JPH03140301A - Production of vinyl chloride polymer - Google Patents
Production of vinyl chloride polymerInfo
- Publication number
- JPH03140301A JPH03140301A JP27956189A JP27956189A JPH03140301A JP H03140301 A JPH03140301 A JP H03140301A JP 27956189 A JP27956189 A JP 27956189A JP 27956189 A JP27956189 A JP 27956189A JP H03140301 A JPH03140301 A JP H03140301A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- polymerization
- compound
- scale
- reaction product
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 title abstract description 18
- 238000004519 manufacturing process Methods 0.000 title description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 16
- -1 aliphatic hydroxylamine compound Chemical class 0.000 claims abstract description 15
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract 2
- 150000002367 halogens Chemical class 0.000 claims abstract 2
- 238000006116 polymerization reaction Methods 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 33
- 238000000576 coating method Methods 0.000 abstract description 20
- 241000251468 Actinopterygii Species 0.000 abstract description 9
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 abstract description 3
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- VSNHCAURESNICA-NJFSPNSNSA-N 1-oxidanylurea Chemical compound N[14C](=O)NO VSNHCAURESNICA-NJFSPNSNSA-N 0.000 description 1
- XSVZEASGNTZBRQ-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfinylphenol Chemical compound OC1=CC=CC=C1S(=O)C1=CC=CC=C1O XSVZEASGNTZBRQ-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- BAYSHFQWTRUCAD-UHFFFAOYSA-N 2-chloro-4-(3-chloro-4-hydroxyphenyl)sulfanylphenol Chemical compound C1=C(Cl)C(O)=CC=C1SC1=CC=C(O)C(Cl)=C1 BAYSHFQWTRUCAD-UHFFFAOYSA-N 0.000 description 1
- PWDGALQKQJSBKU-UHFFFAOYSA-N 2-chloro-4-(3-chloro-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Cl)C(O)=CC=C1S(=O)(=O)C1=CC=C(O)C(Cl)=C1 PWDGALQKQJSBKU-UHFFFAOYSA-N 0.000 description 1
- NXVGUNGPINUNQN-UHFFFAOYSA-N 2-phenylpropan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C1=CC=CC=C1 NXVGUNGPINUNQN-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OQYYLPLRBBDFLA-UHFFFAOYSA-N 3-(3-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC(S(=O)(=O)C=2C=C(O)C=CC=2)=C1 OQYYLPLRBBDFLA-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- AKHZFKHOIVFHCH-UHFFFAOYSA-N 4-(4-hydroxy-2-methylphenyl)sulfonyl-3-methylphenol Chemical compound CC1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1C AKHZFKHOIVFHCH-UHFFFAOYSA-N 0.000 description 1
- IBNFPRMKLZDANU-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)sulfanyl-2-methylphenol Chemical compound C1=C(O)C(C)=CC(SC=2C=C(C)C(O)=CC=2)=C1 IBNFPRMKLZDANU-UHFFFAOYSA-N 0.000 description 1
- FVAIEHAPKZFAGH-UHFFFAOYSA-N 6,6-dimethylheptanoyl 6,6-dimethylheptaneperoxoate Chemical compound CC(CCCCC(=O)OOC(CCCCC(C)(C)C)=O)(C)C FVAIEHAPKZFAGH-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 239000007844 bleaching agent Substances 0.000 description 1
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 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
- 238000007872 degassing Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 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 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- ZUSSTQCWRDLYJA-UHFFFAOYSA-N n-hydroxy-5-norbornene-2,3-dicarboximide Chemical compound C1=CC2CC1C1C2C(=O)N(O)C1=O ZUSSTQCWRDLYJA-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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、塩化ビニル系重合体の製造法に関し、さらに
詳しくは重合器内壁、およびその他単量体が接触する部
分にスケールが付着するのを防止するための、塩化ビニ
ル系重合体の製造法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing vinyl chloride polymers, and more specifically to a method for preventing scale from adhering to the inner wall of a polymerization vessel and other parts that come in contact with monomers. The present invention relates to a method for producing a vinyl chloride polymer for preventing.
（従来の技術）
従来、塩化ビニル系重合体を水性媒体中で重合するに際
して、重合器内壁等にスケールが付着するのを防止する
ために、重合器内部表面に薬剤を塗布する方法が種々提
案されている６その塗布剤として、例えば、電子供与性
化合物と電子受容性化合物の混合物（特公昭５３−２８
３４７号）、脂肪族アミンと芳香族アミンと酸素含有置
換基を置換基として有する芳香族化合物の反応生成物（
特公昭５７−１５２８号）、千オシフェノールと漂白剤
との反応生成物（特表昭５６−５００４１７）などが開
示されているが、これらの塗布剤を使用しても、２０〜
７０バツチの重合を繰り返し行うと、重合器の内壁等に
スケールが付着し、重合器の除熱能力が低下したり、重
合中に剥離したスケールが製品中に混入し、これがフィ
ッシュ・アイの原因となるなどして、製品の品質を低下
させるなどの問題があった。また、これらの混合物から
なる塗布剤は、スケール付着防止効果の持続性が不十分
であるばかりではなく、これらが重合系内に塩化ビニル
などの単量体に対してわずか数ｐｐｎ＋残留するだけで
も重合の遅延や、重合体粒子の粗粒化、フィンシュアイ
の増加または製品の着色等の原因となるという欠点があ
った。(Prior art) Various methods have been proposed to apply chemicals to the inner surface of the polymerization vessel in order to prevent scale from adhering to the inner walls of the polymerization vessel when vinyl chloride polymers are polymerized in an aqueous medium. 6 As the coating agent, for example, a mixture of an electron-donating compound and an electron-accepting compound (Japanese Patent Publication No. 53-28
No. 347), a reaction product of an aliphatic amine, an aromatic amine, and an aromatic compound having an oxygen-containing substituent as a substituent (
Japanese Patent Publication No. 57-1528) and a reaction product of 1,000 oscyphenol and bleach (Japanese Patent Publication No. 56-500417) have been disclosed, but even if these coating agents are used,
If 70 batches of polymerization are repeated, scale will adhere to the inner walls of the polymerization vessel, reducing the heat removal ability of the polymerization vessel, and the scale peeled off during polymerization may be mixed into the product, which is the cause of fish eyes. This caused problems such as deterioration of product quality. In addition, coating agents made of mixtures of these not only have insufficient sustainability of the scale adhesion prevention effect, but also cause damage even if they remain in the polymerization system only a few ppn+ compared to monomers such as vinyl chloride. This method has disadvantages such as delay in polymerization, coarsening of polymer particles, increase in fins, and coloring of products.
