KR20150037250A - Method of preparing vinyl chloride-based polymers by suspension polymerization system - Google Patents
Method of preparing vinyl chloride-based polymers by suspension polymerization system Download PDFInfo
- Publication number
- KR20150037250A KR20150037250A KR20130116707A KR20130116707A KR20150037250A KR 20150037250 A KR20150037250 A KR 20150037250A KR 20130116707 A KR20130116707 A KR 20130116707A KR 20130116707 A KR20130116707 A KR 20130116707A KR 20150037250 A KR20150037250 A KR 20150037250A
- Authority
- KR
- South Korea
- Prior art keywords
- polymerization
- weight
- vinyl chloride
- trivalent metal
- suspension
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000010557 suspension polymerization reaction Methods 0.000 title claims description 25
- 229920000915 polyvinyl chloride Polymers 0.000 title claims 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 68
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 238000006703 hydration reaction Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 230000036571 hydration Effects 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000003505 polymerization initiator Substances 0.000 claims description 9
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 13
- 239000002455 scale inhibitor Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 241000251468 Actinopterygii Species 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 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
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 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 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- -1 diaryl peroxide Chemical class 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- ZKEUVTROUPQVTM-UHFFFAOYSA-N 1-pentylperoxypentane Chemical compound CCCCCOOCCCCC ZKEUVTROUPQVTM-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
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 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 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- UXKQNCDDHDBAPD-UHFFFAOYSA-N 4-n,4-n-diphenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UXKQNCDDHDBAPD-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OIMLLKWVBAQLDN-UHFFFAOYSA-N C(CCCCCC(C)(C)C)(=O)OOCCCC.C(C)(C)OOC(C)C Chemical compound C(CCCCCC(C)(C)C)(=O)OOCCCC.C(C)(C)OOC(C)C OIMLLKWVBAQLDN-UHFFFAOYSA-N 0.000 description 1
- BVLLNHZIXWWTEW-UHFFFAOYSA-N CCCCCCCCOC(C1=CC=CC=C1C(OCCCCCCCC)=O)=O.Cl Chemical compound CCCCCCCCOC(C1=CC=CC=C1C(OCCCCCCCC)=O)=O.Cl BVLLNHZIXWWTEW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 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
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000010667 large scale reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 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 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-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
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 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
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-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
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
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
- C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
- C08F2/004—Scale prevention in a polymerisation reactor or its auxiliary parts by a prior coating on the reactor walls
-
- 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
- C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
- C08F2/005—Scale prevention in a polymerisation reactor or its auxiliary parts by addition of a scale inhibitor to the polymerisation medium
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
본 발명은 현탁 중합계 염화비닐계 중합체의 제조방법에 관한 것으로, 본 발명에 따르면, 신규 스케일 방지제 도입에 의해 스케일 부착을 억제하고 제열 효율을 상승시킬 수 있고, 반응기 세척시간을 단축시켜 반응생산성을 높일 수 있을 뿐 아니라, 재중합을 예방하여 돌기 품질도 개선할 수 있는 효과를 제공할 수 있다. The present invention relates to a process for producing a suspension polymerized vinyl chloride polymer. According to the present invention, scale adhesion can be suppressed by introducing a new scale inhibitor, heat recovery efficiency can be increased, reaction- It is possible to provide an effect of preventing recondensation and improving the quality of protrusions.
Description
본 발명은 현탁 중합계 염화비닐 중합체의 제조방법에 관한 것으로서, 더욱 상세하게는 신규 스케일 방지제를 도입하여 스케일 부착 억제에 의한 제열 효율 상승 및 반응기 세척시간 단축을 통하여 반응생산성을 높이고, 재중합을 예방함으로써 돌기 품질도 개선할 수 있는 현탁 중합계 염화비닐 중합체의 제조방법에 관한 것이다.
The present invention relates to a process for producing a suspension polymerized vinyl chloride polymer, and more particularly, to a process for producing a vinyl chloride polymer by suspension polymerization, which comprises introducing a new scale inhibitor to increase the heat- And a process for producing the vinyl chloride polymer.
염화비닐 중합체는 우수한 경제성과 함께 가공이 쉽고 중합 공정이 간단하여 여러 분야에서 이용되어 왔다. 염화비닐계 중합체는 염화비닐 또는 염화비닐과 공중합 가능한 단량체와의 혼합물을 중합시킨 혼성 중합체를 일컫는다.The vinyl chloride polymer has been used in various fields because of its excellent economical efficiency, easy processing, and simple polymerization process. The vinyl chloride polymer refers to an interpolymer obtained by polymerizing a mixture of vinyl chloride or a monomer copolymerizable with vinyl chloride.
간단히 중합 온도를 조절함으로써 중합도가 다른 중합체를 제조할 수 있고, 중합도에 따라 다른 특성을 갖기 때문에 경질과 연질 분야로 적용이 가능하다.
By controlling the polymerization temperature in a simple manner, polymers having different polymerization degrees can be produced, and they can be applied to hard and soft fields because they have different characteristics depending on their degree of polymerization.
우선, 경질 분야에서는 파이프, 필름, 창틀 등의 용도로 사용되고 있으며, 연질 분야에서는 전선 피복, 랩 필름, 시트 등의 용도로 사용되고 있다.Firstly, it is used for pipes, films, window frames and the like in the hard field, and is used for electric wire coating, wrap film and sheet in the soft field.
또한, 염화비닐 중합체의 중합 방식은 유화중합법과 현탁중합법으로 주로 제조되며, 현탁중합법에서는 물, 현탁 안정제, 염화비닐 단량체, 개시제를 사용하여 중합이 이루어지고, 150㎛ 정도의 입자로 중합되어 건조 후 바로 가공이 가능하다. 이렇게 중합된 염화비닐 중합체는 전기 절연 특성이 우수하며, 내화학성이 뛰어나 화학용기로도 많이 이용된다.The polymerization method of the vinyl chloride polymer is mainly produced by the emulsion polymerization method and the suspension polymerization method. In the suspension polymerization method, polymerization is carried out using water, a suspension stabilizer, a vinyl chloride monomer and an initiator, It can be processed immediately after drying. The polymerized vinyl chloride polymer is excellent in electrical insulation properties and excellent in chemical resistance, and is widely used as a chemical container.
유화중합법은 물, 유화제, 염화비닐 단량체, 개시제를 사용하여 중합하게 되는데, 유화중합법으로 제조된 염화비닐 중합체는 점도 안정성이 우수하며 제품 가공시 흐름성이 좋은 특성을 지니고, 발포성이 우수하여 바닥재로 많이 쓰인다.
The emulsion polymerization is carried out by using water, an emulsifier, a vinyl chloride monomer, and an initiator. The vinyl chloride polymer produced by the emulsion polymerization method has excellent viscosity stability, good flow properties during product processing, It is often used as flooring.
통상적으로 염화비닐 단량체의 현탁중합은 회분식으로 행해지고, 염화비닐 단량체 및 개시제 첨가제를 넣은 후 중합 온도까지 승온하여 중합 반응을 개시시킨다. 그리고 발열 반응에 의하여 열이 발생하면 재킷에 냉각수를 흘려 중합 온도를 유지하도록 하는 방법을 통하여 염화비닐계 중합체를 중합한다.Usually, the suspension polymerization of the vinyl chloride monomer is carried out batchwise, the vinyl chloride monomer and the initiator additive are added, and the temperature is raised to the polymerization temperature to initiate the polymerization reaction. When heat is generated by the exothermic reaction, the vinyl chloride polymer is polymerized by flowing cooling water through the jacket to maintain the polymerization temperature.
이렇게 현탁중합을 통하여 염화비닐 중합체를 생산하는데 있어서 고효율 및 생산량 증대 효과를 얻기 위하여 최근 국내외 기업에서는 100m3 이상의 대형화 반응기술로 이행하는 추세이다. 대형 반응기는 생산성 증대 효과가 우수하나, 그에 따른 여러 문제점들이 수반된다.
In order to obtain a high efficiency and a production increase effect in the production of the vinyl chloride polymer through the suspension polymerization, the domestic and foreign companies are moving to a large-scale reaction technology of 100 m 3 or more. Large reactors are excellent in increasing productivity, but they are accompanied by various problems.
특히 반응기가 대형화됨에 따라 재킷이 차지하는 제열 면적이 상대적으로 작아지기 때문에 제열 능력을 설정함에 있어 매우 신중할 필요가 있다. 제열 효율을 낮추는 원인 중의 하나는 반응 중 생성되는 스케일(scale)을 들 수 있다.
Particularly, as the reactor becomes larger, the jacket occupies a relatively small area, so it is necessary to be very careful in setting the heat-separating ability. One of the reasons for lowering the heat removal efficiency is the scale generated during the reaction.
일반적인 염화비닐 중합시 반응기 내벽에 발생하는 스케일은 휘시아이 및 열안정성, 전환율 감소, 반응기 세척시간, 제열효율 등에 영향을 주어 물성 및 생산성 저하의 원인이 된다. 즉, 반응기 내벽에 스케일이 발생하는 경우 열 전달이 잘 이루어지지 않아 반응시간이 길어지는 문제가 발생한다. 또한 심한 경우 제열이 잘 이루어지지 않아 반응 중 비정상적으로 반응 압력이 상승하여 반응기 폭발의 위험을 가져올 수 있다. 또한 대형반응기화 될수록 재킷 제열능력이 떨어짐에 따라 발생하는 스케일을 억제하는 것이 안정상으로도 중요한 문제로 부각되고 있다.
In general vinyl chloride polymerization, the scale generated on the inner wall of the reactor affects the thermal stability, the conversion rate, the reactor cleaning time, the thermal efficiency and the like, thereby causing deterioration of physical properties and productivity. That is, when scale is generated on the inner wall of the reactor, the heat transfer is not performed well and the reaction time becomes long. In addition, in severe cases, heat removal is not performed well, resulting in abnormally increased reaction pressure during the reaction, which may lead to explosion of the reactor. In addition, as the reactor becomes larger, the ability to suppress the scale caused by the deterioration of the jacket heat-dissipating ability becomes an important issue.
또한 환류 응축기를 사용하는 반응기가 늘어남에 따라 환류 응축기의 세척(cleaning) 상태가 매우 중요한 품질 편차 요소로 작용할 수 있다. 환류 응축기는 그 표면적이 넓게 제조된 만큼 표면 성질이 매우 중요하고, 그에 따라 스케일이 발생한 경우 제열 효율에 극심한 저하를 가져온다. 게다가 환류 응축기에 쌓인 스케일은 세척에도 어려움이 있어 다음 배치의 돌기 품질에도 악 영향을 끼치게 된다.
Also, as the reactor using the reflux condenser is increased, the cleaning state of the reflux condenser can be a very important quality deviation factor. Since the reflux condenser has a large surface area, its surface property is very important, and when scale is generated, there is a drastic decrease in the heat removal efficiency. In addition, the scale built up in the reflux condenser is difficult to clean and will adversely affect the quality of the next batch of projections.
이러한 문제점을 해결하기 위하여, 미국특허 5,780,104호에서는 페놀계 화합물을 염기성 수용액에 녹여 반응기 내벽에 코팅하는 방법을 통하여 반응기 내벽의 스케일 발생을 억제하는 기술을 개시하였고, 미국특허 4,451,625호에서는 금속 하이드록사이드를 반응기에 코팅하는 방법을 통해 스케일 발생을 억제한 기술을 개시하였다. In order to solve such a problem, U.S. Patent No. 5,780,104 discloses a technique for inhibiting scale formation on the inner wall of a reactor by dissolving a phenolic compound in a basic aqueous solution and coating the inner wall of the reactor. In U.S. Patent No. 4,451,625, A method of coating a catalyst on a reactor is disclosed.
이들은 현재에도 사용되는 방법들로서 적용 물질이 다양화되고 있으나, 대부분이 염기성 수용액을 사용함으로 중합 중 부반응으로 발생하는 HCl에 의한 코팅 막이 파괴되는 단점과 색상이 매우 진한 검정색이기 때문에 염화비닐 중합체의 백색도 저하의 원인으로 작용할 수 있다는 단점 들이 존재하였다.However, since most of the materials are used in a basic aqueous solution, the coating film is destroyed by HCl which is generated as a side reaction during polymerization, and since the color is very dark black, the whiteness of the vinyl chloride polymer Which is the cause of the problem.
이뿐 아니라, 방법을 일본공개특허 1998-120708호에서는 중합반응 개시시 탄소수 12~31의 포화 고급 지방산 및 탄소수 15~31의 포화 고급 알코올을 첨가하여 스케일을 억제하는 기술을 제안하였지만, 상기 물질들이 0.1~3중량부로 첨가되어 제조원가를 높이는 문제가 있다. 또한 일본공개특허 1998-265511호에서는 중합율에 따라 교반력을 변화시킴으로써 반응기 내벽의 응집률을 낮추는 방법에 대해 기술하였으나, 스케일 개선 효과가 미미하였다.
In addition, Japanese Unexamined Patent Publication No. 1998-120708 proposes a technique for suppressing scale by adding a saturated higher fatty acid having 12 to 31 carbon atoms and a saturated higher alcohol having 15 to 31 carbon atoms at the start of the polymerization reaction. However, To 3 parts by weight, which raises the manufacturing cost. Also, in Japanese Laid-Open Patent Application No. 1998-265511, a method of lowering the coagulation rate of the inner wall of the reactor by changing the agitation force according to the polymerization rate has been described, but the scale improvement effect is insignificant.
