JPS6126804B2 - - Google Patents
Info
- Publication number
- JPS6126804B2 JPS6126804B2 JP16505678A JP16505678A JPS6126804B2 JP S6126804 B2 JPS6126804 B2 JP S6126804B2 JP 16505678 A JP16505678 A JP 16505678A JP 16505678 A JP16505678 A JP 16505678A JP S6126804 B2 JPS6126804 B2 JP S6126804B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- rubber
- vinyl chloride
- resin composition
- weight
- 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.)
- Expired
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 156
- 239000011342 resin composition Substances 0.000 claims description 101
- 238000006116 polymerization reaction Methods 0.000 claims description 98
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 93
- 239000000178 monomer Substances 0.000 claims description 74
- 239000000203 mixture Substances 0.000 claims description 73
- 229920005989 resin Polymers 0.000 claims description 66
- 239000011347 resin Substances 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 57
- 229920000642 polymer Polymers 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 27
- 238000012685 gas phase polymerization Methods 0.000 claims description 25
- 229920001971 elastomer Polymers 0.000 claims description 24
- -1 alkyl methacrylate Chemical compound 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 19
- 239000007870 radical polymerization initiator Substances 0.000 claims description 19
- 229920000126 latex Polymers 0.000 claims description 17
- 239000004816 latex Substances 0.000 claims description 17
- 150000001993 dienes Chemical class 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229920003051 synthetic elastomer Polymers 0.000 claims description 15
- 239000005061 synthetic rubber Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 13
- 239000005060 rubber Substances 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000010559 graft polymerization reaction Methods 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 7
- 150000005673 monoalkenes Chemical class 0.000 claims description 7
- 150000002825 nitriles Chemical class 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 5
- 239000000701 coagulant Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- 229920005992 thermoplastic resin Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000000465 moulding Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000007796 conventional method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229920000578 graft copolymer Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 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 5
- 239000003960 organic solvent Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 3
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000746 allylic group Chemical group 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008961 swelling Effects 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 229920001890 Novodur Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 235000011148 calcium chloride Nutrition 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 229920006174 synthetic rubber latex Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DSPZRAREZHBQMV-UHFFFAOYSA-N (4-butylcyclohexyl) (4-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(CCCC)CCC1OC(=O)OOC(=O)OC1CCC(CCCC)CC1 DSPZRAREZHBQMV-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 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 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive 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
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 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
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、耐衝撃性、耐候性、耐熱性、透明性
に優れた性質を有し、かつ成形加工に際する生産
性の優れた塩化ビニル樹脂組成物の製造方法に関
する。
スチレン系樹脂を使用したゴム―樹脂組成物は
高分子学会発行「ABS樹脂」に記載されている
様に、樹脂相とゴム相から成り立つ高分子複合体
のうちで樹脂相にスチレン系樹脂を使用するゴム
―樹脂組成物を総称し、広い意味のABS樹脂と
呼ばれ、耐衝撃性ABS樹脂、耐候性ABS樹脂、
耐熱性ABS樹脂、透明性ABS樹脂などを含むも
のであつた、スチレン系樹脂を使用したゴム―樹
脂組成物と塩化ビニル重合体とからなる組成物は
スチレン系樹脂を使用したゴム―樹脂組成物の組
成によつて耐衝撃性、耐候性、耐熱性、透明性な
どに優れた性質を有することはすでによく知られ
ている。
しかし、従来の製造法によるスチレン系樹脂を
使用したゴム―樹脂組成物と塩化ビニル重合体と
からなる組成物は次に述べる粉体特性および生産
性に関する欠点が克服されていないため、加工に
際する生産性は充分とは言えない。
スチレン系樹脂を使用したゴム―樹脂組成物
と塩化ビニル重合体からなる組成物を成形加工
するには、予じめ、スチレン系樹脂を使用した
ゴム―樹脂組成物と塩化ビニル重合体を混合し
て後、成形加工する。混合する方法としてはス
チレン系樹脂を使用したゴム―樹脂組成物と塩
化ビニル重合体を加熱混合して後、造粒機でペ
レツト状として得る方法や加熱混合してゲル状
とした後、パウダーコンパウンドとして得る方
法がある。しかし、いづれにしても加熱混合な
どの工程を必要とし煩雑である。
又、スチレン系樹脂を使用したゴム―樹脂組
成物は塊状重合法、懸濁重合法により製造する
技術が検討されているが、まだ一般的でなく市
販されるもののほとんどは乳化重合法により製
造されるため、加熱混合する際には微粉体の飛
散が発生し、労働安全衛生上からも煩雑な微粉
体取扱い設備を必要とする。
加工に際する生産性を向上させるには、嵩密
度の高い重合体組成物を用いることが経済性上
好ましいことは、すでに知られている。しかし
スチレン系樹脂を使用したゴム―樹脂組成物は
ほとんどが乳化重合法により製造されるため
に、ほとんどのスチレン系樹脂を使用したゴム
樹脂組成物の嵩密度（JIS―K6721に従つて測
定される。）は0.4〜0.45ｇ／cm3程度であり、市
販の塩化ビニル重合体（嵩密度は0.5〜0.55
ｇ／cm3程度である。）と混合してもほとんど嵩
密度は増加せず、スチレン系樹脂を使用したゴ
ム―樹脂組成物含率15％の混合物の嵩密度は約
0.45ｇ／cm3で優れているとは言えない。
通常、重合体を成形加工機に供給する際には
ホツパーに重合体を投入して実施される。この
際に重合体がスムースに流動することが好まし
いことはよく知られている。
しかし、乳化重合によつて製造されるスチレ
ン系樹脂を使用したゴム―樹脂組成物は通常は
流動性は良いとは言えない。又、塩化ビニル重
合体と混合しても流動性は改善されない。
スチレン系樹脂を使用したゴム―樹脂組成物
と塩化ビニル重合体とからなる組成物の優れた
耐衝撃性、耐候性、耐熱性、透明性を発揮する
には、成形加工機において両重合体の粒子をバ
ラバラに破壊して両重合体が充分にまざり合う
ように機械的力と熱を充分に与える必要があ
る。
本発明者はこれらの問題点を解決すべく鋭意研
究を続けた結果、塩化ビニル単量体に対して活性
であるスチレン系樹脂を使用したゴム―樹脂組成
物として塩化ビニル単量体蒸気雰囲気中で気相重
合させることにより、加熱混合などの煩雑な工
程を必要とせず、微粉体の飛散が発生せず、組
成物の嵩密度が0.7ｇ／cm3以上であり、流動性
が優れ、かつ両重合体が予じめ粒子の内で混合
されたスチレン系樹脂を使用したゴム―樹脂組成
物と塩化ビニル重合体とからなる組成物を製造す
る方法を見いだし研究を完成した。
すなわち、本発明は塩化ビニル単量体に対して
活性であるスチレン系樹脂組成物を使用したゴム
―樹脂組成物を基物質として用い、重合圧力が塩
化ビニル単量体の飽和蒸気圧より低く、かつ基物
質の混合流動を妨げない範囲の圧力でラジカル重
合開始剤を用いて気相重合することを特徴とする
塩化ビニル樹脂組成物の製造方法に関する。
以下、本発明を詳細に説明する。
本発明では、耐衝撃性、耐候性、耐熱性、透明
性などに優れた塩化ビニル樹脂組成物を得ること
を目的としており、スチレン系樹脂を使用したゴ
ム―樹脂組成物を使用することは必要不可欠であ
る。
また、本発明では前述の粉体特性および生産性
の改善のために塩化ビニル単量体との気相重合方
法を採用しているが、スチレン系樹脂を使用した
ゴム―樹脂組成物は塩化ビニル単量体に対して活
性であるためにスチレン系樹脂を使用したゴム―
樹脂組成物質を基物質として使用する場合は通常
の塩化ビニル単量体の気相体の気相重合法では実
施できない。有機高分子物質を基物質として塩化
ビニル単量体を気相重合する方法に関する全ての
出願特許（たとえば、特公昭46―30290、特公昭
48―12433、特公昭52―44918、特公昭53―
13475、特開昭46―40698、特開昭47―12583、特
開昭50―119887）には、通常の塩化ビニル単量体
の気相重合法では、基物質である有機高分子物質
が塩化ビニル単量体に不活性であるものに限定さ
れる。
本発明にかかわる基物質が“活性である”と
は、塩化ビニル単量体に対して膨潤および又は溶
解することを称し、本発明において必要不可欠で
あるスチレン系樹脂を使用したゴム樹脂組成物は
すでに知られている様に、該組成物の成分に起因
し塩化ビニル単量体に対して著しく膨潤および又
は膨潤する状態が存在する。該膨潤および又は溶
解が起ると、基物質同志の溶着が起り、基物質が
巨大粒子化したり団塊を形成すると共に反応器壁
に付着し、反応操作が困難となり更には不可能と
なる、したがつて本発明の目的とする前述の粉体
特性および生産性の優れた塩化ビニル樹脂組成物
をえることはできない。
すなわち、本発明のスチレン系樹脂を使用した
ゴム―樹脂組成物を基物質として使用する場合に
は以下詳述する様に特定の条件下においてのみ可
能となる。まず、本発明で基物質として使用され
るスチレン系樹脂を使用したゴム―樹脂組成物に
ついて説明する。
本発明に用いられる基物質は樹脂相とゴム相か
ら成り立つ高分子複合体でありかつ樹脂相にスチ
レン系樹脂を使用するゴム―樹脂組成物であり、
ゴム状重合組成物にメタアクリル酸アルキルエス
テル、ビニル芳香族化合物、不飽和ニトリル化合
物、アクリル酸アルキルエステルの内１種又は２
種以上の混合物を主成分として共重合させて製造
される。
ゴム状重合組成物としてはジエン系合成ゴム又
はアルキル基の炭素数が２〜８のアクリル酸アル
キルエステルおよび又はアルキル基の炭素数が２
〜８のアクリル酸アルキルエステルと共重合可能
なモノビニリデル化合物をアクリル酸アルキルエ
ステルと重合可能な炭素２重結合を２個以上含み
少なくとも１個はアリル基であるアリル系架橋剤
を用いて共重合したゴム状重合体である。
ジエン系合成ゴムとしてはポリブタジエン、ポ
リイソプレン、ポリクロロプレン、ブタジエン−
スチレン共重合物、ブタジエン―アクリロニトリ
ル共重合物、ブタジエン―αメチルスチレン共重
合物が例示できる。
アルキル基の炭素数が２〜８のアクリル酸アル
キルエステルとしてはアクリル酸エチル、アクリ
ル酸プロピル、アクリル酸ｎ―ブチル、アクリル
酸ペンチル、アクリル酸ヘキシル、アクリル酸ｎ
―オクチル、アクリル酸２―エチルヘキシル酸で
あり、単独あるいは混合して使用することができ
る。
又、これと共重合可能なモノビニリデン化合物
としては後で述べるビニル芳香族、化合物、不飽
和ニトリル化合物、メタアクリル酸アルキルエス
テルおよび酢酸ビニル、プロピオン酸ビニル等の
ビニルエステルが例示できる。
アリル系架橋剤としてはジアリルフタレート、
ジアリルマレート、ジアリルフマレート、ジアリ
ルセパケート等の多塩基酸のジ又はトリアリルエ
ステル、トリアリルシアヌレート、トリアリルイ
ソシアヌレート、トリアリルホスフエート等のト
リアリル化合物、アリルメタクリレート、アリル
アクリレート、アリルイタコネート、モノアリル
フマレート、モノアリルマレート等の重合性カル
ボン酸のアリルエステル、ジアリルエーテル等が
例示できる。
本発明に用いるゴム状重合組成物は通常の乳化
重合でえられ、乳化剤としては脂肪族石けん、ス
ルホン酸等の公知の界面活性剤が使用でき、過酸
化物や酸化還元系等の公知の重合開始剤以外に重
合度調節剤、PH調節剤等も必要に応じて添加す
ることができる。
本発明に用いるゴム状重合組成物に共重合可能
なメタアクリル酸アルキルエステルはアルキル基
の炭素数が１〜４であつて、メタアクリル酸メチ
ル、メタアクリル酸エチル、メタアクリル酸プロ
ピル、メタアクリル酸イソプロピル、メタアクリ
ル酸ｎ―ブチル、メタアクリル酸イソブチル、メ
タアクリル酸ターシヤリーブチルが例示でき単独
又は混合して使用できる。
又、同様にビニル芳香族化合物としてはスチレ
ン、ビニルトリエン、αメチルスチレン、クロロ
スチレン、ブロスチレン、ビニルカルバゾール等
が挙げられるがその他α―置換スチレン、核置換
スチレンおよびその誘導体を含まれる。不飽和ニ
トリルとしてはアクリロニトリルとメタクリロニ
トリルが挙げられる。アクリル酸アルキルエステ
ルについてはすべでに述べた。
これらをゴム状重合組成分に共重合させるには
乳化重合法が用いられる。水性分散体中にラジヤ
ル重合開始剤の存在下でゴム状重合組成物のラテ
ツクスとこれら単量体を重合させる。又、架橋剤
を用いて架橋しつつ共重合してもよい。又、これ
ら単量体のみを別に同様の乳化重合して後、ゴム
状重合、組成物とラテツクス状態で混合しても良
く、ゴム状重合組成物にこれら単量体を共重合し
た組成物に更にこれら単量体のみを重合してえた
組成物をラテツクス状態で混合してもよい。この
様にして得られた基物質を用い以下の条件で塩化
ビニル単量体雰囲気中で気相重合を行なう。
つまり、本発明にかかわる重合圧力は重合温度
における塩化ビニル単量体の飽和蒸気圧より低い
圧力でありかつ、基物質であるスチレン系樹脂を
使用したゴム―樹脂組成物の粒子が変調をきたさ
ず、反応器内での該粒子の混合流動を妨げない範
囲の圧力でなければならない。前述した様に重合
圧力が該圧力以上になると、スチレン系樹脂を使
用したゴム―樹脂組成物は塩化ビニル単量体に対
して著しく膨潤ないしは溶解し、基物質同志の溶
着が起り、基物質が巨大粒子化したり団塊を形成
すると共に反応器壁に付着し、反応操作が困難と
なり更には不可能となると共に前述の粉体特性お
よび生産性の優れた本発明の目的とする塩化ビニ
ル樹脂組成物をえることはできない。
該圧力を本発明にかかわる重合圧力の上限とす
るが、該重合圧力の上限は一概に決められるもの
でなく、スチレン系樹脂を使用したゴム―樹脂組
成物の成分に依存し、後述する様にそれぞれのス
チレン系樹脂を使用したゴム―樹脂組成物によつ
て異なる。又、重合圧力の下限は特に限定される
ものではないが、重合圧力をＰp、重合温度にお
ける塩化ビニル単量体の飽和蒸気圧力をＰsおよ
び両者の比をＰr（Ｐr＝Ｐp／Ｐs×100％の関係が
ある）で表わすと、すでによく知られている様に
Ｐrが45％以下では気相重合における生産性が急
激に減少し、製造コストが増加して好ましくな
い。Ｐr＝45％下限に決める事が好ましい。
重合温度は塩化ビニル単量体の重合に通常用ら
れる温度であればよく、40〜70℃が採用される。
重合時間はラジカル重合開始剤の種類・量によつ
て規定されるが通常の反応時間でよく、例えば２
〜８時間である。
ラジカル重合開始剤としてはアゾビスイソブチ
ロニトリル、アゾビスジメチルバレロニトリルな
どのアゾ化合物、ジイソプロピルパーオキシジカ
ーボネート、ラウロイルパーオキサイト、ビス
（４―ｔブチルシクロヘキシル）バーオキシジカ
ーボネートなどの有機過酸化物が例示でき、通常
の塩化ビニル単量体の重合に用いられる油溶性の
ラジカル重合開始剤が用いられる。
ラジカル重合開始剤の添加は必要に応じて重合
開始時およびまたは重合中適宜添加して重合する
ことができる。ラジカル重合開始剤の添加方法は
スチレン系樹脂を使用したゴム―樹脂組成物が塩
化ビニル単量体および通常用いられる一般的な有
機溶剤に活性を有し、膨潤したり溶解したりする
ために、通常よく使用されるこれら有機溶剤に前
記ラジカル重合開始剤を溶解した溶液に該基物質
を浸漬して後、溶剤を除去する含浸法は採用でき
ない。又、液状のラジカル重合開始剤を直接添加
する方法は基物質の量に比較して液状ラジカル重
合開始剤の量が極度に微少量のため著しく不均一
に添加されるために好ましい。
本発明に採用されるラジカル重合開始剤の添加
方法は、沸点がラジカル重合開始剤を添加してい
る温度の圧力条件において、添加温度以下である
有機溶剤に前記ラジカル重合開始剤を溶解した溶
液を該基物質にスプレーして添加すると同時に有
機溶剤を蒸発させラジカル重合開始剤のみを基物
質に担持させるスプレー法である。有機溶剤とし
て特に好ましくは塩化ビニル単量体がある。
又、本発明に採用されるもう一つのラジカル重
合開始剤の添加方法は、充分に微粉化されたラジ
カル重合剤を該基物質に均一に分散する様に混合
撹拌しつつ直接添加する方法である。
本発明を実施するに際し、通常の塩化ビニル単
量体の気相重合法で知られている様に塩化ビニル
単量体の気相重合を実施する前に予じめおよび又
は重合の途中で安定化剤をはじめとする成形加工
する際に用いられる添加剤を反応を阻害しない範
囲において添加でき、添加剤が均一に分散された
塩化ビニル樹脂組成物をえることができる。添加
剤の添加方法は添加剤の性状によつてラジカル重
合開始剤の添加方法と同様の方法が採用される。
又、基物質の含率は、重合温度、重合時間及び重
合開始剤の種類と添加量によつて自由にコントロ
ール出来る。
重合操作の形式に回分式、半回分式、連続式の
いづれでもよく、重合装置の形式は機械的撹拌装
置（たとえば２重ラセン帯翼など）を備えたベツ
セル重合機も採用されるし、ガス流動式重合機も
採用される。又、機械的撹拌装置を内蔵したガス
流動式重合機でも本発明は実施できる。
次に、本発明を実施するのに好ましい実施態様
について説明する。
まず、耐衝撃性と耐熱性を強化した塩化ビニル
樹脂組成物をえる場合に、以下の組成のものを基
物質として使用する。すなわち、スチレン系樹脂
を使用したゴム―樹脂組成物が、第１図において
座標点BCQRSで囲まれる範囲（但しRQおよび
RS線上を除く）にある組成を有するアクリロニ
トリル、αメチルスチレンおよびメタアクリル酸
メチルの混合物を乳化重合させてえられた共重合
物（Ａ）およびジエン系合成ゴム35〜65重量％に
第２図において座標点、EFGHIで囲まれる範囲
にある組成を有するスチレン又はスチレンとアク
リロニトリルを含むことのあるメタアクリル酸メ
チル65〜35重量％を乳化重合してえられた共重合
物（Ｂ）からなり、かつジエン系合成ゴムの組成
が全体の５〜30重量％である耐熱性・耐衝撃性・
熱可塑性樹脂組成物である。
なお、第１図および第２図における組成は、下
表の通りである。
The present invention relates to a method for producing a vinyl chloride resin composition that has excellent properties in impact resistance, weather resistance, heat resistance, and transparency, and has excellent productivity during molding. Rubber-resin compositions using styrene resin are polymer composites consisting of a resin phase and a rubber phase, and a styrene resin is used in the resin phase, as described in "ABS resin" published by the Society of Polymer Science and Technology. A general term for rubber-resin compositions that can be used, and is called ABS resin in a broad sense, including impact-resistant ABS resin, weather-resistant ABS resin,
A composition consisting of a rubber-resin composition using a styrene-based resin and a vinyl chloride polymer, which includes a heat-resistant ABS resin, a transparent ABS resin, etc., is a rubber-resin composition using a styrene-based resin. It is already well known that, depending on its composition, it has excellent properties such as impact resistance, weather resistance, heat resistance, and transparency. However, compositions made of rubber-resin compositions using styrene resins and vinyl chloride polymers produced using conventional manufacturing methods have the following drawbacks regarding powder properties and productivity, and therefore cannot be processed easily. The productivity of doing so cannot be said to be sufficient. In order to mold a composition consisting of a rubber-resin composition using a styrene resin and a vinyl chloride polymer, the rubber-resin composition using a styrene resin and the vinyl chloride polymer are mixed in advance. After that, it is molded. The mixing method is to heat mix a rubber-resin composition using styrene resin and vinyl chloride polymer, and then obtain pellets using a granulator, or heat mix to form a gel, and then form a powder compound. There is a way to get it. However, either method requires a process such as heating and mixing, which is complicated. In addition, technologies for manufacturing rubber-resin compositions using styrene resins using bulk polymerization and suspension polymerization are being considered, but they are not yet common and most of the products on the market are manufactured using emulsion polymerization. As a result, fine powder scatters during heating and mixing, and from the standpoint of occupational safety and health, complicated fine powder handling equipment is required. It is already known that in order to improve productivity during processing, it is economically preferable to use a polymer composition with a high bulk density. However, since most rubber-resin compositions using styrene resins are manufactured by emulsion polymerization, the bulk density (measured according to JIS-K6721) of most rubber resin compositions using styrene resins is ) is about 0.4 to 0.45 g/ cm3 , and commercially available vinyl chloride polymer (bulk density is 0.5 to 0.55
It is about g/ cm3 . ), there is almost no increase in bulk density, and the bulk density of a rubber-resin composition mixture containing 15% using styrene resin is approximately
It cannot be said that it is excellent at 0.45g/cm 3 . Usually, when supplying a polymer to a molding machine, it is carried out by charging the polymer into a hopper. It is well known that it is preferable for the polymer to flow smoothly in this case. However, rubber-resin compositions using styrene resins produced by emulsion polymerization usually do not have good fluidity. Further, even if it is mixed with a vinyl chloride polymer, the fluidity is not improved. In order to demonstrate the excellent impact resistance, weather resistance, heat resistance, and transparency of a rubber-resin composition using styrene resin and a vinyl chloride polymer, it is necessary to combine both polymers in a molding machine. It is necessary to apply sufficient mechanical force and heat to break the particles apart and mix the two polymers sufficiently. As a result of intensive research to solve these problems, the present inventor has developed a rubber-resin composition using a styrene resin that is active against vinyl chloride monomers in a vinyl chloride monomer vapor atmosphere. By carrying out gas phase polymerization, there is no need for complicated processes such as heating and mixing, there is no scattering of fine powder, the bulk density of the composition is 0.7 g/cm 3 or more, and it has excellent fluidity. We have completed our research by discovering a method for producing a composition consisting of a vinyl chloride polymer and a rubber-resin composition using a styrene resin in which both polymers are mixed in advance within the particles. That is, the present invention uses a rubber-resin composition using a styrene resin composition active against vinyl chloride monomer as a base material, and the polymerization pressure is lower than the saturated vapor pressure of the vinyl chloride monomer. The present invention also relates to a method for producing a vinyl chloride resin composition, characterized in that gas phase polymerization is carried out using a radical polymerization initiator at a pressure within a range that does not impede the mixing and flow of base materials. The present invention will be explained in detail below. The purpose of the present invention is to obtain a vinyl chloride resin composition with excellent impact resistance, weather resistance, heat resistance, transparency, etc., and it is necessary to use a rubber-resin composition using styrene resin. It is essential. In addition, in the present invention, a gas phase polymerization method with vinyl chloride monomer is adopted in order to improve the powder properties and productivity mentioned above, but the rubber-resin composition using styrene resin does not contain vinyl chloride. Rubber that uses styrenic resin because it is active against monomers.
When a resin composition material is used as a base material, it cannot be carried out by the usual gas phase polymerization method of a gas phase material of vinyl chloride monomer. All patent applications related to the gas phase polymerization of vinyl chloride monomers using organic polymeric substances as base materials (for example, Japanese Patent Publication No. 46-30290, Japanese Patent Publication No. 46-30290,
48-12433, Special Publication Showa 52-44918, Special Publication Showa 53-
13475, JP-A No. 46-40698, JP-A No. 47-12583, JP-A No. 50-119887), in the ordinary gas phase polymerization method of vinyl chloride monomer, the base organic polymer substance is chlorinated. Limited to those that are inert to vinyl monomers. When the base material used in the present invention is "active", it means that it swells and/or dissolves in vinyl chloride monomer, and the rubber resin composition using the styrene resin, which is essential in the present invention, is As is already known, conditions exist which result in significant swelling and/or swelling of the vinyl chloride monomer due to the components of the composition. When the swelling and/or dissolution occurs, the base materials adhere to each other, and the base materials become large particles or form lumps and adhere to the walls of the reactor, making reaction operations difficult or even impossible. Therefore, it is not possible to obtain a vinyl chloride resin composition having excellent powder characteristics and productivity as described above, which is the object of the present invention. That is, when the rubber-resin composition using the styrene resin of the present invention is used as a base material, it is possible only under specific conditions as detailed below. First, a rubber-resin composition using a styrene resin used as a base material in the present invention will be explained. The base material used in the present invention is a polymer composite consisting of a resin phase and a rubber phase, and is a rubber-resin composition using a styrene resin in the resin phase,
One or two of methacrylic acid alkyl esters, vinyl aromatic compounds, unsaturated nitrile compounds, and acrylic acid alkyl esters are added to the rubbery polymer composition.
It is produced by copolymerizing a mixture of more than one species as the main component. As the rubbery polymer composition, diene-based synthetic rubber or acrylic acid alkyl ester having an alkyl group of 2 to 8 carbon atoms and/or an alkyl group having 2 to 8 carbon atoms are used.
The monovinylidel compound copolymerizable with an acrylic acid alkyl ester of ~8 was copolymerized with an acrylic acid alkyl ester using an allylic crosslinking agent containing two or more polymerizable carbon double bonds and at least one of which is an allyl group. It is a rubbery polymer. Diene-based synthetic rubbers include polybutadiene, polyisoprene, polychloroprene, and butadiene.
Examples include styrene copolymer, butadiene-acrylonitrile copolymer, and butadiene-α-methylstyrene copolymer. Examples of acrylic acid alkyl esters in which the alkyl group has 2 to 8 carbon atoms include ethyl acrylate, propyl acrylate, n-butyl acrylate, pentyl acrylate, hexyl acrylate, and n-acrylate.
-octyl, acrylic acid, 2-ethylhexylic acid, and can be used alone or in combination. Examples of monovinylidene compounds that can be copolymerized with this include vinyl aromatics, compounds, unsaturated nitrile compounds, methacrylic acid alkyl esters, and vinyl esters such as vinyl acetate and vinyl propionate, which will be described later. Diaryl phthalate as an allyl crosslinking agent,
Di- or triallyl esters of polybasic acids such as diallyl maleate, diallyl fumarate, diallyl sepacate, triallyl compounds such as triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, allyl methacrylate, allyl acrylate, allyl itaco Examples include allyl esters and diallyl ethers of polymerizable carboxylic acids such as ester, monoallyl fumarate, and monoallyl maleate. The rubbery polymer composition used in the present invention can be obtained by ordinary emulsion polymerization, and known surfactants such as aliphatic soaps and sulfonic acids can be used as emulsifiers, and known surfactants such as peroxides and redox systems can be used. In addition to the initiator, a degree of polymerization regulator, a pH regulator, etc. can also be added as necessary. The alkyl methacrylates copolymerizable with the rubbery polymer composition used in the present invention have an alkyl group having 1 to 4 carbon atoms, and include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methacrylate. Examples include isopropyl acid, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate, which can be used alone or in combination. Similarly, vinyl aromatic compounds include styrene, vinyltriene, α-methylstyrene, chlorostyrene, brostyrene, vinylcarbazole, etc., and also α-substituted styrene, nuclear-substituted styrene, and derivatives thereof. Unsaturated nitriles include acrylonitrile and methacrylonitrile. Acrylic acid alkyl esters have already been mentioned. An emulsion polymerization method is used to copolymerize these into a rubbery polymer composition. These monomers are polymerized with the latex of the rubbery polymeric composition in the presence of a radial polymerization initiator in an aqueous dispersion. Alternatively, copolymerization may be carried out while crosslinking using a crosslinking agent. Alternatively, these monomers may be separately subjected to similar emulsion polymerization and then mixed with the rubber-like polymer composition in a latex state. Furthermore, a composition obtained by polymerizing only these monomers may be mixed in a latex state. Using the base material thus obtained, gas phase polymerization is carried out in a vinyl chloride monomer atmosphere under the following conditions. In other words, the polymerization pressure according to the present invention is lower than the saturated vapor pressure of vinyl chloride monomer at the polymerization temperature, and the particles of the rubber-resin composition using the styrene resin as the base material are not modulated. , the pressure must be within a range that does not impede the mixed flow of the particles within the reactor. As mentioned above, when the polymerization pressure exceeds this pressure, the rubber-resin composition using the styrene resin will swell or dissolve significantly in the vinyl chloride monomer, and the base materials will weld together, causing the base materials to melt. The vinyl chloride resin composition, which is the object of the present invention, forms large particles or forms lumps and adheres to the walls of the reactor, making reaction operations difficult or even impossible. You can't get it. This pressure is the upper limit of the polymerization pressure related to the present invention, but the upper limit of the polymerization pressure cannot be determined unconditionally, and depends on the components of the rubber-resin composition using the styrene resin, and as described below. It varies depending on the rubber-resin composition using each styrene resin. Further, the lower limit of the polymerization pressure is not particularly limited, but the polymerization pressure is P p , the saturated vapor pressure of vinyl chloride monomer at the polymerization temperature is P s , and the ratio of the two is P r (P r = P p / P s × 100%) As is already well known, if P r is less than 45%, the productivity in gas phase polymerization will rapidly decrease and the production cost will increase, which is undesirable. . It is preferable to set P r =45% as the lower limit. The polymerization temperature may be any temperature normally used for polymerizing vinyl chloride monomers, and 40 to 70°C is employed.
The polymerization time is determined by the type and amount of the radical polymerization initiator, but it may be a normal reaction time, for example, 2
~8 hours. Examples of radical polymerization initiators include azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, organic polymers such as diisopropyl peroxydicarbonate, lauroyl peroxide, and bis(4-t-butylcyclohexyl)peroxydicarbonate. Examples include oxides, and oil-soluble radical polymerization initiators commonly used in the polymerization of vinyl chloride monomers are used. The radical polymerization initiator can be added at the start of polymerization and/or during polymerization, if necessary. The method for adding the radical polymerization initiator is that rubber-resin compositions using styrene resins are active in vinyl chloride monomers and commonly used organic solvents, and therefore swell and dissolve. It is not possible to employ an impregnation method in which the base material is immersed in a solution of the radical polymerization initiator dissolved in these organic solvents, which are commonly used, and then the solvent is removed. Further, the method of directly adding a liquid radical polymerization initiator is preferable because the amount of the liquid radical polymerization initiator is extremely small compared to the amount of the base material, so that it is added extremely unevenly. The method of adding the radical polymerization initiator employed in the present invention is to dissolve a solution of the radical polymerization initiator in an organic solvent whose boiling point is below the addition temperature under pressure conditions at the temperature at which the radical polymerization initiator is being added. This is a spray method in which the radical polymerization initiator is added to the base material by spraying, and at the same time, the organic solvent is evaporated to support only the radical polymerization initiator on the base material. Particularly preferred organic solvent is vinyl chloride monomer. Another method of adding a radical polymerization initiator employed in the present invention is to directly add a sufficiently finely divided radical polymerization agent to the base material while mixing and stirring so as to uniformly disperse it. . When carrying out the present invention, the vinyl chloride monomer is stabilized in advance and/or during the polymerization, as is known in the conventional gas phase polymerization method of vinyl chloride monomer. Additives used during molding, such as curing agents, can be added within a range that does not inhibit the reaction, and a vinyl chloride resin composition in which the additives are uniformly dispersed can be obtained. The method for adding the additive may be the same as the method for adding the radical polymerization initiator depending on the properties of the additive.
Further, the content of the base substance can be freely controlled by controlling the polymerization temperature, polymerization time, and the type and amount of the polymerization initiator. The type of polymerization operation may be batch, semi-batch, or continuous, and the type of polymerization equipment may be a Betssel polymerization machine equipped with a mechanical stirring device (for example, double helical band blades, etc.), or a gas polymerization machine. A fluidized polymerization machine is also used. The present invention can also be carried out using a gas flow polymerization machine equipped with a mechanical stirring device. Next, preferred embodiments for carrying out the present invention will be described. First, when obtaining a vinyl chloride resin composition with enhanced impact resistance and heat resistance, the following composition is used as a base material. In other words, the rubber-resin composition using styrene resin is in the range surrounded by coordinate point BCQRS in Figure 1 (however, RQ and
A copolymer (A) obtained by emulsion polymerization of a mixture of acrylonitrile, α-methylstyrene, and methyl methacrylate having a composition (excluding those on the RS line) and a diene-based synthetic rubber with a composition of 35 to 65% by weight (see Figure 2). Consists of a copolymer (B) obtained by emulsion polymerization of 65 to 35% by weight of styrene or styrene and methyl methacrylate, which may contain acrylonitrile, having a composition in the range surrounded by the coordinate point EFGHI, Heat resistance, impact resistance, and diene synthetic rubber composition account for 5 to 30% by weight.
It is a thermoplastic resin composition. The compositions in FIGS. 1 and 2 are as shown in the table below.
【表】
本発明に用いられる基物質である耐衝撃性と耐
熱性を強化したスチレン系樹脂を使用したゴム―
樹脂組成物（以下、耐熱性のスチレン系樹脂を使
用したゴム―樹脂組成物と称す）としては組成物
の成分としてαメチルスチレンを含むことが重要
であり、ジエン系合成ゴム又はジエン系単量体と
αメチルスチンを共重合したゴム状重合組成物に
スチレン、アクリロニトリルおよび又はαメチル
スチレン、メタアクリル酸メチルを含んでグラフ
ト共重合させさ組成物とαメチルスチレン、アク
リロニトリル、又はαメチルスチレン、メタアク
リル酸メチルを主成分として共重合させた組成物
をラテツクス状態で混合してえられる。
上記の特に耐熱性が優れた組成物の一方の組成
物の一方の組成分であるアクリロニトリル、αメ
チルスチレンおよびメタクリル酸メチルの共重合
物（Ａ）をえる単量体混合物は第１図において、
点A.B.C.Dを頂点とする四角形部分内にあり、か
つマクリロニトリルが15重量％を越え20重量％以
下の部分及びアクリロニトリルや３重量％以上15
重量％以下であつてα―メチルスチレンが60重量
％を越える部分内にある組成すなわち点B.C.Q・
Ｒ・Ｓを頂点とする六角形部分内に該当する組成
を採用する必要がある。
乳化重合方法は通常の方法に従つて実施すれば
よい。たとえば、前記単量体混合物を水性分散体
中でラジカル重合開始剤の存在下に処理すればよ
い。
上記の特に耐熱性が優れた組成物の他方の組成
分は合成ゴムが約35〜65重量％とスチレン又はス
チレンとアクリロニトリルを含むことのあるメタ
アクリル酸メチル約65〜35重量％とのグラフト共
重合物（Ｂ）である。グラフト共重合物（Ｂ）は
単量体組成として第２図において点EFGHIを頂
点とする五角形部分内に該当するものを採用する
ことが必要である。
グラフト共重合物（Ｂ）は乳化重合法によつて
製造される。この場合ジエン系合成ゴムを予め水
性分散体中に分散させておき、これに単量体をそ
の添加速度が重合速度よりも遅くならぬ様に調節
しながら連続的に添加して行き、グラフト共重合
物に対する単量体の比が低く保たれる必要があ
る。又、ジエン系合成ゴムの粒子径が比較的大な
ることが望ましく、特にその約80重量％以上が約
0.1μ以上の粒子径を有する大粒子ラテツクスが
好んで使用される。
又、共重合体（Ａ）とグラフト共重合体（Ｂ）
の混合後の組成はジエン系合成ゴムが約５〜30重
量％になる様に混合するのが好ましい。混合は共
重合物（Ａ）とグラフト共重合物（Ｂ）のそれぞ
れのラテツクスを混合し、塩析して凝固したもの
を乾燥させてから使用すればよい。混合に際し
て、常用の安定剤、顔料、充填剤、可塑剤などの
加工助剤を添加してもよい。
以上で得られた耐熱性のスチレン系樹脂を使用
したゴム―樹脂組成物を基物質として気相重合す
る場合は、重合圧力をＰr＜52％とするのが好ま
しい。Ｐr＞52％になると該基物質は重合条件下
で塩化ビニル単量体に溶解をしはじめ、該基物質
の粒子の混合流動が困難になり、Ｐr≧60％にな
ると該基物質は塩化ビニル単量体に完全に溶解し
餅状となり反応操作は実施できない。
次に耐衝撃性と耐候性を強化した塩化した塩化
ビニル組成物をえる場合には以下の組成のものを
基物質として使用するのが好ましい。すなわち、
スチレン系樹脂を使用したゴム―樹脂組成物が、
アルキル基の炭素数が２〜８であるアクリル酸ア
ルキルエステル又はアクリル酸アルキルエステル
が少なくとも80重量％とこれと共重合可能な他の
モノビニリデン化合物20重量％以下との混合物
と、これらと重合可能な炭素二重結合を２個以上
含み、且つそのうち少なくとも１個がアリル基で
ある多官能性単量体0.1〜８重量％との共重合体
20〜80重量部の水溶性分散液にアルキル基の炭素
数が１〜４であるメタクリル酸アルキルエステル
０〜100重量％、ビニル芳香族化合物０〜80重量
％、不飽和ニトリル０〜50重量％およびこれらの
単量体と共重合可能なモノビニリデン基を含む単
量体を0.1〜８重量％の共重合可能な架橋剤で１
部又は全部架橋しながら80〜20重量部グラフトし
てなる耐候性・耐衝撃性重合体である。該耐衝撃
性と耐候性を強化したスチレン系樹脂を使用した
ゴム―樹脂組成物（以下、耐候性のスチレン系樹
脂を使用したゴム―樹脂組成物と称す。）は特開
昭50―88169や特公昭51―5674などに述べられて
いる方法に従つて乳化重合法によつて製造するの
が好ましい。
すなわち、ゴム状重合組成物としてアルキル基
の炭素数が２〜８のアクリル酸アルキルエステル
又は同様のアクリル酸アルキルエステルが少なく
とも80重量％とこれと共重合可能な他のモノビニ
リデン化合物20重量％以下との混合物をこれと重
合可能なアリル系架橋剤を0.1〜８重量％用いて
架橋しつつ乳化重合する。続いて、このアリル系
架橋剤で交叉結合したアクリル酸アルキルエステ
ル重合体の水性分散液の存在下でグラフト重合す
る。グラフト成分はアルキル基の炭素数が１〜４
のメタアクリル酸アルキルエステル０〜100重量
％、ビニル芳香族化合物０〜80重量％、不飽和ニ
トリル０〜50重量％であり、必要ならば他の共重
合可能な単量体０〜20重量％を使用することがで
きる。ここではグラフト単量体に共重合可能な多
官能性の架橋剤を使用してグラフト重合を行いつ
つ架橋することが重要である。このため架橋剤は
前述のアリル系架橋剤又は一分子中に共重合可能
な二個以上のビニリデン基を有する架橋剤が用い
られる。その使用量はグラフト単量体に対して
0.1〜８重量％である。
メタアクリル酸アルキルエステルは単独に使用
することが出来るが、これを芳香族ビニル化合物
で80重量％まで置換することが出来る。更に不飽
和ニトリルと併用する場合には50重量％まで置換
することができる。又、ビニル芳香族化合物と不
飽和ニトリル化合物との二成分で前記と同量まで
置換することができる。ビニル芳香族化合物と不
飽和ニトリルとの組み合せにあつては前者は80〜
50重量％と後者が20〜50重量％が使用できる。
グラフト単量体成分は架橋剤とともに架橋しつ
つグラフト重合される。架橋剤はグラフト単量体
の全部又は一部を架橋してもよいがグラフト単量
体の20重量％以上架橋するのが好ましい。グラフ
ト単量体と架橋剤は一度に仕込んでもよいし、そ
の全量又は一部を連続的又は間欠的に加えてもよ
い。更にグラフト単量体は全てを混合してもよい
が、前記成分範囲で組成を変更しつつ二段又はそ
れ以上多段で重合してもよい。
ゴム状重合組成物は通常の乳化重合でえられ、
この組成物の水性分散液の平均粒子径は0.06〜
0.3μの範囲のものが望ましい。
グラフト重合はこの様にして得たゴム状重合組
成物の水性分散液中で通常の乳化重合法で行なわ
れる。
このグラフト重合組成物は噴霧乾燥によるか、
又は塩析凝固して、洗浄した後、乾燥することに
より回収される。
以上で得られた耐候性のスチレン系樹脂を使用
したゴム―樹脂組成物を基物質として気相重合す
る場合は、重合圧力をＰr≦90％とするのが好ま
しい。Ｐrが90％以上では該基物質は塩化ビニル
単量体に著しく活性があるため該基物質の粒子の
溶着が起り、反応操作の実施が困難となる。
次に、耐衝撃性と透明性を強化した塩化ビニル
組成物を得る場合には以下の組成のものを基物質
として使用するのが好ましい。すなわち、スチレ
ン系樹脂を使用したゴム―樹脂組成物がゴム粒子
の径が0.2μ以下のものを90％以上量含む水性ラ
テツクスに、水に0.1％以上量溶解しかつ重合可
能なモノオレフイン系単量体、あるいは、この様
なモノオレフイン系単量体およびそれと共重合可
能な非水溶性のスチレン系単量体との混合物と水
溶性ないし解離性のラテツクス凝結剤を重合条件
下におき、ゴム粒子の径が0.2μ以下のものが90
％以上量にあるうちに凝結とグラフト重合を同時
に行なわせたモノオレフイン―ゴム系耐衝撃性・
透明性重合物である。
該耐衝撃性と透明性を強化したスチレン系樹脂
を使用したゴム―樹脂組成物（以下、耐衝撃性・
透明性のスチレン系樹脂を使用したゴム―樹脂組
成物と称す。）は、組成物の成分としてアクリロ
ニトリル、スチレン、メタアクリル酸エステル、
アクリル酸エステルの中から選ばれた成分を含む
ことが重要であり、これはジエン系合成ゴムの水
性ラテツクス中で、アクリロニトリルスチレン、
メタアクリル酸エステル、アクリル酸エステルの
中から選ばれた成分を主成分としてグラフト共重
合してえられる。
特に耐衝撃性・透明性の優れた組成物のジエン
系合成ゴムは水性ラテツクス状にある粒子径が
0.2μ以下のものを90％以上含有していなければ
ならない。
ジエン系合成ゴムにグラフト重合させるグラフ
ト成分の１つは重合可能なエチレン系の不飽和基
を含有して通常の重合条件（たとえば温度40〜70
℃、大気圧）において、水に0.1％以上溶解する
モノオレフイン系単量体であり、アクリロニトリ
ル、メタアクリル酸メチル、アクリル酸メチル、
アクリル酸エチルが例示でき、その他酢酸ビニ
ル、塩化ビニル、無水マレイン酸、アクリルアミ
ド、アクリル酸、メタアクリル酸なども使用でき
る。グラフト成分である他方の成分は非水溶性の
スチレン系化合物であり、スチレン、αメチルス
チレンが例示でき、前記モノオレフイン系単量体
と共存して使用される。
グラフト重合はジエン系合成ゴムの水性ラテツ
クス中で、水溶性ないし解離性のラテツクス凝結
剤の存在下で実施され、ジエン系合成ゴムの粒子
径が0.2μ以下のものが90％以上量あるうちにグ
ラフト重合が開始されなければならず、凝結とグ
ラフト重合は同時に進行させなければならない。
使用できる凝結剤は、塩化ナトリウム、硫酸ナ
トリウム、塩化カルシウム、燐酸などカチオンと
アニオンとを組合せて生じる化合物、水溶性アル
コール、ケトン、エステルアルデヒド、ニトリ
ル、酸アミドなど水溶性有機化合物が例示でき、
単種又は２種以上の混合物で使用される。
以上により、得られた耐衝撃性・透明性のスチ
レン系樹脂組成物を使用したゴム―樹脂組成物を
基物質として気相重合する場合には、重合圧力を
Ｐr≦74％とするのが好しい。Ｐrが74％以上にな
ると該基物質の粒子は著しく溶着し、反応器壁に
付着して混合流動が著しく困難となる。
本発明の実施によつて得られる塩化ビニル樹脂
組成物は従来の方法によつて得られる塩化ビニル
樹脂組成物に比較して以下に要約して述べる様に
優れた特徴がある。
気相重合工程においてスチレン系樹脂を使用
したゴム―樹脂組成物と塩化ビニル重合体が均
一に混合された添加剤を含むことのある塩化ビ
ニル樹脂組成物が得られ、成形加工に際する煩
雑な加熱混合工程を必要としない。又、成形加
工に際して本発明によつて得られる塩化ビニル
樹脂組成物は粒子の飛散が発生せず、労働環境
は衛生的である。
本発明によつて得られる塩化ビニル樹脂組成
物は従来の方法によつて得られる塩化ビニル樹
脂組成物（スチレン系樹脂を使用したゴム―樹
脂組成物の含有率15％における嵩密度は約0.45
ｇ／cm3である。）に比較して嵩密度が0.7ｇ／cm3
と高く、加工に際する生産性が優れている。
本発明によつて得られる塩化ビニル樹脂組成
物は通常の懸濁重合法によつて得られる塩化ビ
ニル重合体の粒子とほぼ同等の粒子径であり、
従来の方法によつて得られる塩化ビニル樹脂組
成物に比較した優れた成形加工に際するホツパ
ー内での流動性を有する。
本発明によつて得られる塩化ビニル樹脂組成
物は塩化ビニル樹脂組成物粒子中でスチレン系
樹脂を使用したゴム―樹脂組成物と塩化ビニル
重合体が均一に混合しているため、容易に均一
な成形加工ができ、優れた耐衝撃性、耐候性、
透明性などを発揮できる。
以下、実施例に基づき本発明を説明する。
実施例 １
(1) 本発明にかかわる基物質である耐熱性のスチ
レン系樹脂を使用したゴム―樹脂組成物の製造
方法
プロペラ撹拌機、還流冷却器、窒素導入管、温
度計および滴下ロートを備えた反応器に
水 250部
オレイン酸ナトリウム ３部
アスコルビン酸 0.2部
硫酸第一鉄水和物 0.0025部
エチレンジアミンテトラ酢酸２ナトリウム0.01
部
を仕込み、脱酸素後窒素気流中で60℃に加熱撹拌
した。次に
キユメントハイドロパーオキサイド 0.3部
第３級ドデシルメルカプタン 0.3部
アクリロニトリル 65部
αメチルスチレン 25部
メタアクリル酸メチル 10部
を滴下ロートに入れ５時間かけて連続的に滴下し
た。滴下後、更に60℃で１時間撹拌を続けた。反
応停止後共重合物
(A)をラテツクス状態でえた。
続いて、前記と同様の反応器に
大粒子高温重合ポリブタジエンラテツクス
84.7部
（固形分として） （50）部
水 215.3部
アスコルビン酸 0.2部
硫酸第一鉄水和物 0.0025部
エチレンジアミントテトラ酢酸２ナトリウム
0.01部
を入れ脱酸素後窒素気流下で60℃に加熱撹拌し
た。次に、
キユメンハイドロパーオキサイド 0.2部
第３混合メルカプタン 0.15部
スチレン 33.4部
アクリロニトリル 8.3部
メタアクリル酸メチル 8.3部
を滴下ロートに入れ、３時間を要して連続的に滴
下した。半量滴下した時、オレイン酸ナトリウム
1.0部を10％溶液として添加した。添加終了後、
更に60℃で１時間撹拌を続けた。反応停止後グラ
フト共重合体(B)をラテツクス状態でえた。
上記の様にして得た共重合体(A)66.7部とグラフ
ト共重合体(B)33.3部をラテツクス状態で混合し、
食塩と塩酸で凝固させ、加熱して粒子を凝集させ
た後、別、水洗、乾燥を行い耐熱性のスチレン
系樹脂を使用したゴム―樹脂組成物をえた。
(2) 本発明にかかわる気相重合の方法
２重ラセン帯翼撹拌機、塩化ビニル単量体蒸気
連絡管、温度計を備えた内容積１のステンレス
製重合器を用いた。
前記の耐熱性のスチレン系樹脂を使用したゴム
―樹脂組成物50ｇおよび微粉状のビス（４―ｔブ
チルシクロヘキシル）パーオキシジカーボネート
2.5ｇを重合器に収容し、真空ポンプで脱気した
後、系を58℃に昇温保持して蒸気圧3.5Kg／cm2Ｇ
の塩化ビニル単量体蒸気を連絡管によつて重合器
に導びいた。重合圧力を重合の間中3.5Kg／cm2Ｇ
に保持して重合を実施した。この時Ｐr＝48％で
ある。４時間後、連絡管の弁を閉じ、重合器内の
塩化ビニル単量体蒸気を排出して重合を停止し
た。
得られた塩化ビニル樹脂組成物は、白色の粉体
で耐熱性のスチレン系樹脂を使用したゴム―樹脂
組成物を29％含有していた。嵩密度（JIS Ｋ―
6721に従つて測定した）は0.7ｇ／cm3であつた。
ホツパーでの流動性は塩化ビニル重合体と同等で
あり、粒径は500〜200μであつた。又、顕微鏡で
観察すると耐熱性のスチレン系樹脂を使用したゴ
ム−樹脂組成物と塩化ビニル重合体ビニル樹脂組
成物中で均一に混合しており、この塩化ビニル樹
脂組成物と、従来の耐熱性のスチレン系樹脂を使
用したゴム―樹脂組成物と塩化ビニル樹脂重合体
を粉末状で混合した塩化ビニル樹脂組成物を比較
して成形加工すると、両者の成形物の強度はほぼ
同等であり、成形加工の生産性は本発明の方が優
れていた。
比較例 １
実施例１で得られた基物質を用い、重合圧力を
4.7Kg／cm2Ｇ（Ｐr＝60％に相当する）とし、その
他の重合の条件は実施例１と同様にして気相重合
を行つた。その結果、基物質は塩化ビニル単量体
蒸気中で溶解し、重合は実施できなかつた。
比較例 ２
実施例１で得られた基物質を用い、重合圧力を
２Kg／cm2Ｇ（Ｐr＝30％）とし、その他の重合条
件は実施例１と同様にして気相重合を行つた。重
合後えられた塩化ビニル樹脂組成物は80ｇで重合
の生産性は著しく低い。
この様に重合の生産性を確保しつつ目的塩化ビ
ニル樹脂組成物を得るには、重合圧力の範囲が限
られ、好ましい範囲は45％≦Ｐr≦52％である。
実施例 ２
実施例１で得られた基物質を用い下記の条件で
気相重合を行なつた。
重合各件 重合圧力 5.9Kg／cm2Ｇ（Ｐr＝52
％）
重合温度 58℃
重合時間 ６時間
重合処方 実施例１の基物質 50ｇ
ビス（４―ｔブチルシクロヘキシ
ル）パーオキシジカーボネート
0.5ｇ
重合後、えられた塩化ビニル樹脂組成物は白色
粉末であり、耐熱性のスチレン系樹脂を使用した
ゴム―樹脂組成物を52％含有していた。耐熱性の
スチレン系樹脂を使用したゴム―樹脂組成物と塩
化ビニル樹脂組成物の粒子中で均一に混合してお
り、嵩密度、流動性、成形加工性とも実施例１と
同様に従来法より優れていた。
実施例 ３
(1) 本発明にかかわる基物質である耐候性のスチ
レン系樹脂を使用したゴム―樹脂組成物の製造
方法
下記混合物をつくり50℃の温度に保つ
水 250部
オレイン酸ナトリウム 1.5部
ホルムアルデヒド縮合ナフタリンスルホン酸ナ
トリウム 0.2 部
ホルムアルデヒドスルホキシル酸ナトリウム
0.4 部
エチレンジアミン四酢酸２ナトリウム 0.01部
硫酸第一鉄７水塩 0.005部
リン酸ナトリウム12水塩 0.5部
上記混合物を窒素気流中で撹拌しつつ、下記混
合液を４時間にわたり添加して重合した。
アクリル酸ブチル 100部
メタアクリル酸アリル １部
キユメンハイドロパーオキサイド 0.2部
添加が終了してから３時間50℃の温度に保つて
重合率95％以上で重合を完結しゴム状重合体分散
液をえた。続いて、下記の混合物を仕込み、窒素
気流中で60℃に保つ。但し、水の量は分散液から
の水と後述する酢酸と苛性カリの添加に要する量
を合計して250部になる様に仕込む。
ゴム状重合体分散液（重合体固形分として）
65部
水 250部
ホルムアルデヒドスルホキシル酸ナトリウム
0.2部
エチレンジアミン四酢酸２ナトリウム 0.01部
硫酸第一鉄７水塩 0.005部
撹拌しながら２％酢酸水溶液を20部加えて、15
分間保つた後、２％苛性カリ水溶液20部加えて分
散液を安定化させた。これに、
メタアクリル酸メチル 25部
スチレン ５部
アクリロニトル ５部
キユメンハイドロパーオキサイド 0.2部
よりなる混合物を４時間に亘り添加して、その後
２時間保つて重合率95％以上で重合を完結た。こ
の分散液に塩化カルシウムを加えて塩析凝固した
のち、加熱して脱水精製して耐候性のスチレン系
樹脂を使用したゴム―樹脂組成の粉粒体をえる。
(2) 本発明にかかわる気相重合の方法
実施例と同様の内容積１のステンレス製重合
器をを使用した。上記基物質50ｇおよび微粉状ビ
ス（４―ｔブチルシクロヘキシル）パーオキシジ
カーボネート0.49ｇを仕込み、真空ポンプで脱気
した後、系を58℃に昇温保持して蒸気圧6.5Kg／
cm2Ｇの塩化ビニル単量体蒸気を連絡管によつて重
合器に導びいた。重合圧力を重合の間中6.5Kg／
cm2Ｇに保持して重合を実施した（この時のＰrは
80％に相当する）。４時間後、連絡管の弁を閉じ
重合器中の塩化ビニル単量体蒸気を排出して重合
を停止した。
重合後、えられた塩化ビニル樹脂組成物は白色
の粉粒体で耐候性のスチレン系樹脂を使用したゴ
ム―樹脂組成物を17％含有していた。嵩密度は
0.7ｇ／cm3で粒子径は50〜200μであつた。顕微鏡
で観察すると耐候性のスチレン系樹脂を使用した
ゴム―樹脂組成物と塩化ビニル重合体は塩化ビニ
ル樹脂組成物の粒子中で均一に混合しており、従
来の混合による方法と比較して成形加工すると、
ホツパーでの流動性は塩化ビニル重合体と同様に
スムースであり成形加工の生産性も向上した。成
形物の強度は従来の方法とほぼ同等であつた。
実施例 ４
実施例３で得られた基物質を用い表１に示す様
に重合圧力とラジカル重合開始剤の量さらに基物
質の量を変更して実施例３と同様の方法で気相重
合を実施した。[Table] Rubber using styrene resin with enhanced impact resistance and heat resistance, which is the base material used in the present invention.
It is important for the resin composition (hereinafter referred to as a rubber-resin composition using a heat-resistant styrene resin) to contain α-methylstyrene as a component of the composition, and diene-based synthetic rubber or diene-based monomer Styrene, acrylonitrile and or α-methylstyrene, methyl methacrylate are graft-copolymerized to a rubber-like polymer composition in which α-methylstyrene and α-methylstyrene are copolymerized. It is obtained by mixing a copolymerized composition containing methyl acrylate as a main component in a latex state. In FIG. 1, the monomer mixture containing the copolymer (A) of acrylonitrile, α-methylstyrene, and methyl methacrylate, which is one component of one of the compositions of the above-mentioned composition particularly excellent in heat resistance, is as follows.
Areas located within the rectangular area with point ABCD as the apex and containing more than 15% by weight and less than 20% by weight of macrylonitrile, and 3% by weight or more of acrylonitrile15
The composition in which α-methylstyrene is less than 60% by weight, that is, the point BCQ.
It is necessary to adopt the corresponding composition within the hexagonal portion with R and S as vertices. The emulsion polymerization method may be carried out according to a conventional method. For example, the monomer mixture may be treated in an aqueous dispersion in the presence of a radical polymerization initiator. The other component of the above particularly heat resistant composition is a graft combination of about 35-65% by weight of synthetic rubber and about 65-35% by weight of styrene or styrene and methyl methacrylate which may contain acrylonitrile. This is a polymer (B). The monomer composition of the graft copolymer (B) must fall within the pentagonal area with the point EFGHI as its apex in FIG. 2. The graft copolymer (B) is produced by emulsion polymerization. In this case, the diene-based synthetic rubber is previously dispersed in an aqueous dispersion, and the monomer is continuously added thereto while controlling the addition rate so that it does not become slower than the polymerization rate. The monomer to polymer ratio needs to be kept low. In addition, it is desirable that the particle size of the diene synthetic rubber is relatively large, and in particular, about 80% by weight or more of the particle size is about
Large particle latex having a particle size of 0.1 micron or more is preferably used. Moreover, copolymer (A) and graft copolymer (B)
The composition after mixing is preferably such that the diene synthetic rubber is about 5 to 30% by weight. For mixing, the respective latexes of the copolymer (A) and the graft copolymer (B) may be mixed, salted out, solidified, and dried before use. During mixing, conventional processing aids such as stabilizers, pigments, fillers, plasticizers, etc. may be added. When a rubber-resin composition using the heat-resistant styrene resin obtained above is subjected to gas phase polymerization as a base material, the polymerization pressure is preferably set to P r <52%. When P r >52%, the base material begins to dissolve in the vinyl chloride monomer under polymerization conditions, making it difficult to mix and flow the particles of the base material, and when P r >60%, the base material begins to dissolve in the vinyl chloride monomer under polymerization conditions. It completely dissolves in the vinyl chloride monomer and becomes cake-like, making it impossible to carry out any reaction operations. Next, when obtaining a chlorinated vinyl chloride composition with enhanced impact resistance and weather resistance, it is preferable to use the following composition as a base material. That is,
A rubber-resin composition using styrene resin is
A mixture of at least 80% by weight of an acrylic alkyl ester or acrylic alkyl ester in which the alkyl group has 2 to 8 carbon atoms and 20% by weight or less of another monovinylidene compound copolymerizable therewith, and polymerizable with these. A copolymer with 0.1 to 8% by weight of a polyfunctional monomer containing two or more carbon double bonds, at least one of which is an allyl group.
20 to 80 parts by weight of an aqueous dispersion containing 0 to 100% by weight of an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, 0 to 80% by weight of a vinyl aromatic compound, and 0 to 50% by weight of an unsaturated nitrile. and a monomer containing a monovinylidene group copolymerizable with these monomers with 0.1 to 8% by weight of a copolymerizable crosslinking agent.
It is a weather-resistant and impact-resistant polymer made by grafting 80 to 20 parts by weight with some or all crosslinking. A rubber-resin composition using a styrene resin with enhanced impact resistance and weather resistance (hereinafter referred to as a rubber-resin composition using a weather-resistant styrene resin) is disclosed in JP-A-50-88169 and others. Preferably, it is produced by emulsion polymerization according to the method described in Japanese Patent Publication No. 51-5674. That is, the rubbery polymer composition contains at least 80% by weight of an acrylic acid alkyl ester having an alkyl group having 2 to 8 carbon atoms or a similar acrylic acid alkyl ester and 20% by weight or less of another monovinylidene compound copolymerizable therewith. Emulsion polymerization is carried out while crosslinking the mixture with 0.1 to 8% by weight of an allylic crosslinking agent that can be polymerized with the mixture. Subsequently, graft polymerization is carried out in the presence of an aqueous dispersion of an acrylic acid alkyl ester polymer cross-linked with this allylic crosslinking agent. The graft component has an alkyl group with 1 to 4 carbon atoms.
0 to 100% by weight of methacrylic acid alkyl esters, 0 to 80% by weight of vinyl aromatic compounds, 0 to 50% by weight of unsaturated nitriles, and if necessary 0 to 20% by weight of other copolymerizable monomers. can be used. Here, it is important to use a polyfunctional crosslinking agent copolymerizable with the graft monomer to carry out graft polymerization and crosslinking. Therefore, as the crosslinking agent, the aforementioned allyl crosslinking agent or a crosslinking agent having two or more copolymerizable vinylidene groups in one molecule is used. The amount used is based on the graft monomer.
It is 0.1 to 8% by weight. Although the methacrylic acid alkyl ester can be used alone, it can be replaced by up to 80% by weight with an aromatic vinyl compound. Furthermore, when used in combination with unsaturated nitrile, it can be substituted up to 50% by weight. Further, the substitution can be made by two components, a vinyl aromatic compound and an unsaturated nitrile compound, up to the same amount as above. In the case of a combination of a vinyl aromatic compound and an unsaturated nitrile, the former is 80~
50% by weight and the latter 20-50% by weight can be used. The graft monomer component is graft-polymerized while being crosslinked together with a crosslinking agent. The crosslinking agent may crosslink all or part of the graft monomer, but preferably crosslinks 20% by weight or more of the graft monomer. The graft monomer and the crosslinking agent may be added at once, or the whole or a portion thereof may be added continuously or intermittently. Further, all of the graft monomers may be mixed together, or they may be polymerized in two or more stages while changing the composition within the above-mentioned range of ingredients. The rubbery polymer composition is obtained by conventional emulsion polymerization,
The average particle size of the aqueous dispersion of this composition is 0.06~
A value in the range of 0.3μ is desirable. Graft polymerization is carried out in the aqueous dispersion of the rubbery polymer composition thus obtained by a conventional emulsion polymerization method. This graft polymerization composition can be prepared by spray drying or
Alternatively, it can be recovered by salting out, coagulating, washing, and drying. When a rubber-resin composition using the weather-resistant styrene resin obtained above is subjected to gas phase polymerization as a base material, the polymerization pressure is preferably set to P r ≦90%. When P r is 90% or more, the base material is extremely active against vinyl chloride monomers, so that particles of the base material are welded together, making it difficult to carry out the reaction operation. Next, when obtaining a vinyl chloride composition with enhanced impact resistance and transparency, it is preferable to use the following composition as a base material. That is, a rubber-resin composition using a styrene resin is added to an aqueous latex containing 90% or more of rubber particles with a diameter of 0.2μ or less, and a monoolefin-based monomer that is soluble in water and polymerizable in an amount of 0.1% or more. polymer, or a mixture of such a monoolefin monomer and a water-insoluble styrene monomer copolymerizable with it, and a water-soluble or dissociable latex coagulant under polymerization conditions to form rubber. 90 for particles with a diameter of 0.2μ or less
% or more of mono-olefin that undergoes coagulation and graft polymerization at the same time - Rubber-based impact resistance.
It is a transparent polymer. Rubber-resin compositions (hereinafter referred to as impact resistance and
It is called a rubber-resin composition that uses transparent styrene resin. ) contains acrylonitrile, styrene, methacrylic ester,
It is important to include a component selected from acrylic acid esters, which in the aqueous latex of diene-based synthetic rubber include acrylonitrile styrene,
It is obtained by graft copolymerization with a main component selected from methacrylic esters and acrylic esters. In particular, diene-based synthetic rubber, which has a composition with excellent impact resistance and transparency, has a particle size that is similar to that of water-based latex.
Must contain 90% or more of particles with a particle diameter of 0.2μ or less. One of the graft components to be graft-polymerized to the diene-based synthetic rubber contains a polymerizable ethylenically unsaturated group under normal polymerization conditions (for example, at a temperature of 40 to 70°C).
It is a monoolefin monomer that dissolves at least 0.1% in water at temperatures (°C, atmospheric pressure), and includes acrylonitrile, methyl methacrylate, methyl acrylate,
Ethyl acrylate is an example, and vinyl acetate, vinyl chloride, maleic anhydride, acrylamide, acrylic acid, methacrylic acid, and the like can also be used. The other component, which is the graft component, is a water-insoluble styrene compound, examples of which include styrene and α-methylstyrene, which are used together with the monoolefin monomer. Graft polymerization is carried out in an aqueous latex of diene-based synthetic rubber in the presence of a water-soluble or dissociable latex coagulant. Graft polymerization must be initiated and coagulation and graft polymerization must proceed simultaneously. Examples of coagulants that can be used include compounds produced by combining cations and anions such as sodium chloride, sodium sulfate, calcium chloride, and phosphoric acid, and water-soluble organic compounds such as water-soluble alcohols, ketones, ester aldehydes, nitriles, and acid amides.
It can be used singly or in a mixture of two or more. As a result of the above, when performing gas phase polymerization using a rubber-resin composition as a base material using the obtained impact-resistant and transparent styrenic resin composition, it is recommended to set the polymerization pressure to P r ≦74%. I like it. When P r exceeds 74%, the particles of the base material are significantly welded and adhered to the reactor wall, making mixing and flow extremely difficult. The vinyl chloride resin composition obtained by carrying out the present invention has superior characteristics as compared to the vinyl chloride resin composition obtained by conventional methods, as summarized below. In the gas phase polymerization process, a rubber-resin composition using a styrene resin and a vinyl chloride polymer can be obtained, which may contain additives, in which a vinyl chloride polymer is uniformly mixed. No heat mixing step is required. Further, during molding, the vinyl chloride resin composition obtained by the present invention does not cause particles to scatter, resulting in a sanitary working environment. The vinyl chloride resin composition obtained by the present invention is different from the vinyl chloride resin composition obtained by the conventional method (the bulk density of the rubber-resin composition using styrene resin at a content of 15% is about 0.45
g/ cm3 . ) has a bulk density of 0.7g/cm 3
and high productivity during processing. The vinyl chloride resin composition obtained by the present invention has approximately the same particle size as the vinyl chloride polymer particles obtained by ordinary suspension polymerization,
It has superior fluidity in the hopper during molding compared to vinyl chloride resin compositions obtained by conventional methods. The vinyl chloride resin composition obtained by the present invention has a rubber-resin composition using a styrene resin and a vinyl chloride polymer uniformly mixed in the vinyl chloride resin composition particles, so that it can be easily uniformly mixed. Can be molded, has excellent impact resistance, weather resistance,
It can demonstrate transparency. The present invention will be explained below based on Examples. Example 1 (1) Method for manufacturing a rubber-resin composition using a heat-resistant styrene resin as a base material according to the present invention Equipped with a propeller stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping funnel. In a reactor, add 250 parts of water, 3 parts of sodium oleate, 0.2 parts of ascorbic acid, 0.0025 parts of ferrous sulfate hydrate, and 0.01 parts of disodium ethylenediaminetetraacetate.
After deoxidizing, the mixture was heated to 60°C and stirred in a nitrogen stream. Next, 0.3 parts of quement hydroperoxide, 0.3 parts of tertiary dodecyl mercaptan, 65 parts of acrylonitrile, 25 parts of α-methylstyrene, and 10 parts of methyl methacrylate were placed in the dropping funnel and continuously added dropwise over 5 hours. After the dropwise addition, stirring was further continued at 60°C for 1 hour. After termination of the reaction, copolymer (A) was obtained in the form of a latex. Next, large-particle high-temperature polymerized polybutadiene latex was placed in the same reactor as above.
84.7 parts (as solid content) (50) parts Water 215.3 parts Ascorbic acid 0.2 parts Ferrous sulfate hydrate 0.0025 parts Disodium ethylene diamine tetraacetate
After adding 0.01 part of the mixture and deoxidizing it, the mixture was heated and stirred at 60°C under a nitrogen stream. Next, 0.2 parts of kyumene hydroperoxide, 0.15 parts of third mixed mercaptan, 33.4 parts of styrene, 8.3 parts of acrylonitrile, and 8.3 parts of methyl methacrylate were placed in the dropping funnel, and the mixture was continuously added dropwise over a period of 3 hours. When half the amount is dropped, sodium oleate
1.0 part was added as a 10% solution. After addition,
Stirring was further continued at 60°C for 1 hour. After termination of the reaction, the graft copolymer (B) was obtained in a latex state. 66.7 parts of the copolymer (A) obtained as above and 33.3 parts of the graft copolymer (B) were mixed in a latex state,
After coagulating with common salt and hydrochloric acid and heating to agglomerate the particles, the particles were washed with water and dried to obtain a rubber-resin composition using a heat-resistant styrene resin. (2) Method of gas phase polymerization according to the present invention A stainless steel polymerization vessel with an internal volume of 1 was equipped with a double helical band blade stirrer, a vinyl chloride monomer vapor communication pipe, and a thermometer. 50 g of a rubber-resin composition using the above-mentioned heat-resistant styrene resin and finely divided bis(4-t-butylcyclohexyl) peroxydicarbonate
After placing 2.5 g in a polymerization vessel and degassing it with a vacuum pump, the system was heated to 58°C and maintained at a vapor pressure of 3.5 Kg/cm 2 G.
of vinyl chloride monomer vapor was introduced into the polymerization vessel through a connecting pipe. Polymerization pressure was kept at 3.5Kg/cm 2 G during polymerization.
