WO2022259658A1 - Resin composition containing modified polyvinyl alcohol polymer, method for producing said resin composition, dispersion stabilizer for suspension polymerization, and method for producing vinyl resin - Google Patents
Resin composition containing modified polyvinyl alcohol polymer, method for producing said resin composition, dispersion stabilizer for suspension polymerization, and method for producing vinyl resin Download PDFInfo
- Publication number
- WO2022259658A1 WO2022259658A1 PCT/JP2022/009813 JP2022009813W WO2022259658A1 WO 2022259658 A1 WO2022259658 A1 WO 2022259658A1 JP 2022009813 W JP2022009813 W JP 2022009813W WO 2022259658 A1 WO2022259658 A1 WO 2022259658A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- polymerization
- polyvinyl alcohol
- vinyl
- mass
- Prior art date
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 130
- 239000011342 resin composition Substances 0.000 title claims abstract description 79
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 47
- 229920005989 resin Polymers 0.000 title claims abstract description 45
- 239000011347 resin Substances 0.000 title claims abstract description 45
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 40
- 239000006185 dispersion Substances 0.000 title claims abstract description 28
- 239000003381 stabilizer Substances 0.000 title claims abstract description 27
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 113
- 229920001519 homopolymer Polymers 0.000 claims abstract description 53
- -1 vinyl compound Chemical class 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004429 atom Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 229910052751 metal Chemical group 0.000 claims abstract description 4
- 239000002184 metal Chemical group 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 82
- 229920000642 polymer Polymers 0.000 claims description 49
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 39
- 238000007127 saponification reaction Methods 0.000 claims description 37
- 238000002835 absorbance Methods 0.000 claims description 25
- 229920001567 vinyl ester resin Polymers 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 49
- 239000002245 particle Substances 0.000 abstract description 36
- 230000005484 gravity Effects 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 description 125
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 107
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 51
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 38
- 238000000034 method Methods 0.000 description 35
- 239000007788 liquid Substances 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 238000007796 conventional method Methods 0.000 description 28
- 238000001035 drying Methods 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000006386 neutralization reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 239000011362 coarse particle Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical class O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 4
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 101100049042 Arabidopsis thaliana PVA11 gene Proteins 0.000 description 3
- 101100049043 Arabidopsis thaliana PVA12 gene Proteins 0.000 description 3
- 101100049044 Arabidopsis thaliana PVA13 gene Proteins 0.000 description 3
- 101100049045 Arabidopsis thaliana PVA14 gene Proteins 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NUIZZJWNNGJSGL-UHFFFAOYSA-N 2-phenylpropan-2-yl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)c1ccccc1 NUIZZJWNNGJSGL-UHFFFAOYSA-N 0.000 description 2
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- DBUPOCYLUHVFHU-UHFFFAOYSA-N carboxyoxy 2,2-diethoxyethyl carbonate Chemical compound CCOC(OCC)COC(=O)OOC(O)=O DBUPOCYLUHVFHU-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- IMHNCCFPIDJWFF-BQYQJAHWSA-N (e)-4-heptoxy-4-oxobut-2-enoic acid Chemical compound CCCCCCCOC(=O)\C=C\C(O)=O IMHNCCFPIDJWFF-BQYQJAHWSA-N 0.000 description 1
- RNERBJNDXXEXTK-VOTSOKGWSA-N (e)-4-hexoxy-4-oxobut-2-enoic acid Chemical compound CCCCCCOC(=O)\C=C\C(O)=O RNERBJNDXXEXTK-VOTSOKGWSA-N 0.000 description 1
- VTWGIDKXXZRLGH-CMDGGOBGSA-N (e)-4-octoxy-4-oxobut-2-enoic acid Chemical compound CCCCCCCCOC(=O)\C=C\C(O)=O VTWGIDKXXZRLGH-CMDGGOBGSA-N 0.000 description 1
- BOFGUJVLYGISIU-AATRIKPKSA-N (e)-4-oxo-4-pentoxybut-2-enoic acid Chemical compound CCCCCOC(=O)\C=C\C(O)=O BOFGUJVLYGISIU-AATRIKPKSA-N 0.000 description 1
- IQBLWPLYPNOTJC-FPLPWBNLSA-N (z)-4-(2-ethylhexoxy)-4-oxobut-2-enoic acid Chemical compound CCCCC(CC)COC(=O)\C=C/C(O)=O IQBLWPLYPNOTJC-FPLPWBNLSA-N 0.000 description 1
- RNERBJNDXXEXTK-SREVYHEPSA-N (z)-4-hexoxy-4-oxobut-2-enoic acid Chemical compound CCCCCCOC(=O)\C=C/C(O)=O RNERBJNDXXEXTK-SREVYHEPSA-N 0.000 description 1