一方、近年大型重合器やりフラックス・コンデンサーを
使用する塩化ビニル系重合体の製造法が工業的規模で採
用されるようになったことにより、スケール防止効果、
およびその持続性に優れた塗布剤が切望されている。す
なわち、大型重合器はその内容積に対して反応熱を除去
するためのジャケットの冷却面積が相対的に小さいため
、重合の生産性を高めるためにはスケールの付着を防止
し、ジャケットの除熱能力を維持させることがきわめて
重要である。また、リフラックス・コンデンサーは内部
の伝熱管などの構造が複雑であるため、−度スケールが
付着すると、この除去作業に多大の時間と労力を要する
。したがって、スケール防止効果およびその持続性に優
れ、かつ品質の低下を招かない塗布剤を開発することは
、極めて重要な技術課題とされるのである。On the other hand, in recent years, the production method of vinyl chloride polymers using large polymerization vessels and flux condensers has been adopted on an industrial scale, and as a result, the scale prevention effect and
There is a strong need for a coating agent with excellent durability. In other words, in large polymerization vessels, the cooling area of the jacket for removing reaction heat is relatively small compared to its internal volume, so in order to increase polymerization productivity, it is necessary to prevent scale adhesion and remove heat from the jacket. Maintaining competency is extremely important. Furthermore, since the reflux condenser has a complicated structure such as internal heat transfer tubes, it takes a great deal of time and effort to remove -degree scale if it adheres to it. Therefore, it is considered an extremely important technical issue to develop a coating agent that has excellent scale prevention effect and its sustainability and does not cause deterioration in quality.
（発明が解決しようとする課題）
本発明の目的は、重合体粒子の粗粒化およびフィッシュ
・アイの増加など品質の低下を招かず、かつスケール防
止の持続性の優れた塗布剤を塗布することにより、重合
器の内壁やりフラックス・コンデンサー等へのスケール
付着防止性の改善された塩化ビニル系重合体の製造法を
提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to apply a coating agent that does not cause deterioration in quality such as coarsening of polymer particles and increase in fish eyes, and has excellent long-lasting scale prevention. The object of the present invention is to provide a method for producing a vinyl chloride polymer with improved ability to prevent scale from adhering to the inner wall of a polymerization vessel, flux, condenser, etc.
（課題を解決するための手段）
本発明のかかる目的は、塩化ビニル単量体または塩化ビ
ニル単量体および塩化ビニルと共重合し得る単量体の混
合物を水性媒体中で重合するに際し、一般式（Ｉ）で表
される化合物（Ａ）と脂肪族ヒドロキシルアミン系化合
物（Ｂ）を反応させて得られる反応生成物を、予め重合
器の内壁およびその他単量体が接触する部分に塗布する
ことによって達成される。(Means for Solving the Problems) The object of the present invention is to provide a general A reaction product obtained by reacting the compound (A) represented by formula (I) with the aliphatic hydroxylamine compound (B) is applied in advance to the inner wall of the polymerization vessel and other parts that come into contact with the monomers. This is achieved by
式中、Ｒ１は−Ｓ−、−５Ｏ−または一８Ｏ□−をわす
。In the formula, R1 represents -S-, -5O- or -8O□-.
本発明におけるスケール除去のだめの塗布剤の原料とし
て用いられる一般式（Ｉ）で表される化合物（Ａ）の代
表例は下記のような化合物である。Representative examples of the compound (A) represented by the general formula (I) used as a raw material for the coating agent for removing scale in the present invention are the following compounds.
このような化合物としては、２，２゛−チオジフェノー
ル、３．３°−チオジフェノール、４，４゛−チオジフ
ェノール、２，２°−ジメチル−４，４′−チオジフェ
ノール、３．３”−ジメチル−４，４゛−チオジフェノ
ール、２，２′−ジクロロ−４，４°−チオジフェノー
ル、３３′−ジクロロ−４，４゛−チオジフェノール、
２，２′−ジ−ｔ−ブチル−４，４”−チオジフェノー
ル、３．３゛−ジーも一ブチルー４，４゛−チオジフェ
ノール、４．４′−チオビス（２−ｔ−ブチル−６−メ
チルフェノール） 、２．２’−チオビス（６−ｔ−ブ
チル−４−メチルフェノール） 、２．２’−スルフィ
ニルジフェノール、３，３“−スルフィニルジフェノー
ル、４．４゛−スルフィニルジフェノール、２．２’−
ジメチル−４，４′−スルフィニルジフェノール、３１
３゛−ジメチル−４，４″−スルフィニルジフェノール
、２，２゛−ジクロロ−４□４′−スルフィニルジフェ
ノール、３．３゛−ジクロロ−４，４゛−スルフィニル
ジフェノール、２．２’−ジーも一ブチルー４．４′−
スルフィニルジフェノール、３．３゛−ジーＬ−ブチル
ー４，４゛−スルフィニルジフェノール、２．２’−ス
ルフォニルジフェノール、３，３゛−スルフォニルジフ
ェノール、４．４°−スルフォニルジフェノール、２．
２°−ジメチル−４，４゛−スルフォニルジフェノール
、３，３゛−ジメチル−４，４゛−スルフォニルジフェ
ノール、２．２’−ジクロロ−４，４゛−スルフォニル
ジフェノール、３．３゛−ジクロロ−４，４゛−スルフ
ォニルジフェノール、４，４゛−ジヒドロキシ−３，３
″、５．５’−テトラメチルジフェニルスルフォン、２
２’−ジーｔ −プチル−４，４”−スルフォニルジフ
ェノール、３．３”−ジーＬ−ブチルー４１４゛−スル
フォニルジフェノールなどが例示される。Such compounds include 2,2'-thiodiphenol, 3.3'-thiodiphenol, 4,4'-thiodiphenol, 2,2'-dimethyl-4,4'-thiodiphenol, 3.3''-dimethyl-4,4'-thiodiphenol, 2,2'-dichloro-4,4'-thiodiphenol, 33'-dichloro-4,4'-thiodiphenol,
2,2'-di-t-butyl-4,4''-thiodiphenol, 3.3'-di-butyl-4,4''-thiodiphenol, 4,4'-thiobis(2-t-butyl -6-methylphenol), 2,2'-thiobis(6-t-butyl-4-methylphenol), 2,2'-sulfinyldiphenol, 3,3"-sulfinyldiphenol, 4.4"-sulfinyl Diphenol, 2.2'-
Dimethyl-4,4'-sulfinyldiphenol, 31
3′-dimethyl-4,4″-sulfinyldiphenol, 2,2′-dichloro-4□4′-sulfinyldiphenol, 3.3′-dichloro-4,4″-sulfinyldiphenol, 2.2′ -Gi also one butyroux 4.4'-
Sulfinyldiphenol, 3.3'-di-L-butyl-4,4'-sulfinyldiphenol, 2,2'-sulfonyldiphenol, 3,3'-sulfonyldiphenol, 4.4'-sulfonyldiphenol, 2 ．．
2'-dimethyl-4,4'-sulfonyldiphenol, 3,3'-dimethyl-4,4'-sulfonyldiphenol, 2,2'-dichloro-4,4'-sulfonyldiphenol, 3.3'-dimethyl-4,4'-sulfonyldiphenol -dichloro-4,4゛-sulfonyldiphenol, 4,4゛-dihydroxy-3,3
″, 5,5′-tetramethyldiphenylsulfone, 2
Examples include 2'-di-t-butyl-4,4''-sulfonyldiphenol and 3.3''-di-L-butyl-414''-sulfonyldiphenol.
また、本発明におけるスケール除去のための塗布剤のも
う一方の原料として用いられる脂肪族ヒドロキシルアミ
ン系化合物（Ｂ）としては、ヒドロキシルアミン、Ｎ、
Ｎ−ジエチルヒドロキシルアミン、ヒドロキシ尿素、Ｎ
−ヒドロキシウレタン、Ｎ−ヒドロキシ−５−ノルボル
ネン−２，３−ジカルボキシイミド、Ｎ−ヒドロキシコ
ハク酸イミドなどが例示される。アルキル基を持つヒド
ロキシルアミンを用いた場合はスケール付着防止効果が
特に顕著であるが、これは窒素原子の非共有電子対の共
鳴効果への寄与の違いにより重合禁止効果に差異が出現
するものと考えられる。In addition, the aliphatic hydroxylamine compound (B) used as the other raw material for the coating agent for scale removal in the present invention includes hydroxylamine, N,
N-diethylhydroxylamine, hydroxyurea, N
Examples include -hydroxyurethane, N-hydroxy-5-norbornene-2,3-dicarboximide, and N-hydroxysuccinimide. When hydroxylamine having an alkyl group is used, the scale adhesion prevention effect is particularly remarkable, but this may be due to differences in the polymerization inhibition effect due to differences in the contribution of the lone pair of nitrogen atoms to the resonance effect. Conceivable.
本発明において、塗布剤として用いられる一般式（Ｉ）
で表される化合物（Ａ）と脂肪族ヒドロキシルアミン系
化合物（Ｂ）との反応生成物の製造方法としては、酸性
触媒の存在下、（Ａ）および（Ｂ）の各々につき少なく
とも１種以上を一括して仕込み同時に反応させるか、（
Ａ）および（Ｂ）の各々の少なくとも１種以上を仕込ん
で反応を開始させた後、（Ａ）および／または（Ｂ）の
一種類以上を追加して仕込みつつ５０℃〜３００°Ｃ好
ましくは６０〜２５０°Ｃの温度で１分〜２０時間にわ
たって反応を行う方法が代表的である。In the present invention, general formula (I) used as a coating agent
A method for producing a reaction product of a compound (A) represented by the formula (A) and an aliphatic hydroxylamine compound (B) includes at least one kind of each of (A) and (B) in the presence of an acidic catalyst. You can prepare it all at once and react at the same time, or (
After charging at least one or more of each of A) and (B) to start the reaction, the temperature is preferably 50°C to 300°C while additionally charging at least one of (A) and/or (B). A typical method is to conduct the reaction at a temperature of 60 to 250°C for 1 minute to 20 hours.
反応は空気中でも不活性ガス雰囲気下でも、また溶媒の
存在下でも実施することができる。ここで用いられる酸
性触媒としては塩酸、硫酸、燐酸などの鉱酸、バラトル
エンスルフォン酸、メタンスルフォン酸、しゅう酸、蟻
酸などの有機酸、塩化アルミニウム、塩化第二鉄、塩化
第一錫、三ふっ化はう素、四塩化チタンなどのルイス酸
が例示される。また酸性触媒の量は、反応温度、所望の
反応時間、前記した原料（Ａ）および（Ｂ）の化合物の
種類や仕込み量にもよって異なるが、通常、一般式（口
で表わされる化合物（Ａ）１モルあたり０．００１−１
モルの範囲である。The reaction can be carried out in air, under an inert gas atmosphere, or in the presence of a solvent. The acidic catalysts used here include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as valatoluenesulfonic acid, methanesulfonic acid, oxalic acid, and formic acid, aluminum chloride, ferric chloride, stannous chloride, and Lewis acids such as borofluoride and titanium tetrachloride are exemplified. Although the amount of the acidic catalyst varies depending on the reaction temperature, desired reaction time, and the types and amounts of the compounds of the raw materials (A) and (B), it is usually a compound represented by the general formula (A). ) 0.001-1 per mole
It is in the molar range.
本発明において、スケール付着防止のための塗布剤とし
て特に有効な反応生成物は、一般式Ｎ）で表わされる化
合物（Ａ）と脂肪族ヒドロキシルアミン系化合物（Ｂ）
を原料とし、（Ａ）および（Ｂ）の全量に対する（Ａ）
の仕込み割合が１５〜９０モル％好ましくは２５〜８０
モル％であるように仕込み、反応させることにより得ら
れる。In the present invention, reaction products that are particularly effective as coating agents for preventing scale adhesion are the compound (A) represented by the general formula N) and the aliphatic hydroxylamine compound (B).
(A) based on the total amount of (A) and (B)
The charging ratio is 15 to 90 mol%, preferably 25 to 80 mol%.
It is obtained by charging and reacting so that the amount is mol %.
前記した一般式（Ｉ）で表される化合物（Ａ）の仕込み
割合が１５モル％未満であると、得られる反応生成物の
アミノ基の数が相対的に増加するのでその強い重合禁止
効果のため、塗布剤が重合系内に溶出または残留すると
重合速度の遅延や重合体粒子の品質の低下などの悪影響
が生じる。また得られる反応生成物中の水酸基の数が減
少し塗膜の親水効果が低下することにより、塩化ビニル
などの単量体の一部が重合器の内壁面などに接触しやす
くなり、そこで重合反応が進行するためと考えられるが
、スケールが増加するので本発明の目的を達成すること
ができない。化合物（Ａ）の仕込み割合が９０モル％を
越えると塗膜の耐水性や重合禁止効果が低下し、スケー
ル防止の持続効果が低下するので好ましくない。すなわ
ち、一般式（Ｉ）で表される化合物（Ａ）および脂肪族
ヒドロキシルアミン系化合物（Ｂ）を特定の割合で反応
させることにより得られる反応生成物からなる塗布剤は
、塗膜の耐水性や親水効果、重合禁止効果などを調和的
に有するので、製品の品質の低下を招かずにスケール防
止効果およびその優れた持続効果を発揮するのである。If the charging ratio of the compound (A) represented by the above-mentioned general formula (I) is less than 15 mol%, the number of amino groups in the resulting reaction product will increase relatively, so that its strong polymerization inhibiting effect will be reduced. Therefore, if the coating agent dissolves or remains in the polymerization system, adverse effects such as a delay in the polymerization rate and a decrease in the quality of polymer particles occur. In addition, the number of hydroxyl groups in the resulting reaction product decreases and the hydrophilic effect of the coating film decreases, making it easier for some monomers such as vinyl chloride to come into contact with the inner wall surface of the polymerization vessel, where polymerization occurs. This is thought to be due to the progress of the reaction, but since the scale increases, the object of the present invention cannot be achieved. If the charging ratio of compound (A) exceeds 90 mol %, the water resistance and polymerization inhibiting effect of the coating film will decrease, and the sustained effect of preventing scale will decrease, which is not preferable. That is, a coating agent made of a reaction product obtained by reacting a compound (A) represented by general formula (I) and an aliphatic hydroxylamine compound (B) in a specific ratio can improve the water resistance of the coating film. Since it harmoniously has a hydrophilic effect, a polymerization inhibiting effect, etc., it exhibits a scale-preventing effect and an excellent long-lasting effect without deteriorating the quality of the product.
本発明による反応生成物の製造方法によれば、得られた
反応生成物の分子量および軟化点は、前記した二成分の
原料の種類、仕込みの割合、反応温度、反応時間、触媒
量などによって変化し、通常、分子量（ＧＰＣによる）
は約２５０〜２，０００、軟化点（ＪＩＳ Ｋ２５３
１ ニよル）ハ約４０〜２ｏ。According to the method for producing a reaction product according to the present invention, the molecular weight and softening point of the obtained reaction product vary depending on the types of the above-mentioned two component raw materials, the charging ratio, the reaction temperature, the reaction time, the amount of catalyst, etc. and usually the molecular weight (by GPC)
is approximately 250 to 2,000, softening point (JIS K253
1 Niyor) Ha about 40~2o.
℃の範囲である。℃ range.
このようにして得られる反応生成物は、通常、これを水
酸化ナトリウムなどアルカリ金属水酸化物の水溶液、ま
たはメタノール、アセトンなどの極性溶剤の溶液として
使用し、スプレーあるいはへヶ塗りなどの公知の方法で
重合器の内壁およびその他攪拌機、パンフル、リフラッ
クス・コンデンサーなど、単量体が接触する部分に塗膜
を形成させる。塗布量は従来の塗布剤を使用する場合と
同程度でよく、一般には固形分で０．００１〜２０ｇ
７ｍ ！、好ましくはＯ，１〜１０ ｇ／ｍ”である。The reaction product obtained in this way is usually used as an aqueous solution of an alkali metal hydroxide such as sodium hydroxide, or as a solution of a polar solvent such as methanol or acetone, and then subjected to known methods such as spraying or painting. This method forms a coating film on the inner wall of the polymerization vessel and other parts that come into contact with the monomer, such as the stirrer, panflux, and reflux condenser. The amount of application may be the same as when using conventional coating agents, and generally the solid content is 0.001 to 20 g.
7m! , preferably O, 1 to 10 g/m''.
また、必要に応じて塗布後の当該表面を加熱乾燥するこ
ともできるし、簡単な水洗を行ってもよい。Moreover, the surface after application can be heated and dried, or simply washed with water, if necessary.
このようにして、内部表面に塗布剤の塗膜を形成させた
重合器を用いて、塩化ビニル系重合体の製造が行われる
が、本発明の方法は、水性媒体中での重合、すなわち！
！！濁重合、乳化重合、微細懸濁重合に適用できる。In this way, a vinyl chloride polymer is produced using a polymerization vessel with a coating film formed on its internal surface, but the method of the present invention involves polymerization in an aqueous medium, that is!
! ! Applicable to turbidity polymerization, emulsion polymerization, and fine suspension polymerization.
本発明において塩化ビニル単量体と共重合し得る単量体
としては、例えば酢酸ビニルなどのアルキルビニルエス
テル、セチルビニルエーテルなどのアルキルビニルエー
テル、エチレンまたはプロピレンなどのα−モノオレフ
ィン類、アクリル酸メチル、メタクリル酸メチルなどの
アクリル類アルキルエステル類が例示されるが、これら
に限定されない。In the present invention, monomers that can be copolymerized with vinyl chloride monomers include, for example, alkyl vinyl esters such as vinyl acetate, alkyl vinyl ethers such as cetyl vinyl ether, α-monoolefins such as ethylene or propylene, methyl acrylate, Examples include, but are not limited to, acrylic alkyl esters such as methyl methacrylate.
