NO772297L - WATER CATALYST MATERIALS FOR POLYMERIZATION - Google Patents
WATER CATALYST MATERIALS FOR POLYMERIZATIONInfo
- Publication number
- NO772297L NO772297L NO772297A NO772297A NO772297L NO 772297 L NO772297 L NO 772297L NO 772297 A NO772297 A NO 772297A NO 772297 A NO772297 A NO 772297A NO 772297 L NO772297 L NO 772297L
- Authority
- NO
- Norway
- Prior art keywords
- weight
- polymerization
- catalyst
- dispersion
- emulsifiers
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 49
- 238000006116 polymerization reaction Methods 0.000 title claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 16
- 239000000463 material Substances 0.000 title claims description 13
- 239000006185 dispersion Substances 0.000 claims description 35
- 239000003995 emulsifying agent Substances 0.000 claims description 24
- 239000000084 colloidal system Substances 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 13
- -1 diaryl peroxides Chemical class 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000011325 microbead Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 125000005634 peroxydicarbonate group Chemical group 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- DZERZCXQZQEUHM-UHFFFAOYSA-N azanium;2,2-dihydroxyoctadecanoate Chemical compound [NH4+].CCCCCCCCCCCCCCCCC(O)(O)C([O-])=O DZERZCXQZQEUHM-UHFFFAOYSA-N 0.000 description 2
- UTZVSVHXTPVFLE-IUJXYRIYSA-N diazanium (Z)-but-2-enedioate styrene Chemical compound [NH4+].[NH4+].C=CC1=CC=CC=C1.[O-]C(=O)\C=C/C([O-])=O UTZVSVHXTPVFLE-IUJXYRIYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002976 peresters Chemical class 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- IZMZREOTRMMCCB-UHFFFAOYSA-N 1,4-dichloro-2-ethenylbenzene Chemical compound ClC1=CC=C(Cl)C(C=C)=C1 IZMZREOTRMMCCB-UHFFFAOYSA-N 0.000 description 1
- ZXFHYTWKGJWGFM-UHFFFAOYSA-N 1-chloroethenyl acetate Chemical compound CC(=O)OC(Cl)=C ZXFHYTWKGJWGFM-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- KUIZKZHDMPERHR-UHFFFAOYSA-N 1-phenylprop-2-en-1-one Chemical compound C=CC(=O)C1=CC=CC=C1 KUIZKZHDMPERHR-UHFFFAOYSA-N 0.000 description 1
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-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
- MENUHMSZHZBYMK-UHFFFAOYSA-N 2-cyclohexylethenylbenzene Chemical compound C1CCCCC1C=CC1=CC=CC=C1 MENUHMSZHZBYMK-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- OZPOYKXYJOHGCW-UHFFFAOYSA-N 2-iodoethenylbenzene Chemical compound IC=CC1=CC=CC=C1 OZPOYKXYJOHGCW-UHFFFAOYSA-N 0.000 description 1
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 1
- SAFZQLDSMLNONX-UHFFFAOYSA-N 2-phenoxyethenylbenzene Chemical compound C=1C=CC=CC=1OC=CC1=CC=CC=C1 SAFZQLDSMLNONX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- HKADMMFLLPJEAG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-enylbenzene Chemical compound FC(F)(F)C=CC1=CC=CC=C1 HKADMMFLLPJEAG-UHFFFAOYSA-N 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
- CEBRPXLXYCFYGU-UHFFFAOYSA-N 3-methylbut-1-enylbenzene Chemical compound CC(C)C=CC1=CC=CC=C1 CEBRPXLXYCFYGU-UHFFFAOYSA-N 0.000 description 1
- AIMDYNJRXHEXEL-UHFFFAOYSA-N 3-phenylprop-1-enylbenzene Chemical compound C=1C=CC=CC=1CC=CC1=CC=CC=C1 AIMDYNJRXHEXEL-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DJYCUKPICQCQKY-UHFFFAOYSA-N 4-ethenyl-1-(4-ethenyl-2-phenylphenoxy)-2-phenylbenzene Chemical compound C=1C=CC=CC=1C1=CC(C=C)=CC=C1OC1=CC=C(C=C)C=C1C1=CC=CC=C1 DJYCUKPICQCQKY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PDAVOLCVHOKLEO-UHFFFAOYSA-N acetyl benzenecarboperoxoate Chemical compound CC(=O)OOC(=O)C1=CC=CC=C1 PDAVOLCVHOKLEO-UHFFFAOYSA-N 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- AFIQVBFAKUPHOA-UHFFFAOYSA-N ethenyl 2-methoxyacetate Chemical compound COCC(=O)OC=C AFIQVBFAKUPHOA-UHFFFAOYSA-N 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- GHXZPUGJZVBLGC-UHFFFAOYSA-N iodoethene Chemical compound IC=C GHXZPUGJZVBLGC-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NUMHUJZXKZKUBN-UHFFFAOYSA-N methyl 4-ethenylbenzoate Chemical compound COC(=O)C1=CC=C(C=C)C=C1 NUMHUJZXKZKUBN-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-N sodium;dodecyl sulfate;hydron Chemical compound [H+].[Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
Vandig katalysatormaterialer for polymerisasjonAqueous catalyst materials for polymerization
Ved polymerisasjon i vandig dispersjon tilføres katalysatorene som vanligvis foreligger som faste materialer, i form av oppløsninger i organiske oppløsningsmidler til polymerisasjons-chargen. Derved innføres oppløsningsmidler i polymerisasjons-chargen, og disse oppløsningsmidler gjenfinnes også i sluttpro-duktet og virker forstyrrende på flere måter. In the case of polymerization in an aqueous dispersion, the catalysts, which are usually present as solid materials, are added in the form of solutions in organic solvents to the polymerization charge. Thereby, solvents are introduced into the polymerization charge, and these solvents are also found in the final product and have a disruptive effect in several ways.
