AU648087B2 - Polyvinyl chloride resin composition - Google Patents
Polyvinyl chloride resin composition Download PDFInfo
- Publication number
- AU648087B2 AU648087B2 AU80213/91A AU8021391A AU648087B2 AU 648087 B2 AU648087 B2 AU 648087B2 AU 80213/91 A AU80213/91 A AU 80213/91A AU 8021391 A AU8021391 A AU 8021391A AU 648087 B2 AU648087 B2 AU 648087B2
- Authority
- AU
- Australia
- Prior art keywords
- parts
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- stage
- polyvinyl chloride
- chloride resin
- 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.)
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- 229920000915 polyvinyl chloride Polymers 0.000 title claims description 88
- 239000004800 polyvinyl chloride Substances 0.000 title claims description 87
- 239000011342 resin composition Substances 0.000 title claims description 64
- 229920001577 copolymer Polymers 0.000 claims description 154
- 239000000203 mixture Substances 0.000 claims description 133
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 84
- 229920002857 polybutadiene Polymers 0.000 claims description 83
- 239000000178 monomer Substances 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 58
- 229920005989 resin Polymers 0.000 claims description 57
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 45
- 229920000642 polymer Polymers 0.000 claims description 38
- 238000006116 polymerization reaction Methods 0.000 claims description 38
- 229920002554 vinyl polymer Polymers 0.000 claims description 32
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 29
- 230000000379 polymerizing effect Effects 0.000 claims description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 27
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 24
- 230000009477 glass transition Effects 0.000 claims description 22
- 230000000052 comparative effect Effects 0.000 claims description 19
- 229920000578 graft copolymer Polymers 0.000 claims description 16
- 230000003287 optical effect Effects 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229920000297 Rayon Polymers 0.000 claims description 6
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 230000002087 whitening effect Effects 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000002964 rayon Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 238000009472 formulation Methods 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 64
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 58
- 239000008367 deionised water Substances 0.000 description 48
- 229910021641 deionized water Inorganic materials 0.000 description 48
- 229940096992 potassium oleate Drugs 0.000 description 46
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 45
- 230000015572 biosynthetic process Effects 0.000 description 35
- 239000000843 powder Substances 0.000 description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- 239000004816 latex Substances 0.000 description 33
- 229920000126 latex Polymers 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 32
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 32
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 32
- 238000003786 synthesis reaction Methods 0.000 description 32
- 239000002245 particle Substances 0.000 description 19
- 230000000704 physical effect Effects 0.000 description 19
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 18
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 18
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 18
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- 238000007711 solidification Methods 0.000 description 17
- 230000008023 solidification Effects 0.000 description 17
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 16
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 16
- 239000008121 dextrose Substances 0.000 description 16
- 239000011790 ferrous sulphate Substances 0.000 description 16
- 235000003891 ferrous sulphate Nutrition 0.000 description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 16
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 15
- 229940048086 sodium pyrophosphate Drugs 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 15
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 11
- 239000000806 elastomer Substances 0.000 description 9
- -1 alkyl methacrylate Chemical compound 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CRQZBQZASKQJAN-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;potassium Chemical compound [K].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O CRQZBQZASKQJAN-BTVCFUMJSA-N 0.000 description 1
- DBGSRZSKGVSXRK-UHFFFAOYSA-N 1-[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]-3,6-dihydro-2H-pyridine-4-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CCC(=CC1)C(=O)O DBGSRZSKGVSXRK-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTNWOCRCBQPEKQ-UHFFFAOYSA-N NG-mono-methyl-L-arginine Natural products CN=C(N)NCCCC(N)C(O)=O NTNWOCRCBQPEKQ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Processing Or Creating Images (AREA)
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Description
AUSTRALIA
PATENTS ACT 1952 COMPLETE SPECIFICATION Form
(ORIGINAL)
FOR OFFICE USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: S Priority: S Related Art: i' ii ii b ~ii' TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: MITSUBISHI RAYON COMPANY LTD.
3-19 KYOBASHI-2-CHOME
CHUO-KU
TOKYO
JAPAN
GRIFFITH HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.
SActual Inventor: Address for Service: Complete Specification for the invention entitled: POLYVINYL CHLORIDE RESIN COMPOSITION.
The following statement is a full description of this invention including the best method of performing it known to me:- MBR-8570 Ai POLYVINYL CHLORIDE RESIN COMPOSITION BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyvinyl chloride resin composition having an excellent impact resistance, particularly a falling weight impact resistance, stress-whitening resistance, and optical characteristics.
2. Description of the Related Art Polyvinyl chloride resin has excellent 10 chemical and physical properties, and therefore, is widely used in many fields. Nevertheless, polyvinyl chloride resin per se has a drawback of an inferior impact resistance, and a large number of proposals have been made for an elimination of this drawback.
15 For example, Japanese Patent Publication (Kokoku) No. 42-20847 proposes a polyvinyl chloride resin composition comprising 30 parts by weight or less of a graft copolymer and 70 parts or more by weight of a polyvinyl chloride resin, wherein said graft copolymer 20 is obtained by graft polymerizing 80 to 30 parts by weight of the monomers as the total of 40 to 80% by weight of a methacrylic acid ester and 60 to 20% by weight of styrene emto 20 onto 70 parts by weight of a polymer composed mainly of 1,3-butadiene, said graft 25 polymerization being conducted by first graft polymerizing the methacrylic acid ester and then graft copolymerizing styrene.
Japanese Patent Publication (Kokoku) 47-23648 proposes a polyvinyl chloride resin composition comprising a graft copolymer and a vinyl chloride resin, wherein said graft copolymer is obtained by graft polymerizing first methyl methacrylate in the presence of an elastomer and then graft polymerizing styrene.
Also, Japanese Patent Publication (Kokoku) No. 57-26536 proposes a polyvinyl chloride resin I 2 composition comprising 3 to 40 parts by weight of a graft copolymer and 97 to 60 parts by weight of a polyvinyl chloride resin, wherein said graft copolymer is obtained by graft polymerizing 65 to 25 parts by weight of monomer group comprising methyl methacrylate, an alkyl acrylate and styren and optionally a polyfunctional crosslinking agent in the presence of to 75 parts by weight of a 1,3-butadiene type elastomer, said graft polymerization being conducted by graft polymerizing in the first stage 50 to 90% by weight of the total amount of a major amount of methyl methacrylate and a minor amount of an alkyl acrylate and optionally a polyfunctional crosslinking agent having an allyl group, in the presence of 35 to 75 parts by weight S 15 of a 1,3-butadiene type elastomer, and then graft polymerizing styrene in the second stage, and further, graft polymerizing 10 to 50% by weight of the total we*. amount of methyl methacrylate and an alkyl acrylate.