また本発明において使用される懸濁剤、乳化剤、重合開
始剤は、通常の塩化ビニルの懸濁重合、乳化重合または
微細懸濁重合において使用されるものである。懸濁剤と
しては例えばポリビニルアルコール、ポリ酢酸ビニルの
部分ケン化物、メチルセルロース、ヒドロキシプロピル
メチルセルロースなどのセルロース誘導体、無水マレイ
ン酸−酢酸ビニル共重合体などの合成高分子物質等が例
示される。また、乳化剤としては、高級脂肪酸のソルビ
タンエステルまたはグリセリンエステル、およびこれら
のポリオキシエチレン付加物などのノニオン性界面活性
剤、ラウリル硫酸ナトリウム、ドデシルベンゼンスルフ
オン酸ナトリウムなどのアニオン性界面活性剤などが例
示される。重合開始剤としては例えばジー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、α−クミルパーオキシネオデ
カネート、ｔ−ブチルパーオキシビバレート、３．５．
５− トリメチルヘキサノイルパーオキサイドおよびア
セチルシクロへキシルスルフォニルパーオキサイドなど
のような有機過酸化物ならびにαα″αチービスイソブ
チロニトリルおよびα、α−アゾビスー２．４−ジメチ
ルバレロニトリルなどのアゾ化合物また、過硫酸アンモ
ニウム、過硫酸カリウム等の過硫酸塩や、キュメンハイ
ドロパーオキサイド、Ｌ−ブチルハイドロパーオキサイ
ド等のハイドロパーオキサイドと還元剤との組合せ等の
一種または二種以上の混合物が挙げられる。Further, the suspending agent, emulsifying agent, and polymerization initiator used in the present invention are those used in ordinary suspension polymerization, emulsion polymerization, or fine suspension polymerization of vinyl chloride. Examples of suspending agents include polyvinyl alcohol, partially saponified products of polyvinyl acetate, cellulose derivatives such as methylcellulose and hydroxypropylmethylcellulose, and synthetic polymer substances such as maleic anhydride-vinyl acetate copolymers. Examples of emulsifiers include sorbitan esters or glycerin esters of higher fatty acids, nonionic surfactants such as polyoxyethylene adducts thereof, and anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate. Illustrated. Examples of the polymerization initiator include di-2-ethylhexyl peroxydicarbonate, jetoxyethylperoxydicarbonate, α-cumylperoxyneodecanate, t-butylperoxybivalate, 3.5.
5- Organic peroxides such as trimethylhexanoyl peroxide and acetylcyclohexylsulfonyl peroxide and the like and azo compounds such as αα″αchibisisobutyronitrile and α,α-azobis-2,4-dimethylvaleronitrile. Other examples include persulfates such as ammonium persulfate and potassium persulfate, and combinations of hydroperoxides such as cumene hydroperoxide and L-butyl hydroperoxide with reducing agents, and the like, or mixtures of two or more thereof.
また、所望に応じてメルカプトアルカノール、チオグリ
コール酸アルキルエステルなどの連鎖移動剤、ケン化度
２０〜５５モル％のポリビニルアルコール類などの油溶
性懸濁助剤、ＰＨ調整剤および重合禁止剤などを使用す
ることもできる。重合は通常３５〜８０℃の温度で攪拌
下に行われ、各成分の仕込み量および仕込み部数などは
、従来塩化ビニル系の重合で行われている慣用の条件で
よく、特に限定されるものではない。If desired, chain transfer agents such as mercaptoalkanol and thioglycolic acid alkyl esters, oil-soluble suspension aids such as polyvinyl alcohols with a degree of saponification of 20 to 55 mol%, PH adjusters, polymerization inhibitors, etc. may be added. You can also use Polymerization is usually carried out at a temperature of 35 to 80°C with stirring, and the amount and number of parts of each component to be charged may be the same as those conventionally used for vinyl chloride polymerization, and are not particularly limited. do not have.
（発明の効果）
かくして、本発明によれば、従来技術に比較して、スケ
ールの付着防止を効果的に行えしかもその効果を長期間
持続できるという点において優れている。またスケール
除去作業に要する時間を大幅に削減できるのみならず、
スケールの付着による重合器の除熱能力の低下を防止で
きるので、高生産性下に塩化ビニル系重合体を製造する
ことができる。また、製品中へのスケールの混入によっ
て生成するフィッシュ・アイを低減することができ、粒
度、多孔性など製品の品質を悪化させることなくスケー
ルの付着を防止できるので、極めて有用である。(Effects of the Invention) Thus, the present invention is superior to the prior art in that scale adhesion can be effectively prevented and the effect can be maintained for a long period of time. In addition, not only can the time required for scale removal work be significantly reduced, but
Since it is possible to prevent the heat removal ability of the polymerization vessel from being reduced due to scale adhesion, vinyl chloride polymers can be produced with high productivity. In addition, it is extremely useful because it can reduce fish eyes that are generated due to the mixing of scale into the product, and it can prevent scale adhesion without deteriorating the quality of the product such as particle size or porosity.
（実施例）
以下に実施例を挙げて本発明をさらに具体的に説明する
。なお、実施例、比較例中の部及び％はとくに断りのな
いかぎり重量基準である。また、各実施例で示した塩化
ビニル系重量体のフィンシュ・アイは次の方法により測
定した。(Example) The present invention will be described in more detail with reference to Examples below. Note that parts and percentages in Examples and Comparative Examples are based on weight unless otherwise specified. Further, the Finnish eye of the vinyl chloride heavy body shown in each example was measured by the following method.
塩化ビニル系重合体１００ｇにジオクチルフタレート４
５ｇ、ステアリン酸カドミウム２ｇ、ステアリン酸バリ
ウム１ｇ１およびグリーントナー１ｇを加えて混合した
後、１４５°Ｃの６インチロールで６分間混練して厚さ
０．４． ｗのシートに引出し、そのシートの表面１０
０ｄ中に観察される透明粒子の数をもって示した。Dioctyl phthalate 4 to 100g of vinyl chloride polymer
After adding and mixing 5 g of cadmium stearate, 1 g of barium stearate, and 1 g of green toner, the mixture was kneaded for 6 minutes with a 6-inch roll at 145°C to a thickness of 0.4. Draw out to the sheet w, and the surface 10 of the sheet
It is indicated by the number of transparent particles observed in 0d.
（比較例１）
内容積９５０１のステンレス製重合器を脱気し、脱イオ
ン水３５０ｋｇ、塩化ビニル単量体２５０ｋｇ、部分ケ
ン化ポリビニルアルコール１４０ ｇ、ジー２−エチル
へキシルパーオキシジカーボネート３０ｇおよびｔ−ブ
チルパーオキシビバレート５０’ｇを仕込んで６２°Ｃ
で５時間、塩化ビニルの重合をおこなった。(Comparative Example 1) A stainless steel polymerization vessel with an internal volume of 9501 kg was degassed, and 350 kg of deionized water, 250 kg of vinyl chloride monomer, 140 g of partially saponified polyvinyl alcohol, 30 g of di-2-ethylhexyl peroxydicarbonate, and Charge 50g of t-butyl peroxyvivalate and heat to 62°C.
Polymerization of vinyl chloride was carried out for 5 hours.
重合終了後、重合器に付着したスケールの重量を測定し
た結果、スケールは液相部で１５ｇ／ｍ”、気相部で１
０ｇ／ｍ”であった。After the polymerization was completed, the weight of the scale attached to the polymerization vessel was measured, and the scale was found to be 15 g/m" in the liquid phase and 1 g/m in the gas phase.
0g/m''.
（比較例２）
４．４゛−スルフォニルジフェノールを０．５％水酸化
ナトリウム水溶液に溶解し、純分濃度０．７５％の塗布
液を調整した後、この塗布液を内容積９５０１のステン
レス製重合器の内壁に２ｇ／ｍｔの塗布量（純分換算、
以下同じ）となるように塗布し、８０°Ｃで１０分間乾
燥した０次いで比較例１と同様の操作で塩化ビニルの重
合を行った。(Comparative Example 2) After dissolving 4.4'-sulfonyldiphenol in a 0.5% aqueous sodium hydroxide solution and preparing a coating solution with a pure concentration of 0.75%, this coating solution was applied to a stainless steel plate with an internal volume of 9501. A coating amount of 2 g/mt (purity equivalent) was applied to the inner wall of the polymerization vessel.
The same applies below) and dried at 80° C. for 10 minutes. Then, vinyl chloride was polymerized in the same manner as in Comparative Example 1.
重合終了後、重合器に付着したスケールの厚みを測定し
た結果、スケールは液相部で９ｇ／ｌ１１２、気相部で
１ｇ７ｍ”であった。After the polymerization was completed, the thickness of the scale adhering to the polymerization vessel was measured, and the scale was found to be 9 g/l112 in the liquid phase and 1 g/7 m'' in the gas phase.
（比較例３）
Ｎ、Ｎ−ジエチルヒドロキシアミンを０．５％水酸化ナ
トリウム水溶液に溶解し、純分濃度０．７５％の塗布液
を調整した後、この塗布液を内容積９５０２のステンレ
ス製重合器の内壁に２ｇ／ｌ１１２の塗布量となるよう
に塗布し、８０°Ｃで１０分間乾燥した。次いで比較例
１と同様の操作で塩化ビニルの重合を行った。(Comparative Example 3) After dissolving N,N-diethylhydroxyamine in a 0.5% aqueous sodium hydroxide solution and preparing a coating liquid with a pure concentration of 0.75%, this coating liquid was applied to a stainless steel plate with an internal volume of 9502 mm. It was applied to the inner wall of the polymerization vessel in an amount of 2 g/l112, and dried at 80°C for 10 minutes. Next, vinyl chloride was polymerized in the same manner as in Comparative Example 1.
重合終了後、重合器に付着したスケールの重量を測定し
た結果、スケールは液相部で１３ｇ１０＋”、気相部で
Ｌｏｇ／ｍ２であった。After the polymerization was completed, the weight of the scale attached to the polymerization vessel was measured, and the scale was found to be 13 g10+'' in the liquid phase and Log/m2 in the gas phase.
（実施例１）
四ロフラスコに一般式（Ｉ）で表される化合物（Ａ）と
して４，４゛−スルフォニルジフェノール５２、５ ｇ
、および脂肪族ヒドロキシルアミン系化合物（Ｂ）とし
てＮ、Ｎ−ジエチルヒドロキシルアミン０．０９ ｇに
水５００ｇを加え溶解したのちに、塩化第二鉄０．２５
ｇを加え、１００℃で４時間反応を行った。反応終了
後室温まで冷却し上澄み液を分離したのち水５００ｇを
添加して水洗脱水後、２０ｍｍＨｇの減圧下に８０℃で
５時間乾燥を行った。その結果、黒褐色の樹脂状の反応
生成物が得られた。(Example 1) 52.5 g of 4,4'-sulfonyldiphenol as compound (A) represented by general formula (I) was placed in a four-hole flask.
, and as the aliphatic hydroxylamine compound (B), 500 g of water was added to 0.09 g of N,N-diethylhydroxylamine and dissolved, and then 0.25 g of ferric chloride was added.
g was added thereto, and the reaction was carried out at 100°C for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, the supernatant liquid was separated, and 500 g of water was added to wash and dehydrate, followed by drying at 80° C. under a reduced pressure of 20 mmHg for 5 hours. As a result, a blackish brown resinous reaction product was obtained.