Således foreligger f.eks. næringsmiddelhygieniskebetenkelig-heter ved i emballasjematerialer å anvende polymerer som inneholder slike oppløsningsmidler. Dessuten kan det oppstå bedrifts-sikkerhetsproblemer ved håndteringen av organiske oppløsnings-midler både ved polymerisasjonén og ved den videre bearbeidelse av oppløsningsmiddelhqldige polymerer. Thus, e.g. food hygiene concerns by using polymers containing such solvents in packaging materials. In addition, company safety problems can arise when handling organic solvents both during polymerization and during the further processing of solvent-containing polymers.
Dessuten er anvendelsen av oppløste faste katalysatormaterialer i organiske oppløsningsmidler uheldig fordi kataly-satoraktiviteten avtar ved lagring av oppløsningen og kataly-satoroppløsningen derfor må oppfriskes helst hver gang før den anvendes. Moreover, the use of dissolved solid catalyst materials in organic solvents is unfortunate because the catalyst activity decreases when the solution is stored and the catalyst solution must therefore preferably be refreshed each time before it is used.
En rekke katalysatorer forhandles dessuten i med vann flegmatisert tilstand, hvorved vanninnholdet kah utgjøre opp til 30 vekt%. Ved oppløsning av disse katalysatorer i organiske oppløsningsmidler oppstår ofte heterogene faser som vanskelig-gjør en nøyaktig dosering av katalysatoren. A number of catalysts are also sold in a phlegmatized state with water, whereby the water content can be up to 30% by weight. When these catalysts are dissolved in organic solvents, heterogeneous phases often occur which make accurate dosing of the catalyst difficult.
Det tas derfor ved oppfinnelsen sikte på å overføre poly-merisas jonskatalysatorer til en lagringsstabil pumpbar hhv. doserbar form, hvorved samtidig fås en finfordelt anvendelses-form av katalysatoren som muliggjør en nøyaktig dosering under unngåelse' av de ulemper som eH anvendelse av katalysatorer oppløst i.organiske oppløsningsmidler forårsaker. The invention therefore aims to transfer polymerisation ion catalysts to a storage-stable pumpable or doseable form, whereby at the same time a finely distributed application form of the catalyst is obtained which enables accurate dosing while avoiding the disadvantages caused by the use of catalysts dissolved in organic solvents.
Oppfinnelsen angår således katalysatormaterialer. som er særpregede ved at de^ består av en vandig dispersjon med 1-40 vekt% i olje oppløselige katalysatorer som er lagringsstabile ved en temperatur over -5°C, fra gruppen dialkyl-, diacyl- hhv. diarylperoxyder og/eller peroxydicarbonater og/eller organiske azoforbindelser og/eller blandede anhydrider av organiske sulfopersyrer og organiske syrer og/eller organiske perestere, 0,01-5 vekt% naturlige eller syntetiske beskyttelseskolloider og/eller. 0,5-20 vekt% anionaktive, kationaktive og/eller ikke-ioniske emulgeringsmidler med en dispersjonspartikkelstørrelse. av under 300 jam, fortrinnsvis 1-100 jlim. The invention thus relates to catalyst materials. which are distinctive in that they consist of an aqueous dispersion with 1-40% by weight of oil-soluble catalysts which are storage-stable at a temperature above -5°C, from the group dialkyl-, diacyl- or diaryl peroxides and/or peroxydicarbonates and/or organic azo compounds and/or mixed anhydrides of organic sulfoperic acids and organic acids and/or organic peresters, 0.01-5% by weight natural or synthetic protective colloids and/or. 0.5-20% by weight anionic, cationic and/or non-ionic emulsifiers with a dispersion particle size. of less than 300 µm, preferably 1-100 µm.
Oppfinnelsen angår også en fremgangsmåte ved fremstilling av katalysatordispersjoner som er finfordelt i vann og som ikke er tilbøyelige til å sedimentere og som inneholder i olje opp-løselige radikalinitiatorer, og fremgangsmåten er særpreget ved at 1-40 vekt% av i olje oppløselige radikalinitiatorer overføres til stabile, pumpbare dispersjoner under innvirkning av sterke skjærkrefter og i nærvær av 0,01-5 vekt% beskyttelseskolloider og/eller 0,5-20 vekt% emulgeringsmidler. The invention also relates to a method for the production of catalyst dispersions which are finely divided in water and which are not prone to sedimentation and which contain oil-soluble radical initiators, and the method is characterized by the fact that 1-40% by weight of oil-soluble radical initiators are transferred to stable, pumpable dispersions under the influence of strong shear forces and in the presence of 0.01-5% by weight of protective colloids and/or 0.5-20% by weight of emulsifiers.
Dispersjonene av faste, i olje oppløselige radikalinitiatorer i vann anvendes for polymerisasjon i vandig dispersjon, fortrinnsvis for suspensjonspolymerisasjonen, og spesielt for mikroperlepolymerisasjonen. The dispersions of solid, oil-soluble radical initiators in water are used for polymerization in aqueous dispersion, preferably for the suspension polymerization, and especially for the microbead polymerization.
Ved denne katalysatortilberedning har det lykkes å overføre i olje oppløselige radikalinitiatorer til en lagringsstabil pumpbar hhv. doserbar form, hvor katalysatoren foreligger i finfordelt tilstand, og samtidig å overvinne de ulemper som i olje opp-løselige radikalinitiatorer som er oppløst i et organisk.opp-løsningsmiddel, er beheftet med. With this catalyst preparation, it has been successful to transfer oil-soluble radical initiators to a storage-stable pumpable or doseable form, where the catalyst is present in a finely divided state, and at the same time to overcome the disadvantages that oil-soluble radical initiators that are dissolved in an organic solvent are subject to.
Anvendelsen av vann som kontinuerlig fase hvori beskyttelseskolloider og/eller emulgeringsmidler er oppløst, begrenser kataly-satortypene til slike som er lagringsstabile over faststoffpunktet, The use of water as a continuous phase in which protective colloids and/or emulsifiers are dissolved limits the catalyst types to those which are storage-stable above the solids point,
•for den kontinuerlige fase. Som det.nederste faststoffpunkt kan •for the continuous phase. As the.lowest solids point can
vanligvis en temperatur av -5°C ansees, men ved tilsetning av smeltepunktsenkende materialer kan området utvides til lavere temperaturer. Oppad er temperaturområdet, bare begrenset av katalysatorens spaltningstemperatur. usually a temperature of -5°C is considered, but by adding melting point lowering materials the range can be extended to lower temperatures. Up is the temperature range, limited only by the catalyst's decomposition temperature.
Alle radikalinitiatorer som er egnet for suspensjonspolymer-isas jon, kan anvendes for dette.formål, idet suspensjonspolymerisa sjonen, hhv. mikroperlepolymerisasjonen, utføres i nærvær av én eller flere av de følgende monomerer: dobbelt éthylenisk umettede monomerer, som f.eks. butadien, isopren, 1, 4-pentadien , 1, 6-hexadien,, i.og 1, 7-octadién, enkelt éthylenisk umettede monomerer, som f.eks. styren eller substituerte styrener som f. eks. meth.y lstyren, 2 , 4-dimethylstyren> ethylen-styren, isopropylstyren, butylstyren, fenylstyren, cyclohexyl-styren'og benzylstyren, halogensubstituerte styrener som f.eks. klorstyren, 2,5-diklorstyren, bromstyren, fluorstyren, trifluor-methylstyren og jodstyren, styrener som er substituert med funksjonelle grupper, som f.eks. cyanstyren, nitrostyren, acetostyren og fenoxystyren, acrylmonomerer og substituerte acrylmonomerer som f.eks. acrylsyre og methacrylsyre og estere derav med 1-18 carbonatomer, cyclohexyl-(meth)-acrylat, benzyl-(meth)-acrylat, isopropyl-(meth)-acrylat, butylacrylat, 2-ethylhexylacrylat, fenyl-(meth)-acrylat, acrylnitril og methacrylnitril, vinylestere og substituerte vinylestere med carboxylsyrer med 1-18 carbonatomer, som f.eks. vinylformiat, vinylacetat, klorvinylacetat, vinylbutyrat, vinylmethoxyacetat og vinylbenzoat, methyl-4-vinylbenzoat og isopropenylacetat, vinylestere med umettede carboxylsyrer med 1-8 carbonatomer, som f.eks. vinylacrylat og vinyl-.methacrylat, vinylhalogenider som f. eks. vinylfluorid, vinyliden-klorid, vinylbromid, vinylidenbromid og vinyljodid, vinylforbindelser med funksjonelle grupper, som f.eks. p-vinylidensulfid, p-vinylfenylfenyloxyd og vinylpyridin, vinylethere som f.eks. vinylmethylether, vinylethylether, vinylpropylether, vinylbutyl-ether og vinyl-2-ethylhexylether, vinylfenylether, vinylketoner som f.eks. vinylethylketon og vinylfenylketon, og allylestere med carboxylsyrer med 1-18 carbonåtomer, men spesielt vinylklorid. All radical initiators which are suitable for suspension polymerization can be used for this purpose, as the suspension polymerization, or the microbead polymerization is carried out in the presence of one or more of the following monomers: doubly ethylenically unsaturated monomers, such as e.g. butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene,, and 1,7-octadiene, single ethylenically unsaturated monomers, such as e.g. styrene or substituted styrenes such as e.g. methylstyrene, 2,4-dimethylstyrene, ethylenestyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene and benzylstyrene, halogen-substituted styrenes such as e.g. chlorostyrene, 2,5-dichlorostyrene, bromostyrene, fluorostyrene, trifluoromethylstyrene and iodostyrene, styrenes which are substituted with functional groups, such as e.g. cyanostyrene, nitrostyrene, acetostyrene and phenoxystyrene, acrylic monomers and substituted acrylic monomers such as e.g. acrylic acid and methacrylic acid and their esters with 1-18 carbon atoms, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isopropyl (meth) acrylate, butyl acrylate, 2-ethylhexyl acrylate, phenyl (meth) acrylate, acrylonitrile and methacrylonitrile, vinyl esters and substituted vinyl esters with carboxylic acids with 1-18 carbon atoms, such as e.g. vinyl formate, vinyl acetate, chlorovinyl acetate, vinyl butyrate, vinyl methoxy acetate and vinyl benzoate, methyl-4-vinyl benzoate and isopropenyl acetate, vinyl esters with unsaturated carboxylic acids with 1-8 carbon atoms, such as e.g. vinyl acrylate and vinyl methacrylate, vinyl halides such as vinyl fluoride, vinylidene chloride, vinyl bromide, vinylidene bromide and vinyl iodide, vinyl compounds with functional groups, such as p-vinylidene sulphide, p-vinylphenylphenyloxide and vinylpyridine, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether and vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl ketones such as e.g. vinyl ethyl ketone and vinyl phenyl ketone, and allyl esters with carboxylic acids with 1-18 carbon atoms, but especially vinyl chloride.