- BOFGUJVLYGISIU-WAYWQWQTSA-N (z)-4-oxo-4-pentoxybut-2-enoic acid Chemical compound CCCCCOC(=O)\C=C/C(O)=O BOFGUJVLYGISIU-WAYWQWQTSA-N 0.000 description 1
- AYAUWVRAUCDBFR-ARJAWSKDSA-N (z)-4-oxo-4-propoxybut-2-enoic acid Chemical compound CCCOC(=O)\C=C/C(O)=O AYAUWVRAUCDBFR-ARJAWSKDSA-N 0.000 description 1
- JCBLAXHZANENIW-UHFFFAOYSA-N 2,4,4-trimethyl-1-(2,4,4-trimethylpentylperoxy)pentane Chemical class CC(C)(C)CC(C)COOCC(C)CC(C)(C)C JCBLAXHZANENIW-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- GQZXRLWUYONVCP-UHFFFAOYSA-N 3-[1-(dimethylamino)ethyl]phenol Chemical compound CN(C)C(C)C1=CC=CC(O)=C1 GQZXRLWUYONVCP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical group CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- KUUZQLFCCOGXKQ-BUHFOSPRSA-N diheptyl (e)-but-2-enedioate Chemical compound CCCCCCCOC(=O)\C=C\C(=O)OCCCCCCC KUUZQLFCCOGXKQ-BUHFOSPRSA-N 0.000 description 1
- QMCVOSQFZZCSLN-VAWYXSNFSA-N dihexyl (e)-but-2-enedioate Chemical compound CCCCCCOC(=O)\C=C\C(=O)OCCCCCC QMCVOSQFZZCSLN-VAWYXSNFSA-N 0.000 description 1
- QMCVOSQFZZCSLN-QXMHVHEDSA-N dihexyl (z)-but-2-enedioate Chemical compound CCCCCCOC(=O)\C=C/C(=O)OCCCCCC QMCVOSQFZZCSLN-QXMHVHEDSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- NFCMRHDORQSGIS-KTKRTIGZSA-N dipentyl (z)-but-2-enedioate Chemical compound CCCCCOC(=O)\C=C/C(=O)OCCCCC NFCMRHDORQSGIS-KTKRTIGZSA-N 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 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
- 150000007524 organic acids Chemical class 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 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
- 238000012545 processing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-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
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- 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
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
-
- 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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Definitions
- the present invention relates to a resin composition containing a modified polyvinyl alcohol polymer and a method for producing the same.
- the present invention also relates to a dispersion stabilizer for suspension polymerization, particularly a dispersion stabilizer suitable for suspension polymerization of vinyl compounds, especially vinyl chloride.
- dispersion stabilizers such as polyvinyl alcohol, methylol Dispersion stabilizers such as cellulose are used, among which polyvinyl alcohol (PVA) has excellent properties and is most commonly used.
- PVA polyvinyl alcohol
- a dispersion stabilizer for suspension polymerization of vinyl compounds an aldehyde-derived carbonyl group is introduced at the end of a polyvinyl alcohol polymer, and an unsaturated double bond is formed by undergoing a dehydration reaction or a deacetic acid reaction during saponification.
- Patent Document 2 describes that the content of unmodified PVA in modified PVA into which unsaturated double bonds are introduced is preferably 25% by mass or less. It is stated that the content was in the range of 10-45%.
- An object of the present invention is to provide a resin composition containing a modified polyvinyl alcohol-based polymer useful as a dispersion stabilizer suitable for
- the present inventors have found a modified polyvinyl alcohol polymer having a dicarboxylic acid monomer unit and a conjugated double bond in the main chain of polyvinyl alcohol, and polyvinyl alcohol wherein the homopolymer of polyvinyl alcohol accounts for 5% by mass of the total 100% by mass of the modified polyvinyl alcohol-based polymer and the homopolymer of polyvinyl alcohol We have found that it is effective to use the following resin composition.
- Patent Document 2 describes that in modified PVA into which unsaturated double bonds are introduced, the content of unmodified PVA is preferably 25% by mass or less. However, in Patent Literature 2, even the lowest content of unmodified PVA is 10% by mass. Patent document 2 does not describe a method for reducing the content of unmodified PVA to 5% by mass or less, nor does it describe an advantageous effect as a dispersion stabilizer obtained thereby.
- a resin composition containing a modified polyvinyl alcohol-based polymer having a structural unit represented by general formula (I) in the main chain and a polyvinyl alcohol homopolymer, wherein the modified polyvinyl In the resin composition, the proportion by mass of the homopolymer of polyvinyl alcohol is 0 to 5% by mass in the total 100% by mass of the alcohol-based polymer and the homopolymer of polyvinyl alcohol.
- X and Y represent a lower alkyl group having 1 to 12 carbon atoms, a hydrogen atom or a metal atom, and may be the same or different.
- Z represents the number of repeating units and is an integer of 0 to 3.
- the UV absorbance (Abs) of a 0.2% by mass aqueous solution at a wavelength of 280 nm and an optical path length of 10 mm is 0.1 or more and 5.0 or less.
- the UV absorbance (Abs) of a 0.2% by mass aqueous solution at a wavelength of 325 nm and an optical path length of 10 mm is 0.01 or more and 1.0 or less.
- the resin composition has a saponification degree of 65 to 99.9 mol%.
- the resin composition contains 0.1 to 5.0 mol % of dicarboxylic acid monomer units.
- a method for producing a resin composition according to the present invention comprising a vinyl ester monomer and an unsaturated monomer deriving a dicarboxylic acid monomer unit represented by general formula (I) a step of obtaining a modified vinyl ester polymer by copolymerizing with a monomer, and a step of saponifying the obtained modified vinyl ester polymer. , intermittently or continuously adding a dicarboxylic acid monomer until a conversion of 90% or more is achieved.
- Another aspect of the present invention is a dispersion stabilizer for suspension polymerization containing the resin composition according to the present invention.
- a vinyl compound monomer or a mixture of a vinyl compound monomer and a monomer copolymerizable therewith is added to water using a dispersion stabilizer for suspension polymerization.
- a method for producing a vinyl-based resin including dispersion and suspension polymerization.
- the dispersion stabilizer for suspension polymerization of the present invention When suspension polymerization of a vinyl compound is carried out using the dispersion stabilizer for suspension polymerization of the present invention, resin particles with high uniformity in particle size are obtained with little formation of coarse particles. Since the formation of coarse particles is small, blocking during polymerization is suppressed, and particles having a highly uniform particle size are obtained, thereby reducing scale adhesion. Moreover, a resin having a high bulk specific gravity can be obtained, and the productivity at the time of resin processing is improved. Thus, the dispersion stabilizer for suspension polymerization of the present invention can have the required properties that have been difficult to achieve with the prior art.
- X and Y represent a lower alkyl group having 1 to 12 carbon atoms, a hydrogen atom or a metal atom, and may be the same or different.
- Z represents the number of repeating units and is an integer of 0 to 3.
- the unsaturated monomer from which the dicarboxylic acid monomer unit in general formula (I) is derived is not particularly limited, but dimethyl maleate, monomethyl maleate, diethyl maleate, monoethyl maleate, and dipropyl maleate.
- Z is preferably 0 to 3, more preferably 1 to 3, even more preferably 1 to 2.
- the content of the modified polyvinyl alcohol-based polymer (modified PVA) having the structural unit represented by the following general formula (I) in the polyvinyl alcohol main chain is large.
- the mass ratio of the modified polyvinyl alcohol polymer in the total 100% by mass of the modified polyvinyl alcohol polymer and the polyvinyl alcohol homopolymer is preferably It is 95% by mass or more, more preferably 96% by mass or more, still more preferably 97% by mass or more, and even more preferably 98% by mass or more.
- a homopolymer of polyvinyl alcohol i.e., an unmodified structural unit that does not contain structural units such as those represented by the general formula (I) and structural units derived from other copolymerizable monomers
- Polyvinyl alcohol (unmodified PVA) is an impurity, and its content is desirably small.
- the mass ratio of the homopolymer (also referred to as "homopolymer content") in the total 100% by mass of the modified polyvinyl alcohol-based polymer and the polyvinyl alcohol homopolymer is preferably 5% by mass or less. , more preferably 4% by mass or less, and still more preferably 3% by mass or less.
- Polyvinyl alcohol includes both completely saponified polyvinyl alcohol obtained by completely saponifying a vinyl ester polymer and partially saponified polyvinyl alcohol in which vinyl ester units partially remain. If the homopolymer content is more than 5% by mass, the content of components with low protective colloid properties increases, and thus the vinyl-based resin particles may increase in size.
- the lower limit of the homopolymer content is not particularly limited, and may be 0% by mass, but from the viewpoint of purification cost, it is typically 0.1% by mass or more, more typically 0.3% by mass or more. be.
- the resin composition according to the present invention contains the above homopolymer, the resin composition is a mixture of a modified polyvinyl alcohol-based polymer having a structural unit represented by general formula (I) and a homopolymer of polyvinyl alcohol.
- the mass ratio of the homopolymer in the total 100% by mass of the modified polyvinyl alcohol-based polymer and the homopolymer of the polyvinyl alcohol is measured by the following procedure. After completely saponifying the resin composition to a degree of saponification of 99.95 mol % or more, it is sufficiently washed with methanol to prepare a resin composition for analysis. The prepared resin composition for analysis is dissolved in pure water and measured by HPLC (high performance liquid chromatograph). Based on the peak area ratio of the obtained HPLC results, the content of the homopolymer in the total 100% by mass of the modified polyvinyl alcohol-based polymer and the homopolymer of the polyvinyl alcohol is calculated.
- HPLC high performance liquid chromatograph
- a modified polyvinyl alcohol polymer shows a peak at 3.5 to 7.0 minutes, and a homopolymer at 7.5 to 10.0 minutes. Since peaks are detected in , the mass ratio of the homopolymer is calculated from these peak area ratios. Specifically, the ratio (%) of the peak area of 7.5 to 10.0 minutes to the total of the peak area of 3.5 to 7.0 minutes and the peak area of 7.5 to 10.0 minutes, the denaturation It is the mass ratio (% by mass) of the homopolymer in the total 100% by mass of the polyvinyl alcohol-based polymer and the homopolymer of the polyvinyl alcohol.
- the ratio (%) of the peak area of 3.5 to 7.0 minutes to the total of the peak area of 3.5 to 7.0 minutes and the peak area of 7.5 to 10.0 minutes, the modified polyvinyl alcohol It is defined as the mass ratio (% by mass) of the modified polyvinyl alcohol polymer in the total 100% by mass of the poly(vinyl alcohol) polymer and the homopolymer of the polyvinyl alcohol.
- HPLC measurement conditions> Column: MCI (registered trademark) GEL CK08EH (manufactured by Mitsubishi Chemical Corporation) Eluent: pure water Mobile phase flow rate: 0.6 ml/min Temperature: 40°C Injection concentration: 0.01 wt% Injection volume: 20 ⁇ L Detector: RI
- the total mass ratio of the modified polyvinyl alcohol-based polymer and the homopolymer of polyvinyl alcohol is 90% by mass or more, typically 95% by mass or more, More typically, it is 98% by mass or more.
- the total mass ratio (also referred to as "the total content of modified PVA and unmodified PVA in the resin composition") is measured by HPLC as described above, and the peak area of 0 to 20 minutes It is defined as the ratio (%) of the sum of the peak area from 3.5 to 7.0 minutes and the peak area from 7.5 to 10.0 minutes to the total of .
- the resin composition according to the present invention preferably has a UV absorbance (Abs) of 0.1 or more and 5.0 or less at a wavelength of 280 nm of a 0.2% by mass aqueous solution measured using a quartz cell with an optical path length of 10 mm. .
- the resin composition according to the present invention preferably has a UV absorbance (Abs) of 0.01 or more and 1.0 or less at a wavelength of 325 nm of a 0.2% by mass aqueous solution measured using a quartz cell with an optical path length of 10 mm. .
- the UV absorbance (Abs) at a wavelength of 325 nm is more preferably 0.03 or more and 0.5 or less, and still more preferably 0.05 or more and 0.25 or less.
- the degree of saponification of the resin composition of the present invention is preferably 65 mol% or more, more preferably 68 mol% or more, and even more preferably 70 mol% or more, from the viewpoint of improving water solubility and facilitating handling. .
- the degree of saponification of the resin composition of the present invention should be 99.9 mol % or less in order to increase the porosity of the particles obtained when the vinyl compound is subjected to suspension polymerization to increase the absorbability of the plasticizer. is preferred, 90 mol % or less is more preferred, and 80 mol % or less is even more preferred.
- the degree of saponification of the resin composition of the present invention is measured according to JIS K6726:1994. That is, it can be obtained by quantifying the remaining acetic acid group (mol%) in the sample with sodium hydroxide and subtracting it from 100.
- the content of dicarboxylic acid monomer units in the resin composition of the present invention is substantially equal to the total number of moles of monomer units constituting the modified polyvinyl alcohol-based polymer and the polyvinyl alcohol homopolymer. It is equal to the ratio (mole %) of the number of moles of the monomer.
- the method for determining the content of dicarboxylic acid monomer units is not particularly limited, and it can be determined by acid value or the like, but it is convenient to determine by carbon NMR ( 13 C-NMR). Specifically, the resin composition is completely saponified to a degree of saponification of 99.95 mol % or more, and then thoroughly washed with methanol to prepare a resin composition for analysis.
- the viscosity-average degree of polymerization of the resin composition of the present invention is preferably 400 or more, more preferably 500 or more, in order to improve the dispersion stability during suspension polymerization of the vinyl resin. Further, the viscosity average degree of polymerization is preferably 4000 or less, more preferably 3000 or less, even more preferably 2000 or less, and even more preferably 1500 or less so as not to reduce the dispersing power. .
- the viscosity average degree of polymerization is measured according to JIS K6726:1994. That is, it is obtained from the intrinsic viscosity [ ⁇ ] measured in dimethyl sulfoxide (DMSO) at 30° C. after completely saponifying and purifying the resin composition.
- DMSO dimethyl sulfoxide
- the method for producing the resin composition according to the present invention is not particularly limited.