この反応生成物を用い比較例２と同様の方法で塗布液を
調整し、内容積９５０１のステンレス製重合器の内壁面
に塗布し、塗布面に脱イオン水を流下し、洗浄した０次
いで比較例１と同様の操作で塩化ビニルの重合を行った
。その結果、スケールは液相部でＩｇ／が、気相部で皆
無であった。Using this reaction product, a coating solution was prepared in the same manner as in Comparative Example 2, and it was coated on the inner wall surface of a stainless steel polymerization vessel with an internal volume of 9,501 mm, and deionized water was poured onto the coated surface to wash it. Polymerization of vinyl chloride was carried out in the same manner as in Example 1. As a result, there was no scale of Ig/ in the liquid phase, but there was no scale in the gas phase.
（実施例２）
化合物（Ａ）として４．４°−チオビス（２−を−ブチ
ル−６−メチルフェノール）４５．０ｇ、および化合物
（Ｂ）としてＮ、Ｎ−ジエチルヒドロキシルアミンｏ、
ｏ ｓ ｇを用いた以外は実施例１と同様の方法で反
応を行ったところ、象牙色の樹脂状の反応生成物が得ら
れた。(Example 2) 45.0 g of 4.4°-thiobis(2-butyl-6-methylphenol) as compound (A), and N,N-diethylhydroxylamine o as compound (B),
When the reaction was carried out in the same manner as in Example 1 except that o s g was used, an ivory resinous reaction product was obtained.
二の反応生成物を用い比較例２と同様の方法で塗布液を
調整し、内容積９５０２のステンレス製重合器の内壁面
に塗布し、脱イオン水を流下し、洗浄した。次いで比較
例１と同様の操作で塩化ビニルの重合を行った。その結
果、スケールは液相部で３ ｇ／ｗ＋”、気相部でＩ
ｇ／ｍ”であった。A coating liquid was prepared in the same manner as in Comparative Example 2 using the reaction product of No. 2, and applied to the inner wall surface of a stainless steel polymerization vessel having an internal volume of 9502 mm, followed by washing with deionized water. Next, vinyl chloride was polymerized in the same manner as in Comparative Example 1. As a result, the scale was 3 g/w+” in the liquid phase and I in the gas phase.
g/m”.
（実施例３）
化合物（Ａ）として３．３’ 、５．５’−テトラメチ
ル−４，４”−ジヒドロキシジフェニルスルフォン５２
．５ｇ、および化合物（Ｂ）としてＮ、Ｎ−ジエチルヒ
ドロキシルアミン１５．３ｇを用いた以外は実施例１と
同様の方法で反応を行ったところ、黒紫色の樹脂状の反
応生成物が得られた。(Example 3) 3.3′,5.5′-tetramethyl-4,4”-dihydroxydiphenylsulfone 52 as compound (A)
．． When the reaction was carried out in the same manner as in Example 1 except that 5 g and 15.3 g of N,N-diethylhydroxylamine were used as compound (B), a black-purple resinous reaction product was obtained. .
この反応生成物を用い比較例２と同様の方法で塗布液を
調整し、内容積９５０１のステンレス製重合器の内壁面
に塗布し、８０゛Ｃで１０分間乾燥した。次いで比較例
１と同様の操作で塩化ビニルの重合を行った。その結果
、スケールは液相部で２ ｇ／ｍ２、気相部で１ｇ７ｍ
２であった。Using this reaction product, a coating solution was prepared in the same manner as in Comparative Example 2, and it was coated on the inner wall of a stainless steel polymerization vessel having an internal volume of 9,501 liters, and dried at 80°C for 10 minutes. Next, vinyl chloride was polymerized in the same manner as in Comparative Example 1. As a result, the scale was 2 g/m2 in the liquid phase and 1 g/m2 in the gas phase.
It was 2.
（実施例４）
化合物（Ａ）として２．２′−チオビス（６−ｔ−ブチ
ル−４−メチルフェノール）４４．５ｇ、および化合物
（Ｂ）としてＮ、 Ｎ−ジエチルヒドロキシルアミン９
．５４ ｇを用いた以外は実施例１と同様の方法で反応
を行ったところ、黒紫色の樹脂状の反応生成物が得られ
た。(Example 4) 44.5 g of 2,2'-thiobis(6-t-butyl-4-methylphenol) as compound (A) and 9 N, N-diethylhydroxylamine as compound (B)
．． When the reaction was carried out in the same manner as in Example 1 except that 54 g was used, a black-purple resinous reaction product was obtained.
この反応生成物を用い比較例２と同様の方法で塗布液を
調整し、内容積９５０ｊ！のステンレス製重合器の内壁
面に塗布し、脱イオン水を流下し、洗浄した。次いで比
較例１と同様の操作で塩化ビニルの重合を行った。その
結果、スケールは液相部で５ｇ／ｌ１１２、気相部で２
ｇ／ｍ”であった。Using this reaction product, a coating solution was prepared in the same manner as in Comparative Example 2, and the internal volume was 950j! It was applied to the inner wall of a stainless steel polymerization vessel and washed with deionized water. Next, vinyl chloride was polymerized in the same manner as in Comparative Example 1. As a result, the scale was 5 g/l112 in the liquid phase and 2 g/l in the gas phase.
g/m”.
以上の結果から明らかであるように、本発明の方法によ
ればスケール防止効果が顕著であることがわかる。As is clear from the above results, it can be seen that the method of the present invention has a remarkable scale prevention effect.
（比較例４）
内容積３５ＩＩｌｆｆのステンレス製重合器を脱気し脱
イオン水１６トンを仕込んだのち、塩化ビニル単量体１
３．５１−ン、部分ケン化ポリビニルアルコール７．５
ｋｇ、ジー２−エチルヘキシルパーオキシジカーボネー
ト３．５ ｋｇを同時に仕込み、５７．５°Ｃの温度で
８時間塩化ビニルの重合を行った。重合が終了し内容物
を排出した後、重合器内を２００４２／ｍｉｎ 、２５
０ ｋｇ／ａｄの高圧水で１５分間洗浄し、以下同様の
操作で重合を繰り返し行った。(Comparative Example 4) After degassing a stainless steel polymerization vessel with an internal volume of 35 IIlff and charging 16 tons of deionized water, 1 ton of vinyl chloride monomer was added.