Som dljeoppløselige radikalinitiatorer for suspensjonspolymerisasjon, hhv. mikroperlepolymerisasjon, egner seg vanligvis dialkyl-, diaryl- eller diacyiperoxyder som ditert.buty1-, dilauryl-, dimyristyl-, dicetyl-, distearyl-, bi.s-2 , 4-diklorbenzoyl-, diacetyl-bg acetylbenzoylperoxyd, perestere som tert.propylper-acetat, tert.butylperacetat, tert.butylperoctoat og tert.butyl-perpivalat, dialkylperoxydicarbonater som diisopropyl-, diethyl-, dihexyl-, dicyclohexyl-, dialkylcyclohexylperoxydicarbonat. og bis-(4-tert. butylcyclohexyl)-peroxydicarbonat, og dessuten dialkylperoxydicarbonatene med alkylkjedelengder på 8-18 carbon atomer, og de blandede anhydrider av organiske .sulfopersyrer og organiske syrer, som acetylcyclohexylsulfbnylperoxyd,og dessuten azoforbindelser som er kjente som polymerisasjonsinitiatorer, som azoisosmørsyrenitril og azovaleronitril. As sparingly soluble radical initiators for suspension polymerization, resp. microbead polymerization, dialkyl-, diaryl- or diacyperoxides such as ditert.buty1-, dilauryl-, dimyristyl-, dicetyl-, distearyl-, bi.s-2 , 4-dichlorobenzoyl-, diacetyl-bg acetylbenzoyl peroxide, peresters such as tert. propyl per-acetate, tert-butyl peracetate, tert-butyl peroctoate and tert-butyl perpivalate, dialkyl peroxydicarbonates such as diisopropyl-, diethyl-, dihexyl-, dicyclohexyl-, dialkylcyclohexylperoxydicarbonate. and bis-(4-tert. butylcyclohexyl)-peroxydicarbonate, and also the dialkylperoxydicarbonates with alkyl chain lengths of 8-18 carbon atoms, and the mixed anhydrides of organic sulfoperic acids and organic acids, such as acetylcyclohexylsulfbnylperoxyd, and also azo compounds which are known as polymerization initiators, which azoisobutyric nitrile and azovaleronitrile.
Radikalinitiatorene kan anvendes i dispersjonen i en mengde av 1-4 0<y>ekt% i avhengighet av om den samlede mengde emulgerings-middeloppløsning som anvendes for polymerisasjonen, anvendes for di.spergering av katalysatoren eller katalysatoren anvendes adskilt i form av en konsentrert dispersjon. The radical initiators can be used in the dispersion in an amount of 1-4 0<y>ect% depending on whether the total amount of emulsifier solution used for the polymerization is used for dispersing the catalyst or the catalyst is used separately in the form of a concentrated dispersion .
Som emulgeringsmidler egner seg anionaktive, kationaktive og ikke-ioniske emulgeringsmidler med en HLB-verdi (hydrofil-lyofil balanse) mellom 5 og 18 og blandinger derav, som f.eks. fettsåper, alkylsulfater og alkylsulfonater med 8-18 carbonatomer i alkylkjeden, alkansulfonater, alkylbenzensulfonater, alkyl-nafthalensulfonater, sulforavsyreester, delvis forestret fosfor-syre, kationaktive alkylammoniumsalter, og alkylfenoler med 6-22 carbonatomer i alkylkjeden og med 5-30 molekylénheter av påkondenserte ethylenoxyder. Ytterligere brukbare emulgeringsmidler er ammoniumsaltet av dlhydroxystearinsyre (DHW 80) eller "Texapon K 12" (=natriumlaurylsulfat). Suitable emulsifiers are anion-active, cation-active and non-ionic emulsifiers with an HLB value (hydrophilic-lyophilic balance) between 5 and 18 and mixtures thereof, such as e.g. fatty soaps, alkyl sulfates and alkyl sulfonates with 8-18 carbon atoms in the alkyl chain, alkanesulfonates, alkylbenzene sulfonates, alkyl-naphthalene sulfonates, sulforaic acid esters, partially esterified phosphoric acid, cationically active alkyl ammonium salts, and alkylphenols with 6-22 carbon atoms in the alkyl chain and with 5-30 molecular units of condensed ethylene oxides . Further usable emulsifiers are the ammonium salt of dlhydroxystearic acid (DHW 80) or "Texapon K 12" (=sodium lauryl sulfate).
Emulgeringsmidlene kan anvendes i en mengde av 0,5-20 vekt%. The emulsifiers can be used in an amount of 0.5-20% by weight.
Emulgeringsmiddelkonsentrasjonen er bl.a. avhengig av om den emulgeringsmiddelmengde som er nødvendig for polymerisasjonen, tilføres sammen med katalysatoren for polymerisasjonen eller om emulgeringsmiddeloppløsningen tilsettes adskilt fra katalysatordispersjonen. The emulsifier concentration is i.a. depending on whether the amount of emulsifier required for the polymerization is added together with the catalyst for the polymerization or whether the emulsifier solution is added separately from the catalyst dispersion.
Emulgeringsmidlene som anvendes for katalysatordispersjonen, kan f.eks. være de samme som anvendes for polymerisasjonen. The emulsifiers used for the catalyst dispersion can e.g. be the same as those used for the polymerization.
Mange ganger kan imidlertid også forskjellige emulgeringsmidler for katalysatordispersjonen og polymerisasjonen finne anvendelse, men det må da påsees at virkningene av emulgeringsmidlene ikke gjensidig opphever hverandre. Dette må påsees f.eks. når det for emulgering av katalysatoren og monomeren er nødvendig med forskjellige HLB-verdier.. Anionaktive emulgeringsmidler blir hyppig unngått ved suspensjonspolymerisasjonen. Many times, however, different emulsifiers can also be used for the catalyst dispersion and polymerization, but it must then be ensured that the effects of the emulsifiers do not mutually cancel each other out. This must be ensured, e.g. when different HLB values are required for the emulsification of the catalyst and the monomer. Anionic emulsifiers are frequently avoided in suspension polymerization.
Som beskyttelseskolloider egner seg syntetiske og naturlige polymere materialer med eventuelt vannoppløselige egenskaper, som polyvinylalkoholer, delvis acetylerte polyvinylalkoholer, vann-oppløselige cellulosederivater, hydroxyethyl-, propyl-, methyl-og carboxymethylcellulose, vannoppløselige stivelsesethere, poly-acrylsyre, vannoppløseiige polyacrylsyrecopolymerer med acryl-amid og/eller alkylestere, poly-N-vinylforbindelser av åpen-kjedede eller sykliske carboxylsyreamider, og polyvinylpyrolidon. Dessuten er f.eks. copolymerer av styren og maleinsyreanhydrid ("Lytron 820") egnede. Beskyttelseskolloidene anvendes vanligvis i en mengde av 0,01-5 vekt%. Suitable protective colloids are synthetic and natural polymeric materials with possibly water-soluble properties, such as polyvinyl alcohols, partially acetylated polyvinyl alcohols, water-soluble cellulose derivatives, hydroxyethyl-, propyl-, methyl- and carboxymethylcellulose, water-soluble starch ethers, polyacrylic acid, water-soluble polyacrylic acid copolymers with acrylamide and/or alkyl esters, poly-N-vinyl compounds of open-chain or cyclic carboxylic acid amides, and polyvinylpyrrolidone. In addition, e.g. copolymers of styrene and maleic anhydride ("Lytron 820") are suitable. The protective colloids are usually used in an amount of 0.01-5% by weight.
Katalysatordispersjonen fremstilles ved at den fordeles i vann som inneholder 0,01-5 vekti beskyttelseskolloider og/eller 0,5-20 vekt% emulgeringsmidler, under innvirkning av sterke skjærkrefter på blandingen. Apparater som i denne sammenheng kan anvendes for erholdelse av slike skjærkrefter, er f.eks. emulger-ingsapparater av typen "Ultra-Turrax", "In-line" blandeapparater, kolloidblandeapparater eller også kolloidstiftmøller, hvorved blandingen når den passerer gjennom blandeapparatet hhv. ved ompumping, overføres til en dispersjon med den nødvendige par-, tikkelstørrelse. Møllen har en rotor-statorkombinasjon med tannede flater som maleelement.. Malegodset får en nedsatt par-tikkelstørrelse og dispergeres når det passerer gjennom møllen under innvirkning av sterke skjær- og friksjonskrefter. Da katalysatorene vanligvis er temperaturømfintlige,. er det gunstig at temperaturen vanligvis ikke overskrider 20°C under nedmalings-prosessen, men temperaturen kan også lett reguleres ved avpasset tilførsel av vann til hhv. ved.vannavkjøling av maskinen. The catalyst dispersion is prepared by spreading it in water containing 0.01-5% by weight of protective colloids and/or 0.5-20% by weight of emulsifiers, under the influence of strong shear forces on the mixture. Devices which in this context can be used for obtaining such shear forces are, for example, emulsifying devices of the "Ultra-Turrax" type, "In-line" mixing devices, colloid mixing devices or also colloid stick mills, whereby the mixture when it passes through the mixing device or by repumping, is transferred to a dispersion with the required particle size. The mill has a rotor-stator combination with toothed surfaces as a grinding element. The grinding material has a reduced particle size and is dispersed when it passes through the mill under the influence of strong shear and frictional forces. As the catalysts are usually temperature sensitive, it is advantageous that the temperature does not usually exceed 20°C during the paint-down process, but the temperature can also be easily regulated by adjusting the supply of water to or by water cooling the machine.
Katalysatorens partikkelstørrelse i dispersjonen er vanligvis under .300 pm, og en partikkelstørrelse for katalysatoren i dispersjonen av 100 pm-1 pm har.vist seg å være gunstig for polymerisasjonen. En liten'partikkelstørrelse for katalysatoren i dispersjonen er gunstig for opptak av katalysatoren i monomereri. Dette er spesielt gunstig når katalysatoren allerede før det egentlige reaksjonsrom, f.eks. allerede langs en strekning for forhåhdsblanding, skal blandes homogent med en monomerdispersjon. The particle size of the catalyst in the dispersion is usually below .300 µm, and a particle size for the catalyst in the dispersion of 100 µm-1 µm has been shown to be favorable for the polymerization. A small particle size for the catalyst in the dispersion is favorable for absorption of the catalyst in monomers. This is particularly advantageous when the catalyst already before the actual reaction room, e.g. already along a section for preliminary mixing, must be mixed homogeneously with a monomer dispersion.