Further, Japanese Patent Publication (Kokoku) No. 2-19145 proposes a polyvinyl chloride resin composition comprising 2 to 40% by weight of a graft copolymer and 60 to 98% by weight of a polyvinyl chloride resin, wherein said graft copolymer is obtained by graft polymerizing 30 to 15 parts by weight of a 25 monomer mixture comprising an alkyl methacrylate and an aromatic vinyl or a monomer mixture comprising an alkyl methacrylate, an aromatic vinyl and an unsaturated nitrile onto 70 to 85 parts by weight of a highly crosslinked butadiene rubber with a particle size of 600 to 3000 A, a total crosslinking agent in an amount of 1 to 10% by weight and a degree of swelling of 7 or less, said graft polymerization being conducted by one stage or multi stage.
In the polyvinyl chloride resin composition proposed in Japanese Patent Publication (Kokoku) No.
42-20847 or 47-23648, however, an ungelled product is liable to remain under extrusion conditions of a low 3 degree of mixing, whereby, for example, a large generation of fish eyes occurs when formed into a sheet, the optical characteristics are poor, the stresswhitening resistance is poor, and the dart falling weight impact strength is too poor. Also, since styrene as the final graft component is polymerized during the preparation of the graft copolymer used, a styrene having a slow polymerization rate often is left, and consequently, remains in the graft copolymer powder and causes an objectionable odor to arise, and thus has a drawback in that the use of such a polyvinyl chloride resin composition is limited.
In the polyvinyl chloride resin composition proposed in Japanese Patent Publication (Kokoku) 15 No. 57-26536, however, although the optical characteristics such as a total light transmittance and haze value are good, a product having a satisfactory stress-whitening resistance and falling weight impact strength cannot be obtained.
Further, in the polyvinyl chloride resin composition proposed in Japanese Patent Publication (Kokoku) No. 2-19145, although the impact resistance is excellent, the optical characteristics such as a total o light transmittance and haze value are poor, and 25 further, the stress-whitening resistance is not satisfactory.
SUMMARY OF THE INVENTION
S
.Accordingly, the objects of the present invention are to eliminate the above-mentioned disadvantages of the prior art and to provide a polyvinyl chloride resin composition having an excellent impact resistance, particularly a falling weight impact resistance, and an excellent stress-whitening resistance and optical characteristics.
Other objects and advantages of th invention will be ap a m the following desc 4 In accordance with the present invention, there is provided a polyvinyl chloride resin composition having excellent impact resistance, stress-whitening resistance and optical characteristics, comprising: 100 parts by weight of a polyvinyl chloride resin and 2 to 40 parts by weight of a multi-stage graft copolymer obtained by polymerizing resin component formable monomers in the range of from more than 30 parts by weight to 50 parts by weight per 100 parts by weight of the multistage graft copolymer, said resin component formable monomers being composed of 25 to 55% by weight of methyl methacrylate, 2 to 15% by weight of an alkyl acrylate having a C 1
C
8 alkyl group and 30 to 60% by weight of an aromatic vinyl monomer in the presence of from 50 parts by weight to less than 70 parts by weight per 100 parts by weight of the multi-stage graft copolymer of a butadiene elastomer having a glass transition temperature of from 0 C to 5°C obtained by copolymerization of a monomer mixture of 70 to 90% by weight of butadiene, 10 to 30% by weight of an aromatic vinyl monomer and a polyfunctional monomer having at least two carbon-carbon double bonds added in an amount corresponding to 3 to 10 parts by weight per 100 parts by weight of total-amount of said butadiene and aromatic vinyl monomer, wherein polymerization of the resin component formable monomers is conducted by polymerizing in the first stage methyl methacrylate in an amount corresponding to 45 to 85% by weight of the total amount of methyl methacrylate and the alkyl acrylate in an amount in the range specified above, subsequently polymerizing in the second stage the aromatic vinyl monomer in an amount in the range specified above in the presence ;of the polymer obtained in the previous stage, and further polymerizing in the third stage the remainder of the methyl methacrylate in the presence of the polymers obtained in .,Asaid first and second stages.
4A- DESCRIPTION OF THE PREFERRED EMBODIMENTS According to the present invention, the abovementioned object can be accomplished by formulating a-- 7 a.
a a.
a a a a a *0 a.
t a a.
a a a a a a a a I I/ 'I 5 multi-stage copolymer with a polyvinyl chloride resin, said multi-stage copolymer being obtained by using a highly crosslinked butadiene elastomer as the rubber component at a ratio within a specific range, and polymerizing resin component formable monomers at a special composition ratio in 3 stages in the presence of the above-mentioned rubber component.
As the polyvinyl chloride resin to be used in the present invention, polyvinyl chloride or a copolymer of 70% by weight or more of vinyl chloride and 30% by weight or less of another monomer copolymerizable therewith can be used. Examples of other copolymerizable monomers include vinyl bromide, vinylidene 0* *0 S'a chloride, vinyl acetate, acrylic acid, methacrylic acid, 15 and ethylene.
The average degree of polymerization of the polyvinyl chloride resin to be used in the present eo invention is not particularly limited, but preferably, such a resin having an average degree of polymerization of 600 to 1,000, more preferably 650 to 900, is used.
The multi-stage copolymer to be used in the present invention is obtained by polymerizing, in 3 stages, methyl methacrylate, an alkyl acrylate and an aromatic vinyl monomer, which are resin component formable 25 monomers, at a specific ratio in the presence of a butadiene elastomer.
The butadiene elastomer component constituting the S. above-mentioned multi-stage copolymer has a glass transition temperature of from -40 0 C to 50C and is obtained by copolymerizing a monomer mixture comprising to 90% by weight of butadiene, 10 to 30% by weight of an aromatic vinyl monomer and a polyfunctional monomer added in an amount corresponding to 3 to 10 parts by weight per 100 parts by weight of the total amount of said butadiene and aromatic vinyl monomer. As the butadiene component, 1,3-butadiene is preferred, and as the aromatic vinyl monomer, styrene, a-methylstyrene, I *I I 6 vinyl toluene, and ring-substituted styrene are exemplified, and these can be used alone or in combination. Of these, styrene is preferable. Further, as the polyfunctional monomer, there are included divinylbenzene, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacaylate, 1,3-butylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate, and among these, divinylbenzene and 1,3-butylene glycol dimethacrylate are most preferred.
The composition ratio of butadiene and the aromatic vinyl monomer, which are the constituents of the S 15 butadiene elastomer, is within the range as specified above; when it is outside this range, the object of the present invention cannot be fully achieved. The amount of polyfunctional monomer used corresponds to 3 to parts by weight of the above-mentioned range, preferably 3 to 8 parts by weight, whereby the butadiene elastomer can be highly crosslinked and the glass transition temperature can also be kept within the temperature range as specified above, thus improving the falling weight impact resistance, stress-whitening resistance 25 and optical characteristics of the resin composition finally obtained.
The ratio of the butadiene elastomer in the multi-stage copolymer must be 50 parts by weight or more but less than 70 parts by weight to 100 parts by weight of the multi-stage copolymer. When the ratio of the butadiene elastomer is less than 50 parts by weight, the improvement of the falling weight resistance and stresswhitening resistance is not sufficient, and when it is parts by weight or more, the moldability and stresswhitening resistance of the resin composition finally obtained become poorer, and thus the molded products obtained do not have satisfactory surface I 'I I 7 characteristics.
In the presence of from 50 parts by weight to less than 70 parts by weight of the butadiene elastomer with such a constitution, resin component formable monomers in the range of from more than 30 parts by weight to parts by weight, said resin component formable monomers at a ratio of 25 to 55% by weight of methyl methacrylate, 2 to 15% by weight of an alkyl acrylate (alkyl group having 1 to 8 carbon atoms), and 30 to by weight of an aromatic vinyl monomer (total 100 parts by weight of the butadiene elastomer and resin component formable monomers) are polymerized, and in the practice of the present invention, during the polymerization of the resin component formable monomers, in the first 15 stage methyl methacrylate in an amount corresponding to 45 to 85% by weight of the total amount of methyl so methacrylate and the alkyl acrylate in an amount within the range specified above are polymerized, then in the second stage, the aromatic vinyl monomer in an amount specified above is polymerized in the presence of the polymer obtained in the previous stage, and thereafter, 0in the thi:d stage, only the remainder of methyl methacrylate is polymerized in the presence of the polymers obtained by the first and second 25 polymerizations, to thereby obtain a multi-stage Ss copolymer.
The combined use of methyl methacrylate and an alkyl acrylate in the first stage polymerization Simproves the flowability of the multi-stage copolymer and prevents the formation of an ungelled product when formulated with a polyvinyl chloride resin, and further, markedly improves the falling weight impact strength of the molded product. The amount of methyl methacrylate must correspond to 45 to 851% by weight of the total amount of methyl methacrylate, preferably 50 to 70% by weight. The use of an amount outside this range reduces the effect of a combined use thereof with an alkyl 8 acrylate, lowers the improvement of the flowability when polymerized into a multi-stage copolymer and when the copolymer is formulated with a polyvinyl chloride resin, causes difficulties in the prevention of the formation of ungelled products, and impairs the surface appearance of the molded product. Further, the falling weight impact strength becomes poorer. For this polymerization in the first stage, the relative use ratio of methyl methacrylate and the alkyl acrylate preferably has a relation of a major amount of methyl methacrylate to a minor amount of the alkyl acrylate.
The alkyl acrylate is used only in the polymerization in the first stage, and the amount thereof used is S* within 2 to 15% by weight of the total amount of the S: 15 resin component formable monomers. When the amount of the alkyl acrylate used is outside this range, the effect of a combined use thereof with methyl methacrylate will be reduced, the improvement of the flowability when polymerized into a multi-stage copolymer is lowered, and even though it may be formulated with a polyvinyl chloride resin, it becomes difficult to fully prevent a formation of ungelled products, and thus the surface appearance of the molded product is impaired.
Further, the falling weight impact strength is 25 unsatisfactory.
The polymerization of an aromatic vinyl monomer in the second stage contributes to an improvement of the surface appearance of the product molded from the resin 0 composition when the resulting multi-stage copolymer is formulated with a polyvinyl chloride resin.
In the polymerization in the third stage, it is important to polymerize only the remainder of methyl methacrylate, which contributes to an improvement of the stress-whitening resistance of the product molded from the resin composition, when the multi-stage copolymer obtained from such a polymerization is formulated with a polyvinyl chloride resin.
I 9 When another monomer such as an alkyl acrylate is used in combination during this polymerization in the third stage, the improvement will be lowered.
As the aromatic vinyl monomer which serves as the resin component formable monomer, the aromatic vinyl monomer constituting the above-mentioned butadiene elastomer can be used, and preferably styrene is used.
As the alkyl acrylate, those having an alkyl group having 1 to 8 carbon atoms can be used, and specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-Fethylhexyl acrylate, and n-octyl acrylate, and these can be used alone or in a combination of two or more kinds thereof. Of these alkyl acrylates, preferably ethyl acrylate and n-butyl :acrylate are used.
As the polymerization initiator used when preparing the above-mentioned multi-stage copolymer, there can be employed persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, and diisopropylbenzene hydroperoxide; and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile.
25 Alternatively, the above-mentioned compound can be combined with compounds such as sulfites, hydrogen sulfites, thiosuJfates, transition metal salts, sodium formaldehyde sulfoxylate, and dextrose, to be used as the redox system initiator.
An emulsion polymerization is preferred as the polymerization method, and the polymerization is preferably carried out at a temperature of about 40 0 C to 0 C, depending on the kind of polymerization initiator used. Known emulsifiers can be used as the emulsifier.
The multi-stagei copolymer latex obtained is coagulated by using a coagulant including acids such as sulfuric acid, hydrochloric acid, ana phosphoric acid, 10 and/or salts such as calcium chloride and sodium chloride, with or without an addition of an appropriate antioxidant or additives, solidified by heat treatment, followed by dehydration and washing and drying, to be formed into a powdery multi-stage copolymer.
In the present invention, as described above, a polyvinyl chloride resin composition having excellent characteristics, which is the object of the present invention, was obtained for the first time by formulating a multi-stage copolymer with a polyvinyl chloride resin. Said copolymer is obtained by satisfying the combination of using a highly crosslinked butadiene elastomer, polymerizing specific amounts of methyl methacrylate and an alkyl acrylate as the resin 15 formable monomers in the first stage in the presence of the butadiene elastomer, polymerizing only a specific amount of an aromatic vinyl monomer in the second stage, and polymerizing only a specific amount of the remainder "e of methyl methacrylate in the third stage.
The polyvinyl chloride resin composition of the present invention is obtained by mixing the above-mentioned multi-stage copolymer and polyvinyl chloride resin, in powdery form, by using, for example, a ribbon blender or Henschel mixer, and kneading the resultant 25 mixture by a known kneader or extruder. The method of mixing the polyvinyl chloride rLsin and the multi-stage copolymer is not limited to such a powder blend, and a polyvinyl chloride resin slurry and a multi-stage S* copolymer latex may be mixed and formed into a powder via coagulation, solidification, washing, and drying, etc. During the mixing according to these various methods, known stabilizers, plasticizers, processing aids, and colorants can be added, if necessary.
The polyvinyl chloride resin composition of the present invention comprises 100 parts by weight of a polyvinyl chloride resin and 2 to 40 parts of the multi-stage copolymer formulated therewith. When the 1 11 amount of the multi-stage copolymer is less than 2 parts by weight, the addition has little effect, and when an amount exceeds 40 parts by weight, other excellent inherent characteristics of the polyvinyl chloride resin are liable to be lost.
EXAMPLES
The present invention will now be further illustrated in de Ail by, but is by no means limited to, the following Examples, wherein "parts" are all by weight unless otherwise noted.
The various characteristics in the Examples and Comparative Examples shown below were measured by the following methods.
Particle size of butadiene elastomer: The average particle size of the butadiene elastomer latex was determined by a transmission electron microscope (JEM-100S, produced by JEOL LTD.
Glass transition temperature: s* The multi-stage copolymer was pressed at 170°C and 30 kg/cm 2 and the tan6 determined by using a DYNAMIC MECHANICAL ANALYZER (DMA 982) produced by E.I.
du Pont de Nemours and Co., and the peak value of the lower temperature of the two peaks was determined as the glass transition temperature of the butadiene elastomer.
25 Transparency (total light transmittance, haze value): The formulated resin composition was kneaded at 180 0 C for 5 minutes, by 8 inch rolls, and then pressed at 190°C under a load of 50 kg/cm 2 for minutes, and using the obtained sample plate having a thickness of 4 mm, an evaluation was conducted based on ASTM-D1003-61.
Falling weight impact strength (Dart impact at of breaking height): The formulated resin composition was molded into a film having a thickness of 0.10 mm at a resin temperature of 190°C, by an extrusion molding machine 1 I1 'i -12 with a screw diameter of 40 mm, and was evaluated based on JIS (Japan Industrial Standard)-K7211 by using a 500 g dart weight, and the height at which 50% of the film was broken was determined to be the 50% breaking height.
Stress-whitening resistance: The formulated resin composition was formed into a sheet having a thickness of 0.5 mm at a resin temperature of 1900C, by an extrusion molding machine with a screw diameter of 40 mm, and by using a dart with a 1 cm tip diameter of the du Pont impact tester, a dart was permitted to fall from a height of 30 cm under a 500 g load to deform the sheet, and the degree of whitening at the deformed portion was evaluated by the visual assessment.
A Not whitened B Slightly whitened C Whitened.
0* Example 1 Synthesis of butadiene elastomer (A-1) 1,3-Butadiene 75 parts Styrene (St) 25 parts Divinylbenzene (DVB) 7 parts Diisopropylbenzene hydroperoxide 0.2 part 25 Sodium pyrophosphate 0.5 part e Ferrous sulfate 0.01 part Dextrose 1 part SPotassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into a autoclave, and the reaction was carried out under stirring at 50 0 C for 12 hours to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 y, glass transition temperature -15 0
C)
Synthesis of multi-stage copolymer (B-1) A multi-stage copolymer was prepared by t 13 using the components of the following composition.
Butadiene elastomer 65 parts (as solids) St 15 parts Methyl methacrylate (MMA) 17 parts Ethyl acrylate (EA) 3 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.7 part Rongalite (sodium formaldehyde sulfoxylate) 0.5 part Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer potassium oleate, S* Rongalite and deionized water were charged into a flask 15 charged with nitrogen, the inner temperature thereof was maintained at 70 0 C, and in the first stage, a mixture of 11 parts of MIA, 3 parts of EA, and 0.28 part of cumene hydroperoxide was dropwise added over 20 minutes and "held therein for 1 hour.
Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of parts of St and 0.3 part of cumene hydroperoxide was continuously added dropwise over one hour, and held therein for 2 hours.
Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the third stage, a mixture of 6 parts of MMA and 0.12 part of cumene hydroperoxide wa. added dropwise over minutes and held therein for one hour, to thus complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of butylated hydroxytoluene (BHT) was added to the multi-stage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 900C. Then, the coagulated product was washed with warm water and dried, to thus obtain Y 14 multi-stage copolymer powder.
Preparation of polyvinyl chloride resin composition The respective components of 100 parts of a polyvinyl chloride resin with an average polymerization degree of 700, 3 parts of dioctyltin mercaptide as the stabilizer, 2 parts of Metablene()P-550 (produced by Mitsubishi Rayon Co., Ltd.) as the lubricant, 1 part of Metablene()P-710 (produced by Mitsubishi Rayon Co., Ltd.) as the lubricant, and 10 parts of the multi-stage copolymer powder obtained in the above were mixed by a Henschel mixer till 110 0 C for 10 minutes, to obtain a polyvinyl chloride resin composition.
when, the physical properties of the 15 composition obtained were measured, and the results are shown in Table 1.
Example 2 Synthesis of butadiene elastomer (A-2) Bd 80 parts St 20 parts DVB 5 parts Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part 25 Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for 12 hours, to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 A, glass transition temperature -23°C) Synthesis of multi-stace copolymer (B-2) A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 60 parts F 15 (as a solid) St 16 parts MMA 20 parts EA 4 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.8 part Rongalite 0.6 part Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer potassium oleate, Rongalite and deionized water were charged into a flask charged with nitrogen and the inner temperature thereof maintained at 70 0 C, and in the first stage, a mixture of 14 parts of MMA, 4 parts of EA and 0.36 part of cumene 15 hydroperoxide was dropwise added over 20 minutes and held therein for 1 hour.
Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of 16 parts of St and 0.32 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for 2 hours.
Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the third stage, a mixture of 6 parts of MMA and 0.12 part 25 of cumene hydroperoxide was added dropwise over minutes and held therein one hour, to thus complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multistage copolymur latex, an aqueous solution of sulfuric acid in a concentration of 0.2% by weight was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chlorideresin composition A polyvinyl chloride resin composition was 16 prepared under the same conditions as in Example 1, except that the multi-stage copolymer was used in place of the multi-stage copolymer powder The physical properties of the composition obtained were measured, and the results are shown in Table 1.
Example 3 Synthesis of butadiene elastomer (A-3) Bd 80 parts St 20 parts DVB 6 parts Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part 15 Dextrose 1 part S. Potassium oleate 2 parts Deionized water 200 parts The respective components of the above S"composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for 12 hours to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 A, glass transition temperature -20 0
C)
S(2) Synthesis of multi-stage copolymer (B-3) 25 A multi-stage copolymer was prepared by S. using the components of the following composition.
Butadiene elastomer 65 parts (as a solid) St 15 parts MMA 17 parts EA 3 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.7 part Rongalite 0.5 part Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer potassium oleate, 17 Rongalite, and deionized water were charged into a flask charged with nitrogen and the inner temperature thereof maintained at 70 0 C, and in the first stage, a mixture of 13 parts of MMA, 3 parts of EA, and 0.32 part of cumene hydroperoxide was dropwise added over 20 minutes and held therein for 1 hour.
Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of parts of St and 0.3 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for 2 hours.
Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the third stage, a mixture or 4 parts of MMA and 0.08 part 15 of cumene hydroperoxide was added dropwise over 0 minutes and held therein for one hour, to thus complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multistage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thereby obtain a multi-stage copolymer powder.
25 Preparation of polyvinyl chloride resin composition A polyvinyl chloride resin composition was prepared under the same conditions as in Example 1, except that the multi-stag8 copolymer was used in place of the multi-stage copolymer powder The physical properties of the composition obtained were measured, and the results are shown in Table 1.
Example 4 Synthesis of butadiene elastomer (A-4) Bd 85 parts St 15 parts 18
DVB
8 parts Diisopropylbenzene hydroperoxide 0.2 par Sodium pyrophosphate 0.5 par Ferrous sulfate 0.01 pa: Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into an autocl& a, and the reaction was carried out under stirring at 500C for 12 t t rt S S
S
S
5C 500 hours to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 p, glass transition temperature -26 0
C)
Synthesis of multi-stage copolymer (B-4) 15 A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 63 parts (as solida) St 18 parts MMA 15 parts EA 4 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.74 part Rongalite 0.5 part 25 Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer potassium oleate, Rongalite, and deionized water were charged into a flask charged with nitrogen, and the inner temperature thereof maintained at 70°C, and in the first stage, a mixture of ?2 parts of MMA, 4 parts of EA, and 0.32 part of cumene 'operoxide was dropwise added over 20 minutes and therein for 1 hour.
Then, in the presence of the polymer obtained the previous stage, in the second stage, a mixture of 18 parts of St and 0.36 part of cumene hydroperoxide was continuously added dropwise over one hour and held Se 5 5* r Es 5 005 5 -19 therein for 2 hours.
Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the third stage, a mixture of 3 parts of MMA and 0.06 part of cumene hydroperoxide was added dropwise over minutes and held therein for one hour, to thereby complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multistage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin composition A polyvinyl chloride resin composition was prepared under the same conditions as in Example 1 except that the multi-stage copolymer was used in place of the multi-stage copolymer powder The physical properties of the composition obtained were measured, and the results are shown in Table 1.
c Example SC, 25 Synthesis of butadiene elastomer Bd 85 parts St 15 parts DVB 4 parts Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for 12 20 hours to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 A, glass transition temperature -33 C) Synthesis of multi-stage copolymer A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 65 parts (as solids) St 20 parts MMA 10 parts EA 5 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.7 part SRongalite 0.5 part Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer potassium oleate, S* Rongalite, and deionized water were charged into a flask charged with nitrogen, and the inner temperature thereof maintained at 700C, and in the first stage, a mixture of 6 parts of MMA, 5 parts of EA and 0.22 part of cumene hydroperoxide was dropwise added over 20 minutes and held therein for 1 hour.
Then, in the presence of the polymer obtained 25 in the previous stage, in the second stage, a mixture of parts of St and 0.4 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for 2 hours.
Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the third stage, a mixture of 4 parts of MMA and 0.08 part of cumene hydroperoxide was added dropwise over minutes and held therein for one hour, to thereby complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multistage copolymer latex, a 0.2 wt% aqueous sulfuric acid 21 solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin composition A polyvinyl chloride resin composition was prepared under the same conditions as in Example 1, except that the multi-stage copolymer was used in place of the multi-stage copolymer powder The physical properties of the composition obtained were measured, and the results are shown in Table 1.
Example 6 15 Synthesis of butadiene elastomer (A-6) Bd 80 parts St 20 parts 1,3-Butylene glycol dimethacrylate 5 parts (1,3-BD) Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part Dextrose 1 part Potassium oleate 2 parts 25 Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 500C for 12 hours to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 A, glass transition temperature Synthesis of multi-stage copolymer (B-6) A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 60 parts (as solids) St 23 parts 22 MMA 14 parts EA 3 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.8 part Rongalite 0.5 part Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer potassium oleate, Rongalite, and deionized water were charged into a flask charged with nitrogen, and the inner temperature thereof maintained at 70 0 C, and in the first stage, a mixture of parts of MMA, 3 parts of EA and 0.26 part of cumene hydroperoxide was dropwise added over 20 minutes and held therein for 1 hour.
15 Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of So. 23 parts of St and 0.46 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for 2 hours.
Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the o third stage, a mixture of 4 parts of MMA and 0.08 part S* of cumene hydroperoxide was added dropwise over minutes and held therein for one hour, to thereby complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multi-stage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin composition A polyvinyl chloride resin composition was prepared under the same conditions as in Example 1 except that the multi-stage copolymer was used in 23 place of the multi-stage copolymer powder The physical properties of the composition obtained were measured, and the results are shown in Table 1.
Example 7 Synthesis of butadiene elastomer (A-7) Bd St 1,3-BD Diisopropylbenzene hydroperoxide Sodium pyrophosphate Ferrous sulfate Dextrose Potassium oleate 75 parts 25 parts 8 parts 0.2 part 0.5 part 0.01 part 1 part 2 parts 0 0 0 *0 0 o 0 0 *0 I Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for 12 hours to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 A, glass transition temperature -15 0
C)
Synthesis of multi-stage copolymer (B-7) A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 65 parts (as solids) St 15 parts MMA 16 parts EA 4 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.7 part kongalite 0.5 part Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer potassium oleate, Rongalite, and deionized water were charged into a flask charged with nitrogen, and the inner temperature thereof 24 maintained at 70 0 C, and in the first stage, a mixture of 11 parts of MMA, 4 parts of EA and 0.3 part of cumene hydroperoxide was dropwise added over 20 minutes and held therein for 1 hour.
Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of parts of St and 0.3 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for 2 hours.
Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the third stage, a mixture of 5 parts of MMA and 0.1 part of 9* cumene hydroperoxide was added dropwise over 50 minutes and held therein for one hour, to thereby complete the 15 polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multistage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thus obtain a multi-stage copolymer powder.
Preparation of polvvinyl chloride resin composition A polyvinyl chloride type resin conrosition 25 was prepared under the same conditions as in Example 1 except that the mul;'i-stage copolymer was used in place of the multi-stage copolymer powder S* The physical properties of the composition obtained were measured, and the results are shown in Table 1.
Comparative Example 1 Synthesis of butadiene elastomer Bd 75 parts St 25 parts Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part 25 Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for 12 hours to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 A, glass transition temperature -28 0
C)
Synthesis of multi-stage copolymer A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 65 parts (as solids) 15 St 16 parts MMA 14 parts EA 5 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.7 part Rongalite 0.5 part Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer potassium oleate, Rongalite, and deionized water were charged into a flask 0* 25 charged with nitrogen, and the inner temperature thereof maintained at 70 0 C, and in the first stage, a mixture of parts of MMA, 3 parts of EA, and 0.26 part of cu. ene S* hydroperoxide was dropwise added over 20 minutes and held therein for 1 hour.
Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of 16 parts of St and 0.32 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for 2 hours.
Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the third stage, a mixture of 4 parts of MMA, 2 parts of EA, 26 and 0.12 part of cumene hydroperoxide was added dropwise over 50 minutes and held therein for one hour, to thereby complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of butylated hydroxytoluene (BHT) was added to the multi-stage copolymer later, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin composition S" ~The respective components of 100 parts of a 15 polyvinyl chloride resin with an average polymerization degree of 700, 3 parts of dioctyltin mercaptide as the stabilizer, 2 parts of Metablene()P-550 (produced by Mitsubishi Rayon Co., Ltd.) as the lubricant, 1 part of Metablene()P-710 (produced by Mitsubishi Rayon Co., Ltd.) as the lubricant, and 10 parts of the multi-stage copolymer powder obtained in the above were mixed by a Henschel mixer till 110 0 C for 10 minutes, to thus a obtain a polyvinyl chloride resin composition.
The physical properties of the composition obtained were measured, and the results are shown in Table 2.
Com arative Example 2 Synthesis of butadiene elastomer Bd 75 parts St 25 parts Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above -27 composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for 12 hours to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 A, glass transition temperature -28 0
C)
Synthesis of multi-stage copolymer A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 65 parts (as solids) St 15 parts MMA 20 parts Potassium oleate 1.2 parts 0 0 s Cumene hydroperoxide 0.7 part Rongalite 0.5 part Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer potassium oleate, Rongalite, and deionized water were charged into a flask charged with nitrogen, and the inner temperature thereof was maintained at 700,, and in the first stage, a mixture of 10 parts of MMA, 15 parts of St, and 0.50 part of cumene hydroperoxide was dropwise added over one Shour and held therein for 2 hours.