3.51-ton, partially saponified polyvinyl alcohol 7.5
kg, and 3.5 kg of di-2-ethylhexyl peroxydicarbonate were charged at the same time, and vinyl chloride was polymerized at a temperature of 57.5°C for 8 hours. After polymerization is completed and the contents are discharged, the inside of the polymerization vessel is heated at 20,042/min, 25
After washing with high pressure water of 0 kg/ad for 15 minutes, polymerization was repeated in the same manner.
このようにして行った重合バッチ数と重合器ジャケット
の総括伝熱係数および得られた重合体粒子のフィッシュ
・アイは、第１表に示すとおりであった。The number of polymerization batches thus carried out, the overall heat transfer coefficient of the polymerization vessel jacket, and the fish eye of the obtained polymer particles were as shown in Table 1.
（比較例５）
内容積３５ｍ’のステンレス製重合器の内壁およびその
他単量体が接触する部分に比較例２で得られた塗布液を
噴霧器で０．５ｇ／ｍ”の塗布量になるように塗布し、
さらに脱イオン水で塗布面を洗浄し、洗浄水を重合系外
に排出した。(Comparative Example 5) The coating solution obtained in Comparative Example 2 was applied to the inner wall of a stainless steel polymerization vessel with an internal volume of 35 m' and other parts that would come into contact with the monomer using a sprayer so that the amount of coating was 0.5 g/m'. Apply to
Furthermore, the coated surface was washed with deionized water, and the washing water was discharged out of the polymerization system.
次いで、比較例４と同様の操作で塩化ビニルの重合を行
い、重合が終了し内容物を排出した後、重合器内を２０
０ ｆ１０＋ｉｎ 、２５０ｋｇ／ｃ１ｉの高圧水で１
５分間洗浄した。再び重合器の内壁に塗布液を塗布し、
以下同様の操作で塩化ビニルの重合を繰り返し行った。Next, vinyl chloride was polymerized in the same manner as in Comparative Example 4. After the polymerization was completed and the contents were discharged, the inside of the polymerization vessel was heated to 20
0 f10+in, 1 with high pressure water of 250 kg/c1i
Washed for 5 minutes. Apply the coating liquid to the inner wall of the polymerization vessel again,
Polymerization of vinyl chloride was then repeated in the same manner.
このようにして行った重合パンチ数と重合器ジャケット
の総括伝熱係数および得られた重合体粒子のフィッシュ
・アイは、第１表に示すとおりであった。The number of polymerization punches thus carried out, the overall heat transfer coefficient of the polymerizer jacket, and the fish eye of the obtained polymer particles were as shown in Table 1.
（実施例５）
実施例１で得られた塗布液を用いた以外は比較例５と同
様の操作で塩化ビニルの重合を繰り返し行った。(Example 5) Polymerization of vinyl chloride was repeated in the same manner as in Comparative Example 5 except that the coating liquid obtained in Example 1 was used.
このようにして行った重合バッチ数と重合器ジャケット
の総括伝熱係数および得られた重合体粒子のフィッシュ
・アイは、第１表に示すとおりであった。The number of polymerization batches thus carried out, the overall heat transfer coefficient of the polymerization vessel jacket, and the fish eye of the obtained polymer particles were as shown in Table 1.
（実施例６）
実施例２で得られた塗布液を用いた以外は比較例５と同
様の操作で塩化ビニルの重合を繰り返し行った。(Example 6) Polymerization of vinyl chloride was repeated in the same manner as in Comparative Example 5 except that the coating liquid obtained in Example 2 was used.
このようにして行った重合バッチ数と重合器ジャケット
の総括伝熱係数および得られた重合体粒子のフィッシュ
・アイは、第１表に示すとおりであった。The number of polymerization batches thus carried out, the overall heat transfer coefficient of the polymerization vessel jacket, and the fish eye of the obtained polymer particles were as shown in Table 1.
第１表より、本発明の方法によれば、繰り返し重合を行
っても長期間にわたって重合器ジャケットの除熱能力を
維持することができ、またフィッシュ・アイが増加する
こともないので高能率で高品質の製品を製造することが
できる。Table 1 shows that according to the method of the present invention, the heat removal ability of the polymerization vessel jacket can be maintained for a long period of time even if polymerization is repeated, and the number of fish eyes does not increase, resulting in high efficiency. Able to manufacture high quality products.
Claims (1)
ニルと共重合し得る単量体との混合物を水性媒体中で重
合するに際し、一般式（ I ）で表される化合物（Ａ）
と脂肪族ヒドロキシルアミン系化合物（Ｂ）を反応させ
て得られる反応生成物を、予め重合器の内壁およびその
他単量体が接触する部分に塗布することを特徴とする塩
化ビニル系重合体の製造法。 一般式（ I ）： ▲数式、化学式、表等があります▼ 〔式中、Ｒ＾１は−Ｓ−、−ＳＯ−または−ＳＯ＿２−
を表わし、Ｒ＾２およびＲ＾３は−Ｈ、−ＯＨ、ハロゲ
ンまたは炭素原子１〜４個の炭化水素基を表わす。〕[Claims] When a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable with vinyl chloride is polymerized in an aqueous medium, a compound represented by the general formula (I) (A)
and an aliphatic hydroxylamine compound (B), and a reaction product obtained by the reaction is applied in advance to the inner wall of a polymerization vessel and other parts that come into contact with the monomer. Law. General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 is -S-, -SO- or -SO_2-
and R^2 and R^3 represent -H, -OH, halogen or a hydrocarbon group having 1 to 4 carbon atoms. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27956189A JP2821697B2 (en) | 1989-10-26 | 1989-10-26 | Method for producing vinyl chloride polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27956189A JP2821697B2 (en) | 1989-10-26 | 1989-10-26 | Method for producing vinyl chloride polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03140301A true JPH03140301A (en) | 1991-06-14 |
| JP2821697B2 JP2821697B2 (en) | 1998-11-05 |
Family
ID=17612691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27956189A Expired - Lifetime JP2821697B2 (en) | 1989-10-26 | 1989-10-26 | Method for producing vinyl chloride polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2821697B2 (en) |
-
1989
- 1989-10-26 JP JP27956189A patent/JP2821697B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2821697B2 (en) | 1998-11-05 |
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