and narrow molecular weight distribution and method for producing the same | |
| JP2007502341A (en) | Flame retardant thermoplastic resin composition | |
| US3300545A (en) | Blends of polystyrene and a graft copolymer of a styrene-methyl methacrylate type mixture on a rubbery polymer of a conjugated 1, 3-diene | |
| TWI496830B (en) | Rubber modified styrene-based resin, preparation thereof and the molding product made therefrom. | |
| CN103183880B (en) | Styrene-acrylonitrile-diene copolymer composition and molded article using same | |
| CN101205274B (en) | Rubber modified styrene series resin composition | |
| CN104610694B (en) | Styrene resin composition and molded article obtained therefrom | |
| JP2006336007A (en) | Polycarbonate based resin composition | |
| CN102977535B (en) | Flame-retardant styrene resin composition and molded article obtained therefrom | |
| JP4833529B2 (en) | Rubber-modified styrenic resin composition | |
| JP4833528B2 (en) | Flame retardant styrene resin composition | |
| JPH047347A (en) | Flame-retarding resin composition | |
| JPS6334897B2 (en) | ||
| JP4514388B2 (en) | Resin composition and molded body thereof | |
| JPH0629356B2 (en) | Thermoplastic resin composition | |
| CN106867128A (en) | Thermoplastic resin composition and molded article formed therefrom | |
| TW200825130A (en) | The rubber composition of modified polystyrene-based resin | |
| JP2007277435A (en) | Flame-retardant thermoplastic resin composition | |
| JPH06166729A (en) | Rubber-modified aromatic vinyl copolymer resin and its production | |
| JPH06228422A (en) | Thermoplastic resin composition | |
| JPS5974151A (en) | Thermoplastic resin composition having excellent resistance to thermal decomposition | |
| JPH04145151A (en) | Flame-retardant resin composition | |
| JPH06116459A (en) | Flame-retardant resin composition | |
| JPH05262940A (en) | Flame retardant resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |