JPH0291102A - Reaction inhibitor for radical polymerization and method for inhibiting reaction of vinyl monomer by use thereof - Google Patents
Reaction inhibitor for radical polymerization and method for inhibiting reaction of vinyl monomer by use thereofInfo
- Publication number
- JPH0291102A JPH0291102A JP24326588A JP24326588A JPH0291102A JP H0291102 A JPH0291102 A JP H0291102A JP 24326588 A JP24326588 A JP 24326588A JP 24326588 A JP24326588 A JP 24326588A JP H0291102 A JPH0291102 A JP H0291102A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- reaction
- tetramethylbutyl
- inhibitor
- vinyl monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 30
- 239000000178 monomer Substances 0.000 title claims abstract description 28
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 23
- 239000002683 reaction inhibitor Substances 0.000 title claims abstract description 21
- 238000010526 radical polymerization reaction Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 13
- 230000002401 inhibitory effect Effects 0.000 title claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 73
- -1 tetramethylbutyl Chemical group 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 239000012736 aqueous medium Substances 0.000 claims abstract description 10
- RDMIJQCFPQDYQN-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)benzene-1,4-diol Chemical group CC(C)(C)CC(C)(C)C1=CC(O)=CC=C1O RDMIJQCFPQDYQN-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical group CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- CLDZVCMRASJQFO-UHFFFAOYSA-N 2,5-bis(2,4,4-trimethylpentan-2-yl)benzene-1,4-diol Chemical compound CC(C)(C)CC(C)(C)C1=CC(O)=C(C(C)(C)CC(C)(C)C)C=C1O CLDZVCMRASJQFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 28
- 241000251468 Actinopterygii Species 0.000 abstract description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000004040 coloring Methods 0.000 abstract description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000004014 plasticizer Substances 0.000 abstract description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010557 suspension polymerization reaction Methods 0.000 description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 3
- BVCOHOSEBKQIQD-UHFFFAOYSA-N 2-tert-butyl-6-methoxyphenol Chemical compound COC1=CC=CC(C(C)(C)C)=C1O BVCOHOSEBKQIQD-UHFFFAOYSA-N 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- 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
- BSJQLOWJGYMBFP-UHFFFAOYSA-N 2-methyl-5-(2,4,4-trimethylpentan-2-yl)benzene-1,4-diol Chemical compound CC1=CC(O)=C(C(C)(C)CC(C)(C)C)C=C1O BSJQLOWJGYMBFP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229950010765 pivalate Drugs 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-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
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-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
- AEPWOCLBLLCOGZ-UHFFFAOYSA-N 2-cyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCCC#N AEPWOCLBLLCOGZ-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VDEOPKZZYCBXJR-UHFFFAOYSA-N CC(C(C)(C)C1=C(O)C=CC(=C1)O)(CC)C Chemical compound CC(C(C)(C)C1=C(O)C=CC(=C1)O)(CC)C VDEOPKZZYCBXJR-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- MOVRNJGDXREIBM-UHFFFAOYSA-N aid-1 Chemical compound O=C1NC(=O)C(C)=CN1C1OC(COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)CO)C(O)C1 MOVRNJGDXREIBM-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- WTNIUNUGWCDPHL-UHFFFAOYSA-N carboxy octan-3-yl carbonate Chemical compound CCC(CCCCC)OC(=O)OC(=O)O WTNIUNUGWCDPHL-UHFFFAOYSA-N 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- UPWGQKDVAURUGE-UHFFFAOYSA-N glycerine monooleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC(CO)CO UPWGQKDVAURUGE-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000001294 propane Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical class [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、フィッシュアイを減少し初期着色性および熱
安定性を向上させたビニル系重合体の生成に有用な、ラ
ジカル重合用反応抑制剤、およびこれを用いたビニル系
単量体の反応抑制方法に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention provides a radical polymerization reaction inhibitor useful for producing vinyl polymers that reduce fish eyes and improve initial coloring and thermal stability. , and a method for inhibiting the reaction of vinyl monomers using the same.
（従来の技術）
従来、ビニル系単量体のラジカル重合に際し、フェノー
ル系化合物、イオウ化合物、Ｎ−オキシド化合物などか
らなる反応抑制剤（反応禁止剤とも称される）を重合系
中へ添加することが行なわれている。これらの内フェノ
ール系化合物としては、例えば２，２−ジー（４′−ヒ
ドロキシフェニル）プロパン、ハイドロキノン、ｐ−メ
トキシフェノール、 ｔｅｒｔ−ブチルヒドロキシアニ
ソール、ｎ−オクタデシル−３−（４−ヒドロキシ−３
，５−ジーｔｅｒｔ−ブチルフェニル）プロピオネート
、２，５−ジーｔｅｒｔ −ブチルハイドロキノン、４
，４′−ブチリデン−ビス−（３−メチル−６−ｔｅｒ
ｔ−ブチルフェノール）、３，５−ジーｔｅｒｔ−ブチ
ルー４−ヒドロキシトルエン、２，２′−メチレンービ
ス−（４−エチル−６−ｔｅｒｔ−ブチルフェノール）
、トリエチレングリコール−ビス（３−（３−ｔｅｒｔ
−ブチル−５−メチル−４−ヒドロキシフェニル）プロ
ピオネート〕、ペンタエリスリチル−テトラキス（３−
（３，５−ジーｔｅｒｔ−ブチルー４−ヒドロキシフェ
ニル）プロピオネート〕、ｔｅｒｔ−ブチルカテコール
、４，４′−チオビス−（６−ｔａｒｔ−ブチル−ｍ−
クレゾール）、トコフェロール等が知られている。(Prior art) Conventionally, during radical polymerization of vinyl monomers, a reaction inhibitor (also called a reaction inhibitor) consisting of a phenol compound, a sulfur compound, an N-oxide compound, etc. is added to the polymerization system. things are being done. Among these, phenolic compounds include, for example, 2,2-di(4'-hydroxyphenyl)propane, hydroquinone, p-methoxyphenol, tert-butylhydroxyanisole, n-octadecyl-3-(4-hydroxy-3
, 5-di-tert-butylphenyl)propionate, 2,5-di-tert-butylhydroquinone, 4
,4'-butylidene-bis-(3-methyl-6-ter
t-butylphenol), 3,5-di-tert-butyl-4-hydroxytoluene, 2,2'-methylene-bis-(4-ethyl-6-tert-butylphenol)
, triethylene glycol-bis(3-(3-tert
-butyl-5-methyl-4-hydroxyphenyl)propionate], pentaerythrityl-tetrakis (3-
(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tert-butylcatechol, 4,4'-thiobis-(6-tart-butyl-m-
cresol), tocopherol, etc.