Polymerization was carried out by maintaining the temperature at At this time, P r =48%. After 4 hours, the valve of the communication pipe was closed, the vinyl chloride monomer vapor in the polymerization vessel was discharged, and the polymerization was stopped. The resulting vinyl chloride resin composition was a white powder and contained 29% of a rubber-resin composition using a heat-resistant styrene resin. Bulk density (JIS K-
6721) was 0.7 g/cm 3 .
The fluidity in the hopper was comparable to that of vinyl chloride polymer, and the particle size was 500 to 200 μ. In addition, when observed under a microscope, a rubber-resin composition using a heat-resistant styrene resin and a vinyl chloride polymer vinyl resin composition were uniformly mixed, and this vinyl chloride resin composition and a conventional heat-resistant When comparing and molding a rubber-resin composition using a styrene-based resin and a vinyl chloride resin composition prepared by mixing a powdered vinyl chloride resin polymer, it was found that the strength of the molded products of the two was almost the same, and the strength of the molded products was almost the same. The processing productivity of the present invention was superior. Comparative Example 1 Using the base material obtained in Example 1, the polymerization pressure was
Gas phase polymerization was carried out at 4.7 Kg/cm 2 G (corresponding to P r =60%) and other polymerization conditions were the same as in Example 1. As a result, the base material dissolved in the vinyl chloride monomer vapor and polymerization could not be carried out. Comparative Example 2 Using the base material obtained in Example 1, gas phase polymerization was carried out at a polymerization pressure of 2 Kg/cm 2 G (P r = 30%) and under the same polymerization conditions as in Example 1. . The vinyl chloride resin composition obtained after polymerization was 80 g, and the productivity of polymerization was extremely low. In this way, in order to obtain the desired vinyl chloride resin composition while ensuring polymerization productivity, the range of polymerization pressure is limited, and the preferred range is 45%≦P r ≦52%. Example 2 Using the base material obtained in Example 1, gas phase polymerization was carried out under the following conditions. Polymerization conditions Polymerization pressure 5.9Kg/cm 2 G (P r = 52
%) Polymerization temperature 58°C Polymerization time 6 hours Polymerization recipe Base material of Example 1 50g Bis(4-t-butylcyclohexyl) peroxydicarbonate
0.5 g After polymerization, the vinyl chloride resin composition obtained was a white powder, containing 52% of a rubber-resin composition using a heat-resistant styrene resin. The rubber-resin composition using heat-resistant styrene resin and the vinyl chloride resin composition are uniformly mixed in the particles, and the bulk density, fluidity, and moldability are the same as in Example 1 and better than the conventional method. It was excellent. Example 3 (1) Method for manufacturing a rubber-resin composition using a weather-resistant styrene resin as a base material related to the present invention Make the following mixture and maintain at a temperature of 50°C Water 250 parts Sodium oleate 1.5 parts Formaldehyde Sodium condensed naphthalene sulfonate 0.2 parts Sodium formaldehyde sulfoxylate
0.4 part Disodium ethylenediaminetetraacetic acid 0.01 part Ferrous sulfate heptahydrate 0.005 part Sodium phosphate dodecahydrate 0.5 part While stirring the above mixture in a nitrogen stream, the following mixed solution was added over 4 hours to polymerize. Butyl acrylate 100 parts Allyl methacrylate 1 part Kyumene hydroperoxide 0.2 parts After the addition is complete, maintain the temperature at 50°C for 3 hours to complete the polymerization with a polymerization rate of 95% or more to obtain a rubbery polymer dispersion. I got it. Next, charge the following mixture and keep it at 60°C in a nitrogen stream. However, the amount of water is such that the total amount of water from the dispersion and the amount required for adding acetic acid and caustic potash, which will be described later, will be 250 parts. Rubbery polymer dispersion (as polymer solids)
65 parts water 250 parts sodium formaldehyde sulfoxylate
0.2 parts disodium ethylenediaminetetraacetate 0.01 parts ferrous sulfate heptahydrate 0.005 parts Add 20 parts of 2% acetic acid aqueous solution while stirring, 15
After holding for a minute, 20 parts of a 2% aqueous solution of potassium hydroxide was added to stabilize the dispersion. To this was added a mixture consisting of 25 parts of methyl methacrylate, 5 parts of styrene, 5 parts of acrylonitrile, and 0.2 parts of kyumene hydroperoxide over a period of 4 hours, and then maintained for 2 hours to complete polymerization with a polymerization rate of 95% or more. Calcium chloride is added to this dispersion to solidify it by salting out, followed by dehydration and purification by heating to obtain a powder having a rubber-resin composition using a weather-resistant styrene resin. (2) Method of gas phase polymerization according to the present invention A stainless steel polymerization vessel with an internal volume of 1 as in the example was used. After charging 50 g of the above base material and 0.49 g of finely powdered bis(4-t-butylcyclohexyl) peroxydicarbonate and degassing with a vacuum pump, the system was heated and maintained at 58°C, and the vapor pressure was 6.5 kg/
cm 2 G of vinyl chloride monomer vapor was introduced into the polymerization reactor via a connecting pipe. The polymerization pressure was set at 6.5Kg/during the polymerization.
Polymerization was carried out while maintaining the temperature at cm 2 G (P r at this time was
equivalent to 80%). After 4 hours, the valve of the communication pipe was closed and the vinyl chloride monomer vapor in the polymerization vessel was discharged to stop the polymerization. After polymerization, the vinyl chloride resin composition obtained was a white powder containing 17% of a rubber-resin composition using a weather-resistant styrene resin. The bulk density is
The particle size was 50-200μ at 0.7g/cm 3 . When observed under a microscope, the rubber-resin composition using a weather-resistant styrene resin and the vinyl chloride polymer are uniformly mixed in the particles of the vinyl chloride resin composition, making it easier to mold than conventional mixing methods. When processed,
The fluidity in the hopper was smooth, similar to that of vinyl chloride polymer, and the productivity of molding processing was also improved. The strength of the molded product was almost the same as that of the conventional method. Example 4 Using the base material obtained in Example 3, gas phase polymerization was carried out in the same manner as in Example 3, changing the polymerization pressure, the amount of radical polymerization initiator, and the amount of the base material as shown in Table 1. carried out.
【表】
重合後、えられた塩化ビニル樹脂組成物は全て
白色粉体であり、実施例３と同様に、従来の方法
と比較して嵩密度、流動性、成形加工性とも優れ
ていた。成形物の強度はほぼ同等であつた。
比較例 ３
実施例３で得られた基物質を用い、重合圧力を
２Kg／cm2Ｇ（Ｐr＝30％に相当する。）とし、その
他は実施例３と同じ条件にて気相重合を行つた。
重合後、えられた塩化ビニル樹脂組成物は85ｇ
で重合の生産性は低く、耐候性のスチレン系樹脂
を使用したゴム―樹脂組成物の含率は59％であつ
た。一般的に使用できる耐候性のスチレン系樹脂
を使用したゴム―樹脂組成物の含率は約20％程度
である。この様に、Ｐrが著しく低い場合には済
的に本発明を実施することはできない。
実施例 ５
実施例３で得られた基物質50ｇ、微粉状アゾビ
スジメチルバレロニトリル0.54ｇを用い、実施例
３と同様に気相重合を行つた。但し、重合時間は
５時間とした。
重合後、えられた塩化ビニル樹脂組成物は実施
例３と同様にホツパー内での流動性および成形加
工における生産性に優れ、又成形物の強度は従来
の方法とほぼ同等であつた。
比較例 ４
実施例３でえられた基物質40ｇとジイソプロピ
ルパーオキシジカーボネート0.15ｇを用いて気相
重合した。重合圧力は7.7Kg／cm2Ｇ（Ｐr＝95％に
相当する。）とした。しかし重合中該基物質の溶
着が起り、基物質の撹拌混合が困難となり、重合
時間が2.5時間で反応操作を停止した。撹拌混合
操作ぎ不充分なため、塩化ビニル単量体の重合量
が少なく、かつ一部団塊状をしていた。
実施例 ６
(1) 本発明にかかわる基物質である耐衝撃性、透
明性のスチレン系樹脂を使用したゴム―樹脂組
成物の製造方法
ブタジエン76.5％、スチレン23.5％からなり、
その粒子径が0.2μ以下の粒子を99％含み、その
固形分濃度が25％である合成ゴムのラテツクスを
用いた。
合成ゴムラテツクス 100部
水 175部
デキストローズ 0.5部
硫酸第一鉄７水和物 0.0025部
以上を還流冷却器付反応器に仕込み、60℃に加
熱撹拌し、続いてこれに
アクリロニトリル 25部
スチレン 25部
メタクリル酸メチル 25部
無水酢酸 0.5部
ドデシルメルカプタン 0.8部
キユメンハイドロパーオキサイド 0.3部
以上の混合物を５時間かけて窒素気流中で連続
追加し、さらに１時間加熱撹拌を行つた。この反
応液を食塩と塩酸により塩析凝固後洗浄し、乾燥
して耐衝撃性、透明性のスチレン系樹脂を使用し
たゴム―樹脂組成物をえた。
(2) 本発明にかかわる気相重合の方法
実施例１と同様の内容積１のステンレス製重
合器を使用した。上記基物質50ｇおよび微粉状ビ
ス（４―ｔブチルシクロヘキシル）パーオキシジ
カーボネート0.49ｇを仕込み、真空ポンプで脱気
した後、系を58℃に昇温保持して蒸気圧力5.8
Kg／cm2Ｇの塩化ビニル単量体蒸気を連絡管によつ
て重合器に導びいた。重合圧力を重合の間中、
5.8Kg／cm2Ｇに保持して重合を実施した。この時
のＰrは73％に相当する。５時間後、連絡管の弁
を閉じ重合器中の塩化ビニル単量体蒸気を排出し
て重合を停止した。
重合後、えられた塩化ビニル樹脂組成物は白色
の粉粒体で耐衝撃性透明性のスチレン樹脂を使用
したゴム―樹脂組成物を20％含有していた。嵩密
度は約0.7ｇ／cm3で粒子径は50〜200μがほとんど
であつた。従来の混合法による塩化ビニル樹脂組
成物と比較して成形加工すると、成形加工時の流
動性、生産性共に優れていた。
比較例 ５
実施例６でえられた基物質50ｇと微粉状ビス
（４―ブチルシクロヘキシル）パーオキシジカー
ボネート0.49ｇを用いて気相重合した。重合圧力
は6.5Kg／cm2Ｇ（Ｐr＝80％に相当する。）とし
て、他は実施例６と同様の重合条件とした。
しかし、重合中、該基物質は著しい粘着性を起
し、反応器壁、撹拌機表面に層状に付着し、撹拌
混合の効果は著しく低くなり、塩化ビニル単量体
の重合速度が著しく減少し重合量は少なかつた。[Table] After polymerization, all of the obtained vinyl chloride resin compositions were white powders, and as in Example 3, they were superior in bulk density, fluidity, and moldability compared to the conventional method. The strengths of the molded products were almost the same. Comparative Example 3 Using the base material obtained in Example 3, gas phase polymerization was carried out at a polymerization pressure of 2 Kg/cm 2 G (corresponding to P r = 30%) and under the same conditions as Example 3. I went. After polymerization, the obtained vinyl chloride resin composition weighs 85g.