Fremstillingen av polymerlatexer av monomerer under anvendelse av katalysatorsystemet ifølge oppfinnelsen, vann, beskyttelseskolloider og/eller emulgeringsmidler utføres ved at katalysatoren tilføres dispergert i beskyttelseskolloidet og/eller i oppløsningen som inneholder emulgeringsmiddél, eller ved at den konsentrerte katalysatordispersjon som bare inneholder en slik mengde av beskyttelseskolloider og/eller emulgeringsmidler som er nødvendig for dispérgering og stabilisering av katalysatoren mot sedimentering, anvendes. De enkelte bestanddeler, som be-skyttelseskolloidoppløsninger, emulgeringsmidler, monomer og katalysatordispersjon/kan tilføres direkte til polymerisasjons-chargen eller langs en såkalt forblandingsstrekning. Som for-blahdingsstrekninger kan nevnes såkalt blanderør med strømnings-forstyrrende innretninger for direkte tilførsel til reaktoren', The production of polymer latexes from monomers using the catalyst system according to the invention, water, protective colloids and/or emulsifiers is carried out by adding the catalyst dispersed in the protective colloid and/or in the solution containing the emulsifier, or by the concentrated catalyst dispersion containing only such an amount of protective colloids and/or emulsifiers which are necessary for dispersing and stabilizing the catalyst against sedimentation are used. The individual components, such as protective colloid solutions, emulsifiers, monomer and catalyst dispersion/can be added directly to the polymerization charge or along a so-called premixing section. So-called mixing pipes with flow-disturbing devices for direct supply to the reactor can be mentioned as pre-expanding sections,
•eller en ringledning som lagrings- og blandestrekning. Efter•or a ring line as a storage and mixing line. After
at autoklaven er blitt oppvarmet til reaksjonstemperaturen, finner polymerisasjonen sted, og det er under polymerisasjonen som regel nødvendig å foreta en avkjøling. Efter at polymerisasjonen er avsluttet, blir den dannede polymerlatex opparbeidet. that the autoclave has been heated to the reaction temperature, the polymerization takes place, and it is usually necessary to cool down during the polymerization. After the polymerization has ended, the polymer latex formed is worked up.
Det er spesielt gunstig å anvende katalysatoren iiform avIt is particularly advantageous to use the catalyst in the form of
en vandig dispersjon ved suspensjons- hhv. mikroperl.epolymerisasjon. Den håndtering av større oppløsningsmiddelmengder som tidligere var vanlig under polymerisasjonen, unngås ved anvendelsen av katalysatormaterialet ifølge' oppfinnelsen. Polymerisatenes pro-duktkvalitet forbedres ved at det ikke lenger må tas hensyn til oppløsningsmidler fra den tradisjonelle katalysatoroppløsning. an aqueous dispersion by suspension or microperl.epolymerization. The handling of larger amounts of solvent which was previously common during the polymerization is avoided by the use of the catalyst material according to the invention. The product quality of the polymers is improved by the fact that solvents from the traditional catalyst solution no longer have to be taken into account.
Det har dessuten lykkes ytterligere å nedsette polymerisasjons-produktenes restflyktighet ved anvendelsen av det foreliggende katalysatormateriale. It has also succeeded in further reducing the residual volatility of the polymerization products when using the present catalyst material.
Eksempel 1Example 1
a) En svakt ammoniakkalsk oppløsning (pH 9-10) av 3 1 vann,a) A weak ammoniacal solution (pH 9-10) of 3 1 water,
3,5 vekt% ammoniumdihydroxystearat og 1 vekti ammoniumstyren-maleat fremstilles i en beholder forsynt med et rø.reverk. Be-holderens innhold pumpes derefter i kretsløp gjennom en mølle av typen "Fryma" under tilsetning av en samlet mengde av 25 vekt% dilåurylperoxyd. Den erholdte dispersjon inneholder ingen andeler som er større enn 300 pm, og 95 vektf av dispersjonspartiklene har en størrelse under 100 pm. 3.5% by weight of ammonium dihydroxystearate and 1% by weight of ammonium styrene maleate are prepared in a container fitted with a stirrer. The container's contents are then pumped in a circuit through a mill of the "Fryma" type while adding a total amount of 25% by weight dilauryl peroxide. The obtained dispersion contains no proportions greater than 300 µm, and 95% by weight of the dispersion particles have a size below 100 µm.
b) Fremgangsmåten ifølge eksempel la) ble gjentatt, men ved anvendelse av 4 vekt% ammoniumdihydroxystearat uten ammonium-styrenmaléat. Den erholdte dispersjon inneholder ingen andeler som er større enn 300 pm, og 95 vekt% av dispersjonspartiklene b) The procedure according to example la) was repeated, but using 4% by weight of ammonium dihydroxystearate without ammonium styrene maleate. The obtained dispersion contains no proportions greater than 300 pm, and 95% by weight of the dispersion particles
har en størrelse under 100 um.have a size below 100 µm.
c) (Mikroperlesuspensjonspolymerisasjon). Fremgangsmåten ifølge eksempel la) ble gjentatt, men ved anvendelse av 1 vekt% av et c) (Microbead suspension polymerization). The procedure according to example la) was repeated, but using 1% by weight of et
alkylsulfonat (C-^)* Dispersjonens egenskaper tilsvarer de egenskaper som er angitt i la) og lb) . alkyl sulphonate (C-^)* The properties of the dispersion correspond to the properties stated in la) and lb).