これらの反応抑制剤は５重合開始前に重合系に添加する
ことによって、生成重合体中のフィッシュアイを減少さ
せる（特開昭４８−８９９９０号および特公昭６０−５
０３６６号公報）ために、また重合反応の途中で添加し
てヒートキックを抑制するために、あるいは重合反応の
終了時に添加して後重合を防止したり、熱履歴による初
期着色性の悪化を防止する（米国特許第３６４２７５６
号明細書、特開昭５７−１８５３０２号および同６２−
５０３号公報）ためなどの目的で使用されている。また
異常反応時における緊急反応停止剤としても用いられて
いる。These reaction inhibitors reduce fish eyes in the resulting polymer by adding them to the polymerization system before the start of polymerization (JP-A-48-89990 and JP-B-Sho 60-5).
(No. 0366 Publication), or added during the polymerization reaction to suppress heat kick, or added at the end of the polymerization reaction to prevent post-polymerization, or to prevent deterioration of initial colorability due to thermal history. (U.S. Pat. No. 3,642,756)
specification, JP-A No. 57-185302 and JP-A No. 62-
503)). It is also used as an emergency reaction stopper in the event of an abnormal reaction.
（発明が解決しようとする課題）
しかし、これらの反応抑制剤はそれぞれの段階における
問題を解決できても、別の段階での重合反応の抑制また
は禁止を充分に行なうことができないため、得られる重
合体のフィッシュアイ、初期着色性、熱安定性等の品質
、あるいは重合器内壁へのスケールの付着等の問題をす
べて満足するには至らなかった。(Problem to be Solved by the Invention) However, even if these reaction inhibitors can solve the problems at each stage, they cannot sufficiently suppress or inhibit the polymerization reaction at another stage. It was not possible to satisfy all of the problems with the quality of the polymer, such as fish eyes, initial coloration, and thermal stability, and with scale adhesion to the inner wall of the polymerization vessel.
したがって、本発明の目的は、ビニル系単量体のラジカ
ル重合反応の抑制および禁止を充分に行なうと共にフィ
ッシュアイを減少し初期着色性および熱安定性に優れた
ビニル系重合体を生成することのできる、ラジカル重合
用反応抑制剤およびこれを用いたビニル系単量体の反応
抑制方法を提供しようとするものである。Therefore, an object of the present invention is to sufficiently suppress and inhibit the radical polymerization reaction of vinyl monomers, reduce fish eyes, and produce a vinyl polymer with excellent initial coloring properties and thermal stability. The present invention aims to provide a radical polymerization reaction inhibitor and a method for inhibiting the reaction of vinyl monomers using the same.
（課題を解決するための手段）
本発明によるラジカル重合用反応抑制剤は、（式中、Ｒ
１は炭素原子数３〜１０のアルキル基。(Means for Solving the Problems) The reaction inhibitor for radical polymerization according to the present invention has the following properties:
1 is an alkyl group having 3 to 10 carbon atoms.
Ｒ２は水素原子、または炭素原子数１以上のアルキル基
であり、Ｒ１，Ｒ２のいずれか一方または両方のアルキ
ル基がテトラメチルブチル基である）で表される化合物
である。R2 is a hydrogen atom or an alkyl group having 1 or more carbon atoms, and the alkyl group of either or both of R1 and R2 is a tetramethylbutyl group.
また、これを用いたビニル系単量体の反応抑制方法は、
水性媒体中でのラジカル重合に際し、重合の開始前、重
合中、および重合終了期のいずれか１つの段階で、重合
系に上記反応抑制剤を添加することを要旨とするもので
ある。In addition, the method for suppressing the reaction of vinyl monomers using this method is as follows:
The gist of the method is to add the above-mentioned reaction inhibitor to the polymerization system during radical polymerization in an aqueous medium at any one of the following stages: before the start of the polymerization, during the polymerization, and at the end of the polymerization.
これを説明すると、上記一般式で示される反応抑制剤は
、そのＲ１が炭素原子数３〜１０のアルキル基で、具体
的にはｎ−プロピル、イソプロピル、ブチル、ｔｅｒｔ
−ブチル、ｎ−ペンチル、ｔｅｒｔ−ペンチル、ネオペ
ンチル、ｎ−ヘキシル、１，１′−ジメチルブチル、ｎ
−ヘプチル、１．１’、３−トリメチルブチル、ｎ−オ
クチル、１．１’、３．３’−テトラメチルブチル、ｎ
−ノニル、１−エチル−１’、３．３’−トリメチルブ
チル、ｎ−デシル、および１，１′３．３′−テトラメ
チルペンチル基などが例示される。また、Ｒ２は水素原
子、または炭素原子数１以上のアルキル基で、これには
メチルまたはエチル基のほか上記Ｒ１で説明したのと同
様の基が例示される。そして、Ｒ１とＲ２のいずれか一
方または両方のアルキル基はテトラメチルブチル基であ
ることが必要とされる。To explain this, in the reaction inhibitor represented by the above general formula, R1 is an alkyl group having 3 to 10 carbon atoms, specifically n-propyl, isopropyl, butyl, tert.