- a production method comprising a step of copolymerizing a modified vinyl ester polymer with a polymer and a step of saponifying the resulting modified vinyl ester polymer is easy and economical, and is preferably used.
- Vinyl ester monomers include vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate and vinyl versatate. is mentioned.
- the unsaturated monomer from which the dicarboxylic acid monomer unit represented by formula (I) is derived is as described above.
- monomers copolymerizable with vinyl ester monomers such as unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, or alkyl esters of these unsaturated monocarboxylic acids, fumaric acid, and itacones.
- unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid
- alkyl esters of these unsaturated monocarboxylic acids fumaric acid, and itacones.
- Unsaturated dicarboxylic acids such as acids or alkyl esters of these unsaturated dicarboxylic acids, nitriles or amides such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, olefin sulfonic acids such as ethylenesulfonic acid, allylsulfonic acid, methallylsulfonic acid Alternatively, these salts, vinyl ethers, vinyl ketones, ⁇ -olefins, vinyl halides, vinylidene halides, etc. can be copolymerized singly or in combination.
- the mixing ratio of the copolymerizable monomers is a total of 10 mol% or less, preferably less than the total number of moles of the vinyl ester monomers and the unsaturated monomers from which the structural units represented by the general formula (I) are derived. A total of 5 mol % or less is appropriate.
- the method for introducing a structural unit containing a dicarboxylic acid monomer unit and a conjugated double bond as shown in general formula (I) is not particularly limited, but (i) an aldehyde or ketone containing a carbonyl group, etc.
- a dehydration reaction or deacetic acid reaction is caused in a drying step to introduce a conjugated double bond into the main chain of polyvinyl alcohol. method.
- drying is performed while heating at 90° C. or higher for 1 hour or longer, preferably 100° C. or higher for 1 hour or longer, and more preferably 120° C.
- the heating conditions for introducing the conjugated double bond by the drying process are preferably, for example, 90 to 180° C. for 1 to 5 hours, more preferably 100 to 160° C. for 1 to 5 hours.
- any of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization may be used as the polymerization method employed to produce the resin composition according to the present invention.
- the polymerization method any method can be adopted from known methods such as bulk polymerization method, solution polymerization method, suspension polymerization method and emulsion polymerization method.
- a solution polymerization method in which polymerization is performed in the presence of an alcoholic solvent or a bulk polymerization method in which polymerization is performed without using a solvent is preferable, instead of a suspension polymerization method and an emulsion polymerization method that require control of the polymer particle size.
- Methanol, ethanol, isopropanol and the like can be used as the alcoholic solvent used in the solution polymerization method, but the solvent is not limited to these. These solvents may be used alone, or two or more of them may be used in combination.
- the polymerization temperature for obtaining the resin composition of the present invention is not particularly limited, it is preferably 0°C or higher and 200°C or lower, more preferably 30°C or higher and 150°C or lower. If the temperature for copolymerization is lower than 0°C, it is not preferable because a sufficient polymerization rate cannot be obtained. Further, when the polymerization temperature is higher than 200° C., it is difficult to obtain the desired modified polyvinyl alcohol polymer.
- a method for controlling the temperature in the range of 0° C. or higher and 200° C. or lower a method of controlling the temperature by an external jacket using a suitable heat medium such as water can be mentioned.
- the polymerization initiator used in obtaining the resin composition of the present invention is not particularly limited, but azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis(4-methoxy-2, 4-dimethylvaleronitrile), azo compounds such as azobisdimethylvaleronitrile, azobismethoxyvaleronitrile, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl- Peroxides such as 2-peroxyphenoxyacetate, peroxydicarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, t-butyl peroxyneodecanoate , ⁇ -cumyl peroxyneode
- the total amount of vinyl ester monomers, dicarboxylic acid monomers, and other copolymerizable monomers may be charged at the initial stage of polymerization for polymerization.
- the dicarboxylic acid monomer is first added to the reaction vessel in an amount of 1 to 30% by mass, preferably 5 to 20% by mass, and the rest is preferably added intermittently or continuously from the initial stage of polymerization (the stage where the polymerization rate is 0 to 1% with respect to the final polymerization rate).
- the intermittent or continuous addition of the dicarboxylic acid monomer is continued until the final polymerization rate reaches 90% or more. It is preferable to continue until the polymerization rate reaches 93% or more of the final polymerization rate, and it is even more preferable to continue until the polymerization rate reaches 95% or more of the final polymerization rate.
- the final polymerization rate when obtaining the resin composition of the present invention is preferably 30% by mass to 97% by mass, more preferably 50% by mass to 94% by mass, and still more preferably 70% by mass to 93% by mass. is. If the final polymerization rate is less than 30%, unreacted raw materials must be discarded or recovered and purified, which is not economically efficient. If the final polymerization rate exceeds 97% by mass, the modified vinyl ester polymer tends to have a branched structure, which may increase the particle size of the vinyl resin.