Eksempel 2Example 2
SuspensjonspolymerisasjonSuspension polymerization
■ a) (Sammenligningsforsøk)■ a) (Comparison test)
2,6 kg vann, 1,4 kg vinylklorid, 20 g dilaurylperoxyd opp-løst i toluen (20%-ig oppløsning) og.3,1 g polyvinylalkohol 2.6 kg of water, 1.4 kg of vinyl chloride, 20 g of dilauryl peroxide dissolved in toluene (20% solution) and 3.1 g of polyvinyl alcohol
(40 mol% acetatinnhold) ble i en laboratorieautoklav. av V4A omrørt med et propellrøreverk med 300 opm og oppvarmet til 52°G. (40 mol% acetate content) was in a laboratory autoclave. of V4A stirred with a propeller stirrer at 300 rpm and heated to 52°G.
pH ble regulert til 5 ved tilsetning av Nal^PO^.. Efter en reak-sjonstid på 8 timer ble det oppnådd en omsetning på 8 5 vekt%, og produktet hadde en K-verdi av 70.- og en midlere kornstørrelse av 120 pm, og 100% av partiklene hadde en størrelse under 300 pm, mens andelen av flyktige materialer var 1,5 vekt%. 1,2 vekt% The pH was adjusted to 5 by adding Nal^PO^. After a reaction time of 8 hours, a conversion of 85% by weight was achieved, and the product had a K value of 70 and an average grain size of 120 pm, and 100% of the particles had a size below 300 pm, while the proportion of volatile materials was 1.5% by weight. 1.2% by weight
ble identifisert som toluen.was identified as toluene.
b) Fremgangsmåten ifølge eksempel 2a) ble gjentatt, men ved anvendelse av 100 g 20%-ig dilaurylperoxyddispersjon som anvendt b) The procedure according to example 2a) was repeated, but using 100 g of 20% dilauryl peroxide dispersion as used
ifølge eksempel la). Polymerisasjonen forløp som beskrevet i eksempel 2a). Katalysatordispersjonen er derfor like godt egnet for polymerisasjon som en katalysatoroppløsning, men katalysatordispersjonen fører til at produktet bare får en restflyktighet av 0,3 vekt% som i det vesentlige består av vann. according to example la). The polymerization proceeded as described in example 2a). The catalyst dispersion is therefore just as suitable for polymerization as a catalyst solution, but the catalyst dispersion leads to the product only having a residual volatility of 0.3% by weight, which essentially consists of water.
Eksempel 3 Mikroperlesuspensjonspolymerisasjon Example 3 Microbead suspension polymerization
a) (Sammenligningsforsøk)a) (Comparison test)
Efter at de var blitt blandet i en ringledning og homogenisert After they had been mixed in a ring line and homogenized
(som beskrevet i tysk.patentskrift nr. 1069387), ble 5850 1 av en 1%-ig emulgeringsmiddeloppløsning (ammoniumsalt av dihydrox.y-stearinsyre), 5850 1 vinylklorid, 40 1 20%-ig dilauroylperoxy-dicarbonatoppløsning og 0,5 1 ethylhexylpercarbonatoppløsning i toluen fylt i en 14 m<3>tårnautoklav, oppvarmet til 50°C og poly-merisert i 18 timer. Det ble erholdt en polymer med en K-verdi av 70 som efter opparbeidelse hadde en. andel av flyktige materialer av 0,5 vekt%. 0,3 vekt% ble identifisert som toluen. (as described in German Patent No. 1069387), 5850 1 of a 1% emulsifier solution (ammonium salt of dihydroxy-γ-stearic acid), 5850 1 vinyl chloride, 40 1 20% dilauroylperoxydicarbonate solution and 0.5 1 ethylhexyl percarbonate solution in toluene filled in a 14 m<3> tower autoclave, heated to 50°C and polymerized for 18 hours. A polymer with a K value of 70 was obtained, which after processing had a. proportion of volatile materials of 0.5% by weight. 0.3% by weight was identified as toluene.
b) Fremgangsmåten ifølge eksempel 3a) ble gjentatt, men med den forskjell at istedenfor den oppløste katalysator ble 36 1 b) The procedure according to example 3a) was repeated, but with the difference that instead of the dissolved catalyst, 36 1
katalysatorsuspensjon (20%-ig) ifølge eksempel la) anvendt. Efter 18 timer ble det dannet en vinylkloridpolymer med en K-verdi av 7 0 og med en andel av flyktige materialer av 0,2 vekt% som i det vesentlige utgjordes av vann. catalyst suspension (20%) according to example la) used. After 18 hours, a vinyl chloride polymer was formed with a K-value of 70 and with a proportion of volatile materials of 0.2% by weight which essentially consisted of water.
