KR20120130412A - Method of preparing vinyl chloride polymer having excellent polymerization productivity - Google Patents
Method of preparing vinyl chloride polymer having excellent polymerization productivity Download PDFInfo
- Publication number
- KR20120130412A KR20120130412A KR1020110048319A KR20110048319A KR20120130412A KR 20120130412 A KR20120130412 A KR 20120130412A KR 1020110048319 A KR1020110048319 A KR 1020110048319A KR 20110048319 A KR20110048319 A KR 20110048319A KR 20120130412 A KR20120130412 A KR 20120130412A
- Authority
- KR
- South Korea
- Prior art keywords
- polymerization
- vinyl chloride
- chloride monomer
- weight
- added
- 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
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 200
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 118
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 20
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 19
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 17
- 230000000977 initiatory effect Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 78
- 239000011347 resin Substances 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 39
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 230000036571 hydration Effects 0.000 claims description 16
- 238000006703 hydration reaction Methods 0.000 claims description 16
- 239000000084 colloidal system Substances 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 13
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- -1 3-imidazoline nitroxide Chemical class 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 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 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 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 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 229960001295 tocopherol Drugs 0.000 claims description 2
- 229930003799 tocopherol Natural products 0.000 claims description 2
- 235000010384 tocopherol Nutrition 0.000 claims description 2
- 239000011732 tocopherol Substances 0.000 claims description 2
- 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 claims description 2
- SADSVWMAICPJTD-UHFFFAOYSA-N (3,5-ditert-butyl-5-hydroxycyclohexa-1,3-dien-1-yl) propanoate Chemical compound C(CC)(=O)OC=1CC(C=C(C=1)C(C)(C)C)(C(C)(C)C)O SADSVWMAICPJTD-UHFFFAOYSA-N 0.000 claims 1
- GWKCSEMZDKMXAM-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-(12-sulfanyldodecoxy)piperidin-4-ol Chemical compound OC1CC(N(C(C1)(C)C)OCCCCCCCCCCCCS)(C)C GWKCSEMZDKMXAM-UHFFFAOYSA-N 0.000 claims 1
- HYTJADYUOGDVRL-UHFFFAOYSA-N n-phenyl-n-(2-phenylpropan-2-yl)aniline Chemical compound C=1C=CC=CC=1C(C)(C)N(C=1C=CC=CC=1)C1=CC=CC=C1 HYTJADYUOGDVRL-UHFFFAOYSA-N 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 35
- 230000001965 increasing effect Effects 0.000 description 14
- 239000003999 initiator Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000004040 coloring Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 235000015041 whisky Nutrition 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 3
- 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 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ZKEUVTROUPQVTM-UHFFFAOYSA-N 1-pentylperoxypentane Chemical compound CCCCCOOCCCCC ZKEUVTROUPQVTM-UHFFFAOYSA-N 0.000 description 1
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 1
- CRJIYMRJTJWVLU-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 3-(5,5-dimethylhexyl)dioxirane-3-carboxylate Chemical compound CC(C)(C)CCCCC1(C(=O)OC(C)(C)CC(C)(C)C)OO1 CRJIYMRJTJWVLU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OQMMZBPPTJEAFF-UHFFFAOYSA-N 2-methylidenebutanedioic acid;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OC(=O)CC(=C)C(O)=O OQMMZBPPTJEAFF-UHFFFAOYSA-N 0.000 description 1
- WFAUFYAGXAXBEG-UHFFFAOYSA-N 2-phenylpropan-2-yl 4,4-dimethylpentaneperoxoate Chemical compound CC(C)(C)CCC(=O)OOC(C)(C)C1=CC=CC=C1 WFAUFYAGXAXBEG-UHFFFAOYSA-N 0.000 description 1
- BVCOHOSEBKQIQD-UHFFFAOYSA-N 2-tert-butyl-6-methoxyphenol Chemical compound COC1=CC=CC(C(C)(C)C)=C1O BVCOHOSEBKQIQD-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKUCMXJFDKFPSH-UHFFFAOYSA-N C(CC)(=O)OC1=CC(=C(C(=C1)C)O)C(C)(C)C.C(COCCOCCO)O Chemical compound C(CC)(=O)OC1=CC(=C(C(=C1)C)O)C(C)(C)C.C(COCCOCCO)O WKUCMXJFDKFPSH-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
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 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
- 239000008346 aqueous phase Substances 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
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 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
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical class CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- ZLAJWQIJAVXCAT-UHFFFAOYSA-N pentyl 7,7-dimethyloctaneperoxoate Chemical compound CCCCCOOC(=O)CCCCCC(C)(C)C ZLAJWQIJAVXCAT-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 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
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical class CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 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
- 239000000700 radioactive tracer Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- VNJISVYSDHJQFR-UHFFFAOYSA-N tert-butyl 4,4-dimethylpentaneperoxoate Chemical compound CC(C)(C)CCC(=O)OOC(C)(C)C VNJISVYSDHJQFR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
본 발명은 염화비닐 중합체를 제조하는 회분식 현탁중합 공정에서 고온 중합수를 사용하여 중합 개시 온도를 조절하고 여기에 중합개시제를 투여함으로써 중합 반응을 개시할 뿐 아니라 초기 중합계 내 염화비닐계 단량체의 농도를 제어함으로써 중합반응 속도 조절을 통해 중합 생산성이 우수할 뿐만 아니라 안정적인 품질 확보가 가능한 염화비닐계 중합체를 제조할 수 있다.The present invention not only initiates the polymerization reaction by controlling the polymerization initiation temperature using high temperature polymerization water and administering the polymerization initiator thereto in a batch suspension polymerization process for producing a vinyl chloride polymer, but also provides a concentration of the vinyl chloride monomer in the initial polymerization system. By controlling the polyvinyl chloride polymer can be produced not only excellent polymerization productivity by controlling the polymerization reaction rate but also stable quality.
Description
본 발명은 중합 생산성이 우수한 염화비닐계 중합체의 제조방법에 관한 것으로서, 보다 상세하게는 보호콜로이드 조제 및 중합 개시제 존재 하에 염화비닐계 단량체를 70 내지 100℃의 고온 중합수를 사용하여 중합시키되, 염화비닐계 단량체를 중합 초기에 전체 염화비닐계 단량체 투입량의 50 내지 80중량%를 투입하고, 중합전환율 12 내지 18%일 때 나머지 염화비닐계 단량체를 투입하고 중합전환율 27 내지 33%일 때 완료함으로써 중합생산성이 우수하며, 휘시아이 및 초기 착색성의 품질이 안정적인 염화비닐 중합체를 제조하는 제조방법에 관한 것이다.The present invention relates to a method for preparing a vinyl chloride polymer having excellent polymerization productivity, and more particularly, to polymerize a vinyl chloride monomer using high temperature polymerization water of 70 to 100 ° C. in the presence of a protective colloid preparation and a polymerization initiator. 50 to 80% by weight of the total amount of vinyl chloride monomer is charged at the initial stage of polymerization, and the remaining vinyl chloride monomer is added when the polymerization conversion rate is 12 to 18%, and the polymerization is completed when the polymerization conversion rate is 27 to 33%. It is related with the manufacturing method which manufactures the vinyl chloride polymer which is excellent in productivity and is stable in quality of whiskey and initial coloring property.
염화비닐계 중합체는 가격이 저렴하면서도, 품질 밸런스가 우수하여 여러 가지 광범위한 분야에서 이용되고 있다.The vinyl chloride polymer is inexpensive and has excellent quality balance and is used in various fields.
염화비닐계 중합체는 크게 페이스트 수지와 스트레이트 수지로 나누어진다. 이 중 페이스트 수지는 유화중합방법으로 제조되는데, 단량체, 물, 계면활성제 등을 균질화 장치를 사용하여 균질화 시킨 후, 중합장치로 옮겨 중합시키며 벽지, 장판 등에 사용된다. 스트레이트 수지는 파이프, 필름, 창틀 등의 경질 분야와 전신 피복, 랩 필름, 시트 등의 연질 분야의 여러 가지 광범위한 분야에서 이용되고 있다.The vinyl chloride polymer is mainly divided into a paste resin and a straight resin. The paste resin is produced by an emulsion polymerization method. The monomer, water, surfactant and the like are homogenized using a homogenizer, and then transferred to a polymerization apparatus to be polymerized. Straight resins are used in various fields such as rigid fields such as pipes, films, window frames, and soft fields such as general-purpose coatings, wrap films, and sheets.
일반적으로 염화비닐계 중합체의 제조비용을 감소시키기 위해서는 반응의 단위 부피당 중합 생산성을 향상시키는 것이 중요하다.Generally, it is important to improve the polymerization productivity per unit volume of the reaction in order to reduce the production cost of the vinyl chloride-based polymer.
이러한 중합 생산성을 향상시키는 방법으로는 중합반응 시간은 일정하고 중합전환율을 증가시켜 한 배치(batch)당 산출량을 증가시키는 방법이 있으며, 다른 방법으로는 중합반응시간을 단축시켜 단위 시간 동안 많은 양을 생산하는 방법이 있다. 그러나 종래 알려져 있는 염화비닐 수지의 제조방법으로는 중합 생산성이 우수하지만, 안정적인 품질 확보에는 불충분한 문제점이 있다.As a method of improving the polymerization productivity, the polymerization reaction time is constant and the polymerization conversion rate is increased to increase the output per batch. In another method, the polymerization reaction time is shortened so that a large amount of the reaction time is increased. There is a way to produce. However, although the polymerization productivity is excellent in the manufacturing method of the conventionally known vinyl chloride resin, there exists an inadequate problem in ensuring stable quality.
일례로 악조노벨사의 미국특허공개 제2005-0080207호는 중합반응기의 내부 압력이 저하되는 시점에 개시제를 추가로 투입함으로써 중합전환율을 증가시키는 방법에 대하여 기술하고 있다. 그러나 상기의 방법에 의해 수득되는 염화비닐계 수지는 중합전환율이 다소 증가하였으나, 중합반응기 내부의 압력이 저하되는 시점이 중합전환율이 70% 이상인 지점이므로 이 시점에서 투입된 개시제에 의한 전환율 향상 효과는 극히 미미하며, 또한 이 때 투입된 개시제가 염화비닐 단량체와 충분히 반응하지 못하여 휘시아이(fish-eye)가 증가하거나 미세입자가 증가하여 초기 착색성이 저하되는 문제점이 있다.As an example, US Patent Publication No. 2005-0080207 to Akzo Novel describes a method of increasing the polymerization conversion rate by additionally adding an initiator at the time when the internal pressure of the polymerization reactor is lowered. However, the polyvinyl chloride resin obtained by the above method slightly increased the polymerization conversion rate. However, since the polymerization conversion rate is 70% or more when the pressure inside the polymerization reactor decreases, the effect of improving the conversion rate by the initiator added at this point is extremely low. In addition, there is a problem in that the initiator is not sufficiently reacted with the vinyl chloride monomer at this time to increase the fish-eye or increase the fine particles to reduce the initial colorability.
또한, 시네츠사의 일본특허공개 제1998-338701호는 유용성 개시제와 수용성 개시제를 중합 초기 병용 사용하여 중합 반응 시간을 단축시키는 방법을 기술하고 있다. 그러나 상기의 방법에 의한 반응 시간 단축 효과는 어느 정도 기대할 수 있지만, 염화비닐계 중합체 제조시, 염화비닐 단량체는 유용성의 성질을 지닌 물질이므로 중합 초기에는 염화비닐 단량체와 중합수인 탈이온수와 대부분 상분리된 상태로 존재하다가 중합 반응이 진행되어 중합전환율 60% 이상인 중합 후기에는 중합체로 전환되지 않은 미반응 염화비닐 단량체의 대부분이 수상에 녹아 존재하므로, 반응 초기에 유용성 개시제와 함께 사용된 수용성 개시제에 의한 반응 시간 단축 효과는 크게 나타나지 않을 뿐만 아니라, 중합 반응 초기에는 수용성 개시제에 의해 생성된 미세 입자가 반응기 내벽에 달라붙어 스케일 생성의 원인이 될 수 있다.Moreover, Japanese Patent Publication No. 1998-338701 to Shinnetz Co., Ltd. discloses a method for shortening the polymerization reaction time by using an oil-soluble initiator and a water-soluble initiator in the initial stage of polymerization. However, although the reaction time shortening effect by the above method can be expected to some extent, in the production of vinyl chloride polymer, the vinyl chloride monomer is a substance having useful properties, so in the initial stage of polymerization, most phase separation from vinyl chloride monomer and deionized water, which is polymerized water, is performed. In the late stage of the polymerization in which the polymerization reaction proceeds and the polymerization conversion is 60% or more, most of the unreacted vinyl chloride monomer which is not converted to the polymer is dissolved in the aqueous phase. Not only does not shorten the reaction time effect, but also at the beginning of the polymerization reaction, the fine particles generated by the water-soluble initiator may stick to the inner wall of the reactor, causing scale generation.
또한, 미쓰비시사의 일본특허등록 제3555301호에서는 반응 초기에 일정 중합온도를 유지시키다가 일정 시점 이후, 중합 온도를 높여 가공성을 높이고자 하였으나, 반응 초기 너무 빨리 반응 온도 변화에 따라 중합 안정성 저하에 따른 휘시아이 증가 또는 초기 착색성 저하의 문제점이 있었다.In addition, Mitsubishi's Japanese Patent Registration No. 35305301 maintains a constant polymerization temperature at the beginning of the reaction, but after a certain point, it tries to increase the workability by increasing the polymerization temperature. There was a problem of increased eye or lowered initial pigmentation.
상술한 바와 같은 종래 기술의 문제점을 해결하기 위한 본 발명의 목적은 보호 콜로이드 조제 및 중합 개시제 존재 하에 염화비닐 단량체를 현탁 중합시켜 염화비닐계 중합체를 제조하는 방법으로서, 중합 생산성이 우수할 뿐만 아니라 휘시아이 및 초기 착색성 등의 안정적인 품질 확보가 가능한 염화비닐계 중합체의 제조방법을 제공하기 위한 것이다.It is an object of the present invention to solve the problems of the prior art as described above, and it is an object of the present invention to provide a method for producing a vinyl chloride polymer by suspension polymerization of a vinyl chloride monomer in the presence of a protective colloid assistant and a polymerization initiator, And a process for producing a vinyl chloride-based polymer capable of securing a stable quality such as initial coloring property.
본 발명의 상기 목적 및 기타 목적들은 하기 설명된 본 발명에 의하여 모두 달성될 수 있다.These and other objects of the present invention can be achieved by the present invention described below.
상기의 목적을 달성하기 위하여, 본 발명은 현탁중합에 의한 염화비닐계 수지의 제조방법에 있어서, 상기 현탁중합은 염화비닐계 단량체를 70 내지 100℃의 고온 중합수를 사용하여 중합시키되, 염화비닐계 단량체를 중합 초기에 전체 염화비닐계 단량체 투입량의 50 내지 80중량%를 투입하고, 중합전환율이 15 내지 30%일 때 나머지 20 내지 50중량%의 염화비닐계 단량체를 투입 개시 및 완료하고 일정 압력에 도달한 시점에 반응 종결제를 투입하는 것을 특징으로 하는 염화비닐계 중합체의 제조방법을 제공한다.In order to achieve the above object, the present invention is a method for producing a vinyl chloride-based resin by suspension polymerization, the suspension polymerization is a vinyl chloride-based monomer polymerized using high temperature polymerization water of 70 to 100 ℃, vinyl chloride 50 to 80% by weight of the total amount of the vinyl chloride monomer is charged at the initial stage of the polymerization, and when the polymerization conversion rate is 15 to 30%, the remaining 20 to 50% by weight of the vinyl chloride monomer is started and completed. Provided is a method for producing a vinyl chloride polymer, characterized in that the reaction terminator is added at the point of reaching.
상기에서 살펴본 바와 같이, 본 발명의 염화비닐계 중합체의 현탁 중합 방법에 따르면, 중합 생산성이 우수하면서 휘시아이 및 초기 착색성 등의 품질이 우수한 고품질의 염화비닐계 중합체의 제조방법을 제공할 수 있다.As described above, according to the suspension polymerization method of the vinyl chloride polymer of the present invention, it is possible to provide a method for producing a high-quality vinyl chloride polymer having excellent polymerization productivity and excellent quality such as fish eye and initial coloring property.
이에 본 발명자들은 상술한 바와 같은 종래 기술의 문제점을 해결하기 위하여 연구를 계속하던 중, 중합 개시온도와 단량체의 농도를 제어하면 상술한 문제점을 해결하고 중합 생산성이 우수할 뿐만 아니라 안정적인 품질 확보가 가능한 것을 확인하고 본 발명을 완성하기에 이르렀다.Therefore, the inventors of the present invention continue to solve the problems of the prior art as described above, by controlling the polymerization initiation temperature and the concentration of the monomer solves the above problems and can ensure a stable quality as well as excellent polymerization productivity It was confirmed that the present invention was completed.
즉, 본 발명은 보호 콜로이드 조제 및 중합 개시제 존재 하에 염화비닐 단량체를 현탁 중합시켜 염화비닐계 중합체를 제조하는 방법으로서, 초기 투입 염화비닐 단량체의 비율을 조절하여 염화비닐 단량체를 연속 추가 투입하는 단계를 포함하여 중합반응 속도 조절을 통해 중합 생산성이 우수할 뿐 아니라 안정적인 품질 확보가 가능한 염화비닐계 중합체의 제조방법을 제공한다.
That is, the present invention provides a process for producing a vinyl chloride polymer by suspension polymerization of a vinyl chloride monomer in the presence of a protective colloid assistant and a polymerization initiator, comprising the steps of continuously adding vinyl chloride monomer by controlling the ratio of the initial vinyl chloride monomer The present invention also provides a method for producing a vinyl chloride-based polymer capable of securing a stable quality as well as excellent polymerization productivity through the control of the polymerization reaction rate.
이하 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 염화비닐계 중합체 중 스트레이트 수지에 대한 것으로, 상기 페이스트 수지와는 달리 현탁중합 방법에 의해 제조된다.The present invention relates to a straight resin in a vinyl chloride polymer, which is produced by a suspension polymerization method, unlike the paste resin.
본 발명에 의한 염화비닐계 중합체의 제조방법은 현탁중합에 의한 염화비닐계 수지의 제조방법에 있어서, 상기 현탁중합은 염화비닐계 단량체를 70 내지 100℃의 고온 중합수를 사용하여 중합시키되, 염화비닐계 단량체를 중합 초기에 전체 염화비닐계 단량체 투입량의 50 내지 80중량%를 투입하고, 중합전환율 12 내지 18%일 때 나머지 20 내지 50중량%의 염화비닐계 단량체를 투입하고, 중합전환율 27 내지 33%일 때 투입을 종료하고 일정 압력에 도달한 시점에 반응 종결제를 투입하는 것을 특징으로 한다.In the method for preparing a vinyl chloride polymer according to the present invention, in the method for preparing a vinyl chloride resin by suspension polymerization, the suspension polymerization polymerizes the vinyl chloride monomer using high temperature polymerized water at 70 to 100 ° C. 50 to 80% by weight of the total amount of the vinyl chloride monomer is charged at the initial stage of the polymerization of the vinyl monomer, and when the polymerization conversion rate is 12 to 18%, the remaining 20 to 50% by weight of the vinyl chloride monomer is added and the polymerization conversion rate is 27 to At 33%, the input is terminated and the reaction terminator is added when a certain pressure is reached.
상기 고온 중합수로는 70 내지 100℃의 범위 내인 것을 반응기에 투입한 다음 중합 개시제의 투입에 의하여 중합 반응을 바로 개시함으로써 승온 배제효과를 달성한다. 특히, 상기 고온 중합수는 73 내지 83℃ 범위 내인 것을 사용하는 것이 경제성 측면에서 보다 바람직하다. 이 때 70℃ 미만의 중합수를 사용하는 경우 염화비닐 중합체 제조시 중합반응을 바로 개시하지 못하고, 목표로 하는 중합온도 도달시까지 가열을 해야 하므로, 배치당 중합 생산성 증대에 제약이 따른다.The high-temperature polymerization reactor is charged into a reactor within a range of 70 to 100 ° C, and then the polymerization reaction is immediately initiated by the introduction of a polymerization initiator, thereby achieving a temperature elevating effect. Particularly, it is more economical to use the high-temperature-polymerized water within the range of 73 to 83 ° C. When the polymerization water below 70 ° C is used at this time, the polymerization reaction can not be started immediately in the production of the vinyl chloride polymer, and heating is required until the target polymerization temperature is reached.
이 같은 70 내지 100℃의 고온 중합수를 준비한 다음, 중합 개시제 투입에 의해 현탁 중합하게 된다. 구체적으로 상기 현탁중합은 상기 고온 중합수에 염화비닐 단량체 및 보호 콜로이드 조제가 혼합되고, 이 혼합용액에 중합 개시제가 투입되어 중합하는 것이 바람직하다. 특히, 상기 현탁중합은 중합 개시제 투입 시의 반응기 내부 온도가 통상의 중합개시온도, 특히 중합개시온도보다 2 내지 5℃ 이상인 것이 바람직하다. 이 경우 개시제의 초기 분해속도 증가 효과가 있다. 이 때 고온 중합수에 염화비닐 단량체 및 보호 콜로이드 조제가 혼합되고, 이 혼합용액에 중합 개시제가 투입되어 중합되는데, 염화비닐 단량체 100중량부에 대하여, 고온 중합수 120 내지 150중량부, 보호 콜로이드 조제 0.03 내지 5중량부 및 중합 개시제는 0.02 내지 0.2중량부를 투입하여 현탁중합한다.The high-temperature polymerized water at 70 to 100 ° C is prepared as described above, and suspension polymerization is carried out by introducing a polymerization initiator. Specifically, it is preferable that the suspension polymerization is carried out by mixing the high-temperature polymerized water with a vinyl chloride monomer and a protective colloid assistant, and adding a polymerization initiator to the mixed solution to polymerize. Particularly, in the suspension polymerization, the internal temperature of the reactor at the time of introducing the polymerization initiator is preferably 2 to 5 ° C or more than the ordinary polymerization initiation temperature, particularly the polymerization initiation temperature. In this case, there is an effect of increasing the initial decomposition rate of the initiator. In this case, the high-temperature polymerization water is mixed with a vinyl chloride monomer and a protective colloid assistant, and a polymerization initiator is added to the mixed solution to polymerize. In 100 parts by weight of the vinyl chloride monomer, 120 to 150 parts by weight of high- 0.03 to 5 parts by weight of the polymerization initiator and 0.02 to 0.2 parts by weight of the polymerization initiator.
참고로, 본 발명의 염화비닐 중합체는 순수하게 염화비닐 단량체로 이루어진 수지뿐 아니라 염화비닐 단량체를 주체로 하고 이것과 공중합 가능한 비닐계 단량체와의 혼합물(수지 전체 조성 중 염화비닐 단량체의 함량이 50중량% 이상)도 포함된다.For reference, the vinyl chloride polymer of the present invention is a mixture of a vinyl chloride monomer mainly composed of a vinyl chloride monomer and a vinyl monomer copolymerizable therewith (the content of the vinyl chloride monomer in the resin composition is 50 wt% %).
이 같은 염화비닐 단량체와 공중합가능한 비닐계 단량체로는 에틸렌, 프로필렌 등의 올레핀 화합물, 초산 비닐, 포로피온산 비닐 등의 비닐 에스테르류, 아크릴로니트릴 등의 불포화 니트릴류, 비닐 메틸 에테르, 비닐 에틸 에테르 등의 비닐 알킬 에테르류, 아크릴산, 메타크릴산 이타콘산, 말레인산 등의 불포화 지방산 및 이들 지방산의 무수물 등의 일반적으로 염화비닐 단량체와 공중합 가능한 단량체를 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the vinyl monomer copolymerizable with such a vinyl chloride monomer include olefin compounds such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl propionate, unsaturated nitriles such as acrylonitrile, vinyl methyl ether, vinyl ethyl ether , Unsaturated fatty acids such as acrylic acid, itaconic acid methacrylate, and maleic acid, and anhydrides of these fatty acids, can be used alone or in combination of two or more kinds of monomers copolymerizable with vinyl chloride monomers.
또한, 본 발명에서 염화비닐계 중합체의 제조 공정을 안정하게 유지하고 안정한 입자를 얻을 목적으로 사용되는 보호 콜로이드 조제로는 수화도가 30 내지 90중량%이고, 상온에서 4% 수용액의 점도가 5 내지 100cps인 비닐알코올계 수지, 메톡시기가 15 내지 40중량%이고 수산화프로필기가 3 내지 20중량%이며 상온에서 측정한 2% 수용액의 점도가 10 내지 20,000cps인 셀룰로오스 및 불포화 유기산으로 이루어진 군으로부터 선택된 1종 이상이다. 상기 보호 콜로이드 조제는 수화도가 85 내지 98%인 비닐알코올계 수지, 및 수화도가 50 내지 60%인 비닐알코올계 수지를 포함하는 것이 바람직한데, 이 범위 내에서 휘시아이 및 초기 착색성이 우수한 효과가 있다. 상기 고 수화도 수지와 저 수화도 수지의 배합지는 타겟으로 하는 물성에 따라 조절하는 것으로, 본 발명에서는 고 수화도 수지와 저 수화도 수지를 0.5~1.5:0.5~1.5의 중량비로 배합하여 사용하는 것이 바람직하다.In addition, the protective colloid preparation used for the purpose of stably maintaining the production process of the vinyl chloride polymer in the present invention and obtaining stable particles has a degree of hydration of 30 to 90% by weight and a viscosity of 4% aqueous solution at room temperature of 5 to Vinyl alcohol-based resin of 100 cps, 15 to 40% by weight of methoxy group, 3 to 20% by weight of propyl hydroxide, 1% selected from the group consisting of cellulose and unsaturated organic acid having a viscosity of 10 to 20,000 cps in a 2% aqueous solution measured at room temperature More than species. The protective colloid preparation preferably includes a vinyl alcohol resin having a degree of hydration of 85 to 98%, and a vinyl alcohol resin having a degree of hydration of 50 to 60%, and has excellent effect of whiskey and initial colorability within this range. There is. The mixing degree of the high hydration degree resin and the low hydration degree resin is adjusted according to the physical property to be targeted. In the present invention, the high hydration degree resin and the low hydration degree resin are mixed in a weight ratio of 0.5 to 1.5: 0.5 to 1.5 .
상기 불포화 유기산의 구체적인 예로는 아크릴산 수지, 메타크릴산 수지, 이타콘산 수지, 푸마르산 수지, 말레인산 수지, 숙신산 수지 또는 젤라틴을 단독 또는 2종 이상 혼합하여 사용할 수 있다.Specific examples of the unsaturated organic acid may include acrylic acid resin, methacrylic acid resin, itaconic acid resin, fumaric acid resin, maleic acid resin, succinic acid resin or gelatin, or a mixture of two or more thereof.
상기 보호 콜로이드 조제는 염화비닐 단량체 100중량부에 대하여 0.03 내지 5중량부를 포함하며, 보다 바람직하게는 0.05 내지 2.5중량부를 포함한다. 상기 함량으로 사용되는 경우에는 조대한 입자가 형성되지 않아 휘시아이가 발생하지 않으며, 미세입자의 증가가 없어 초기 착색성이 우수한 효과가 있다.The protective colloid assistant comprises 0.03 to 5 parts by weight, more preferably 0.05 to 2.5 parts by weight, based on 100 parts by weight of the vinyl chloride monomer. When used in the above amount, coarse particles are not formed and no fish eye is generated, and there is no increase in fine particles, so that the initial coloring property is excellent.
나아가, 본 발명에서 사용가능한 중합 개시제로는 디큐밀 퍼옥사이드, 디펜틸 퍼옥사이드, 디-3,5,5-트리메틸 헥사노일퍼옥사이드, 디라우로일퍼옥사이드 등의 디아실퍼옥사이드류나, 디이소프로필퍼옥시디카보네이트, 디-sec-부틸퍼옥시디카보네이트, 디-2-에틸헥실퍼옥시디카보네이트 등의 퍼옥시디카보네이트류, t-부틸퍼옥시 네오데카노에이트, t-부틸퍼옥시네오헵타노에이트, t-아밀퍼옥시 네오데카노에이트, 큐밀 퍼옥시네오데카노에이트, 큐밀 퍼옥시네오헵타노에이트, 1,1,3,3-테트라메틸부틸 퍼옥시네오데카노에이트 등의 퍼옥시 에스테르, 아조비스-2,4-디메틸발레로니트릴 등의 아조 화합물, 포타슘 퍼설페이트, 암모늄퍼설페이트 등의 설페이트류 등이 있으며, 이들의 단독 또는 2종 이상의 조합에 의한 사용이 가능하다. 그 사용량은 제조 공정, 생산성, 품질 등의 요인에 의하여 결정되는데, 일반적으로 총 투입되는 염화비닐 단량체 100중량부에 대하여 중합개시제의 총 사용량은 0.02 내지 0.2중량부의 사용이 가능하며, 가장 적절하게는 0.04 내지 0.12중량부의 사용이 바람직하다. 개시제 사용량이 적정 량보다 적을 때에는 반응시간이 지연되어 생산성이 저하되고 적정량보다 과량 사용시에는 중합 과정 중에서 개시제가 완전히 소모되지 못하고 최종 수지 제품에 잔류하여 수지의 열 안정성 및 색상 품질을 저하시킨다.Further, as the polymerization initiator usable in the present invention, diacyl peroxides such as dicumyl peroxide, dipentyl peroxide, di-3,5,5-trimethylhexanoyl peroxide and diaryl peroxide, diisopropyl Peroxydicarbonates such as peroxydicarbonate, di-sec-butylperoxydicarbonate and di-2-ethylhexyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t Peroxyesters such as amyl peroxyneodecanoate, cumyl peroxyneodecanoate, cumyl peroxyneoheptanoate, and 1,1,3,3-tetramethylbutyl peroxyneodecanoate, azobis -2,4-dimethylvaleronitrile, and sulfates such as potassium persulfate and ammonium persulfate, and they may be used alone or in combination of two or more thereof. The amount of the polymerization initiator is determined by factors such as manufacturing process, productivity, and quality. Generally, the total amount of polymerization initiator can be used in an amount of 0.02 to 0.2 parts by weight based on 100 parts by weight of the total amount of vinyl chloride monomer. Preference is given to the use of 0.04 to 0.12 parts by weight. When the amount of the initiator used is less than the proper amount, the reaction time is delayed and the productivity is decreased. When the amount of the initiator is excessively used, the initiator is not completely consumed in the polymerization process and remains in the final resin product to deteriorate the thermal stability and color quality of the resin.
본 발명에서는 반응을 중단하기 위해 사용 가능한 반응 종결제는 염화비닐계 중합체의 제조에 있어서 일반적으로 사용되는 종류를 사용하면 충분한 것으로 예를 들면, 트리에틸렌 글리콜-비스-3-(3-t-부틸-4-하이드록시-5-메틸페닐)프로피오네이트, 하이드로퀴논, p-메톡시 페놀, t-부틸하이드록시아니솔, n-옥타데실-3-(4-히드록시-3,5-디-t-부틸 페닐)프로피오네이트, 2,5-디-t-부틸 하이드로퀴논, 4,4-부틸리덴비스(3-메틸-6-t-부틸 페놀), t-부틸 카테콜, 4,4-티오비스(6-t-부틸-m-크레졸), 토코페롤 등의 페놀 화합물, N-N-디페닐-p-페닐렌 디아민, 4,4-비스(디메틸벤질)디페닐 아민 등의 아민 화합물, 2-페닐 니트로닐 니트록사이드(2-phenyl nitronyl nitroxide), 3-이미다졸린 니트록사이드(3-imidazoline nitroxide), 4-하이드록시-2,2,6,6-테트라메틸-피페리딘-1-옥시(4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxy) 등의 니트릴 화합물, 도데실 메르캅탄, 1,2-디페닐-2-티올 등의 유황 화합물 등을 단독 또는 2종 이상 혼합하여 사용할 수 있다.In the present invention, the reaction species which can be used for stopping the reaction may be selected from those generally used in the production of the vinyl chloride polymer, for example, triethylene glycol-bis-3- (3-t-butyl Hydroxyphenyl) propionate, hydroquinone, p-methoxyphenol, t-butylhydroxyanisole, n-octadecyl-3- (4- t-butylphenyl) propionate, 2,5-di-t-butylhydroquinone, 4,4-butylidenebis (3-methyl- Phenol compounds such as 4-thiobis (6-t-butyl-m-cresol) and tocopherol, amine compounds such as NN-diphenyl-p-phenylenediamine and 4,4-bis (dimethylbenzyl) 2-phenyl nitronyl nitroxide, 3-imidazoline nitroxide, 4-hydroxy-2,2,6,6-tetramethyl-piperidine 4-hydroxy-2,2,6,6-tetrameth yl-piperidine-1-oxy), dodecyl mercaptan, and sulfur compounds such as 1,2-diphenyl-2-thiol may be used alone or in combination of two or more.
본 발명에 있어서, 필요에 따라 중합 조절제, 연쇄 이동제, pH 조절제, 산화 방지제, 가교제, 대전 방지제, 스케일 방제제, 계면활성제 등을 중합 개시 전 또는 중합 후에 중합계에 첨가해도 좋고, 중합 중에 그 일부를 분할 또는 연속적으로 중합계에 첨가해도 좋다.In the present invention, a polymerization regulator, a chain transfer agent, a pH adjuster, an antioxidant, a crosslinking agent, an antistatic agent, a scale control agent, a surfactant, etc. may be added to the polymerization system before or after polymerization initiation, May be added to the polymerization system in a divided manner or continuously.
즉, 본 발명에서는 보호콜로이드 조제 및 중합 개시제의 존재하에 염화비닐 단량체를 현탁 중합시켜 염화비닐계 중합체를 제조하는 방법으로서, 70 내지 100℃의 고온 중합수를 사용하여 중합 반응을 바로 개시하며, 중합 개시로부터 반응 전 공정에 걸쳐 중합 온도를 목표로 하는 평균 중합도에 따른 중합 기준 온도로 유지하고, 중합전환율이 15 내지 30%일 때 나머지 염화비닐 단량체를 투입 시작 및 완료하는 것을 기술적 특징으로 한다.In other words, in the present invention, a vinyl chloride-based polymer is prepared by suspending and polymerizing a vinyl chloride monomer in the presence of a protective colloid preparation and a polymerization initiator. The polymerization reaction is immediately initiated using high-temperature polymerization water of 70 to 100 ° C., and polymerization. It is characterized by maintaining the polymerization reference temperature according to the average degree of polymerization aimed at the polymerization temperature from the start to the reaction before the reaction, and when the polymerization conversion rate is 15 to 30%, starting and completing the addition of the remaining vinyl chloride monomer.
이 때 중합 기준 온도란 목표하고자 하는 평균 중합도에 따라 결정되는 것으로 본 발명에서의 중합 기준 온도는 30 내지 80℃ 범위 내를 만족하는 것이 바람직하다.In this case, the polymerization reference temperature is determined according to the desired average degree of polymerization, and the polymerization reference temperature in the present invention preferably satisfies the range of 30 to 80 캜.
상기 중합 기준 온도는 각 설비 특성에 따라 그리고 제조업체별로 조금씩 차이가 날 뿐 아니라 목표로 하는 평균 중합도의 모든 경우에 대하여 본 명세서 내에서 언급할 수 없는 것으로, 몇 가지 경우를 예로 들어보면, 평균 중합도 800을 목표로 할 경우 중합 기준 온도는 63 내지 65℃, 1000을 목표로 할 경우 중합 기준 온도는 56 내지 58℃, 평균 중합도 1300을 목표로 할 경우 중합 기준 온도는 52 내지 54℃, 그리고 평균 중합도 1700을 목표로 할 경우 47 내지 49℃ 범위 내를 기준으로 하는 것이 바람직하다.The polymerization reference temperature is not only slightly different depending on the characteristics of each facility and by manufacturer, and cannot be mentioned in the present specification in all cases of the target average degree of polymerization, and in some cases, the average degree of polymerization 800 When aiming at the polymerization reference temperature is 63 to 65 ℃, if the aim at 1000 the polymerization reference temperature is 56 to 58 ℃, the average degree of polymerization 1300 target polymerization temperature is 52 to 54 ℃, and the average degree of polymerization 1700 If it aims to be preferably based on the 47 to 49 ℃ range.
물론 본 발명에서 목표로 하는 평균 중합도는 이에 제한하는 것은 아니며, 본 발명에서의 중합 기준 온도 범위인 30 내지 80℃ 내의 온도를 만족할 수 있다면, 목표로 하는 평균 중합도는 700 미만 값, 혹은 1700 초과 값도 가능하다.Of course, the aimed average degree of polymerization in the present invention is not limited thereto. If the temperature within the range of 30 to 80 占 폚, which is the polymerization reference temperature range in the present invention, can be satisfied, the target average degree of polymerization may be less than 700, It is also possible.
본 발명에 의한 염화비닐계 중합체의 현탁중합 방법은 70 내지 100℃의 고온 중합수를 사용하여 중합반응을 바로 개시하고, 초기에 염화비닐 단량체의 투입 비율을 전체 염화비닐 단량체 투입량의 50 내지 80%까지 조절하며, 중합전환율 15 내지 30% 기간에 남은 염화비닐 단량체를 연속 추가하는 단계를 포함한다.In the suspension polymerization method of the vinyl chloride polymer according to the present invention, the polymerization reaction is immediately started using high temperature polymerization water of 70 to 100 ° C., and the initial ratio of the vinyl chloride monomer is 50 to 80% of the total amount of the vinyl chloride monomer. And the step of continuously adding the vinyl chloride monomer remaining in the polymerization conversion rate of 15 to 30%.
구체적으로 초기 염화비닐 단량체의 투입 비율은 전체 염화비닐 단량체 투입량의 50 내지 80중량%를 투입하는 것이 바람직하나, 특히 바람직하게는 전체 염화비닐 단량체 투입량의 60 내지 70중량%를 투입하는 것이다.Specifically, the input ratio of the initial vinyl chloride monomer is preferably 50 to 80% by weight of the total amount of vinyl chloride monomer, but particularly preferably 60 to 70% by weight of the total amount of vinyl chloride monomer.
초기 염화비닐 단량체의 투입 비율이 전체 염화비닐 단량체 투입량의 50중량% 미만인 경우, 미세 입자가 증가되어 초기 착색성이 나빠지며, 연속 추가 투입된 염화비닐 단량체에 의한 중합시간이 너무 길어져 배치당 중합 생산성 증대 효과가 미미하다. 초기 염화비닐 단량체의 투입비율이 전체 염화비닐 단량체 투입량의 80중량%를 초과하여 투입하는 경우에는 나중에 연속 추가 투입되는 염화비닐 단량체가 감소하므로 배치당 중합 생산성 증대 효과가 미미하다.When the initial ratio of the vinyl chloride monomer is less than 50% by weight of the total amount of the vinyl chloride monomer, the fine particles are increased and the initial colorability is deteriorated, and the polymerization time by the continuously added vinyl chloride monomer is too long, thereby increasing the polymerization productivity per batch. Is insignificant. When the input ratio of the initial vinyl chloride monomer is more than 80% by weight of the total amount of the vinyl chloride monomer input, since the addition of the vinyl chloride monomer continuously added later, the effect of increasing the polymerization productivity per batch is insignificant.
또한, 중합에 투입되는 전체 염화비닐 단량체의 투입량의 30 내지 40중량%의 염화비닐 단량체를 초기 중합체에 해당하는 중합전환율 15 내지 30% 범위 내에서 연속 투입하는 것이 바람직하며, 정확한 중합전환율 시점의 측정이 불가한 점을 감안하여 실제 적용시에는 대략 12 내지 18% 범위 내에 투입 시작하여, 27 내지 33% 범위 내에 투입 종료하는 것이 보다 바람직하다. 이 때 중합전환율이 15% 부근, 최저 12% 미만인 시기에 염화비닐 단량체를 연속 추가 투입하게 되면 중합 반응에 의해 중합 반응계의 체적 수축량 간소가 너무 적어서 연속적으로 추가 투입될 수 있는 염화비닐 단량체의 함량이 소량으로 제한되어 배치(batch)당 중합 생산성 증대 효과가 제한되므로 바람직하지 않으며, 반면 중합전환율이 30% 부근, 최대 33%를 초과한 기간에 염화비닐 단량체를 연속적으로 추가 투입하게 되면 반응 말기 중합계 내의 염화비닐 중합체에 균일한 열 전달이 이루어지지 못하기 때문에 최종 염화비닐계 중합체의 물성 조절이 힘들어지고, 결과적으로 휘시아이 및 초기 착색성 등의 물질이 안정적인 염화비닐계 중합체를 제조하기 어려운 단점이 있다.In addition, it is preferable to continuously add 30 to 40% by weight of the vinyl chloride monomer of the total amount of the vinyl chloride monomer added to the polymerization within the range of 15 to 30% of the polymerization conversion rate corresponding to the initial polymer, and to accurately measure the timing of the polymerization conversion rate. In view of this impossibility, it is more preferable to start the charging in the range of approximately 12 to 18% and finish the feeding in the range of 27 to 33% in actual application. At this time, if the addition of vinyl chloride monomer is continuously added at the time when the polymerization conversion rate is around 15% and less than 12%, the volumetric shrinkage amount of the polymerization reaction system is too small by the polymerization reaction so that the amount of the vinyl chloride monomer that can be added continuously is It is not preferable because it is limited to a small amount and thus the effect of increasing the productivity of polymerization per batch is limited.However, continuous addition of vinyl chloride monomer at a time when the polymerization conversion rate is around 30% and exceeds 33% is maximum, and the polymerization stage is terminated. It is difficult to control the physical properties of the final vinyl chloride-based polymer because uniform heat transfer is not made to the vinyl chloride polymer in the interior, and as a result, it is difficult to prepare a vinyl chloride-based polymer in which materials such as whiskey and initial coloring properties are stable. .
염화비닐 단량체가 중합반응에 의해 염화비닐계 중합체로 변환할 때 염화비닐계 중합체의 비중이 크기 때문에 중합 반응이 진행되는 동시에 중합반응계의 체적 수축이 발생하며, 중합반응계의 체적 수축은 다음과 같은 식으로부터 산출할 수 있다.When the vinyl chloride monomer is converted into the vinyl chloride polymer by the polymerization reaction, the vinyl chloride polymer has a large specific gravity, so that the polymerization reaction proceeds and the volume shrinkage of the polymerization reaction system occurs. The volume shrinkage of the polymerization reaction system is expressed by the following equation .
[수학식 1][Equation 1]
V=M×C/100×(1/d1-1/d2)V = M × C / 100 × (1 / d1-1 / d2)
상기 식에서 V는 중합반응에 의한 체적 수축량, M은 염화비닐계 단량체의 중량, C는 염화비닐계 단량체의 염화비닐계 중합체로의 중합전환율, d1은 염화비닐계 단량체의 비중, d2는 염화비닐계 중합체의 비중을 나타낸다.In the above formula, V is the volume shrinkage by the polymerization reaction, M is the weight of the vinyl chloride monomer, C is the conversion rate of the vinyl chloride monomer to the vinyl chloride polymer, d1 is the specific gravity of the vinyl chloride monomer, d2 is vinyl chloride Specific gravity of the polymer is shown.
즉, 본 발명의 중합 도중 전환율이 30% 부근, 최대 33% 이하에서 합일/재분산이 가장 활발히 일어나기 때문에 수지 입자의 내부 형태 조절이 가능하므로, 이에 적절한 기간 도중 염화비닐 단량체를 추가 투입함으로써 추가 투입된 염화비닐 단량체가 안정한 형태의 염화비닐계 중합체로 전환되어 배치당 중합 생산성 증대를 기대할 수 있다.That is, since the coalescence / redispersion is most actively performed at a conversion rate of about 30% and a maximum of 33% or less during the polymerization according to the present invention, it is possible to control the internal shape of the resin particles. Therefore, by additionally adding vinyl chloride monomer during an appropriate period, The vinyl chloride monomer can be converted into a vinyl chloride type polymer in a stable form and the polymerization productivity per batch can be expected to increase.
한편 본 발명에 사용된 반응기로는 염화비닐계 중합체의 현탁 중합에 일반적으로 사용되고 있는 교반 장치를 사용하면 충분하며, 구체적인 예로서 교반기로는 교반 날개 타입이 패들(paddle)형, 패치 패들(pitched paddle)형, 블루머 진(bloomers gin)형, 파우도라(pfaudler)형, 터빈(turbine)형, 프로펠러(propeller)형 등을 단독 또는 2종 이상의 교반 날개와 조합된 교반기를 사용할 수 있으며, 배플로는 판형, 원통형, D형, 루프형 또는 핑거형 등을 사용할 수 있다.As the reactor used in the present invention, it is sufficient to use a stirrer generally used for suspension polymerization of a vinyl chloride polymer. As a concrete example, a stirrer may be a paddle type, a pitched paddle A blender gin type, a pfaudler type, a turbine type, a propeller type and the like, or a mixer combined with two or more stirring blades may be used. A plate type, a cylindrical type, a D type, a loop type, or a finger type.
상기 제조된 염화비닐계 중합체 슬러리는 통상의 반응 조건으로 유동층 건조기로 수분을 제거하고 최종 염화비닐 중합체를 제조할 수 있다.The produced vinyl chloride-based polymer slurry may be subjected to a fluidized bed dryer under ordinary reaction conditions to remove moisture to prepare the final vinyl chloride polymer.
결과적으로, 본 발명에서의 현탁중합은 염화비닐 단량체 100중량부에 대하여, 고온 중합수 120 내지 150중량부, 중합개시제 0.02 내지 0.2중량부, 및 보호 콜로이드 조제 0.03 내지 5중량부를 포함하여 실시되는 것을 특징으로 한다.As a result, the suspension polymerization in the present invention is carried out including 120 to 150 parts by weight of the high temperature polymerization water, 0.02 to 0.2 parts by weight of the polymerization initiator, and 0.03 to 5 parts by weight of the protective colloid preparation based on 100 parts by weight of the vinyl chloride monomer. It features.
하기 실시예에서도 규명된 바와 같이, 본 발명의 방법에 따르면, 염화비닐계 단량체를 현탁 중합하되, 고온 중합수를 사용하여 중합 개시 온도를 조절하고, 여기에 중합 개시제를 투여함으로써 중합 반응을 개시할 뿐 아니라 초기 중합계 내 염화비닐계 단량체의 농도를 제어함으로써 중합반응 속도 조절을 통해 중합 생산성이 우수할 뿐 아니라 안정적인 품질 확보가 가능한 염화비닐계 중합체를 제조할 수 있다.
According to the method of the present invention as described in the following examples, the polymerization reaction is initiated by suspension polymerization of a vinyl chloride monomer, the polymerization initiation temperature is controlled using high temperature polymerization water, and a polymerization initiator is added thereto In addition, by controlling the concentration of the vinyl chloride monomer in the initial polymerization system, it is possible to produce a vinyl chloride-based polymer capable of securing a stable quality as well as an excellent polymerization productivity through the control of the polymerization reaction rate.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
[실시예][Example]
실시예Example 1 One
환류 응축기를 가지는 내부 용적 1m3의 반응기에 74℃ 탈이온수 390kg을 투입하고, 수화도가 87.5%인 폴리비닐알코올 80g, 수화도가 54.5%인 폴리비닐알코올 120g, 하이드록시프로필메틸 셀룰로오스 50g을 반응기에 일괄 투입하고, 염화비닐 단량체 230kg을 투입한 후 디-2-에틸헥실퍼옥시디카보네이트 30g, t-부틸퍼옥시 네오데카노에이트 120g을 투입하여 반응을 개시하였다.390 kg of deionized water at 74 ° C. was added to a reactor having a reflux condenser of 1 m 3 , 80 g of polyvinyl alcohol having a degree of hydration of 87.5%, 120 g of polyvinyl alcohol having a degree of hydration of 54.5%, and 50 g of hydroxypropylmethyl cellulose were added to the reactor. Into a batch, 230 kg of vinyl chloride monomer was added, 30 g of di-2-ethylhexyl peroxydicarbonate and 120 g of t-butylperoxy neodecanoate were added to initiate a reaction.
중합 반응 전 과정 동안 반응 온도를 목표로 하는 평균 중합도 1000을 달성하기 위해 57℃로 유지하면서 반응을 진행시키고, 중합전환율이 15 내지 30% 기간에 염화비닐 단량체를 120kg을 연속하여 추가 투입하였다. 중합반응기 압력이 6.0kg/cm2에 도달한 시점 (중합전환율이 대략 85%에 상당하는 시점)에 반응 종결제로서 4-하이드록시-2,2,6,6-테트라메틸-피페리딘-1-옥실 15g, 트리에틸렌 글리콜-비스-3-(3-t-부틸-4-하이드록시-5-메틸페닐)프로피오네이트를 60g 첨가한 다음 미반응 단량체를 회수하고, 수지 슬러리를 중합반응기에서 회수하였다. 이렇게 하여 얻어진 슬러리를 통상의 방법으로 유동층 건조기에서 건조하여 염화비닐 중합체를 얻었다.During the entire polymerization process, the reaction was carried out while maintaining the temperature at 57 ° C. to achieve an average degree of polymerization of 1000, which was aimed at the reaction temperature, and 120 kg of vinyl chloride monomer was added continuously in a polymerization conversion period of 15 to 30%. 4-hydroxy-2,2,6,6-tetramethyl-piperidine- as a terminator at the time when the polymerization reactor pressure reached 6.0 kg / cm 2 (when the polymerization conversion rate was approximately 85%). 15 g of 1-oxyl and 60 g of triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate were added and the unreacted monomers were recovered, and the resin slurry was added to the polymerization reactor. Recovered. The slurry thus obtained was dried in a fluidized bed drier by a conventional method to obtain a vinyl chloride polymer.
실시예Example 2 2
상기 실시예 1에서 초기에 염화비닐 단량체 240kg을 투입하고, 중합전환율이 15 내지 30%인 기간에 염화비닐 단량체 120kg을 연속 추가 투입한 것 외에는 상기 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.In Example 1, the polymerization was performed and evaluated under the same conditions as in Example 1, except that 240 kg of vinyl chloride monomer was initially added and 120 kg of vinyl chloride monomer was continuously added in a period of 15 to 30% of the polymerization conversion rate. .
실시예Example 3 3
상기 실시예 1에서 초기에 염화비닐 단량체 230kg을 투입하고, 중합전환율 15 내지 30%인 기간에 염화비닐 단량체 150kg을 연속 추가 투입한 것 외에는 상기 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.230 kg of a vinyl chloride monomer was initially added in Example 1, and polymerization was performed and evaluated under the same conditions as in Example 1, except that 150 kg of a vinyl chloride monomer was continuously added in a period of 15 to 30% polymerization conversion rate.
실시예Example 4 4
상기 실시예 1에서 초기에 염화비닐 단량체 250kg을 투입하고, 중합전환율이 15 내지 30%인 기간에 염화비닐 단량체 130kg을 연속 추가 투입한 것 외에는 상기 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.The polymerization was performed and evaluated under the same conditions as in Example 1, except that 250 kg of vinyl chloride monomer was initially added in Example 1, and 130 kg of vinyl chloride monomer was continuously added in a period of 15 to 30% polymerization conversion rate. .
실시예Example 5 5
상기 실시예 1에서 초기에 염화비닐 단량체 280kg을 투입하고, 중합전환율이 15 내지 30%인 기간에 염화비닐 단량체 120kg을 연속 추가 투입한 것 외에는 상기 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.The polymerization was carried out and evaluated under the same conditions as in Example 1, except that 280 kg of the vinyl chloride monomer was initially added in Example 1, and 120 kg of the vinyl chloride monomer was continuously added during the polymerization conversion period of 15 to 30%. .
실시예Example 6 6
상기 실시예 1에서 초기에 염화비닐 단량체 260kg을 투입하고, 중합전환율이 15 내지 30%인 기간에 염화비닐 단량체 120kg을 연속 추가 투입한 것 외에는 상기 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.The polymerization was carried out and evaluated under the same conditions as in Example 1, except that 260 kg of vinyl chloride monomer was initially added in Example 1, and 120 kg of vinyl chloride monomer was continuously added during the polymerization conversion period of 15 to 30%. .
실시예Example 7 7
상기 실시예 1에서 83℃ 탈이온수를 투입하고 중합 반응 전 과정 동안 반응 온도를 목표로 하는 평균 중합도 800을 달성하기 위해 65℃로 유지하면서 반응을 진행시키고, 초기에 염화비닐 단량체 230kg을 투입한 후, 중합전환율이 15 내지 30% 기간에 염화비닐 단량체 120kg을 연속 추가 투입한 다음 중합 반응기 압력이 8.0kg/cm2에 도달한 시점에 반응 종결제를 투입한 것을 제외하고는 상기 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.In Example 1, 83 ° C. deionized water was added and the reaction was carried out while maintaining the temperature at 65 ° C. to achieve an average polymerization degree of 800, which is a target of the reaction temperature during the entire polymerization reaction, and 230 kg of vinyl chloride monomer was initially added. In the same manner as in Example 1, except that 120 kg of vinyl chloride monomer was continuously added in a polymerization conversion period of 15 to 30%, and then a reaction terminator was added when the polymerization reactor pressure reached 8.0 kg / cm 2 . The polymerization was carried out and evaluated under the conditions.
실시예Example 8 8
상기 실시예 1에서 83℃ 탈이온수를 투입하고 중합 반응 전 과정 동안 반응 온도를 목표로 하는 평균 중합도 800을 달성하기 위해 65℃로 유지하면서 반응을 진행시키고, 초기에 염화비닐 단량체 280kg을 투입한 후, 중합전환율이 15 내지 30% 기간에 염화비닐 단량체 120kg을 연속 추가 투입한 다음 중합 반응기 압력이 8.0kg/cm2에 도달한 시점에 반응 종결제를 투입한 것을 제외하고는 상기 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.In Example 1, 83 ° C. deionized water was added and the reaction was carried out while maintaining the temperature at 65 ° C. to achieve an average polymerization degree of 800, which is a target of the reaction temperature during the entire polymerization reaction, and initially 280 kg of vinyl chloride monomer was added thereto. In the same manner as in Example 1, except that 120 kg of vinyl chloride monomer was continuously added in a polymerization conversion period of 15 to 30%, and then a reaction terminator was added when the polymerization reactor pressure reached 8.0 kg / cm 2 . The polymerization was carried out and evaluated under the conditions.
상기 실시예들에서 초기 염화비닐 단량체 투입비율은 실시예 1이 약 68.7%, 실시예 2가 약 66.6%, 실시예 3이 약 60.5%, 실시예 4가 65.8%, 실시예 5가 70%, 실시예 6이 65%, 실시예 7이 약 65.7%, 실시예 8이 약 60.5%, 실시예 9가 70%이었으며, 비교예 1은 초기에 전량 투입하였고, 비교예 2는 약 48.5%, 비교예 3은 약 90.8%, 비교예 4는 약 93.8%, 비교예 5는 약 65.7%, 비교예 6은 75%, 비교예 7은 약 48.5%, 비교예 8은 약 93.8%, 비교예 9는 약 71.4%였다.In the above examples, the initial vinyl chloride monomer loading rate was about 68.7% in Example 1, about 66.6% in Example 2, about 60.5% in Example 3, 65.8% in Example 4, 70% in Example 5, Example 6 was 65%, Example 7 was about 65.7%, Example 8 was about 60.5%, and Example 9 was 70%, Comparative Example 1 was initially added in all, and Comparative Example 2 was about 48.5%, compared Example 3 is about 90.8%, Comparative Example 4 is about 93.8%, Comparative Example 5 is about 65.7%, Comparative Example 6 is 75%, Comparative Example 7 is about 48.5%, Comparative Example 8 is about 93.8%, Comparative Example 9 About 71.4%.
비교예Comparative example 1 One
환류 응축기를 가지는 내부 용적 1m3의 반응기에 50℃ 탈이온수 390kg을 투입하고, 수화도가 78%인 폴리비닐알코올 120g, 수화도가 40%인 폴리비닐알코올 80g, 하이드록시프로필메틸 셀룰로오스 50g을 반응기에 일괄 투입하고, 염화비닐 단량체 300kg을 투입한 후 디-2-에틸헥실퍼옥시디카보네이트 30g, t-부틸퍼옥시 네오데카노에이트 120g을 투입한 후 중합반응 온도를 평균 중합도 1000을 달성하기 위해 중합반응 전 과정 동안 57℃로 유지하면서 반응을 진행시켰다.390 kg of deionized water at 50 ° C. was introduced into a reactor having a reflux condenser of 1 m 3 , and 120 g of polyvinyl alcohol having 78% hydration, 80 g of polyvinyl alcohol having 40% hydration, and 50 g of hydroxypropylmethyl cellulose were added to the reactor. Was added in a batch, 300 kg of vinyl chloride monomer was added, 30 g of di-2-ethylhexyl peroxydicarbonate and 120 g of t-butylperoxy neodecanoate were added, followed by polymerization to achieve an average degree of polymerization of 1000. The reaction was carried out while maintaining the temperature at 57 ℃ during the entire reaction.
중합반응기 압력이 6.0kg/cm2에 도달한 시점에 반응 종결제로서 4-하이드록시-2,2,6,6-테트라메틸-피페리딘-1-옥실 15g, 트리에틸렌 글리콜-비스-3-(3-t-부틸-4-하이드록시-5-메틸페닐)프로피오네이트를 60g 첨가한 다음 미반응 단량체를 회수하고, 수지 슬러리를 중합반응기에서 회수하였다. 이렇게 하여 얻어진 슬러리를 통상의 방법으로 유동층 건조기에서 건조하여 염화비닐 중합체를 얻었다.When the pressure of the polymerization reactor reached 6.0 kg / cm 2 , 15 g of 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl as the reaction terminator and 15 g of triethylene glycol- - (3-t-butyl-4-hydroxy-5-methylphenyl) propionate was added and the unreacted monomer was recovered and the resin slurry was recovered in a polymerization reactor. The slurry thus obtained was dried in a fluidized bed drier by a conventional method to obtain a vinyl chloride polymer.
비교예Comparative example 2 2
상기 실시예 1에서 초기에 염화비닐 단량체 170kg을 투입하고, 중합전환율 15 내지 30% 기간에 염화비닐 단량체 180kg를 연속 추가 투입한 것 외에는 실시예 1과 동일 조건으로 중합을 행하고 평가하였다.In Example 1, 170 kg of the vinyl chloride monomer was initially added, and polymerization was carried out under the same conditions as in Example 1, except that 180 kg of the vinyl chloride monomer was continuously added in the polymerization conversion rate of 15 to 30%.
비교예Comparative example 3 3
상기 실시예 1에서 초기에 염화비닐 단량체 300kg을 투입하고, 중합전환율 15 내지 30% 기간에 염화비닐 단량체 30kg를 연속 추가 투입한 것 외에는 실시예 1과 동일 조건으로 중합을 행하고 평가하였다.In Example 1, 300 kg of vinyl chloride monomer was initially added, and polymerization was carried out under the same conditions as in Example 1 except that 30 kg of vinyl chloride monomer was continuously added in a polymerization conversion rate of 15 to 30%.
비교예Comparative example 4 4
상기 실시예 1에서 초기에 염화비닐 단량체 300kg을 투입하고, 중합전환율 5 내지 15% 기간에 염화비닐 단량체 200kg를 연속 추가 투입한 것 외에는 실시예 1과 동일 조건으로 중합을 행하고 평가하였다.In Example 1, 300 kg of vinyl chloride monomer was initially added, and polymerization was carried out under the same conditions as in Example 1, except that 200 kg of vinyl chloride monomer was continuously added in a polymerization conversion rate of 5 to 15%.
비교예Comparative example 5 5
상기 실시예 1에서 초기에 염화비닐 단량체 230kg을 투입하고, 중합전환율 40 내지 50% 기간에 염화비닐 단량체 120kg를 연속 추가 투입한 것 외에는 실시예 1과 동일 조건으로 중합을 행하고 평가하였다.230 kg of vinyl chloride monomer was initially charged in Example 1, and polymerization was carried out under the same conditions as in Example 1 except that 120 kg of vinyl chloride monomer was continuously added in a polymerization conversion period of 40 to 50%.
비교예Comparative example 6 6
상기 실시예 1에서 초기에 염화비닐 단량체 300kg을 투입하고, 중합전환율 15 내지 30% 기간에 염화비닐 단량체 50kg를 연속 추가 투입한 것 외에는 실시예 1과 동일 조건으로 중합을 행하고 평가하였다.In Example 1, 300 kg of vinyl chloride monomer was initially charged, and polymerization was carried out under the same conditions as in Example 1 except that 50 kg of vinyl chloride monomer was continuously added in a polymerization conversion rate of 15 to 30%.
비교예Comparative example 7 7
50℃ 탈이온수를 390kg 투입하고, 수화도가 78%인 폴리비닐알코올 120g, 수화도가 40%인 폴리비닐알코올 80g, 하이드록시프로필메틸 셀룰로오스 50g을 반응기에 일괄 투입하고, 염화비닐 단량체 300kg을 투입한 후 디-2-에틸헥실퍼옥시디카보네이트 30g, t-부틸퍼옥시 네오데카노에이트 120g을 투입한 후 중합반응 온도를 평균 중합도 800을 달성하기 위해 중합반응 전 과정 동안 65℃로 유지하면서 반응을 진행시키고, 중합반응기 압력이 8.0kg/cm2에 도달한 시점에 반응 종결제를 첨가한 다음 미반응 단량체를 회수하고 수지 슬러리를 중합반응기에서 회수하였다. 이렇게 하여 얻어진 슬러리를 통상의 방법으로 유동층 건조기에서 건조하여 염화비닐 중합체를 얻었다.390 kg of deionized water at 50 ° C. was added, 120 g of polyvinyl alcohol having a degree of hydration of 78%, 80 g of polyvinyl alcohol having a degree of hydration of 40%, and 50 g of hydroxypropylmethyl cellulose were added to a reactor, and 300 kg of vinyl chloride monomer was added thereto. After adding 30 g of di-2-ethylhexyl peroxydicarbonate and 120 g of t-butyl peroxy neodecanoate, the reaction was carried out while maintaining the polymerization temperature at 65 ° C. during the entire polymerization process to achieve an average degree of polymerization of 800. It proceeded, the reaction terminator was added at the time when the polymerization reactor pressure reached 8.0 kg / cm <2> , the unreacted monomer was collect | recovered, and the resin slurry was collect | recovered in the polymerization reactor. The slurry thus obtained was dried in a fluidized bed drier by a conventional method to obtain a vinyl chloride polymer.
비교예Comparative example 8 8
상기 실시예 1에서 83℃ 탈이온수 390kg을 투입하고, 중합반응 평균 중합도 800을 달성하기 위해 중합반응 전 과정 동안 65℃로 유지하면서 반응을 진행시켰으며, 초기에 염화비닐 단량체 300kg을 투입하고, 중합전환율이 5 내지 15% 기간에 염화비닐 단량체 20kg을 연속 추가 투입한 것 외에는 실시예 1과 동일 조건으로 중합을 행하고 평가하였다.In Example 1, 390 kg of deionized water was added to 83 ° C., and the reaction was performed while maintaining the temperature at 65 ° C. during the entire polymerization process to achieve a polymerization degree of polymerization degree 800. Initially, 300 kg of vinyl chloride monomer was added to the polymerization. The polymerization was carried out under the same conditions as in Example 1 except that 20 kg of vinyl chloride monomer was continuously added in the conversion period of 5 to 15%.
비교예Comparative example 9 9
상기 실시예 1에서 83℃ 탈이온수 390kg을 투입하고, 중합반응 평균 중합도 800을 달성하기 위해 중합반응 전 과정 동안 65℃로 유지하면서 반응을 진행시켰으며, 초기에 염화비닐 단량체 230kg을 투입하고, 중합전환율이 40~50% 기간에 염화비닐 단량체 120kg을 연속 추가 투입한 것 외에는 실시예 1과 동일 조건으로 중합을 행하고 평가하였다.In Example 1, 390 kg of deionized water was added to 83 ° C., and the reaction was performed while maintaining the temperature at 65 ° C. during the entire polymerization process in order to achieve an average polymerization degree of 800. The polymerization was carried out under the same conditions as in Example 1 except that 120 kg of vinyl chloride monomer was continuously added in the conversion period of 40 to 50%.
[시험예][Test Example]
상기 실시예 1 내지 9 및 비교예 1 내지 9에서 제조된 염화비닐계 중합체의 가공물성과 중합 반응 도중 중합전환율을 하기의 방법으로 측정하고, 그 결과를 하기 표 1 및 표 2에 나타내었다.The workability of the vinyl chloride polymers prepared in Examples 1 to 9 and Comparative Examples 1 to 9 and the polymerization conversion rate during the polymerization reaction were measured by the following methods, and the results are shown in Tables 1 and 2 below.
* 중합 반응계의 체적 수축 측정: 반응기 내부 상부에 설치된 수위(level) 측정 장치를 이용하여 측정하였다.* Measurement of volumetric shrinkage of polymerization system: Measured using a level measuring apparatus installed in the upper part of the reactor.
* 중합전환율의 측정: 가스크로마토그라피를 장착한 부탄 트레이서(Butain tracer)를 이용하여 측정하였다. 일정 중합 조건에서 시간에 따른 염화비닐 단량체와 부탄과의 비율에 따른 중합전환율 곡선을 중합 조건 때마다 작성해 두면, 중합 조건에 따른 중합전환율을 정밀도 좋게 측정할 수 있다.* Measurement of the polymerization conversion rate: It was measured using a butane tracer equipped with gas chromatography. When the polymerization conversion curve according to the ratio of vinyl chloride monomer and butane over time under constant polymerization conditions is prepared for each polymerization condition, the polymerization conversion rate according to the polymerization conditions can be measured with high accuracy.
* 중합시간 측정: 개시제가 투입된 시점부터 반응이 종료될 때까지 시간을 측정하였다.* Polymerization time measurement: The time from when the initiator was introduced until the end of the reaction was measured.
* 중합 생산성 평가: 배치당 생산량 단위 시간 당 생산되는 염화비닐계 중합체 산출량을 측정하였다.* Evaluation of polymerization productivity: The amount of vinyl chloride-based polymer produced per unit time of production per batch was measured.
* 중합도 측정: ASTM D1 243-79에 의해 측정하였다.* Measurement of polymerization degree: Measured by ASTM D1 243-79.
* 겉보기 비중 측정: ASTM D1 895-89에 의거하여 측정하였다.* Apparent Specific Gravity: Measured according to ASTM D1 895-89.
* 평균 입경 및 입자 분포도 측정: ASTM D1 705의 입자 분포 측정법에 의거하여 평균입경 및 #200의 체를 통과한 시료의 중량%를 구하여 측정하였다.* Measurement of average particle size and particle distribution: The average particle size and the weight percentage of the sample passed through the sieve of # 200 were measured according to the particle distribution measurement method of ASTM D1 705 and measured.
* 초기 착색성 평가: 얻어진 수지 100중량부에 주석계 안정제 1중량부, 납계 안정제 0.5중량부, 안정제 1.5중량부, 가소제 45중량부를 배합하고, 롤을 이용하여 150℃로 5분간 혼련한 뒤 시트를 얻었다. 상기 시트를 절단하고 겹치고 프레스 성형을 통해 압축 시트를 작성하였다. 이를 육안으로 관찰하고 다음과 같은 기준으로 평가하였다.Evaluation of initial coloring property: 1 part by weight of a tin stabilizer, 0.5 part by weight of a lead stabilizer, 1.5 parts by weight of a stabilizer, and 45 parts by weight of a plasticizer were compounded in 100 parts by weight of the obtained resin and kneaded using a roll at 150 DEG C for 5 minutes. . The sheet was cut and overlapped, and a compression sheet was formed through press molding. This was observed with the naked eye and evaluated according to the following criteria.
◎ - 비교예 1을 기준으로 하고, 이와 동일한 정도의 착색도를 갖고 실용상 문제가 없는 수준일 경우≪ - > - On the basis of Comparative Example 1, when the degree of coloration is the same as that of Comparative Example 1 and there is no practical problem
○ - 비교예 1을 기준으로 하고, 약간 뒤떨어지지만 이상이 없는 정도의 착색도를 갖고 실용상 문제가 없는 수준일 경우○ - In the case of Comparative Example 1 as a standard and having a degree of discoloration of a little behind but no abnormality and practically no problem
× - 비교예 1 대비 착색도가 명백히 차이가 나며, 색조가 다른 실용상 문제가 있는 수준일 경우× - When the degree of discoloration relative to Comparative Example 1 is clearly different and the color tone is at a level with a practical problem
* 휘시아이(fish-eye)수: 염화비닐계 중합체 100중량부, DOP 45중량부, 스테아린산 바륨 0.1중량부, 주석계 안정제 0.2중량부, 카본블랙 0.1중량부를 140℃의 6인치 롤을 이용하여 5분간 혼합 혼련한 다음 두께 0.3mm의 시트를 만들고, 이 시트의 400cm2 중의 백색 투명 입자수로 나타내었다.Fish-eye water: 100 parts by weight of vinyl chloride polymer, 45 parts by weight of DOP, 0.1 part by weight of barium stearate, 0.2 part by weight of tin stabilizer and 0.1 part by weight of carbon black were melt- After mixing and kneading for 5 minutes, a sheet having a thickness of 0.3 mm was formed, and this sheet was expressed by the number of white transparent particles in 400 cm 2 .
(min)Polymerization time
(min)
(Kg)Polymerization yield
(Kg)
(g/cc)In volume ratio
(g / cc)
(#200)Particle distribution
(# 200)
(min)Polymerization time
(min)
(Kg)Polymerization yield
(Kg)
(g/cc)In volume ratio
(g / cc)
(#200)Particle distribution
(# 200)
상기 표 1에 나타낸 바와 같이, 70 내지 100℃ 범위 내 고온 중합수를 사용하여 중합을 개시한 다음, 초기 염화비닐 단량체의 투입 비율은 전체 염화비닐 단량체 투입량의 50~80%를 투입하고, 중합전환율 15 내지 30% 기간에 염화비닐 단량체를 연속 추가 투입한 실시예 1 내지 9에서는 초기 착색성, 휘시아이 등 측정한 물성 전반에 걸쳐 개선된 결과를 확인할 수 있었다.As shown in Table 1, after the polymerization is started using high temperature polymerization water in the range of 70 to 100 ℃, the input ratio of the initial vinyl chloride monomer is added 50 to 80% of the total amount of the vinyl chloride monomer, polymerization conversion rate In Examples 1 to 9 in which the vinyl chloride monomer was additionally added in the 15 to 30% period, the improved results were obtained throughout the measured physical properties such as initial coloring property and whiskey.
이에 반해, 상기 표 2에서 보듯이, 고온 중합수를 사용하지 않고 염화비닐 단량체도 반응 중에 추가하지 않은 비교예 1 및 7에서는 휘사아이가 많고, 중합생산성이 좋지 않았으며, 고온 중합수는 사용하였으나, 염화비닐 단량체를 중합전환율 15 내지 30%를 벗어난 기간에 투여한 비교예 4 내지 8에서는 휘시아이가 많고, 중합 생산성 증대 효과가 미미함을 알 수 있다. 또 비교예 5 내지 6, 9에서와 같이 중합전환율 30% 이후 너무 늦게 염화비닐 단량체를 연속 추가 투입하여 초기 착색성과 휘시아이 측면에서 불량한 결과가 나왔으며, 비교예 2에서와 같이 초기 염화비닐 단량체의 투입 비율이 전체 염화비닐 단량체 투입량의 50% 미만인 경우, 미세 입자가 증가되어 초기 착색성이 나빠지며, 중합 생산성 증대 효과가 미미함을 알 수 있다.On the other hand, as shown in Table 2, in Comparative Examples 1 and 7 in which no high temperature polymerized water and no vinyl chloride monomer were added during the reaction, there were a lot of volatiles and poor polymerization productivity, and high temperature polymerized water was used. In Comparative Examples 4 to 8 in which the vinyl chloride monomer was administered in a period outside the polymerization conversion rate of 15 to 30%, it was found that the amount of whiskey was large and the effect of increasing the polymerization productivity was insignificant. In addition, as in Comparative Examples 5 to 6 and 9, the addition of vinyl chloride monomer was continuously added too late after the polymerization conversion rate was 30%, resulting in poor initial coloring and volatilization, and as shown in Comparative Example 2, If the input ratio is less than 50% of the total amount of the vinyl chloride monomer, fine particles are increased, the initial colorability is poor, it can be seen that the effect of increasing the polymerization productivity is insignificant.
따라서, 본 발명의 발명에 따른 실시예 1 내지 9의 경우 중합 생산성과 안정적인 품질 확보 측면에서 가장 유리한 공정임을 확인 할 수 있었다.
Therefore, in the case of Examples 1 to 9 according to the invention of the present invention it was confirmed that the most advantageous process in terms of ensuring the polymerization productivity and stable quality.
Claims (10)
상기 현탁중합은 염화비닐계 단량체를 70 내지 100℃의 고온 중합수를 사용하여 중합시키되, 염화비닐계 단량체를 중합 초기에 전체 염화비닐계 단량체 투입량의 50 내지 80중량%를 투입하고, 중합전환율이 15 내지 30%일 때 나머지 20 내지 50중량%의 염화비닐계 단량체를 투입 개시 및 완료하고 일정 압력에 도달한 시점에 반응 종결제를 투입하는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.In the production method of a vinyl chloride resin by suspension polymerization,
In the suspension polymerization, the vinyl chloride monomer is polymerized using high temperature polymerized water at 70 to 100 ° C., but the vinyl chloride monomer is charged at 50 to 80 wt% of the total amount of the vinyl chloride monomer in the initial stage of polymerization, and the polymerization conversion rate is 15 to 30% of the remaining 20 to 50% by weight of the vinyl chloride monomer, the method of producing a vinyl chloride-based polymer, characterized in that the start and completion of the input and the reaction terminator is added when a certain pressure is reached.
상기 현탁중합은 염화비닐계 단량체를 70 내지 100℃의 고온 중합수를 사용하여 중합시키되, 염화비닐계 단량체를 중합 초기에 전체 염화비닐계 단량체 투입량의 50 내지 80중량%를 투입하고, 중합전환율 12 내지 18%일 때 나머지 20 내지 50중량%의 염화비닐계 단량체를 투입하고, 중합전환율 27 내지 33%일 때 투입을 종료하고 일정 압력에 도달한 시점에 반응 종결제를 투입하는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The method of claim 1,
In the suspension polymerization, the vinyl chloride monomer is polymerized using high temperature polymerized water at 70 to 100 ° C., but the vinyl chloride monomer is charged at 50 to 80 wt% of the total amount of the vinyl chloride monomer in the initial stage of polymerization, and the polymerization conversion rate is 12 20 to 50% by weight of the remaining 20 to 50% by weight of the vinyl chloride monomer, and when the polymerization conversion rate of 27 to 33%, the end of the addition and the reaction terminator is added to the reaction terminator when a certain pressure is reached Method for producing a vinyl polymer.
상기 현탁중합은 상기 고온 중합수에 염화비닐 단량체 및 보호 콜로이드 조제가 혼합되고, 이 혼합용액에 중합 개시제가 투입되어 중합되는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The method of claim 1,
Wherein the suspension polymerization is carried out by mixing the high-temperature polymerized water with a vinyl chloride monomer and a protective colloid assistant, and introducing a polymerization initiator into the mixed solution to polymerize the vinyl chloride-based polymer.
상기 현탁중합은 염화비닐 단량체 100중량부에 대하여, 고온 중합수 120 내지 150중량부, 보호 콜로이드 조제 0.03 내지 5중량부 및 중합 개시제는 0.02 내지 0.2중량부인 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The method of claim 3,
Wherein the suspension polymerization is performed at a high temperature of 120 to 150 parts by weight, a protective colloid preparation of 0.03 to 5 parts by weight and a polymerization initiator of 0.02 to 0.2 parts by weight per 100 parts by weight of the vinyl chloride monomer .
상기 현탁중합은 중합 개시제 투입 시의 반응기 내부 온도가 중합개시온도 이상인 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The method of claim 3,
Wherein the suspension polymerization is carried out at a temperature within the reactor at the time when the polymerization initiator is charged into the polymerization reactor at a polymerization initiation temperature or higher.
상기 반응 종결제는 트리에틸렌 글리콜-비스-3-(3-t-부틸-4-하이드록시-5-메틸페닐)프로피오네이트, 하이드로퀴논, p-메톡시 페놀, t-부틸하이드록시아니솔, n-옥타데실-3-(4-히드록시-3,5-디-t-부틸 페닐)프로피오네이트, 2,5-디-t-부틸 하이드로퀴논, 4,4-부틸리덴비스(3-메틸-6-t-부틸 페놀), t-부틸 카테콜, 4,4-티오비스(6-t-부틸-m-크레졸), 토코페롤, N-N-디페닐-p-페닐렌 디아민, 4,4-비스(디메틸벤질)디페닐 아민, 2-페닐 니트로닐 니트록사이드, 3-이미다졸린 니트록사이드, 4-하이드록시-2,2,6,6-테트라메틸-피페리딘-1-옥시, 도데실 메르캅탄 및 1,2-디페닐-2-티올로 이루어진 군으로부터 1종 이상 선택되는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The method of claim 1,
The reaction termination may be carried out in the presence of a base such as triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, hydroquinone, p-methoxyphenol, di-t-butylhydroquinone, 4,4-butyrylidene bis (3-hydroxy-3,5-di-t-butylphenyl) propionate, 4-thiobis (6-t-butyl-m-cresol), tocopherol, NN-diphenyl-p-phenylenediamine, (Dimethylbenzyl) diphenylamine, 2-phenylnitronylnitroxide, 3-imidazoline nitroxide, 4-hydroxy-2,2,6,6-tetramethyl-piperidin- -Oxy, dodecyl mercaptan, and 1,2-diphenyl-2-thiol. The vinyl chloride-based polymer according to claim 1,
상기 보호 콜로이드 조제는 수화도가 30 내지 90중량%이고 상온에서 4% 수용액의 점도가 5 내지 100cps인 비닐알코올계 수지, 메톡시기가 15 내지 40중량%이고 수산화프로필기가 3 내지 20중량%이며 상온에서 측정한 2% 수용액의 점도가 10 내지 20,000cps인 셀룰로오스, 아크릴산 수지, 메타크릴산 수지, 이타콘산 수지, 푸마르산 수지, 말레인산 수지, 숙신산 수지 및 젤라틴으로 이루어진 군으로부터 1종 이상 선택된 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The method of claim 3,
The protective colloid preparation is a vinyl alcohol resin having a degree of hydration of 30 to 90% by weight and a viscosity of 4% aqueous solution at 5 to 100 cps at room temperature, 15 to 40% by weight of methoxy group, 3 to 20% by weight of propyl hydroxide, and room temperature At least one selected from the group consisting of cellulose, acrylic acid resin, methacrylic acid resin, itaconic acid resin, fumaric acid resin, maleic acid resin, succinic acid resin, and gelatin having a viscosity of 10 to 20,000 cps, measured in Method for producing vinyl chloride polymer.
상기 비닐알코올계 수지는 수화도가 85 내지 98%인 비닐알코올계 수지 및 수화도 50 내지 60%인 비닐알코올계 수지의 혼합물인 것을 특징으로 하는 염화비닐계 중합체의 제조방법.8. The method of claim 7,
The vinyl alcohol-based resin is a vinyl chloride-based polymer production method, characterized in that a mixture of a vinyl alcohol resin having a degree of hydration of 85 to 98% and a vinyl alcohol resin having a degree of hydration of 50 to 60%.
상기 중합전환율 12 내지 18%일 때 나머지 20 내지 50중량%의 염화비닐계 단량체를 투입하는 것은 연속 투입으로 실시되는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.The method of claim 1,
The method for producing a vinyl chloride-based polymer, characterized in that the addition of the remaining 20 to 50% by weight of the vinyl chloride monomer when the polymerization conversion rate is 12 to 18%.
상기 염화비닐계 단량체의 추가 투입량은 중합에 투입되는 전체 염화비닐 단량체의 투입량의 30 내지 40중량% 범위이며, 중합전환율 15 내지 30% 범위 내에서 투입하는 것을 특징으로 하는 염화비닐계 중합체의 제조방법.
The method of claim 1,
The addition amount of the vinyl chloride monomer is in the range of 30 to 40% by weight of the total amount of the vinyl chloride monomer added to the polymerization, the method of producing a vinyl chloride-based polymer, characterized in that the addition within the range of 15 to 30% polymerization conversion rate. .
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| WO2016195434A1 (en) * | 2015-06-05 | 2016-12-08 | 주식회사 엘지화학 | Method for preparing vinyl chloride-based copolymer and vinyl chloride-based copolymer prepared therefrom |
| KR20160143495A (en) * | 2015-06-05 | 2016-12-14 | 주식회사 엘지화학 | Thermoplastic resin composition, preparation method thereof and thermoplastic resin molded article produced by the same |
| US10336847B2 (en) | 2015-06-05 | 2019-07-02 | Lg Chem, Ltd. | Vinyl chloride-based polymer, method for preparing the same, and thermoplastic resin composition containing the same |
| CN116622014A (en) * | 2022-02-11 | 2023-08-22 | 石河子天域新实化工有限公司 | Thermal stability refining production process method of polyvinyl chloride resin |
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| JP3599953B2 (en) * | 1997-05-16 | 2004-12-08 | 株式会社カネカ | Method for producing vinyl chloride polymer |
| KR100983702B1 (en) * | 2006-08-22 | 2010-09-24 | 주식회사 엘지화학 | Process for producing vinyl chloride polymer with excellent processability |
| KR101168400B1 (en) * | 2008-07-07 | 2012-07-25 | 주식회사 엘지화학 | Suspension polymerization method for polyvinylchloride and polyvinylchloride produced thereby |
| WO2011055867A1 (en) * | 2009-11-04 | 2011-05-12 | 주식회사 엘지화학 | Vinyl chloride-based polymer |
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| WO2016195434A1 (en) * | 2015-06-05 | 2016-12-08 | 주식회사 엘지화학 | Method for preparing vinyl chloride-based copolymer and vinyl chloride-based copolymer prepared therefrom |
| KR20160143495A (en) * | 2015-06-05 | 2016-12-14 | 주식회사 엘지화학 | Thermoplastic resin composition, preparation method thereof and thermoplastic resin molded article produced by the same |
| US10287377B2 (en) | 2015-06-05 | 2019-05-14 | Lg Chem, Ltd. | Method of preparing vinyl chloride-based copolymer and vinyl chloride-based copolymer prepared thereby |
| US10336847B2 (en) | 2015-06-05 | 2019-07-02 | Lg Chem, Ltd. | Vinyl chloride-based polymer, method for preparing the same, and thermoplastic resin composition containing the same |
| CN116622014A (en) * | 2022-02-11 | 2023-08-22 | 石河子天域新实化工有限公司 | Thermal stability refining production process method of polyvinyl chloride resin |
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