- the polymerization rate measure 5.0 g of the polymerization liquid, dry it at 150° C. for 30 minutes, and determine the concentration of the polymerization liquid from the mass of the dry matter after volatilization of unreacted monomers and solvent. The mass of the polymer polymerized at that time is calculated, and the rate of polymerization is calculated from the ratio of the polymer to the total charged amount of the monomers.
- an antioxidant such as citric acid may be added to the polymerization system in an amount of 1 ppm or more and 100 ppm or less (based on the weight of the vinyl ester monomer).
- the saponification method for producing the resin composition of the present invention is not particularly limited. It is preferable to use it in combination.
- Alcohols include methanol, ethanol, butanol, and the like.
- concentration of the modified vinyl ester polymer in alcohol can be selected from the range of 20 to 50 mass %.
- Alkali catalysts such as hydroxides and alcoholates of alkali metals such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate can be used as alkali catalysts, and acid catalysts such as hydrochloric acid, An aqueous inorganic acid solution such as sulfuric acid, and an organic acid such as p-toluenesulfonic acid can be used.
- the amount of these catalysts used is preferably 1 to 100 millimol equivalents relative to the vinyl ester monomer.
- the saponification temperature is not particularly limited, it is usually in the range of 10 to 70°C, preferably in the range of 30 to 50°C.
- the reaction is usually carried out over 0.5-3 hours.
- the dispersion stabilizer for suspension polymerization of the present invention may be the resin composition of the present invention alone, and has a structural unit represented by general formula (I) in the main chain within a range that does not impair the gist of the present invention.
- the modified polyvinyl alcohol-based polymer, polyvinyl alcohol-based polymers other than the homopolymer of polyvinyl alcohol, and other various additives may be contained. Examples of such additives include polymerization modifiers such as aldehydes, halogenated hydrocarbons and mercaptans; polymerization inhibitors such as phenol compounds, sulfur compounds and N-oxide compounds; pH adjusters; cross-linking agents; antifungal agents, antiblocking agents; antifoaming agents and the like.
- the dispersion stabilizer for suspension polymerization of the present invention preferably contains the modified polyvinyl alcohol polymer in an amount of 10% by mass or more, and preferably 30% by mass or more. More preferably, it is contained in an amount of 70% by mass or more.
- the dispersion stabilizer for suspension polymerization of the present invention can be suitably used particularly for suspension polymerization of vinyl compounds. Therefore, according to another aspect of the present invention, a vinyl compound monomer or a mixture of a vinyl compound monomer and a monomer copolymerizable therewith using a dispersion stabilizer for suspension polymerization is dispersed in water to carry out suspension polymerization.
- Vinyl compounds include vinyl halides such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid, methacrylic acid, esters and salts thereof; maleic acid, fumaric acid, esters and anhydrides thereof; Styrene, acrylonitrile, vinylidene chloride, vinyl ether and the like.
- the dispersion stabilizer for suspension polymerization according to one embodiment of the present invention is particularly suitably suspended with vinyl chloride alone or with a monomer capable of copolymerizing vinyl chloride with vinyl chloride. Used for turbidity polymerization.
- Examples of monomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylate esters such as methyl (meth)acrylate and ethyl (meth)acrylate; ethylene, ⁇ -olefins such as propylene; unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid; acrylonitrile, styrene, vinylidene chloride, vinyl ether and the like.
- the dispersion stabilizer for suspension polymerization of the present invention can be used alone or in combination with other stabilizers such as cellulose derivatives and surfactants.
- a vinyl chloride resin having a high bulk specific gravity of resin particles, a uniform particle size distribution, and excellent physical properties can be obtained.
- the polymerization method of the vinyl compound will be specifically described with examples, but the method is not limited to these.
- the dispersion stabilizer for suspension polymerization described above is added in an amount of 0.01% by mass to 0.3% by mass, preferably 0.3% by mass, based on the vinyl compound monomer. 0.04% by mass to 0.15% by mass is added.
- the polymerization initiator may be one conventionally used for the polymerization of vinyl compounds, including peroxydicarbonate such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate.
- peroxydicarbonate such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate.
- perester compounds such as t-butyl peroxyneodecanoate and ⁇ -cumyl peroxyneodecanoate, acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate Peroxides, azo compounds such as azobis-2,4-dimethylvaleronitrile and azobis(4-methoxy-2,4-dimethylvaleronitrile), potassium persulfate, ammonium persulfate, hydrogen peroxide, etc. alone or in combination can be used
- polymerization modifiers chain transfer agents, gelation modifiers, antistatic agents, pH adjusters, etc. that are appropriately used in the polymerization of vinyl compounds.