25 Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of parts of MMA and G02 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for one hour, to thereby complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multistage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin
I
es es 0
S
SO
S
S.
S
S
S* *0 0*S *5
S
500 28 composition A polyvinyl chloride resin composition was prepared under the same conditions as in Comparative Example 1, except that the multi-stage copolymer was used in place of the multi-stage copolymer powder The physical properties of the composition obtained were measured, and the results are shown in Table 2.
Comparative Example 3 Synthesis of butadiene elastomer Bd 90 parts St 10 parts DVB 1 part 15 Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 5000 for 12 hours to prepare a butadiene elastomer 25 (Conversion 98%, average particle size 0.08 p, glass transition temperature -43 0
C)
Synthesis of multi-stage copolymer A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 60 parts (as a solid) St
MMA
Potassium oleate Cumene hydroperoxide Rongalite Deionized water (as a whole) 25 parts 15 parts 1.2 parts 0.8 part 0.6 part 200 parts 29 Of the components of the above composition, the butadiene elastomer potassium oleate, Rongalite, and deionized water were charged into a flask charged with nitrogen, and the inner temperature thereof maintained at 70 0 C, and in the first stage, a mixture of parts of MMA and 0.30 part of cumene hydroperoxide was dropwise added over 20 minutes and held therein for 1 hour. Then, in the presence of the polymer obtained in the previous stage, in the second stage a mixture of 25 parts of St and 0.5 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for one hour, to thereby complete the polymerization to obtain a multi-stage copolymer latex. After 0.5 part of BHT was added to the multi-stage copolymer 15 latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water dried, to go thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin composition A polyvinyl chloride resin composition was prepared under the same conditions as in Comparative Example 1 except that the multi-stage copolymer 25 was used in place of the multi-stage copolymer powder The physical properties of the composition obtained were measured, and the results are shown in 0 Table 2.
Comparative Example 4 Synthesis of butadiene elastomer Bd 85 parts St 15 parts DVB 1 part Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part 30 Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for 12 hours to prepare a butadiane elastomer (Conversion 98%, average particle size 0.08 A, glass transition temperature -38 0
C)
Synthesis of multi-stage copolymer A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 60 parts (as solids) S 15 St 23 parts MMA 15 parts EA 2 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.8 part Rongalite 0.6 part Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer pctassium oleate, Rongalite, and deionized water were charged into a flask 25 charged with nitrogen, and the inner temperature thereof maintained at 70 0 C, and in the first stage, a mixture of parts of MMA, 2 parts of EA and 0.24 part of cumene i: hydroperoxide was dropwise added over 20 minutes and held therein for 1 hour.
Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of 23 parts of St and 0.46 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for 2 hours.
Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the third stage, a mixture of 5 parts of MMA and 0.10 part 31 of cumene hydroperoxide was added dropwise over minutes and held therein for one hour, to thereby complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multistage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin composition o* A polyvinyl chloride resin composition was S.prepared under the same conditions as in Comparative Example 1 except that the multi-stage copolymer was used in place of the multi-stage copolymer powder The physical properties of the composition obtained were measured, and the results are shown in Table 2.
Comparative Example Synthesis of butadiene elastomer Bd 80 parts St 20 parts 25 DVB 5 parts eoo Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for 12 hours to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 A, glass transition temperature I I 32 Synthesis of multi-stage copolymer A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 80 parts (as solids) St 8 parts MMA 12 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.4 part Rongalite 0.3 part Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene type elastomer potassium oleate, S* Rongalite, and deionized water were charged into a flask charged with nitrogen, and the inner temperature thereof maintained at 70 0 C, and in the first stage, a mixture of 9 parts of MMA and 0.18 part of cumene hydroperoxide was dropwise added over 20 minutes and held therein for 1 hou..
Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of 8 parts of St and 0.16 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for 2 hours.
25 Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the third stage, a mixture of 3 parts of MMA and 0.6 part of cumene hydroperoxide was added dropwise over 50 minutes and held therein for one hour, to thereby complete the polymerization to obtain a multi-stage copolymer.
After 0.5 part of BHT was added to the multistage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, ti thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin 33 composition A polyvinyl chloride resin composition was prepared under the same conditions as in Comparative Example 1 except that the multi-stage copolymer was used in place of the multi-stage copolymer powder The physical properties of the composition obtained were measured, and the results are shown in Table 2.
Comparative Example 6 Synthesis of butadiene elastomer Bd 75 parts St 25 parts DVB 6 parts 15 Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for 12 hours to prepare a butadiene elastomer 25 (Conversion 98%, average particle size 0.08 A, glass transition temperature -17 0
C)
Synthesis of multi-stage copolviner 9: A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 65 parts (as solids) St 15 parts MMA 14 parts EA 6 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.7 part Rongalite 0.5 part 34 Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer potassium oleate, Rongalite, and deionized water were charged into a flask charged with nitrogen, and the inner temperature thereof maintained at 70 0 C, and in the first stage, a mixture of 11 parts of MMA, 3 parts of EA and 0.28 part of cumene hydroperoxide was dropwise added over 20 minutes and held therein for 1 hour.
Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of parts of St and 0.3 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for 2 hours.
15 Thereafter, in the presence of the polymers *obtained in the first stage and the second stage, in the third stage, a mixture of 3 parts of MMA, 3 parts of EA and 0.12 part of cumene hydroperoxide was added dropwise over 50 minutes and held therein for one hour, to thereby complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multistage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed 25 by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin composition A polyvinyl chloride type resin composition was prepared under the same conditions as in Comparative Example 1 except that the multi-stage copolymer was used in place of the multi--stage copolymer powder The physical properties of the composition obtained were measured, and the results are shown in Table 2.
1 1. 35 Comparative Example 7 Synthesis of butadiene elastomer Bd 75 parts St 25 parts DVB 8 parts Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for g 15 12 hours to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 A, glass transition temperature -13 0
C)
Synthesis of multi-stage copolymer A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 65 parts (as solids) St 14 parts MMA 21 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.7 part Rongalite 0.5 part Deionized water (as a whole) 200 parts Of the components of the above composition, the butadiene elastomer potassium oleate, Rongalite, and deionized water were charged into a flask charged with nitrogen, and the inner temperature thereof maintained at 70 0 C, and in the first stage, a mixture of 6 parts of MMA, 14 parts of St and 0.40 part of cumene hydroperoxide was dropwise added over one hour and held therein for 1 hour.
Then, in the presence of the polymer obtained 36 in the previous stage, in the second stage, a mixture of parts of MMA and 0.30 part of cumene hydroperoxide was added dropwise over 50 minutes and held therein for 2 hours, to thereby complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multistage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin composition A polyvinyl chloride resin composition was 15 prepared under the same conditions as in Comparative Example 1 except that the multi-stage copolymer was used in place of the multi-stage copolymer powder The physical properties of the composition obtained were measured, and the results are shown in Table 2.