상술한 종래 기술의 문제점을 해결하기 위하여, 본 발명자들은 반응기 내부 및 환류 응축기 내부의 스케일 억제를 통하여 휘시아이 특성이 향상되고, 재킷의 제열효과를 높여 결과적으로 생산성 향상 및 전환율 향상의 효과를 가져오는 염화비닐 중합체의 제조방법에 대한 다양한 해결 방안을 검토하던 중, 특정 3가 금속 황산염을 반응기 내벽에 코팅하거나, 중합 중에 투입하면 반응기에 스케일 발생을 억제하여 휘시아이 특성을 개선하고, 열안정성 개선의 효과가 있으며, 나아가서는 제열효율 증대 및 세척시간 단축으로 인해 전환율 향상 및 생산성 향상을 제공할 수 있다는 것을 확인하고 본 발명을 완성하기에 이르렀다.
In order to solve the problems of the prior art described above, the present inventors have found that by controlling the scale inside the reactor and the inside of the reflux condenser, the fish eye characteristics are improved and the jacket heating effect is enhanced, In studying various solutions for the production method of the vinyl chloride polymer, when the specific trivalent metal sulfate is coated on the inner wall of the reactor or added during the polymerization, scaling is suppressed in the reactor to improve the fish eye characteristics, And further, it is possible to improve the conversion efficiency and the productivity by increasing the thermal efficiency and shortening the cleaning time. Thus, the present invention has been accomplished.
즉, 본 발명의 목적은 반응기 내벽, 및 환류 응축기의의 스케일을 줄일 수 있는 현탁중합계 염화비닐 중합체의 제조방법을 제공하려는데 있다.
That is, an object of the present invention is to provide a method for producing a suspension vinyl chloride polymer capable of reducing the scale of the reactor inner wall and the reflux condenser.
또한, 본 발명의 목적은 스케일 방지제를 내벽과 환류 응축기 내벽에 코팅 또는 투입함으로써 반응기 내벽의 스케일 발생을 억제하는 동시에 휘시 아이 품질과 열안정성을 개선하며, 재킷을 통한 반응기 제열 효율을 향상시킴으로써 결과적으로 품질과 생산성이 우수한 현탁중합계 염화비닐 중합체의 제조방법을 제공하려는데 있다.
It is also an object of the present invention to provide a method of manufacturing a reactor, which comprises coating or injecting an anti-scale agent on the inner wall and the inner wall of the reflux condenser, thereby suppressing scale formation on the inner wall of the reactor, improving the quality of the fish eye and improving thermal stability, The present invention provides a method for producing a suspension-polymerized vinyl chloride polymer which is excellent in quality and productivity.
상기의 목적을 달성하기 위하여, 본 발명에 따르면, In order to achieve the above object, according to the present invention,
현탁 안정제, 중합 개시제 및 염화비닐 단량체의 현탁 중합계에 있어서, 상기 중합계는 3가 금속 황산염을 포함하는 것을 특징으로 하는 현탁 중합계, 및 상기 현탁 중합계를 사용하는 것을 특징으로 하는 염화비닐계 중합체의 제조방법을 각각 제공한다.
A suspension polymerization system comprising a suspension stabilizer, a polymerization initiator and a vinyl chloride monomer, wherein the polymerization system comprises a trivalent metal sulfate, and a suspension polymerization system characterized by using the suspension polymerization system Respectively. ≪ / RTI >
본 발명의 현탁 중합계 염화비닐 중합체의 제조방법에 따르면, 신규 스케일 방지제 도입에 의해 스케일 부착을 억제하고 제열 효율을 상승시킬 수 있고, 반응기 세척시간을 단축시켜 반응생산성을 높일 수 있을 뿐 아니라, 재중합을 예방하여 돌기 품질도 개선할 수 있는 효과를 제공할 수 있다.
According to the process for producing a suspension polymerization-type vinyl chloride polymer of the present invention, the scale adhesion can be suppressed by introducing the new scale inhibitor, the heat removal efficiency can be raised, the reactor cleaning time can be shortened, The effect of preventing the polymerization and improving the quality of the protrusion can be provided.
이하, 본 발명에 대하여 보다 상세하게 설명한다.
Hereinafter, the present invention will be described in more detail.
우선, 본 발명은 현탁 안정제, 중합 개시제 및 염화비닐 단량체의 현탁 중합계에 있어서, 상기 중합계는 3가 금속 황산염을 포함하는 것을 기술적 특징으로 한다.
First, the present invention is characterized in that in the suspension polymerization system of a suspension stabilizer, a polymerization initiator and a vinyl chloride monomer, the polymerization system includes a trivalent metal sulfate.
본 발명에서 사용하는 용어 “3가 금속 황산염”은 달리 특정하지 않는 한 수용액 상태에서 산성을 띠며 특히 알칼리 (토)금속계의 아황산염/황산염/과황산염을 모두 배제하고, 3가의 금속을 포함하는 황산염을 지칭한다.
The term " trivalent metal sulfate " used in the present invention is acidic in an aqueous solution state, unless otherwise specified, and specifically excludes sulfites / sulfates / persulfates of alkali metals and includes sulfates containing trivalent metals Quot;
구체적인 예로, 상기 3가 금속 황산염은 현탁 중합 반응기의 내부 코팅물로 포함된 것을 특징으로 한다.
As a specific example, the trivalent metal sulfate is characterized by being contained as an inner coating of a suspension polymerization reactor.
또 다른 예로, 상기 3가 금속 황산염은 일례로 현탁 중합 반응기에 구비된 환류 응축기의 내부 코팅물로 포함된 것을 특징으로 한다.
As another example, the trivalent metal sulfate may be included, for example, as an internal coating of a reflux condenser provided in a suspension polymerization reactor.
또 다른 예로, 상기 3가 금속 황산염은 중합 도중 반응기에 포함된 것을 특징으로 한다. As another example, the trivalent metal sulfates are characterized in that they are included in the reactor during polymerization.
구체적인 예로, 상기 3가 금속 황산염은 중합의 전환율 30 내지 80%, 혹은 30 내지 60% 지점에 포함된 것일 수 있다. 참고로, 중합전환율 30% 이전에 투입시 물과 염화비닐 단량체의 계면안정성을 저하시키고 pH에 변화를 주어, 그에 따른 입경, 가소제 흡수율, 미세입자 함량에 변화를 줄 수 있으며, 80% 이후에 투입시 스케일 발생 후이므로 투입 효과를 얻을 수 없다.
As a specific example, the trivalent metal sulfate may be contained at a conversion rate of 30 to 80%, or 30 to 60% of the polymerization. For reference, it is possible to lower the interfacial stability of water and vinyl chloride monomer by changing the pH and to change the particle diameter, the plasticizer absorption rate and the fine particle content when the polymerization conversion rate is 30% or less, Since the scale is generated after the scale is turned on, the input effect can not be obtained.
또한, 상기 3가 금속 황산염은 연속 투입, 간헐 투입 혹은 일괄 투입된 것일 수 있다.
In addition, the trivalent metal sulfate may be continuously charged, intermittently charged or batch charged.
구체적인 적용예를 살펴보면, 염화비닐계 단량체를 중합시 부원료 투입 전 반응기를 세척한 단계에서 3가 금속 황산염을 반응기 내벽 및 환류 응축기에 코팅하여 중합을 개시하거나, 현탁 안정제, 중합 개시제 및 염화비닐 단량체의 존재 하에 중합을 개시하고, 중합 중 스케일 발생이 일어나는 시점인 중합전환율 30~80% 시점에 연속적 또는 간헐적, 일괄적으로 3가 금속 황산염을 투입함으로써 반응기 내벽에 발생되는 스케일을 억제할 수 있다.
As concrete examples of application, when the vinyl chloride monomer is polymerized, the polymerization is started by coating the inner wall of the reactor and the reflux condenser with the trivalent metal sulfate in the step of washing the reactor before the addition of the raw material, or the suspension stabilizer, the polymerization initiator and the vinyl chloride monomer And the scale generated at the inner wall of the reactor can be suppressed by injecting the trivalent metal sulfate continuously or intermittently at the time of polymerization conversion of 30 to 80% at the time of occurrence of scale during the polymerization.
상기 3가 금속 황산염은 현탁 중합에 사용되는 염화비닐 단량체 100중량부에 대하여 일례로, 0.005 내지 0.1중량부 혹은 0.005 내지 0.06 중량부 범위 내인 것일 수 있다. 상기 하한치 미만에서는 스케일 방지 효과가 미미하여 원하는 목적을 달성할 수 없고, 상한치 초과시에는 염화비닐 중합수의 pH 변화를 초래하고 그 결과 최종 수지의 물성과 입경 변화를 초래할 수 있고 제조단가 측면에서도 적절하지 않다.
The trivalent metal sulfate may be 0.005 to 0.1 part by weight or 0.005 to 0.06 part by weight per 100 parts by weight of the vinyl chloride monomer used in the suspension polymerization. Below the lower limit, the effect of preventing scale is insignificant and the desired purpose can not be achieved. When the upper limit is exceeded, the pH of the vinyl chloride polymerized water is changed. As a result, the physical properties and particle size of the final resin may be changed, .
상기 3가 금속 황산염은 일례로, Ga3+, Fe3+, Al3+, In3+, Ru3+, Sc3+, Y3+ 중에서 선태된 1 이상의 3가 금속을 포함하는 황산염 일 수 있다. 3가 금속 황산염은 금속 부식 방지제 역할 뿐 아니라, 수중에 존재하는 금속 이온을 포착하는 수처리제 역할도 수행할 수 있어 반응기 벽면의 부식하여 발생된 금속 이온 또는 단량체에 함유되어 물성에 악영향을 주는 금속이온들과 착물을 형성하여 스케일 발생을 억제하고 열안정성에 좋은 영향을 줄 수 있다.
The trivalent metal sulfate may be, for example, a sulfate including at least one trivalent metal selected from Ga3 +, Fe3 +, Al3 +, In3 +, Ru3 +, Sc3 + and Y3 +. The trivalent metal sulfate acts not only as a metal corrosion inhibitor but also as a water treatment agent for capturing metal ions present in the water. Therefore, metal ions generated by corrosion of the reactor wall surface or metal ions which are contained in monomers and adversely affect physical properties To form a complex, thereby suppressing scale generation and having a good effect on thermal stability.
상기 현탁 안정제는 일례로, 수화도가 30 내지 90중량%이고 상온에서 4~5% 수용액의 점도가 10 내지 60cps인 비닐 알코올계 수지, 메톡시기가 15 내지 40중량%이고 수산화프로필기가 3 내지 20중량%이며 상온에서 측정한 2% 수용액의 점도가 10 내지 20,000cps인 셀룰로오스 및 불포화 유기산 중에서 선택된 1종 이상인 것일 수 있다.
Examples of the suspension stabilizer include a vinyl alcohol resin having a hydration degree of 30 to 90% by weight and a viscosity of 4 to 5% aqueous solution at room temperature of 10 to 60 cps, a propyl methacrylate resin having a methoxy group content of 15 to 40% By weight and a viscosity of 2% aqueous solution measured at room temperature is 10 to 20,000 cps, and an unsaturated organic acid.
상기 현탁 안정제의 함량은 일례로, 현탁 중합에 사용되는 염화비닐 단량체 100중량부에 대하여 0.03 내지 5중량부 범위 내일 수 있다.
The content of the suspension stabilizer may be, for example, 0.03 to 5 parts by weight based on 100 parts by weight of the vinyl chloride monomer used in the suspension polymerization.
상기 중합 개시제의 함량은 일례로, 현탁 중합에 사용되는 염화비닐 단량체 100중량부에 대하여 0.02 내지 0.2중량부 범위 내일 수 있다.
The content of the polymerization initiator is, for example, 0.02 to 0.2 parts by weight per 100 parts by weight of the vinyl chloride monomer used in the suspension polymerization.
상술한 현탁 중합계를 사용하고 염화비닐계 중합체를 제조하는 방법을 제공할 수 있다.
There can be provided a method for producing a vinyl chloride polymer by using the suspension polymerization system described above.
구체적으로, 염화비닐 단량체는 중합수가 투입되고, 분산제 및 개시제가 투입된 다음 투입되는 것일 수 있다. Specifically, the vinyl chloride monomer may be such that the polymerization water is introduced, and the dispersant and the initiator are charged and then charged.
상기 염화비닐 단량체에는 공중합 단량체를 병용할 수 있으며, 일례로 에틸렌, 프로필렌 등의 올레핀 화합물, 초산 비닐, 프로피온산 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 등과 같은 공중합가능한 비닐계 단량체들 중에서 선택된 1종 이상을 사용할 수 있다.The vinyl chloride monomer may be used in combination with a copolymerizable monomer. Examples thereof include olefins 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, methacrylic acid, itaconic acid, and maleic acid, and anhydrides of these fatty acids, and the like.
상기 염화비닐 단량체의 현탁 중합시 공정을 안정적으로 유지하면서 안정한 입자를 얻도록 사용하는 보호 콜로이드 조제는 일례로, 수화도가 31 내지 90 중량%이고 상온에서 4% 수용액의 점도가 10 내지 60 cps인 비닐알콜계 수지, 메톡시기가 15 내지 40 중량%이고 수산화프로필 기가 3 내지 20 중량%이며 상온에서 측정한 2% 수용액의 점도가 10 내지 20,000 cps인 셀룰로오스 및 불포화 유기산으로 이루어진 군으로부터 선택된 1종 이상을 염화비닐 단량체 100 중량부 기준으로 0.03 내지 5 중량부 범위 내로 사용할 수 있다. As the protective colloid assistant used to obtain stable particles while stably polymerizing the vinyl chloride monomer, for example, a protective colloid composition having a hydration degree of 31 to 90% by weight and a viscosity of 4% aqueous solution at room temperature of 10 to 60 cps A polyvinyl alcohol resin, at least one selected from the group consisting of cellulose and an unsaturated organic acid having a methoxy group content of 15 to 40% by weight, a hydroxyl group content of 3 to 20% by weight and a 2% aqueous solution viscosity measured at room temperature of 10 to 20,000 cps Can be used within the range of 0.03 to 5 parts by weight based on 100 parts by weight of the vinyl chloride monomer.
참고로, 상기 하한치 미만에서는 액적 안정성이 저하되고, 상한치 초과시에는 비드 형성에 의해 휘시아이 특성이 현저하게 저감될 수 있다.
For reference, liquid droplet stability is lowered below the lower limit value, and when the upper limit value is exceeded, the fish eye characteristic can be remarkably reduced by forming the beads.
구체적인 예로, 상기 보호 콜로이드 조제는 수화도가 85 내지 98 %인 비닐알콜계 수지(고수화도 수지), 수화도가 62 내지 82 %인 비닐알콜계 수지(중수화도 수지) 및 수화도가 50 내지 60 %인 비닐알콜계 수지(저수화도 수지) 중에서 선택된 1 이상 및 셀룰로오스 현탁안정제를 포함하는 것일 수 있다. As a specific example, the protective colloid preparation may be a polyvinyl alcohol resin having a degree of hydration of 85 to 98% (high water-solubility resin), a vinyl alcohol resin having a water-solubility of 62 to 82% (water-insolubility resin) % Of a polyvinyl alcohol resin (low hydration resin), and a cellulose suspension stabilizer.
상기 고, 중, 저 수화도 수지의 배합 비는 타겟 물성에 따라 조절하는 것으로, 본 발명에서는 고, 중, 저 수화도 수지 3종을 배합 사용하는 것이 바람직할 수 있다.
The blending ratio of the high-, middle-, and low-hydration resins is adjusted according to the target physical properties. In the present invention, it may be preferable to mix and use three kinds of high-, medium- and low-hydration resins.
또 다른 예로, 상기 보호 콜로이드 조제는 수화도가 85 내지 98 %인 비닐알콜계 수지(고수화도 수지) 0.04 중량부, 수화도가 62 내지 82 %인 비닐알콜계 수지(중수화도 수지) 0.05 중량부 및 수화도가 50 내지 60 %인 비닐알콜계 수지(저수화도 수지) 0.02 중량부 및 셀룰로오스 현탁안정제 0.01 중량부를 배합한 것일 수 있다.
As another example, the protective colloid preparation may contain 0.04 parts by weight of a polyvinyl alcohol resin having a degree of hydration of 85 to 98% (high water-solubility resin), 0.05 parts by weight of a vinyl alcohol resin having a degree of hydration of 62 to 82% And 0.02 parts by weight of a vinyl alcohol resin (low hydration resin) having a hydration degree of 50 to 60% and 0.01 part by weight of a cellulose suspension stabilizer.
상기 불포화 유기산은 일례로 아크릴산 중합체, 메타크릴산 중합체, 이타콘산 중합체, 푸마르산 중합체, 말레인산 중합체, 숙신산 중합체 및 젤라틴 중에서 선택된 1종 이상일 수 있다.
The unsaturated organic acid may be at least one selected from acrylic acid polymer, methacrylic acid polymer, itaconic acid polymer, fumaric acid polymer, maleic acid polymer, succinic acid polymer and gelatin.
본 발명에서 사용하는 중합 개시제는 일례로 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-부틸퍼옥시 네오헵타노에이트, 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, 이들을 단독 또는 2종 이상 배합하여 사용할 수 있다. Examples of the polymerization initiator used in the present invention include diacyl peroxides such as dicumyl peroxide, dipentyl peroxide, di-3,5,5-trimethylhexanoyl peroxide and diaryl peroxide, diisopropyl peroxide Butyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxyneodecanoate, Amyl peroxyneodecanoate, cumyl peroxyneodecanoate, cumyl peroxyneoheptanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, and the like, azobis- Azo compounds such as 2,4-dimethylvaleronitrile, and sulfates such as potassium persulfate and ammonium persulfate. These may be used alone or in combination of two or more.
상기 중합 개시제의 함량은 제조 공정, 생산성, 품질 등 다양한 요인에 의해 결정되는데, 염화비닐 단량체 총 100 중량부에 대하여 총 함량이 0.02~0.2 중량부, 혹은 0.04~0.12 중량부 범위 내일 수 있다.
The content of the polymerization initiator is determined by various factors such as the production process, productivity, quality, etc. The total content of the polymerization initiator may be 0.02 to 0.2 parts by weight, or 0.04 to 0.12 parts by weight based on 100 parts by weight of the total amount of the vinyl chloride monomer.
또한 본 발명에서 현탁 중합반응을 중단시키기에 산화방지제를 적용할 수 있다. In the present invention, an antioxidant may be applied to stop the suspension polymerization reaction.
상기 산화방지제는 염화비닐 중합체의 제조시 사용되는 종류를 사용하면 충분하며, 일례로 트리에틸렌 글리콜-비스-[3-(3-t-부틸-5-메틸-4-하이드록시 페닐)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, 도데실 메르캅탄, 1,2-디페닐-2-티올 등의 유황 화합물, 트리페닐 포스파이트, 디페닐데실 포스파이트, 페닐이소데실 포스파이트, 트리(노닐페닐) 포스파이트 및 트리라우릴 트리티오 포스파이트 등의 인산계 산화방지제를 단독 또는 2종 이상 혼합하여 사용할 수 있다.
As the antioxidant, it is sufficient to use a kind used in the production of the vinyl chloride polymer, and examples thereof include triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate Butylhydroxyanisole, n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 2,5 Di-t-butylhydroquinone, 4,4-butylidenebis (3-methyl-6-t-butylphenol), t- butylcatechol, 4,4-thiobis -Cresol) and tocopherol, amine compounds such as N, N-diphenyl-p-phenylenediamine and 4,4-bis (dimethylbenzyl) diphenylamine, dodecylmercaptan, 1,2- Phenyl-2-thiol and the like, phosphoric acid antioxidants such as triphenyl phosphite, diphenyldecyl phosphite, phenyl isodecyl phosphite, tri (nonylphenyl) phosphite and triruryl trithiophosphite Or two or more species And it can be used.
본 발명에서는, 필요에 따라 중합 조절제, 연쇄 이동제, pH 조절제, 산화 방지제, 가교제, 대전 방지제, 스케일 방지제, 계면활성제 등을 중합 개시 전후 중합계에 첨가하거나, 혹은 중합 도중 일부를 분할 또는 연속하여 첨가할 수 있다. In the present invention, the polymerization system, chain transfer agent, pH adjuster, antioxidant, crosslinking agent, antistatic agent, anti-scale agent and surfactant may be added to the polymerization system before or after the polymerization is started, can do.
본 발명에 사용된 반응기는 염화비닐 중합체의 현탁 중합에 통상 사용되는 교반 장치를 사용할 수 있으며, 일례로 교반기는 교반 날개 타입이 패들 (paddle)형, 피치 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 교반기 등을 사용할 수 있고, 배플은 판형, 원통형, D형, 루프형 또는 핑거형 등을 사용할 수 있다.
The reactor used in the present invention may be an agitator commonly used in the suspension polymerization of a vinyl chloride polymer. For example, the agitator may be a paddle type, a pitched paddle type, a bloomers a baffle plate, a cylindrical type, a D-type, a baffle type, and the like can be used as a baffle type, a baffle type, a gin type, a pfaudler type, a turbine type, a propeller type, A loop type, a finger type, or the like can be used.
상기 현탁 중합에서 수득된 염화비닐 중합체 슬러리는 통상의 반응 조건하에 유동층 건조기로 수분 제거 및 건조하는 공정을 통해 고 품질의 염화비닐 중합체를 제공할 수 있다.
The vinyl chloride polymer slurry obtained in the suspension polymerization can be provided with a high quality vinyl chloride polymer through a process of removing water by a fluidized bed drier and drying it under ordinary reaction conditions .
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명을 이에 한정하려는 것은 아니다.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention, but the present invention is not limited thereto.
실시예Example 1 One
환류 응축기 및 교반기가 부착된 내부 용적 5L의 스테인레스 중합기 내벽에 황산알루미늄 500ppm 을 고르게 도포하고 자켓 온도를 80도로 상승시켜 10분간 유지하였다. 그 후에 중합수 1800g(150중량부) 수화도가 88 %인 폴리 비닐 알코올 0.012 중량부, 수화도가 72%인 폴리 비닐 알코올 0.03 중량부, 수화도가 55 %인 폴리 비닐 알코올 0.022 중량부, 하이드록시프로필메틸 셀룰로오스 0.006 중량부, t-부틸퍼옥시 네오데카노네이트(BND) 0.080 중량부를 첨가한 뒤 교반하에 내부를 진공 펌프로 탈기하고, 염화비닐 단량체 1200g(100중량부)를 투입하여 상기 중합기 온도를 반응 전 과정 동안 목표로 하는 평균 중합도 1000을 달성하기 위한 중합 기준 온도 58℃로 유지하면서 반응을 진행시키고 중합반응기 압력이 1.0 kg/cm2 변화가 있는 시점에 중합을 정지시켰다. 500 ppm of aluminum sulfate was uniformly applied to the inner wall of a 5 L stainless steel polymerization reactor equipped with a reflux condenser and a stirrer, and the jacket temperature was raised to 80 degrees and maintained for 10 minutes. Thereafter, 0.012 part by weight of polyvinyl alcohol having a degree of hydration of 88%, a polyvinyl alcohol having a degree of hydration of 72%, 0.03 part by weight of polyvinyl alcohol having a degree of hydration of 55%, 0.022 part by weight of polyvinyl alcohol having a degree of hydration of 55% 0.006 part by weight of hydroxypropylmethylcellulose and 0.080 part by weight of t-butylperoxyneodecanonate (BND) were added. Then, the inside of the autoclave was degassed with a vacuum pump while stirring, 1200 g of vinyl chloride monomer (100 parts by weight) the polymerization while maintaining the reference temperature 58 ℃ to achieve an average polymerization degree of 1000 and proceed with the polymerization reaction the reactor pressure to the group to the target temperature during the reaction process before the polymerization was stopped at the time that the 1.0 kg / cm 2 changes.
미 반응 단량체를 회수하고 수지 슬러리를 중합반응기에서 회수하였다. 이렇게 하여 얻어진 슬러리를 통상의 방법으로 유동층 건조기에서 건조하여 염화 비닐 중합체를 수득하였다.
Unreacted monomers were 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.
실시예Example 2 2
상기 실시예 1에서 중합전에 황산 알루미늄을 코팅한 것 대신에 중합의 전환율이 30~80%인 시점에 황산알루미늄 0.05 중량부를 연속투입한 것을 제외하고는 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.Polymerization was carried out under the same conditions as in Example 1, except that 0.05 part by weight of aluminum sulfate was continuously added at the point of time when the polymerization conversion rate was 30 to 80%, instead of coating aluminum sulfate before polymerization in Example 1, Respectively.
참고로, 상기 중합의 전환율은 가스크로마토크래피를 장착한 부탄 트레이서(Butanin tracer)를 이용하여 측정하였다. 참고로, 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.
For reference, the conversion of the polymerization was measured using a butanin tracer equipped with a gas chromatograph. For reference, it is possible to precisely measure the polymerization conversion ratio according to polymerization conditions by preparing a polymerization conversion curve according to the ratio of vinyl chloride monomer and butane over time under a certain polymerization condition at each polymerization condition.
실시예Example 3 3
상기 실시예 1에서 중합전에 황산 알루미늄을 코팅한 것 대신에 중합이 30% 진행된 때에 황산알루미늄 0.025중량부를 투입하고, 60% 진행된 때에 황산알루미늄 0.025 중량부를 투입하는 것을 제외하고는 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.
The procedure of Example 1 was repeated except that 0.025 part by weight of aluminum sulfate was added at 30% progress of polymerization and 0.025 part by weight of aluminum sulfate was added at 60% And the polymerization was carried out.
실시예Example 4 4
상기 실시예 1에서 중합전에 황산 알루미늄을 코팅한 것 대신에 중합이 60% 진행된 때에 황산알루미늄 0.05중량부를 투입하는 것을 제외하고는 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.
Polymerization was carried out under the same conditions as in Example 1, except that 0.05 parts by weight of aluminum sulfate was added at the time when 60% polymerization proceeded, instead of coating aluminum sulfate before polymerization in Example 1.
비교예Comparative Example 1 One
상기 실시예 1에서 중합전에 반응기에 황산알루미늄을 도포하지 않는 것을 제외하고는 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.
Polymerization was conducted and evaluated under the same conditions as in Example 1 except that aluminum sulfate was not applied to the reactor before polymerization in Example 1 above.
비교예Comparative Example 2 2
상기 실시예 1에서 중합전에 반응기에 황산 알루미늄 대신 페놀계 화합물 0.05중량부를 염기성 수용액에 녹여 반응기 내벽에 코팅하는 것을 제외하고는 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.
Polymerization was conducted and evaluated in the same manner as in Example 1, except that 0.05 part by weight of a phenolic compound instead of aluminum sulfate was dissolved in a basic aqueous solution and coated on the inner wall of the reactor before the polymerization in Example 1.
[시험예][Test Example]
상기 실시예 1~4 및 비교예 1~2에서 각각 제조된 염화비닐 중합체의 물성을 하기의 방법으로 측정하고, 그 결과를 하기 표 1 및 2에 나타내었다.The physical properties of the vinyl chloride polymer prepared in each of Examples 1 to 4 and Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Tables 1 and 2 below.
* 평균 입경: ASTM D-1243-79에 의해 측정하였다. * Average particle size: Measured by ASTM D-1243-79.
* 겉보기 비중(B.D.): ASTM D 1895-89에 의거하여 측정하였다. * Apparent Specific Gravity (BD): Measured according to ASTM D 1895-89.
* 가소제 흡수율(중량%): ASTM D 3367-95에 의거하여 시료에 흡수되는 디옥틸프탈레이트(DOP) 량을 흡수전의 시료 중량에 대한 중량%로 나타내었다. * Plasticizer absorption rate (% by weight): The amount of dioctyl phthalate (DOP) absorbed into the sample according to ASTM D 3367-95 is expressed in weight% with respect to the sample weight before absorption.
* 열 안정성: 건조된 염화비닐 중합체를 195℃ 오븐에 넣은 뒤 흑색이 될 때까지 필요한 시간을 측정하였다. * Thermal Stability: The dried vinyl chloride polymer was placed in an oven at 195 ° C. and the time required for it to become black was measured.
* 스케일 발생여부 : 중합 후 반응기 크리닝 단계 시 agitator 와 baffle 에 붙어있는 스케일을 건조후 중량을 측정하여 비교함 * Whether or not the scale is generated : The scale attached to the agitator and the baffle is weighed and measured after cleaning the reactor after polymerization.
* 휘시아이(fish-eye)수 (개): 염화비닐 중합체 100중량부, 디옥틸 프탈레이트(DOP) 45중량부, 스테아린산 바륨 0.1중량부, 주석계 안정제 0.2중량부, 카본블랙 0.1중량부를 140℃의 6인치 롤을 이용하여 4분간 혼합 혼련한 다음 두께 0.3mm의 시트를 만들고, 이 시트의 100cm2 중의 백색 투명 입자 수로 나타내었다. * Fish eye number (fish-eye) (dog): a vinyl polymer 100 parts by weight of dioctyl phthalate chloride (DOP) 45 parts by weight of stearic acid, barium, 0.1 part by weight of tin based stabilizer, 0.2 parts by weight of carbon black 0.1 parts by weight of 140 ℃ Kneaded using a 6-inch roll of 4 mm thick to prepare a sheet having a thickness of 0.3 mm and the number of white transparent particles in 100 cm 2 of the sheet.
상기 표 1에서 보듯이, 중합반응 개시 전 황산알루미늄으로 반응기를 코팅한 실시예 1의 경우 가소제 흡수율, 열안정성, 스케일 발생여부, 휘시아이 측면에서 황산알루미늄을 미투입한 비교예 1 혹은 페놀 수지로 대체한 비교예 2 대비 향상 효과를 확인할 수 있었다. 또한 실시예 1의 반응기 코팅 대신 연속, 간헐, 일시적으로 투입한 실시예 2 내지 4 또한 실시예 1과 동등 내지는 유사한 효과를 확인할 수 있었다.
As shown in Table 1, in the case of Example 1 in which the reactor was coated with aluminum sulfate prior to the initiation of the polymerization reaction, the plasticizer absorptivity, thermal stability, occurrence of scale, Comparative Example 1 in which aluminum sulfate was not added in terms of water- It was confirmed that the contrast enhancement effect of Comparative Example 2 was replaced. In addition, similar or similar effects to those of Examples 2 to 4 and Example 1 in which continuous, intermittent, and temporary dosing were performed in place of the reactor coating of Example 1 were confirmed.
나아가, 상기 실시예 2 내지 4에서 황산알루미늄의 함량 변화, 투입시기 변화 등에 따른 추가적인 영향을 살펴보도록 하기의 추가 실험예들을 수행하였다. Furthermore, the following additional experimental examples were conducted to examine the further effect of the change in the content of aluminum sulfate, the change in the injection time, etc. in the above Examples 2 to 4.
추가 Add 실험예Experimental Example 1: One:
상기 실시예 2에서 중합이 30~80% 진행된 때에 황산알루미늄 0.05중량부를 연속적으로 투입한 것 대신에 황산알루미늄 0.003중량부를 연속적으로 투입한 것을 제외하고는 실시예 2과 동일한 조건 하에 중합을 수행하고 평가하였다.
Polymerization was carried out under the same conditions as in Example 2 except that 0.003 part by weight of aluminum sulfate was continuously added instead of 0.05 part by weight of aluminum sulfate at the time of 30 to 80% Respectively.
추가 Add 실험예Experimental Example 2: 2:
상기 실시예 2에서 중합이 30~80% 진행된 때에 황산알루미늄 0.05중량부를 연속적으로 투입한 것 대신에 황산알루미늄 0.15중량부를 연속적으로 투입한 것을 제외하고는 실시예 2과 동일한 조건 하에 중합을 수행하고 평가하였다.
Polymerization was carried out under the same conditions as in Example 2 except that 0.15 part by weight of aluminum sulfate was continuously added instead of 0.05 part by weight of aluminum sulfate at 30 to 80% Respectively.
추가 Add 실험예Experimental Example 3: 3:
상기 실시예 3에서 중합이 10~30% 진행된 때에 황산알루미늄 0.05중량부를 연속적으로 투입한 것을 제외하고는 실시예 3과 동일한 조건 하에 중합을 수행하고 평가하였다.
Polymerization was conducted and evaluated under the same conditions as in Example 3, except that 0.05 parts by weight of aluminum sulfate was continuously added when the polymerization proceeded 10 to 30% in Example 3 above.
추가 Add 실험예Experimental Example 4: 4:
상기 실시예 3에서 중합이 80% 진행된 시점부터 반응 종료 시까지 황산알루미늄 0.05중량부를 연속적으로 투입한 것을 제외하고는 실시예 3과 동일한 조건 하에 중합을 수행하고 평가하였다.
Polymerization was carried out under the same conditions as in Example 3 except that 0.05 part by weight of aluminum sulfate was continuously added from the time when 80% of the polymerization proceeded to the end of the reaction in Example 3.
추가 Add 실험예Experimental Example 5: 5:
상기 실시예 1에서 중합이 30% 진행된 시점에 황산 알루미늄 0.0015 중량부를 투입하고, 60% 진행된 시점에 황산알루미늄 0.0015중량부를 투입한 것을 제외하고는 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.
Polymerization was carried out under the same conditions as in Example 1 except that 0.0015 parts by weight of aluminum sulfate was added at the time when the polymerization proceeded at 30% in Example 1, and 0.0015 parts by weight of aluminum sulfate was added at the time of 60% progress.
추가 Add 실험예Experimental Example 6: 6:
상기 실시예 1에서 중합이 30% 진행된 시점에 황산 알루미늄 0.075 중량부를 투입하고, 60% 진행된 시점에 황산알루미늄 0.075중량부를 투입한 것을 제외하고는 실시예 1과 동일한 조건 하에 중합을 수행하고 평가하였다.Polymerization was carried out under the same conditions as in Example 1 except that 0.075 part by weight of aluminum sulfate was added at the time when the polymerization proceeded at 30% in Example 1 and 0.075 part by weight of aluminum sulfate was added at the time of 60% progress.