- the charging ratio of each component, the polymerization temperature, etc. in carrying out the polymerization of the vinyl compound may be determined according to the conditions conventionally used in the suspension polymerization of the vinyl compound, and there is no particular reason for limitation.
- Example 1 1410 g of vinyl acetate, 700 g of methanol, 1.8 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization.
- Table 1 shows the polymerization rate at the end of the continuous addition of the dicarboxylic acid monomer, the final polymerization rate, and the polymerization rate at the end of the continuous addition of the dicarboxylic acid monomer relative to the final polymerization rate.
- unreacted vinyl acetate is removed by a conventional method
- a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method
- saponification is performed at 40° C. for 1 hour
- neutralization treatment is performed.
- PVA1 was obtained by drying at 110° C. for 2 hours.
- Modification rate (dicarboxylic acid monomer unit content), saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, and The viscosity average degree of polymerization was measured by the analytical method previously described. Table 1 shows the results.
- a 0.2% by mass aqueous solution of PVA1 is placed in a sample container (quartz cell) with an optical path length of 10 mm, and an ultraviolet-visible-near-infrared spectrophotometer (spectrophotometer UV1800 manufactured by Shimadzu Corporation) is used to measure wavelengths of 280 nm and 325 nm. , the UV absorbance of a 0.2% by mass aqueous solution of PVA1 was measured. Table 1 shows the results.
- the average particle size was measured in accordance with JIS Z8815: 1994, 60 mesh (250 ⁇ m opening), 80 mesh (180 ⁇ m opening), 100 mesh (150 ⁇ m opening), 150 mesh (106 ⁇ m opening), 200 mesh ( Using a sieve with an opening of 75 ⁇ m), the average particle diameter (D50) at a cumulative frequency of 50% (based on mass) and the mass ratio of particles of 250 ⁇ m or more were determined.
- Example 2 1410 g of vinyl acetate, 700 g of methanol, 3.1 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization.
- PVA2 was obtained by drying at 110° C. for 2 hours.
- the modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA2 were compared with Example 1. It was measured by the same method.
- suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA2 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
- Example 3 1410 g of vinyl acetate, 700 g of methanol, 3.1 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization.
- PVA3 was obtained by drying at 110° C. for 2 hours.
- the modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA3 were compared with Example 1. It was measured by the same method.
- suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA3 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
- Example 4 1410 g of vinyl acetate, 700 g of methanol, 4.3 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.15 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization.
- PVA4 was obtained by drying at 110° C. for 2 hours.
- the modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA4 were compared with Example 1. It was measured by the same method.
- the physical properties of vinyl chloride obtained by carrying out suspension polymerization of vinyl chloride under the same conditions as in Example 1 were measured, except that PVA4 was used. Table 1 shows the results.
- Example 5 1410 g of vinyl acetate, 700 g of methanol, 5.6 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.2 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization.
- PVA5 was obtained by drying at 110° C. for 2 hours. Modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA5 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA5 was used, and physical properties of the resulting vinyl chloride resin were measured. Table 1 shows the results.
- Example 6 1410 g of vinyl acetate, 700 g of methanol, 7.4 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.25 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization.
- PVA6 was obtained by drying at 110° C. for 2 hours. Modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA6 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA6 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
- Example 7 1410 g of vinyl acetate, 700 g of methanol, 9.3 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.3 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization.
- PVA7 was obtained by drying at 110° C. for 2 hours.
- the modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA7 were compared with Example 1. It was measured by the same method.
- suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA7 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
- Example 8 1410 g of vinyl acetate, 700 g of methanol, 3.7 g of diethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, diethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization.
- PVA8 was obtained by drying at 110° C. for 2 hours. Modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA8 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA8 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
- PVA9 was obtained by drying at 110° C. for 2 hours.
- the modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA9 were compared with Example 1. It was measured by the same method.
- suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA9 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
- Comparative example 2 1410 g of vinyl acetate, 700 g of methanol, 3.1 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization.
- PVA10 was obtained by drying at 110° C. for 2 hours.
- the modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA10 were compared with Example 1. It was measured by the same method.
- suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA10 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
- PVA13 was obtained by drying at 110° C. for 2 hours.
- the modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA13 were compared with Example 1. It was measured by the same method. Further, the physical properties of the vinyl chloride resin obtained by suspension polymerization of vinyl chloride under the same conditions as in Example 1 were measured, except that PVA13 was used. Table 2 shows the results.
- the modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA14 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA14 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
- Polymerization was carried out by continuous addition over 10 hours at a rate of 18 g. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, and a sodium hydroxide methanol solution is added to the obtained polymer by a conventional method, saponified at 40° C. for 1 hour, and then neutralized. C. for 2 hours to obtain PVA15.