-butyl, n-pentyl, tert-pentyl, neopentyl, n-hexyl, 1,1'-dimethylbutyl, n
-heptyl, 1.1', 3-trimethylbutyl, n-octyl, 1.1', 3.3'-tetramethylbutyl, n
Examples include -nonyl, 1-ethyl-1', 3,3'-trimethylbutyl, n-decyl, and 1,1'3,3'-tetramethylpentyl. Further, R2 is a hydrogen atom or an alkyl group having one or more carbon atoms, and examples thereof include methyl or ethyl groups as well as the same groups as explained for R1 above. The alkyl group of one or both of R1 and R2 is required to be a tetramethylbutyl group.
このように定義される化合物の内でも、とくに２−（１
，１’、３．３’テトラメチルブチル）ハイドロキノン
、２，５−ジ（１，１’、３．３″テトラメチルブチル
）ハイドロキノン、または２−（１，１’、３．３’テ
トラメチルブチル）−５−メチルハイドロキノンが本発
明の目的達成のために好適である。Among the compounds defined in this way, 2-(1
, 1', 3.3'tetramethylbutyl)hydroquinone, 2,5-di(1,1',3.3''tetramethylbutyl)hydroquinone, or 2-(1,1',3.3'tetramethyl) Butyl)-5-methylhydroquinone is suitable for achieving the objectives of the invention.
上記反応抑制剤は、ビニル単量体のラジカル重合反応に
おいて特に有効であり、このビニル単量体は少なくとも
１個の末端基ＣＨ，＝Ｃ＜を有する重合性オレフィン糸
上ツマ−であって、これには例えば、塩化ビニル、臭化
ビニル、塩化ビニリデン等のハロゲン化ビニルまたはハ
ロゲン化ビニリデン；メチルアクリレート、エチルアク
リレート、ブチルアクリレート、オクチルアクリレート
。The reaction inhibitor is particularly effective in the radical polymerization reaction of a vinyl monomer, and the vinyl monomer is a polymerizable olefin thread polymer having at least one terminal group CH,=C<, These include, for example, vinyl halides or vinylidene halides such as vinyl chloride, vinyl bromide, vinylidene chloride; methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate.
シアノエチルアクリレート等のアクリル酸エステル；メ
チルメタアクリレート、ブチルメタアクリレート等のメ
タアクリル酸エステル；α−メチルスチレン、ビニルト
ルエン、クロロスチレン等のスチレンおよびその誘導体
；ビニルアセテート；ビニルナフタレン；ブタジェン、
イソプレン、クロロプレン等のジオレフィン；およびこ
れらのモノマーと他の共重合可能なオレフィンモノマー
との混合物などが挙げられる。Acrylic acid esters such as cyanoethyl acrylate; Methacrylic acid esters such as methyl methacrylate and butyl methacrylate; Styrene and its derivatives such as α-methylstyrene, vinyltoluene, and chlorostyrene; Vinyl acetate; Vinylnaphthalene; Butadiene,
Examples include diolefins such as isoprene and chloroprene; and mixtures of these monomers and other copolymerizable olefin monomers.
本発明の反応抑制剤はビニル系単量体のラジカル重合反
応であれば、例えば溶液重合、乳化重合、懸濁重合、塊
状重合等、いずれの重合形式であっても適用することが
できる。The reaction inhibitor of the present invention can be applied to any radical polymerization reaction of vinyl monomers, such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.
以下１本発明によるビニル系単量体の反応抑制方法を、
水性媒体中でのラジカル反応による懸濁重合の場合を例
として説明する。The following 1 method for suppressing the reaction of vinyl monomers according to the present invention,
The case of suspension polymerization by radical reaction in an aqueous medium will be explained as an example.
反応抑制剤は、その使用目的に応じて、重合の開始前、
重合中および重合終了期の内、少なくとも１つの段階に
おいて重合系に添加される。その添加量は一般にはビニ
ル系単量体１００重量部当りｏ、ｏｏｏｓ〜０．５重量
部程度である。Depending on the purpose of use, the reaction inhibitor may be used before the start of polymerization.
It is added to the polymerization system at least one stage during the polymerization and at the end of the polymerization. The amount added is generally from o,oos to 0.5 parts by weight per 100 parts by weight of the vinyl monomer.
これを具体的に説明すると、生成重合体中のフィッシュ
アイを減少させる目的で重合前に添加するときは、ビニ
ル系単量体１００重量部当りｏ、ｏｏｏｓ〜０．００５
重量部とするのが好ましい。この場合。To explain this specifically, when added before polymerization for the purpose of reducing fish eyes in the produced polymer, o,ooos to 0.005 parts by weight per 100 parts by weight of vinyl monomer.
Preferably, it is expressed in parts by weight. in this case.
水性媒体を予め加温して仕込むと、−層有効である。If the aqueous medium is heated and prepared in advance, the -layer will be effective.
所定の重合添加率に達した時点で重合反応を終了させ、
その後の後重合を防止する目的で重合終了期に添加する
場合は、仕込んだビニル系単量体１００重量部当りｏ、
ｏｏｓ〜０．０５重量部とするのが好ましい。The polymerization reaction is terminated when a predetermined polymerization addition rate is reached,
When added at the end of polymerization for the purpose of preventing subsequent post-polymerization, o per 100 parts by weight of the vinyl monomer charged.
It is preferable to set it as oos - 0.05 part by weight.
また、緊急時に懸濁重合反応を完全に停止させる目的で
重合系中に添加するときは、仕込んだビニル系単量体１
００重量部当り０．２〜０．５重量部とするのが好まし
い。In addition, when adding it to the polymerization system for the purpose of completely stopping the suspension polymerization reaction in an emergency, the charged vinyl monomer 1
The amount is preferably 0.2 to 0.5 parts by weight per 00 parts by weight.