Comparative Example 8 Synthesis of butadiene elastomer Bd 80 parts St 20 parts 1,3-BD 1 part .I Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for 12 hours to prepare a butadiene type elastomer (Conversion 98%, average particle size 0.08 A, glass 37 transition temperature -32 0
C.
Synthesis of multi-stage copolymer A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 65 parts (as solids) St 16 parts MMA 15 parts EA 4 parts Potassium oleate 1.2 parts Cumene hydroperoxide 0.8 part Rongalite 0.5 part Deionized water (as a whole) 200 parts Of the components of the above composition, 15 the butadiene alastomer potassium oleate, Rongalite, and deionized water were charged into a flask charge with nitrogen, and the inner temperature thereof maintained at 70 0 C, and in the first stage, a mixture of parts of MMA, 4 parts of EA and 0.28 part of cumene hydroperoxide was dropwise added over 20 minutes and S* held therein for 1 hour.
S..Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of 16 parts of St and 0.32 part of cumene hydroperoxide was continuously added dropwise over one hour and held therein for 2 hours.
Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the third stage, a mixture of 5 parts of MMA and 0.1 part of cumene hydroperoxide was added dropwise over 50 minutes and held therein for one hour, to thereby complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multistage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90°C. Then, the coagulated product was washed with warm water and 38 dried, to thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin composition A polyvinyl chloride resin composition was prepared under the same conditions as in Comparative Example 1 except that the multi-stage copolymer was used in place of the multi-stage copolymer powder l) The physical properties of the composition obtained were measured, and the results are shown in Table 2.
Comparative Example 9 Synthesis of butadiene elastomer Bd 75 parts St 25 parts 1,3-BD 5 parts Diisopropylbenzene hydroperoxide 0.2 part Sodium pyrophosphate 0.5 part Ferrous sulfate 0.01 part Dextrose 1 part Potassium oleate 2 parts Deionized water 200 parts The respective components of the above composition were charged into an autoclave, and the reaction was carried out under stirring at 50 0 C for 12 hours to prepare a butadiene elastomer (Conversion 98%, average particle size 0.08 I, glass transition temperature -21 0
C)
Synthesis of multi-staqe copolymer A multi-stage copolymer was prepared by using the components of the following composition.
Butadiene elastomer 65 parts (as a solid) St 17 parts MMA 10 parts EA 8 parts Potassium oleate 1.2 parts 39 Cumene hydroperoxide 0.8 part Rongalite 0.5 part Deionized water (as a whole) 200 parts Of the component of the above composition, the butadiene elastomer potassium oleate, Rongalite, and deionized water were charged into a flask charged with nitrogen and the inner temperature thereof maintained at 70 0 C, and in the first stage, a mixture of 8 parts of MMA, 8 parts of EA, and 0.32 part of cumene hydroperoxide was dropwise added over 20 minutes and held therein for 1 hour.
Then, in the presence of the polymer obtained in the previous stage, in the second stage, a mixture of S. 17 parts of St and 0.34 part of cumene hydroperoxide was 15 continuously added dropwise over one hour and held therein for 2 hours.
Thereafter, in the presence of the polymers obtained in the first stage and the second stage, in the third stage, a mixture of 2 parts of MMA and 0.04 part of cumene hydroperoxide was added dropwise over minutes and held therein for one hour, to thereby complete the polymerization to obtain a multi-stage copolymer latex.
After 0.5 part of BHT was added to the multistage copolymer latex, a 0.2 wt% aqueous sulfuric acid solution was added to coagulate the copolymer, followed by a solidification by a heat treatment at 90 0 C. Then, the coagulated product was washed with warm water and dried, to thus obtain a multi-stage copolymer powder.
Preparation of polyvinyl chloride resin composition A polyvinyl chloride type resin composition was prepared under the same conditions as in Comparative Example 1 except that the multi-stage copolymer was used in place of the multi-stage copolymer powder The physical properties of the composition 9, 4 40 obtained were measured, and the results are shown in Table 2.
6* *e S S
S
S@RS*
S S
SS
S
S.
S S
S.
S.
S SSS
SS
S S 5 C C C C C C CCC C CC C C e C CC C C CC. CC Table 1 Multi-stage copolyrer Composition ratio of Physical properties of polyvinyl chloride composition Composition ratio of Glass Content of Composition ratio of resin resin composition butadiens elastomer tamper- butadiens formable monoers (parts) Transparency Stress FallinL ature elastonmer whit- weight of in multi- Polyvinyl Hulti- Total Haze ening strength Bd St DVB 1,3-BD buta- stage First Second Third chloride ytaga light value rosia- (dart diene copolymer stagetage stags resin copolymer trans- tance impact (1 (parts) (parts) elas- mittance toner breaking height) (parts) NMMA EA St HHMMA (parts) (parts) (2 (em) Example 1 75 25 7 0 -15 65 11 3 15 4 100 10 84.9 5.0 A 124 2 80 20 5 0 -23 60 14 4 16 6 100 10 84.7 5.4 A 103 3 80 20 6 0 -20 65 13 3 15 4 100 10 84.9 3.6 A 112 S 4 85 15 8 0 -26 63 12 4 18 3 100 10 84.8 4.3 A 118 85 15 4 0 -33 65 6 5 20 4 100 10 85.0 5.2 A 132 S 6 80 20 0 5 -25 60 10 3 23 4 100 10 84.0 5.6 A 100 S 7 75 25 0 8 -15 65 11 4 15 5 100 10 84.3 4.9 A 115 5 5 S *W S S 4 9 @4 0 a .4 a..
4
I
Table 2 Multi-stage copolymer Composition ratio of Physical properties of polyvinyl chloride composition Composition ratio of Glass Content of Composition ratio of resin resin conposition butadiene type elastomer temper- butadiene formable monomers (parts) Transparency Stress Falling ature elastomer whit- weight of in multi- Polyvinyl Hulti- Total Haze ening strength Bd St DVB 1,3-BD buta- stage First Second Third chloride stage light value resis- (dart diane copolymer stage stage stage resin copolymer trans- tance impact (parts) (parts) elas- mittance tomer breaking height) (parts) (parts) (parts) (cm) Comparative Example 1 75 -28 65 MMA EA St MHA EA 3 16 4 2 -28 65 MMA St MHA 15 2 75 25 0 100 10 83.9 6.9 C 64 100 10 82.5 7.2 3 C 63 I 100 10 80.1 11.6 C 71
I
3 90 10 0 -43 0 -38 4 85 15 1 60 MMA EA 2 St MMA 100 10 82.7 6.8 C 69 23 80 20 5 0 -25 6 75 25 6 0 -17 7 75 25 8 0 -13 MMA St MMA 9 8 3 100 10 76.3 12.4 C 114 100 10 84.1 5.8 C 101 65 MMA EA St MIA EA 11 7 15 3 3 65 MMA St MMA 100 10 83.3 6.1 B 98 6 14 8 80 20 0 1 65 MMA EA St 4 16 100 10 83.0 6.5 C 66 100 10 81.5 7.1 B C 87 9 75 25 0 5 -21 6 MMA EA 8 8 St MMA 17 2 43 The present invention exhibits a superior feature in that a polyvinyl resin composition having an excellent falling weight impact resistance, stress whitening resistance and optical characteristics can be obtained, for the first time, by formulating into a polyvinyl chloride resin a multi-stage copolymer obtained by a combination of using a highly crosslinked butadiene elastomer, polymerizing combined monomers in specific amounts of methyl methacrylate and alkyl acrylate as the resin component formable monomers in the first stage in the presence of the butadiene elastomer, polymerizing only a specific amount of an aromatic vinyl monomer in the second stage, and polymerizing only a specific amount of the remainder of methyl methacrylate S 15 in the third stage.