Claims (3)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19762629467 DE2629467A1 (en) | 1976-06-30 | 1976-06-30 | Aqueous CATALYST CONFECTION |
Publications (1)
Publication Number | Publication Date |
---|---|
NO772297L true NO772297L (en) | 1978-01-02 |
Family
ID=5981896
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO772297A NO772297L (en) | 1976-06-30 | 1977-06-29 | WATER CATALYST MATERIALS FOR POLYMERIZATION |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS533984A (en) |
DE (1) | DE2629467A1 (en) |
FR (1) | FR2356675A1 (en) |
NL (1) | NL7704506A (en) |
NO (1) | NO772297L (en) |
SE (1) | SE7707558L (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5594902A (en) * | 1979-01-11 | 1980-07-18 | Hitachi Chem Co Ltd | Preparation of particulate polymer with uniform fine particle diameter |
NL8000260A (en) * | 1980-01-16 | 1981-08-17 | Akzo Nv | AQUEOUS PEROXIDE EMULSION AND ITS USE IN SUSPENSION (CO-) POLYMERIZATION REACTIONS. |
US4950422A (en) * | 1981-01-06 | 1990-08-21 | Akzona Incorporated | Peroxide emulsions containing an anti-freezing compound |
US5260390A (en) * | 1980-01-16 | 1993-11-09 | Akzo N.V. | Peroxide emulsions containing an antifreezing compound |
SE435844C (en) * | 1980-01-28 | 1989-04-17 | Kenobel Ab | SET FOR POLYMERIZATION OF VINYL CHLORIDE AND WATER DISPERSION BEFORE USING POLYMERIZATION OF VINYL CHLORIDE |
SE435843B (en) | 1980-01-28 | 1984-10-22 | Kenogard Ab | SET FOR POLYMERIZATION OF VINYL CHLORIDE AND WATER DISPERSION FOR USE IN POLYMERIZATION OF VINYL CHLORIDE |
JPH044321B2 (en) * | 1980-05-19 | 1992-01-28 | ||
JPH048442B2 (en) * | 1980-05-19 | 1992-02-17 | ||
JPS5728106A (en) * | 1980-07-25 | 1982-02-15 | Nippon Oil & Fats Co Ltd | Organic peroxide emulsified in water |
JPS5968303A (en) * | 1982-10-12 | 1984-04-18 | Nippon Oil & Fats Co Ltd | Production of aqueous suspension of solid organic peroxide |
JPS60149608A (en) * | 1984-01-13 | 1985-08-07 | Mitsui Toatsu Chem Inc | Polymerization of vinyl chloride |
JPS61130315A (en) * | 1984-11-30 | 1986-06-18 | Nippon Oil & Fats Co Ltd | Suspension polymerization of vinyl chloride unsaturated monomer |
JPH0196205A (en) * | 1987-10-09 | 1989-04-14 | Nippon Zeon Co Ltd | Production of conjugated diene copolymer |
JP5921486B2 (en) * | 2013-05-16 | 2016-05-24 | 株式会社コバヤシ | Method for producing starch resin pellets |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5321188B2 (en) * | 1972-04-27 | 1978-06-30 |
-
1976
- 1976-06-30 DE DE19762629467 patent/DE2629467A1/en not_active Ceased
-
1977
- 1977-04-11 JP JP4048477A patent/JPS533984A/en active Pending
- 1977-04-25 NL NL7704506A patent/NL7704506A/en not_active Application Discontinuation
- 1977-05-03 FR FR7713364A patent/FR2356675A1/en not_active Withdrawn
- 1977-06-29 NO NO772297A patent/NO772297L/en unknown
- 1977-06-29 SE SE7707558A patent/SE7707558L/en unknown
Also Published As
Publication number | Publication date |
---|---|
DE2629467A1 (en) | 1978-01-05 |
SE7707558L (en) | 1977-12-31 |
FR2356675A1 (en) | 1978-01-27 |
NL7704506A (en) | 1978-01-03 |
JPS533984A (en) | 1978-01-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
NO772297L (en) | WATER CATALYST MATERIALS FOR POLYMERIZATION | |
Yamak | Emulsion polymerization: effects of polymerization variables on the properties of vinyl acetate based emulsion polymers | |
DK160206B (en) | METHOD OF PREPARING POLYMER LATEX | |
US3980603A (en) | Microsuspension polymerization process to yield vinyl halide polymer latex involving delayed addition of bulk monomer mix | |
US6177525B1 (en) | Process for preparing microemulsion polymer particles using high shear forces | |
CN100509882C (en) | Dextrin for producing PVC gloves and production thereof | |
CZ282405B6 (en) | Process for preparing aqueous suspension of a solid, free radicals forming initiator, suspension prepared in such a manner, apparatus for making such process and polymerization process of ethylenically unsaturated monomers employing said suspension | |
NO141995B (en) | PROCEDURE FOR THE PREPARATION OF A VINYL CHLORIDE POLYMER | |
US3867331A (en) | Process for making emulsion polymerized preplasticized vinyl resins | |
US10414879B2 (en) | Process to produce fluoropolymer-based latex with mechanical stability | |
CN102325807A (en) | Process for polymerization of vinyl chloride | |
NO762283L (en) | ||
CN105985479A (en) | Preparation of acrylate modified vinyl chloride-vinyl acetate copolymerized resin through microsuspension polymerization | |
JP2001522394A (en) | Method for producing particulate homopolymers and copolymers from microsuspension in a tubular reactor | |
NO761219L (en) | ||
AU2002229689B2 (en) | Method for preparing latex | |
JP2002534567A (en) | Aqueous peroxide emulsion | |
JPH0343402A (en) | Suspension polymerization | |
DK149897B (en) | PROCEDURE FOR POLYMERIZATION OF VINYL CHLORIDE IN THE PRESENT OF A STABILIZING POLYMER LATEX | |
NO143352B (en) | PROCEDURE FOR THE PREPARATION OF A VINYL CHLORIDE POLYMER | |
JP4632003B2 (en) | Method for producing aqueous solution of styrene / acrylic acid copolymer salt, paper using the aqueous solution of copolymer salt, etc. | |
KR20090039955A (en) | Producing method of filler vinyl chloride polymer for plastisol | |
JPH0588252B2 (en) | ||
NO855126L (en) | CO-SUSPENDING AID SYSTEM FOR USE BY POLYMERIZATION OF ETHYLENIC Saturated MONOMERS. | |
JP2003183311A (en) | Manufacturing method of vinyl polymer |