この反応抑制剤を重合系中へ添加する方法は、重合形式
に応じて適宜選択することができるが。The method of adding this reaction inhibitor into the polymerization system can be appropriately selected depending on the type of polymerization.
例えば液状または粉末状のまま直接重合系へ投入しても
よく、またメタノール、トルエンなどの溶剤によって溶
解、希釈して投入してもよい、また乳化剤、懸濁剤など
を用いて反応抑制剤が水に分散した懸濁液を調製し、こ
れを重合系へ投入して添加することもできる。For example, it may be directly introduced into the polymerization system in liquid or powder form, or it may be dissolved or diluted with a solvent such as methanol or toluene, or the reaction inhibitor may be added using an emulsifier or suspending agent. It is also possible to prepare a suspension in water and add it to the polymerization system.
水性媒体中における懸濁重合は重合開始剤および分散剤
の存在下において通常０〜１００℃で行なわれる。Suspension polymerization in an aqueous medium is usually carried out at 0 to 100°C in the presence of a polymerization initiator and a dispersant.
この際用いられる分散剤としては１例えばメチルセルロ
ース、ヒドロキシエチルセルロース、ヒドロキシプロピ
ルセルロース、ヒドロキシプロピルメチルセルロースな
どの水溶性セルロースエーテル；部分けん化ポリビニル
アルコール、アクリル酸重合体、ポリビニルピロリドン
、無水マレイン酸−酢酸ビニル共重合体等の合成高分子
化合物；でんぷん、ゼラチンなどの天然高分子物質；ソ
ルビタンモノラウレート、ソルビタントリオレート、グ
リセリントリステアレート、エチレンオキシドプロピレ
ンオキシドブロックコポリマーなどの油溶性乳化剤；ポ
リオキシエチレンソルビタンモノラウレート、ポリオキ
シエチレングリセリンオレ−ト、ラウリン酸ナトリウム
などの水溶性乳化剤があり、これらは一種または二種以
上の組み合わせで使用しても差し支えない。Examples of dispersants used in this case include 1. Water-soluble cellulose ethers such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose; partially saponified polyvinyl alcohol, acrylic acid polymer, polyvinylpyrrolidone, and maleic anhydride-vinyl acetate copolymer. synthetic polymer compounds such as starch, gelatin, etc.; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan triolate, glycerin tristearate, ethylene oxide propylene oxide block copolymer; polyoxyethylene sorbitan monolaurate There are water-soluble emulsifiers such as polyoxyethylene glycerinoleate, sodium laurate, etc., and these may be used alone or in combination of two or more.
また重合開始剤としては、例えばジイソプロピルパーオ
キシジカーボネート、ジー２−エチルヘキシルパーオキ
シジカーボネート、ジェトキシエチルパーオキシジカー
ボネートなどのパーカーボネート化合物； ｔａｒｔ−
ブチルパーオキシピバレート、ｔｅｒｔ−ヘキシルパー
オキシピバレート、ｔｅｒｔ−ブチルパーオキシネオデ
カネート、α−クミルパーオキシネオデカネートなどの
パーエステル化合物；アセチルシクロヘキシルスルホニ
ルパーオキシド、２．４．４−トリメチルペンチル−２
−パーオキシフェノキシアセテート、３，５．５− ト
リメチルヘキサノイルパーオキシドなどの過酸化物；α
、α″アゾビスイソブチロニトリル、α、α′−アゾビ
スー２．４−ジメチルバレロニトリル、α、α′−アゾ
ビス（４−メトキシ−２，４−ジメチルバレロニトリル
）などのアゾ化合物；さらには過硫酸カリウム、過硫酸
アンモニウム、過酸化水素などがあり、これらは一種ま
たは二種以上の組み合わせで使用することができる。こ
れらの重合開始剤は通常仕込まれるビニル系単量体１０
０重量部当り０．０３〜０．３重量部添加される。Examples of the polymerization initiator include percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and jetoxyethyl peroxydicarbonate; tart-
Perester compounds such as butyl peroxy pivalate, tert-hexyl peroxy pivalate, tert-butyl peroxy neodecanate, α-cumyl peroxy neodecanate; acetyl cyclohexyl sulfonyl peroxide, 2.4.4-trimethyl Pentyl-2
- Peroxides such as peroxyphenoxy acetate, 3,5.5-trimethylhexanoyl peroxide; α
, α″azobisisobutyronitrile, α,α′-azobis-2,4-dimethylvaleronitrile, α,α′-azobis(4-methoxy-2,4-dimethylvaleronitrile); There are potassium persulfate, ammonium persulfate, hydrogen peroxide, etc., and these can be used singly or in combination of two or more.These polymerization initiators are usually charged with vinyl monomer 10
It is added in an amount of 0.03 to 0.3 parts by weight per 0 parts by weight.
水性媒体中における懸濁重合に際しての他の条件、例え
ば重合器への水性媒体、ビニル系単量体、場合によって
は他のコモノマー、分散助剤１重合開始剤などの仕込み
方法、これらの仕込み割合、重合温度などは特に制約さ
れず１通常行なわれる条件でよく、さらにこの重合系に
は、必要に応じてビニル系単量体の重合に適宜使用され
る、重合度調整剤、連鎖移動剤、ＰＨ調整剤、ゲル化改
良剤、帯電防止剤、抗酸化剤、スケール防止剤などを添
加することも任意である。Other conditions during suspension polymerization in an aqueous medium, such as the method of charging the aqueous medium, vinyl monomer, other comonomers in some cases, dispersion aid 1 polymerization initiator, etc. to the polymerization vessel, and the ratio of these charges There are no particular restrictions on the polymerization temperature, etc., and the conditions that are normally used may be used. Furthermore, the polymerization system may contain polymerization degree regulators, chain transfer agents, It is also optional to add a PH adjuster, a gelling improver, an antistatic agent, an antioxidant, a scale inhibitor, and the like.
（実施例）
以下、本発明の具体的態様を実施例および比較例により
説明するが１本発明はこれに限定されるものではない。(Examples) Hereinafter, specific aspects of the present invention will be explained using Examples and Comparative Examples, but the present invention is not limited thereto.
（ビニル系重合体の製造）
実施例１゜
内容積１．２ｄの攪拌器付きのオートクレーブに、部分
けん化ポリビニルアルコール１５０ｇとヒドロキシプロ
ピルメチルセルロース１００ｇを溶解した加温（６０℃
）水６００ｋｇを仕込んだ。次いでこれに２−（１，１
’、３．３’テトラメチルブチル）ハイドロキノン４ｇ
を添加した後、さらに塩化ビニル４００ｋｇを仕込み、
温度５３℃で１０分間攪拌して塩化ビニルを重合系中に
充分に分散させた。その後１重合開始剤としてジー２−
エチルへキシルジカーボネート２００ ｇを添加し１重
合系の温度を５７℃に昇温しで重合を開始させた。重合
反応が終了に近づき内圧が６ ｋｇ／ａＪに降下した時
点で重合を終了させた。(Manufacture of vinyl polymer) Example 1 150 g of partially saponified polyvinyl alcohol and 100 g of hydroxypropyl methyl cellulose were dissolved in an autoclave with an internal volume of 1.2 d and equipped with a stirrer and heated to 60°C.
) 600 kg of water was charged. Then add 2-(1,1
',3.3'tetramethylbutyl)hydroquinone 4g
After adding, 400 kg of vinyl chloride was added,
The mixture was stirred at a temperature of 53° C. for 10 minutes to sufficiently disperse vinyl chloride in the polymerization system. Then, as a polymerization initiator,
200 g of ethylhexyl dicarbonate was added and the temperature of the first polymerization system was raised to 57°C to initiate polymerization. The polymerization was terminated when the polymerization reaction approached completion and the internal pressure decreased to 6 kg/aJ.
生成重合体を含む反応混合物から未反応単量体を回収し
た後、脱水、乾燥して重合体を得た。After recovering unreacted monomers from the reaction mixture containing the produced polymer, the monomers were dehydrated and dried to obtain a polymer.
実施例２゜
２−（１，１’、３．３’テトラメチルブチル）ハイド
ロキノンの代わりに、２，５−ジ（１，１’、３．３’
テトラメチルブチル）ハイドロキノン４ｇを使用したほ
かは、実施例１と同様にして重合体を得た。Example 2゜2,5-di(1,1',3.3') instead of 2-(1,1',3.3'tetramethylbutyl)hydroquinone
A polymer was obtained in the same manner as in Example 1, except that 4 g of (tetramethylbutyl)hydroquinone was used.
実施例３゜
２−（１，１’、３．３″テトラメチルブチル）ハイド
ロキノンの代わりに、２−（１，１’、３．３’テトラ
メチルブチル）−５−メチルハイドロキノン４ｇを使用
したほかは、実施例１と同様にして重合体を得た。Example 3 4g of 2-(1,1',3.3'tetramethylbutyl)-5-methylhydroquinone was used instead of 2-(1,1',3.3'tetramethylbutyl)hydroquinone. Other than that, a polymer was obtained in the same manner as in Example 1.
比較例１゜
２−（１，１’、３．３’テトラメチルブチル）ハイド
ロキノンの代わりに、２，５−ジーｔｅｒｔ−ブチルハ
イドロキノン４ｇを使用したほかは、実施例１と同様に
して重合体を得た。Comparative Example 1 A polymer was produced in the same manner as in Example 1, except that 4 g of 2,5-di-tert-butylhydroquinone was used instead of 2-(1,1',3.3'tetramethylbutyl)hydroquinone. I got it.
比較例２゜
２−（１，１’、３．３’テトラメチルブチル）ハイド
ロキノンの代わりに、ｔｅｒｔ−ブチルヒドロキシアニ
ソール４ｇを使用したほかは、実施例１と同様にして重
合体を得た。Comparative Example 2 A polymer was obtained in the same manner as in Example 1, except that 4 g of tert-butylhydroxyanisole was used instead of 2-(1,1',3.3'tetramethylbutyl)hydroquinone.
比較例３゜
２−（１，１″、３．３’テトラメチルブチル）ハイド
ロキノンを全く使用しなかったほかは、実施例１と同様
にして重合体を得た。Comparative Example 3 A polymer was obtained in the same manner as in Example 1, except that no 2-(1,1'', 3,3'tetramethylbutyl)hydroquinone was used.
（得られた重合体についての各種特性試験）上記実施例
１〜３および比較例１〜３において得られた各重合体に
ついて、下記に示す方法で、ロール成形によるフィッシ
ュアイ（ロールフィッシュアイ）と押出成形によるフィ
ッシュアイ（押出フィッシュアイ）の発生状態、初期着
色性、および重合器内壁へのスケール付着状態を調べた
ところ、第１表に示す結果が得られた。(Various property tests on the obtained polymers) Each of the polymers obtained in Examples 1 to 3 and Comparative Examples 1 to 3 above was tested for fish eyes (roll fish eyes) by roll forming using the method shown below. The occurrence of fish eyes due to extrusion molding (extrusion fish eyes), initial coloration, and scale adhesion to the inner wall of the polymerization vessel were investigated, and the results shown in Table 1 were obtained.