Claims (9)
1. A polyvinyl chloride resin composition having excellent impact resistance, stress-whitening resistance and optical characteristics, comprising: 100 parts by weight of a polyvinyl chloride resin and 2 to 40 parts by weight of a multi-stage graft copolymer obtained by polymerizing resin component formable monomers in the range of from more than 30 parts by weight to 50 parts by weight per 100 parts by weight of the multi- stage graft copolymer, said resin component formable monomers being composed of 25 to 55% by weight of methyl methacrylate, 2 to 15% by weight of an alkyl acrylate having a C 1 C, alkyl group and 30 to 60% by weight of an aromatic vinyl monomer in the presence of from 50 parts by weight to less than 70 parts by weight per 100 parts by weight of the multi-stage graft copolymer of a butadiene elastomer having a glass transition temperature of from 0 C to 50C obtained by copolymerization of a monomer mixture of 70 to 90% by weight of butadiene, 10 to 30% by weight of an aromatic vinyl monomer and a polyfunctional monomer having at least two carbon-carbon double bonds added in an amount corresponding to 3 to 10 parts by weight per 100 parts by weight of total amount of said butadiene 25 and aromatic vinyl monomer, wherein polymerization of the *0 resin component formable monomers is conducted by polymerizing in the first stage methyl methacrylate in an amount corresponding to 45 to 85% by weight of the total amount of methyl methacrylate and the alkyl acrylate in an o 30 amount in the range specified above, subsequently polymerizing in the second stage the aromatic vinyl monomer in an amount in the range specified above in the prelsence of the polymer obtained in the previous stage, and further polymerizing in the third stage the remainder of the methyl Se 35 methacrylate in the presence of the polymers obtained in said first and second stages. 45
2. A polyvinyl chloride resin composition according to claim 1, wherein the butadiene is 1,3-butadiene.
3. A polyvinyl chloride resin composition according to claim 1 or 2 wherein the aromatic vinyl monomer as the constituent of the butadiene elastomer is styrene.
4. A polyvinyl chloride resin composition according to any preceding claim wherein the polyfunctional monomer is divinylbenzene or 1,3-butylene glycol dimethacrylate.
A polyvinyl chloride resin composition according to any preceding claim wherein the amount of the polyfunctional monomer is used in an amount corresponding to 3 to 8 parts by weight per 100 parts by weight of the total amount of said butadiene and aromatic vinyl monomer.
6. A polyvinyl chloride resin composition according to any preceding claim wherein the amount of methyl methacrylate used in the first stage polymerization is an amount corresponding to 50 to 70% by weight of the total amount of methyl methacrylate.
7. A polyvinyl chloride resin composition according S. 20 to any preceding claim wherein the relative use ratio of methyl methacrylate and the alkyl acrylate in the first stage polymerization has a relationship of a major amount S: of methyl methacrylate and a minor amount of the alkyl Sacrylate. 25
8. A polyvinyl chloride resin composition according to any preceding claim wherein the aromatic vinyl monomer of the resin component formable monomers is styrene. i
9. A polyvinyl chloride resin composition according to any preceding claim wherein the alkyl acrylate is ethyl 30 acrylate rr n-butyl acrylate. 46 A polyvinyl chloride resin composition having excellent impact resistance, stress-whitening resistance and optical characteristics substantially as hereinbefore described with reference to any one of the foregoing examples apart from the comparative examples. Dated this 8th day of February 1994 MITSUBISHI RAYON COMPANY LIMITED By its Patent Attorneys: GRIFFITH HACK CO Fellows Institute of Patent Attorneys of Australia. I f I POLYVINYL CHLORIDE RESIN COMPOSITION ABSTRACT OF THE DISCLOSURE A polyvinyl chloride resin composition having a superior in falling weight impact resistance, stress- whitening resistance and optical characteristics, comprising a formulation of 100 parts by weight of a polyvinyl chloride resin and 2 to 40 parts by weight of a multi-stage copolymer obtained by polymerizing a resin component formable monomers in the range of from more than 30 parts by weight to 50 parts by weight, said resin component formable monomer being composed of a ratio of 25 to 55% by weight of methyl methacrylate, 2 to 15% by weight of an alkyl acrylate (alkyl group having 1 to 6 carbon atoms) and 30 to 60% by weight of an aromatic vinyl monomer in the presence of from 50 parts by weight to less than 70 parts by weight of a 15 butadiene elastomer having a glass transition temperature ranging from -40 0 C to 5 0 C obtained by a copolymerization of a monomer mixture of 70 to 90% by weight of butadiene, 10 to 30% by weight of an aromatic S* vinyl monomer and a polyfunctional monomer added in an amount corresponding to 3 to 10 parts by weight per 100 parts by weight of a total amount of the butadiene and aromatic vinyl monomer, wherein a polymerization of the resin component formable monomer is conducted by polymerizing in the first stage methyl methacrylate in an amount corresponding to 45 to 85% by weight of the total amount of methyl methacrylate and the alkyl acrylate in an amount in the range specified above, subsequently polymerizing in the second stage the aromatic vinyl monomer in an amount in the range specified above in the presence of the polymer obtained in the previous stage, and further polymerizing in the third stage the remainder of methyl methacrylate in the presence of the polymers obtained in the first and second stages. U -I
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4362845A (en) * | 1980-12-18 | 1982-12-07 | Mitsubishi Rayon Co., Ltd. | Polyvinyl chloride-base resin and multistage graft resin composition |
| AU589312B2 (en) * | 1987-02-13 | 1989-10-05 | Kureha Kagaku Kogyo K.K. | PVC-based resin composition |
| AU627190B2 (en) * | 1988-06-14 | 1992-08-20 | Mitsubishi Rayon Company Limited | Polyvinyl chloride resin composition |
-
1990
- 1990-07-24 JP JP19526890A patent/JPH0480884A/en active Pending
-
1991
- 1991-07-05 AU AU80213/91A patent/AU648087B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4362845A (en) * | 1980-12-18 | 1982-12-07 | Mitsubishi Rayon Co., Ltd. | Polyvinyl chloride-base resin and multistage graft resin composition |
| AU589312B2 (en) * | 1987-02-13 | 1989-10-05 | Kureha Kagaku Kogyo K.K. | PVC-based resin composition |
| AU627190B2 (en) * | 1988-06-14 | 1992-08-20 | Mitsubishi Rayon Company Limited | Polyvinyl chloride resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0480884A (en) | 1992-03-13 |
| AU8021391A (en) | 1992-01-30 |
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