(g/cc)Apparent specific gravity
(g / cc)
상기 표 1, 2에서 보듯이, 중합전환율 30~80% 시점에 연속적으로 황산알루미늄을 투입한 실시예 2와 그 양을 조절한 추가 실험예 1,2의 결과를 대비하면, 투입 량에 따른 효과를 확인할 수 있었다. 구체적으로 0.005 중량부 이하로 투입한 추가 실험예 1에서는 스케일 방지 효과가 미미하였고, 0.15 중량부 이상으로 투입한 추가 실험예 2에서는 물성 변동이 크게 나타남을 확인할 수 있다. As shown in Tables 1 and 2, when the results of Example 2 in which aluminum sulfate was continuously added at a polymerization conversion rate of 30 to 80% and in Experimental Examples 1 and 2 in which the amount of aluminum sulfate was adjusted were compared, . Specifically, the addition of 0.005 parts by weight or less of the additive test example 1 showed insufficient effect of preventing scale, and the additive test sample 2 of 0.15 parts by weight or more showed a significant change in physical properties.
또한 실시예 1과, 중합전환율 30~80% 시점에 황산알루미늄을 분할 투입한 추가 실험예 5,6의 결과를 대비하면, 총 합량이 0.005 중량부 미만 투입한 추가 실험예 5에서는 스케일 제거 효과가 미미하였고, 총 합량이 0.15중량부 투입한 추가 실험예 6에서는 물성에 악영향을 미침을 확인할 수 있다.
Further, when the results of Experimental Examples 5 and 6 in which aluminum sulfate was separately added at a polymerization conversion rate of 30 to 80% were compared with Example 1, in Experiment Example 5 in which the total amount was less than 0.005 part by weight, And in Experimental Example 6 in which the total amount is 0.15 part by weight, it is confirmed that the physical properties are adversely affected.
나아가 실시예 3과, 투입 시기를 조절한 추가 실험예 3,4의 결과를 대비하면, 투입 시기별 효과를 확인할 수 있었다. 구체적으로 전환률 30% 미만에 투입된 추가 실험예 3에서는 입경 및 휘시아이 물성에 영향을 미쳤으며, 전환률 80% 초과하여 투입된 추가 실험예 4에서는 스케일 제거에 효과가 없음을 확인할 수 있었다.
Further, by comparing the results of Experimental Examples 3 and 4 in which the injection timing is controlled, the effects of the injection timing can be confirmed. Specifically, Experimental Example 3 added at a conversion rate of less than 30% influenced particle size and physical properties, and it was confirmed that Scale removal was not effective in the additional Experimental Example 4 in which the conversion rate exceeded 80%.
따라서, 본 발명의 방법에 따른 실시예 1~4에서, 염화비닐 중합체의 기본 물성에 큰 변화 없이 스케일 억제, 휘시아이와 열안정성 개선 등 경제적 측면에서 가장 간단하면서도 유리한 공정을 제공할 수 있음을 규명하였다.Thus, in Examples 1 to 4 according to the method of the present invention, it was found that it is possible to provide the simplest and most advantageous process in economical aspects such as scale inhibition, .
Claims (12)
A suspension polymerization system comprising a suspension stabilizer, a polymerization initiator and a vinyl chloride monomer, wherein the polymerization system comprises a trivalent metal sulfate.
상기 3가 금속 황산염은 현탁 중합 반응기의 내부 코팅물로 포함된 것을 특징으로 하는 현탁 중합계.
The method according to claim 1,
Wherein said trivalent metal sulphate is contained as an inner coating of a suspension polymerization reactor.
상기 3가 금속 황산염은 현탁 중합 반응기에 구비된 환류 응축기의 내부 코팅물로 포함된 것을 특징으로 하는 현탁 중합계.
The method according to claim 1,
Wherein the trivalent metal sulfate is contained as an inner coating of a reflux condenser provided in a suspension polymerization reactor.
상기 3가 금속 황산염은 중합 도중 반응기에 포함된 것을 특징으로 하는 현탁 중합계.
The method according to claim 1,
Wherein the trivalent metal sulfate is included in the reactor during polymerization.
상기 3가 금속 황산염은 중합의 전환율 30 내지 80% 지점에 포함된 것을 특징으로 하는 현탁 중합계
5. The method of claim 4,
Wherein the trivalent metal sulfate is contained at a point of 30-80% conversion of the polymerization.
상기 3가 금속 황산염은 연속 투입, 간헐 투입 혹은 일괄 투입된 것을 특징으로 하는 현탁 중합계.
5. The method of claim 4,
Wherein the trivalent metal sulfate is continuously charged, intermittently charged or batch charged.
상기 3가 금속 황산염은 현탁 중합에 사용되는 염화비닐 단량체 100중량부에 대하여 0.005 내지 0.1중량부 범위 내인 것을 특징으로 하는 현탁 중합계.
The method according to claim 1,
Wherein the trivalent metal sulfate is present in an amount of 0.005 to 0.1 part by weight based on 100 parts by weight of the vinyl chloride monomer used in the suspension polymerization.
상기 3가 금속 황산염은 황산알루미늄인 것을 특징으로 하는 현탁 중합계.
The method according to claim 1,
Wherein the trivalent metal sulfate is aluminum sulfate.
상기 현탁 안정제는 수화도가 30 내지 90중량%이고 상온에서 4~5% 수용액의 점도가 10 내지 60cps인 비닐 알코올계 수지, 메톡시기가 15 내지 40중량%이고 수산화프로필기가 3 내지 20중량%이며 상온에서 측정한 2% 수용액의 점도가 10 내지 20,000cps인 셀룰로오스 및 불포화 유기산 중에서 선택된 1종 이상인 것을 특징으로 하는 현탁 중합계.
The method according to claim 1,
The suspension stabilizer has a vinyl alcohol-based resin having a hydration degree of 30 to 90% by weight and a viscosity of 4 to 5% aqueous solution at room temperature of 10 to 60 cps, a methoxy group of 15 to 40% by weight and a hydroxylated propyl group of 3 to 20% The suspension polymerization system according to claim 1, wherein the 2% aqueous solution measured at room temperature has a viscosity of 10 to 20,000 cps and is at least one selected from the group consisting of cellulose and unsaturated organic acids.
상기 현탁 안정제는 현탁 중합에 사용되는 염화비닐 단량체 100중량부에 대하여 0.03 내지 5중량부 범위 내인 것을 특징으로 하는 현탁 중합계.
The method according to claim 1,
Wherein the suspension stabilizer is in the range of 0.03 to 5 parts by weight based on 100 parts by weight of the vinyl chloride monomer used in the suspension polymerization.
상기 중합 개시제의 양은 현탁 중합에 사용되는 염화비닐 단량체 100중량부에 대하여 0.02 내지 0.2중량부 범위 내인 것을 특징으로 하는 현탁 중합계.
The method according to claim 1,
Wherein the amount of the polymerization initiator is in the range of 0.02 to 0.2 parts by weight based on 100 parts by weight of the vinyl chloride monomer used in the suspension polymerization.
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