ロールフィッシュアイ：
生成重合体 ｌＯＯ重量部Ｌ）ＯＰ
（フタル酸ジオクチル）５０〃三塩基性硫酸鉛
０．５〃ステアリン酸鉛
１．５〃酸化チタン ０．１
〃カーボンブラツク ０．０５ ＩＩ上
記処方にしたがって調製した配合物２５ｇを、混線用６
′ロールによって１４０℃で５分間混練し、幅１０Ｇ、
厚さ０．２ｎｗ＋＋のシートを成形した。得られたシー
トについて１００ｄ当りの透明粒子数を計数し、これを
ロールフィッシュアイの指標とした。Rollfish eye: Produced polymer lOO parts by weight L) OP
(Dioctyl phthalate) 50 Tribasic lead sulfate
0.5 Lead stearate
1.5 Titanium oxide 0.1
〃Carbon Black 0.05 II 25g of the mixture prepared according to the above recipe was added to 6
' Knead with rolls at 140℃ for 5 minutes, width 10G,
A sheet with a thickness of 0.2 nw++ was molded. The number of transparent particles per 100 d of the obtained sheet was counted, and this was used as an index of roll fish eyes.
押出フィッシュアイ：
生成重合体 １００ 重量部ＤＯ
Ｐ（フタル酸ジオクチル）５０〃
エポキシ化大豆油 ３．０〃着色剤（ブ
ルー） ｏ、ｏｏｚｌ＋上記処方に
したがって調製した配合物を、ヘンシェルミキサーを用
いて１２０℃で１０分間混合し。Extruded fisheye: Produced polymer 100 parts by weight DO
P (dioctyl phthalate) 50 Epoxidized soybean oil 3.0 Colorant (blue) o, oozl + The formulation prepared according to the above recipe was mixed for 10 minutes at 120° C. using a Henschel mixer.
得られた混合物を押出機によって幅４０．厚さ０．５Ｉ
ｒｎ のフィルムに成形した。このフィルムについてフ
ィルム１ｋｇ当りの直径０．３ｍｍ以上の透明粒子の個
数を計数し、これを押出フィッシュアイの指標とした。The resulting mixture was extruded to a width of 40 mm. Thickness 0.5I
It was molded into a rn film. For this film, the number of transparent particles with a diameter of 0.3 mm or more per 1 kg of film was counted, and this was used as an index of extrusion fish eyes.
初期着色性：
生成重合体 １００ 重量部ＤＯ
Ｐ（フタル酸ジオクチル） ＳＯジブブチ錫ラう
レート１．０
上記処方にしたがって調製した配合物を、６′ロールを
用いて１６０℃で５分間混練した後５シート状に成形し
た。得られたシート状物を１６０℃で５分間プレスして
５ ａｍ Ｘ ５ ｃｍ Ｘ １■（厚さ）に成形し、
成形品の着色の程度が一般品並をＢとして。Initial colorability: Produced polymer 100 parts by weight DO
P (dioctyl phthalate) SO dibutytin laurate 1.0 The compound prepared according to the above recipe was kneaded at 160°C for 5 minutes using a 6' roll, and then formed into 5 sheets. The obtained sheet-like material was pressed at 160°C for 5 minutes to form it into a size of 5 am x 5 cm x 1 inch (thickness).
The degree of coloring of the molded product is B if it is on par with general products.
これより良いものをＡ、悪いものを順にＣ，Ｄとした。Those that were better than this were designated as A, and those that were worse were designated as C and D, respectively.
重合器内壁へのスケール付着 態：
重合器内を純水で洗浄後、肉眼ｗ１察した。その状態を
次の基準で評価した。Scale adhesion to the inner wall of the polymerization vessel Condition: After washing the inside of the polymerization vessel with pure water, it was observed with the naked eye w1. The condition was evaluated based on the following criteria.
Ａ：重合器の内面にスケール付着が殆どない。A: There is almost no scale adhesion on the inner surface of the polymerization vessel.
Ｂ：重合器内面の気液界面部分にスケールが付着してい
た。B: Scale was attached to the gas-liquid interface on the inner surface of the polymerization vessel.
Ｃ：重合器の内面全体にスケールが付着していた。C: Scale was adhered to the entire inner surface of the polymerization vessel.
第１表
但し、表中、
１ ： ２−（１，１’、３．３’テトラメチルブチル
）ハイドロキノン
ＩＩ ： ２．５−ジ（１，１’、３．３’テトラメチ
ルブチル）ハイドロキノン
Ｉ［１： ２−（１，１’、３．３’テトラメチルブチ
ル）−５−メチルハイドロキノン
ＩＶ：２，５−ジーｔｅｒｔ−ブチルハイドロキノンｖ
： ｔｅｒｔ−ブチルヒドロキシアニソールを示す。Table 1 However, in the table, 1: 2-(1,1',3.3'tetramethylbutyl)hydroquinone II: 2,5-di(1,1',3.3'tetramethylbutyl)hydroquinone I [1: 2-(1,1',3.3'tetramethylbutyl)-5-methylhydroquinone IV: 2,5-di-tert-butylhydroquinone v
: Indicates tert-butylhydroxyanisole.
（ビニル系重合体の製造）
実施例４゜
部分けん化ポリビニルアルコール１５０ｇとヒドロキシ
プロピルメチルセルロースｌｏｏｇとを水６００眩に溶
解して得られた懸濁液を、内容積１．２ｒｎ’の攪拌器
付きオートクレーブに仕込んだ。次いでこれに塩化ビニ
ル４００ｋｇとジー２−エチルへキシルジカーボネート
２００ｇとを仕込んで充分に攪拌した後、重合系内の温
度を５７℃に昇温し、攪拌を続けながら重合させた。重
合反応が終了に近づき内圧が６ｋｇ／−に降下した時点
で、２−（１，１’、３．３’テ１−ラメチルブチル）
ハイドロキノン１２０ｇを添加し１重合系の温度を８０
℃まで昇温しで、未反応単量体を重合系より回収した１
重合系の温度を８０℃で３０分間保持した後、冷却し、
生成重合体を含む反応混合物を脱水、乾燥して重合体を
得た。(Production of vinyl polymer) Example 4 A suspension obtained by dissolving 150 g of partially saponified polyvinyl alcohol and hydroxypropyl methyl cellulose in 600 g of water was placed in an autoclave with an internal volume of 1.2 rn' equipped with a stirrer. I prepared it in. Next, 400 kg of vinyl chloride and 200 g of di-2-ethylhexyl dicarbonate were charged and stirred sufficiently, and then the temperature inside the polymerization system was raised to 57° C., and polymerization was carried out while stirring was continued. When the polymerization reaction approaches completion and the internal pressure drops to 6 kg/-, 2-(1,1',3.3'te-1-ramethylbutyl)
Add 120g of hydroquinone and lower the temperature of the polymerization system to 80
1. Unreacted monomers were recovered from the polymerization system by raising the temperature to ℃.
After maintaining the temperature of the polymerization system at 80 ° C. for 30 minutes, cooling it,
The reaction mixture containing the produced polymer was dehydrated and dried to obtain a polymer.