The polymerization productivity was low, and the content of the rubber-resin composition using weather-resistant styrene resin was 59%. The content of a rubber-resin composition using a generally available weather-resistant styrene resin is about 20%. As described above, the present invention cannot be implemented economically if P r is extremely low. Example 5 Gas phase polymerization was carried out in the same manner as in Example 3 using 50 g of the base material obtained in Example 3 and 0.54 g of finely powdered azobisdimethylvaleronitrile. However, the polymerization time was 5 hours. After the polymerization, the obtained vinyl chloride resin composition had excellent fluidity in the hopper and productivity in molding as in Example 3, and the strength of the molded product was almost the same as that of the conventional method. Comparative Example 4 Gas phase polymerization was carried out using 40 g of the base material obtained in Example 3 and 0.15 g of diisopropyl peroxydicarbonate. The polymerization pressure was 7.7 Kg/cm 2 G (corresponding to P r =95%). However, welding of the base material occurred during polymerization, making stirring and mixing of the base material difficult, and the reaction operation was stopped after the polymerization time was 2.5 hours. Due to insufficient stirring and mixing, the amount of vinyl chloride monomer polymerized was small, and some of the polymerized vinyl chloride monomers were in the form of lumps. Example 6 (1) Method for manufacturing a rubber-resin composition using an impact-resistant, transparent styrene resin as a base material related to the present invention Consisting of 76.5% butadiene and 23.5% styrene,
A synthetic rubber latex containing 99% particles with a particle diameter of 0.2 μ or less and a solid content concentration of 25% was used. Synthetic rubber latex 100 parts Water 175 parts Dextrose 0.5 parts Ferrous sulfate heptahydrate 0.0025 parts The above was charged into a reactor equipped with a reflux condenser, heated to 60°C and stirred, and then acrylonitrile 25 parts Styrene 25 parts Methacryl Methyl acid 25 parts Acetic anhydride 0.5 parts Dodecyl mercaptan 0.8 parts Kyumene hydroperoxide 0.3 parts The above mixture was continuously added over 5 hours in a nitrogen stream, and the mixture was further heated and stirred for 1 hour. This reaction solution was salted out and solidified with common salt and hydrochloric acid, washed, and dried to obtain a rubber-resin composition using an impact-resistant and transparent styrene resin. (2) Method of gas phase polymerization according to the present invention A stainless steel polymerization vessel having an internal volume of 1 as in Example 1 was used. After charging 50 g of the above base material and 0.49 g of finely divided bis(4-t-butylcyclohexyl) peroxydicarbonate and degassing with a vacuum pump, the system was heated to 58°C and maintained at a vapor pressure of 5.8.
Kg/cm 2 G of vinyl chloride monomer vapor was introduced into the polymerization vessel through a connecting pipe. the polymerization pressure throughout the polymerization,
Polymerization was carried out while maintaining the pressure at 5.8 Kg/cm 2 G. P r at this time corresponds to 73%. After 5 hours, the valve of the communication pipe was closed and the vinyl chloride monomer vapor in the polymerization vessel was discharged to stop the polymerization. After polymerization, the resulting vinyl chloride resin composition was a white powder containing 20% of a rubber-resin composition using an impact-resistant transparent styrene resin. The bulk density was about 0.7 g/cm 3 and the particle size was mostly 50 to 200 μ. When molded compared to vinyl chloride resin compositions produced by conventional mixing methods, both fluidity and productivity during molding were superior. Comparative Example 5 Gas phase polymerization was carried out using 50 g of the base material obtained in Example 6 and 0.49 g of finely divided bis(4-butylcyclohexyl) peroxydicarbonate. The polymerization pressure was 6.5 Kg/cm 2 G (corresponding to P r =80%), and the other polymerization conditions were the same as in Example 6. However, during polymerization, the base material becomes extremely sticky and adheres to the reactor wall and the surface of the stirrer in a layered manner, which significantly reduces the effectiveness of stirring and mixing, and significantly reduces the polymerization rate of vinyl chloride monomer. The amount of polymerization was small.
第１図は本発明の特許請求の範囲第２項の実施
態様にかかわる基物質の一方の組成分たる共重合
物Ａを製造するために使用される単量体の組成比
を示す図、第２図は本発明の特許請求の範囲第２
項の実施態様にかかわる基物質の他方の組成分た
るグラフト共重合物Ｂを製造するために使用され
る単量体の組成比を示す図である。
FIG. 1 is a diagram showing the composition ratio of monomers used to produce copolymer A, which is one component of the base material according to the embodiment of claim 2 of the present invention. Figure 2 shows the second claim of the present invention.
FIG. 3 is a diagram showing the composition ratio of monomers used to produce graft copolymer B, which is the other component of the base material according to the embodiment of the above section.
Claims (1)
ン系樹脂を使用したゴム―樹脂組成物を基物質と
して用い、重合圧力が塩化ビニル単量体の飽和蒸
気圧より低く、かつ基物質の混合流動を妨げない
範囲の圧力でラジカル重合開始剤を用いて気相重
合することを特徴とする塩化ビニル樹脂組成物の
製造方法。 ２ スチレン系樹脂を使用したゴム―樹脂組成物
が、第１図において座標点BCQRSで囲まれる範
囲（但し、RQおよびRS線上を除く）にある組成
を有するアクリロニトリル、αメチルスチレンお
よびメタアクリル酸メチルの混合物を乳化重合さ
せてえられた共重合物およびジエン系合成ゴム35
〜65重量％に第２図において座標点EFGHIで囲
まれる範囲にある組成を有するスチレン又はスチ
レンとアクリロニトリルを含むことのあるメタア
クリル酸メチル65〜35重量％を乳化重合してえら
れた共重合物からなり、かつジエン系合成ゴムの
組成が全体の５〜30重量％である耐熱性・耐衝撃
性熱可塑性樹脂組成物である特許請求の範囲第１
項記載の製造方法。 ３ スチレン系樹脂を使用したゴム―樹脂組成物
がアルキル基の炭素数が２〜８であるアクリル酸
アルキルエステル又はアクリル酸アルキルエステ
ルが少なくとも80重量％とこれと共重合可能な他
のモノビニリデン化合物20重量％以下との混合物
と、これらと重合可能な炭素二重結合を２個以上
含み、且つそのうち少なくとも１個がアリル基で
ある多官能性単量体0.1〜８重量％との共重合体
20〜80重量部の水溶性分散液にアルキル基の炭素
数が１〜４であるメタクリル酸アルキルエステル
０〜100重量％、ビニル芳香族化合物０〜80重量
％、不飽和ニトリル０〜50重量％およびこれらの
単量体と共重合可能なモノビニリデン基を含む単
量体を0.1〜８重量％の共重合可能な架橋剤で１
部又は全部架橋しながら80〜20重量部グラフトし
てなる耐候性・耐衝撃性重合体である特許請求の
範囲第１項記載の製造方法。 ４ スチレン系樹脂を使用したゴム―樹脂組成物
が、ゴム粒子の径が0.2μ以下のものを90％以上
量含む水性ラテツクスに、水に0.1％以上量溶解
し、かつ重合可能なモノオレフイン系単量体、あ
るいは、この様なモノオレフイン系単量体および
それと共重合可能な非水溶性のスチレン系単量体
との混合物と水溶性ないし解離性のラテツクス凝
結剤を重合条件下におき、ゴム粒子の径が0.2μ
以下のものが90％以上量にあるうちに凝結とグラ
フト重合を同時に行なわせたモノフオレイン―ゴ
ム系耐衝撃性透明性重合物である特許請求の範囲
第１項記載の製造方法。 ５ 重合圧力が重合温度における塩化ビニル単量
体の飽和蒸気圧の45％から52％の間である特許請
求の範囲第２項記載の製造方法。 ６ 重合圧力が重合温度による塩化ビニル単量体
の飽和蒸気圧の45％から90％の間である特許請求
の範囲第３項記載の製造方法。 ７ 重合圧力が重合温度における塩化ビニル単量
体の飽和蒸気圧の45％から74％の間にある特許請
求の範囲第４項記載の製造方法。[Claims] 1. A rubber-resin composition using a styrene resin active against vinyl chloride monomer is used as a base material, the polymerization pressure is lower than the saturated vapor pressure of the vinyl chloride monomer, A method for producing a vinyl chloride resin composition, characterized in that gas phase polymerization is carried out using a radical polymerization initiator at a pressure within a range that does not impede the mixing and flow of base materials. 2 A rubber-resin composition using a styrene resin contains acrylonitrile, α-methylstyrene, and methyl methacrylate having a composition within the range surrounded by the coordinate point BCQRS in Figure 1 (excluding areas on the RQ and RS lines). Copolymer obtained by emulsion polymerization of a mixture of and diene-based synthetic rubber 35
A copolymer obtained by emulsion polymerization of 65 to 35% by weight of styrene or styrene and 65 to 35% by weight of methyl methacrylate, which may contain acrylonitrile, having a composition in the range surrounded by the coordinate point EFGHI in Figure 2. Claim 1, which is a heat-resistant/impact-resistant thermoplastic resin composition, comprising a diene-based synthetic rubber in an amount of 5 to 30% by weight of the total composition.
Manufacturing method described in section. 3 A rubber-resin composition using a styrene resin contains at least 80% by weight of an acrylic acid alkyl ester or an acrylic acid alkyl ester in which the alkyl group has 2 to 8 carbon atoms, and other monovinylidene compounds copolymerizable therewith. A copolymer of 0.1 to 8% by weight of a polyfunctional monomer containing two or more polymerizable carbon double bonds and at least one of which is an allyl group.
20 to 80 parts by weight of an aqueous dispersion containing 0 to 100% by weight of an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, 0 to 80% by weight of a vinyl aromatic compound, and 0 to 50% by weight of an unsaturated nitrile. and a monomer containing a monovinylidene group copolymerizable with these monomers with 0.1 to 8% by weight of a copolymerizable crosslinking agent.
2. The method according to claim 1, which is a weather-resistant/impact-resistant polymer obtained by grafting 80 to 20 parts by weight while partially or completely crosslinking. 4 Rubber using styrene resin - A monoolefin resin composition that can be dissolved in water in an amount of 0.1% or more and polymerizable in an aqueous latex containing 90% or more of rubber particles with a diameter of 0.2μ or less A monomer or a mixture of such a monoolefin monomer and a water-insoluble styrenic monomer copolymerizable therewith with a water-soluble or dissociable latex coagulant are placed under polymerization conditions, Rubber particle diameter is 0.2μ
The manufacturing method according to claim 1, wherein the monophorein-rubber-based impact-resistant transparent polymer is obtained by simultaneously performing coagulation and graft polymerization while the following is present in an amount of 90% or more. 5. The production method according to claim 2, wherein the polymerization pressure is between 45% and 52% of the saturated vapor pressure of the vinyl chloride monomer at the polymerization temperature. 6. The manufacturing method according to claim 3, wherein the polymerization pressure is between 45% and 90% of the saturated vapor pressure of the vinyl chloride monomer depending on the polymerization temperature. 7. The production method according to claim 4, wherein the polymerization pressure is between 45% and 74% of the saturated vapor pressure of the vinyl chloride monomer at the polymerization temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16505678A JPS5592706A (en) | 1978-12-30 | 1978-12-30 | Production of vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16505678A JPS5592706A (en) | 1978-12-30 | 1978-12-30 | Production of vinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5592706A JPS5592706A (en) | 1980-07-14 |
| JPS6126804B2 true JPS6126804B2 (en) | 1986-06-23 |
Family
ID=15804997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16505678A Granted JPS5592706A (en) | 1978-12-30 | 1978-12-30 | Production of vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5592706A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57212246A (en) * | 1981-06-23 | 1982-12-27 | Kureha Chem Ind Co Ltd | Vinyl chloride resin composition |
| JPS59108005A (en) * | 1982-12-13 | 1984-06-22 | Tokuyama Soda Co Ltd | Production of vinyl chloride polymer |
-
1978
- 1978-12-30 JP JP16505678A patent/JPS5592706A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5592706A (en) | 1980-07-14 |
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