比較例４゜
２−（１，１’、３．３’テトラメチルブチル）ハイド
ロキノンの代わりに、２，５−ジーｔａｒｔ−ブチルハ
イドロキノン１２０ｇを使用したほかは、実施例４と同
様にして重合体を得た。Comparative Example 4 A polymer was produced in the same manner as in Example 4, except that 120 g of 2,5-di-tart-butylhydroquinone was used instead of 2-(1,1',3.3'tetramethylbutyl)hydroquinone. I got it.
比較例５゜
２−（１，１’、３．３’テトラメチルブチル）ハイド
ロキノンの代わりに、２，２−ジ（４′−ヒドロキシフ
ェニル）プロパン１２０ｇを使用したほかは、実施例４
と同様にして重合体を得た。Comparative Example 5 Example 4 except that 120 g of 2,2-di(4'-hydroxyphenyl)propane was used instead of 2-(1,1',3.3'tetramethylbutyl)hydroquinone.
A polymer was obtained in the same manner as above.
比較例６゜
２−（１，１’、３．３’テトラメチルブチル）ハイド
ロキノンを全く使用しなかったほかは、実施例４と同様
にして重合体を得た。Comparative Example 6 A polymer was obtained in the same manner as in Example 4, except that no 2-(1,1',3.3'tetramethylbutyl)hydroquinone was used.
（得られた重合体についての各種特性試験）上記実施例
４および比較例４〜６によって得られた各重合体につい
て、前記と同様の方法で初期着色性を、また下記に示す
方法で可塑剤吸収性（ドライアップ）と熱安定性とを測
定した。その結果を第２表に示す。(Various property tests on the obtained polymers) For each of the polymers obtained in Example 4 and Comparative Examples 4 to 6, the initial colorability was tested in the same manner as above, and the plasticizer was tested in the method shown below. Absorption (dry up) and thermal stability were measured. The results are shown in Table 2.
亙星菫盈取立±
プラベンダー社製プラスチ・コーダーのプラネタリ−ミ
キサー（ジャケット温度：８３℃）に１重合体４００ｇ
を投入し、６０ｒ／ｓで混練しながら４分間加熱した後
、ＤＯＰ２００ｇを添加した。プラネタリ−ミキサーの
混練トルクがＤＯＰの添加時から最小になるまでの時間
をドライアップ時間とし、可塑剤吸収性の指標とした。1st Polymer 400g in a Plasticorder planetary mixer (jacket temperature: 83℃) made by Prabender Co., Ltd.
After heating for 4 minutes while kneading at 60 r/s, 200 g of DOP was added. The time from the addition of DOP until the kneading torque of the planetary mixer reached its minimum was defined as the dry-up time, and was used as an index of plasticizer absorption.
然支定炙上
前述した初期着色性の評価において調製したロールシー
トを、炉内温度１８５℃のオーブン中に入れ、ロールシ
ートが完全に黒化するまでの時間を測定した。The rolled sheet prepared in the above-mentioned initial coloring evaluation was placed in an oven with an internal temperature of 185° C., and the time required for the rolled sheet to completely blacken was measured.
第２表 但し、表中Ｉおよび■は第１表と同じ。Table 2 However, I and ■ in the table are the same as in Table 1.
ＶＩ：２，２−ジ（４′−ヒドロキシフェニル）プロパ
ン を示す。VI: 2,2-di(4'-hydroxyphenyl)propane.
（ビニル系重合体の製造） 実施例５゜ 内容積１．２ｒｒｒの攪拌器付きオートクレーブに。(Manufacture of vinyl polymer) Example 5゜ In an autoclave with an internal volume of 1.2 rrr equipped with a stirrer.
部分けん化ポリビニルアルコール１５０ｇおよびヒドロ
キシプロピルメチルセルロース１００ ｇを溶解した水
６００ ｋｇを仕込んだ。次いでこれに塩化ビニル４０
０ｋｇとジー２−エチルへキシルジカーボネート２００
ｇとを仕込んで充分に攪拌した後１重合系内の温度を５
７℃に昇温し、攪拌を続けながら重合させた。重合を始
めてから２時間後に、２−（１，１’３．３′テトラメ
チルブチル）−５−メチルハイドロキノン１２００ｇを
添加し、それによって重合反応が完全に停止したことを
確認した。600 kg of water in which 150 g of partially saponified polyvinyl alcohol and 100 g of hydroxypropyl methylcellulose were dissolved was charged. Then add 40% vinyl chloride to this.
0kg and di-2-ethylhexyl dicarbonate 200
After charging and stirring thoroughly, the temperature in the polymerization system was lowered to 5.
The temperature was raised to 7°C, and polymerization was carried out while stirring was continued. Two hours after starting the polymerization, 1200 g of 2-(1,1'3.3'tetramethylbutyl)-5-methylhydroquinone was added, thereby confirming that the polymerization reaction had completely stopped.
比較例７゜
２−（１，１’、３．３’テトラメチルブチル）−５−
メチルハイドロキノンの代わりに、２，２−ジ（４１−
ヒドロキシフェニル）プロパン〔ビスフェノールＡ〕１
２００ ｇを使用したほかは、実施例５と同様にして重
合反応の停止を試みたところ１重合反応が著しく抑制さ
れたが完全に停止するには至らなかった。Comparative Example 7゜2-(1,1',3.3'tetramethylbutyl)-5-
Instead of methylhydroquinone, 2,2-di(41-
hydroxyphenyl)propane [bisphenol A] 1
An attempt was made to stop the polymerization reaction in the same manner as in Example 5, except that 200 g was used, and although one polymerization reaction was significantly suppressed, it was not completely stopped.
なお、上記において重合器のジャケット温度が反応混合
物の温度（５７℃）を完全に上回っ゛たときに、重合反
応が完全に停止したと判定した。In the above, it was determined that the polymerization reaction had completely stopped when the jacket temperature of the polymerization vessel completely exceeded the temperature of the reaction mixture (57°C).
（発明の効果）
本発明の反応抑制剤は、
■重合開始前に重合系に添加して重合させることにより
、得られる重合体のフィッシュアイの減少と初期着色性
の向上が図れるほか１重合器内壁へのスケールの付着を
防止することができる：■重合反応の途中で重合系に添
加して重合させることにより、得られる重合体の可塑剤
吸収性と熱安定性を向上することができる；
■重合終了期または緊急時の反応停止剤として、従来の
ものよりも重合反応を完全に停止することができる；
等、ビニル系単量体の反応の抑制または停止を有効に行
ない、とくに水性媒体中での懸濁重合の反応抑制または
停止に有用である。(Effects of the Invention) The reaction inhibitor of the present invention can be added to the polymerization system before the start of polymerization to reduce fish eyes and improve the initial coloring property of the resulting polymer. It can prevent scale from adhering to the inner wall: ■ By adding it to the polymerization system during the polymerization reaction and polymerizing it, it can improve the plasticizer absorption and thermal stability of the resulting polymer; ■As a reaction terminator at the end of polymerization or in emergencies, it can stop the polymerization reaction more completely than conventional ones; etc. It can effectively suppress or stop the reaction of vinyl monomers, especially in aqueous media. It is useful for inhibiting or stopping the reaction of suspension polymerization in
Claims (1)
＾２は水素原子、または炭素原子数１以上のアルキル基
であり、Ｒ＾１、Ｒ＾２のいずれか一方または両方のア
ルキル基がテトラメチルブチル基である）で表されるラ
ジカル重合用反応抑制剤。 ２、ビニル系単量体を水性媒体中でラジカル重合させる
に際し、 一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＾１は炭素原子数３〜１０のアルキル基、Ｒ
＾２は水素原子、または炭素原子数１以上のアルキル基
であり、Ｒ＾１、Ｒ＾２のいずれか一方または両方のア
ルキル基がテトラメチルブチル基である）で表される反
応抑制剤を、重合の開始前、重合中、および重合終了期
のいずれか１つの段階で、重合系に添加することを特徴
とするビニル系単量体の反応抑制方法。 ３、反応抑制剤が、２−（１，１′，３，３′テトラメ
チルブチル）ハイドロキノン、２，５−ジ（１，１′，
３，３′テトラメチルブチル）ハイドロキノン、または
２−（１，１′，３，３′テトラメチルブチル）−５−
メチルハイドロキノンである、請求項１または２記載の
、ラジカル重合用反応抑制剤またはビニル系単量体の反
応抑制方法。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 is an alkyl group having 3 to 10 carbon atoms, R
^2 is a hydrogen atom or an alkyl group having 1 or more carbon atoms, and either or both of the alkyl groups of R^1 and R^2 is a tetramethylbutyl group) Reaction for radical polymerization Suppressant. 2. When performing radical polymerization of vinyl monomers in an aqueous medium, there are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is an alkyl group having 3 to 10 carbon atoms, R
^2 is a hydrogen atom or an alkyl group having 1 or more carbon atoms, and either or both of the alkyl groups of R^1 and R^2 is a tetramethylbutyl group). A method for inhibiting the reaction of a vinyl monomer, which comprises adding the vinyl monomer to a polymerization system at any one of the following steps: before the start of polymerization, during polymerization, and at the end of polymerization. 3. The reaction inhibitor is 2-(1,1',3,3'tetramethylbutyl)hydroquinone, 2,5-di(1,1',
3,3'tetramethylbutyl)hydroquinone, or 2-(1,1',3,3'tetramethylbutyl)-5-
The reaction inhibitor for radical polymerization or the method for inhibiting the reaction of a vinyl monomer according to claim 1 or 2, wherein the reaction inhibitor is methylhydroquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24326588A JPH0291102A (en) | 1988-09-28 | 1988-09-28 | Reaction inhibitor for radical polymerization and method for inhibiting reaction of vinyl monomer by use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24326588A JPH0291102A (en) | 1988-09-28 | 1988-09-28 | Reaction inhibitor for radical polymerization and method for inhibiting reaction of vinyl monomer by use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0291102A true JPH0291102A (en) | 1990-03-30 |
| JPH0369924B2 JPH0369924B2 (en) | 1991-11-05 |
Family
ID=17101297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24326588A Granted JPH0291102A (en) | 1988-09-28 | 1988-09-28 | Reaction inhibitor for radical polymerization and method for inhibiting reaction of vinyl monomer by use thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0291102A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04142311A (en) * | 1990-10-03 | 1992-05-15 | Nippon Zeon Co Ltd | Production of vinyl chloride copolymer for paste |
-
1988
- 1988-09-28 JP JP24326588A patent/JPH0291102A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04142311A (en) * | 1990-10-03 | 1992-05-15 | Nippon Zeon Co Ltd | Production of vinyl chloride copolymer for paste |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0369924B2 (en) | 1991-11-05 |
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