- the modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA15 were compared with Example 1. It was measured by the same method. Suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA15 was used, and the physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
- Comparative Examples 1 to 6 since the homopolymer content in the resin composition was high, the vinyl chloride resin particles were coarsened, the amount of coarse particles was large, and scale adhesion was large. Since Comparative Example 7 did not contain the structure represented by the general formula (I), the vinyl chloride resin particles were coarsened, the amount of coarse particles was large, and scale adhesion was large. On the other hand, when the resin compositions shown in Examples 1 to 8 are used, the formation of coarse particles in the vinyl chloride resin is small, particles having a highly uniform particle size are obtained, the bulk specific gravity is high, and scale Adhesion was also low. Therefore, the dispersion stabilizers (PVA1 to PVA8) according to Examples 1 to 8 are industrially extremely advantageous.
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Abstract
Provided is a resin composition that contains a modified polyvinyl alcohol polymer useful as a dispersion stabilizer suitable for obtaining resin particles having minute and highly uniform particle sizes, few coarsened particles, and a high bulk specific gravity when suspension-polymerization of a vinyl compound such as vinyl chloride is carried out. The resin composition contains, in a main chain, a modified polyvinyl alcohol polymer having the structural unit shown in general formula (I) and a homopolymer of polyvinyl alcohol. The mass percentage of the homopolymer of polyvinyl alcohol in a total of 100 mass% of the modified polyvinyl alcohol polymer and the homopolymer of polyvinyl alcohol is 0 to 5 mass%. (In the formula, X and Y represent a lower alkyl group having 1 to 12 carbon atoms, a hydrogen atom, or a metal atom, and may be the same or different. Z represents the number of repeating units and is an integer from 0 to 3.)
Description
本発明は、変性ポリビニルアルコール系重合体を含有する樹脂組成物及びその製造方法に関する。また、本発明は、懸濁重合用分散安定剤、とりわけビニル系化合物、特に塩化ビニルの懸濁重合に適した分散安定剤に関する。
The present invention relates to a resin composition containing a modified polyvinyl alcohol polymer and a method for producing the same. The present invention also relates to a dispersion stabilizer for suspension polymerization, particularly a dispersion stabilizer suitable for suspension polymerization of vinyl compounds, especially vinyl chloride.
塩化ビニル単量体又は塩化ビニル単量体とこれに共重合し得る単量体との混合物を懸濁重合する場合において、各種の分散安定剤を使用することは必須であり、ポリビニルアルコール、メチロールセルロース等の分散安定剤が用いられているが、中でもポリビニルアルコール(PVA)は優れた性質を有しており、一般に最も使用されている。例えば、ビニル系化合物の懸濁重合用分散安定剤として、ポリビニルアルコール系重合体の末端にアルデヒド由来のカルボニル基を導入し、ケン化時に脱水反応又は脱酢酸反応を受けることで不飽和二重結合を導入することや(例えば特許文献1参照)、ビニルアルコール系重合体の分子の主鎖に特定モノマー由来の不飽和二重結合を導入する方法が提案されている(例えば特許文献2~3参照)。特許文献2には、不飽和二重結合が導入された変性PVAにおいて、未変性PVAの含有量が25質量%以下であるのが好ましいことが記載されており、実施例においては未変性PVAの含有量が10~45%の範囲であったことが記載されている。
In the suspension polymerization of a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith, it is essential to use various dispersion stabilizers, such as polyvinyl alcohol, methylol Dispersion stabilizers such as cellulose are used, among which polyvinyl alcohol (PVA) has excellent properties and is most commonly used. For example, as a dispersion stabilizer for suspension polymerization of vinyl compounds, an aldehyde-derived carbonyl group is introduced at the end of a polyvinyl alcohol polymer, and an unsaturated double bond is formed by undergoing a dehydration reaction or a deacetic acid reaction during saponification. (see, for example, Patent Document 1), and a method of introducing an unsaturated double bond derived from a specific monomer into the main chain of the vinyl alcohol polymer molecule has been proposed (see, for example, Patent Documents 2 and 3). ). Patent Document 2 describes that the content of unmodified PVA in modified PVA into which unsaturated double bonds are introduced is preferably 25% by mass or less. It is stated that the content was in the range of 10-45%.
これらの方法では、近年用いられる大型重合缶等、様々なタイプの重合缶に充分対応できていない。すなわち、不均一な粒子径のビニル系樹脂粒子となってスケール付着が増加したり、分散力が強い一方で保護コロイド性に乏しく粗大化したビニル系樹脂粒子が得られ加工性が低下したり、分散力が乏しく可塑剤吸収性の低いビニル系樹脂粒子となったり、微細なビニル系樹脂粒子ではあるがかさ比重が低い等の不具合が生じることから、ユーザからの要求性能を安定して満足するビニル系樹脂粒子を安定して得るのには不十分であった。
These methods are not adequately compatible with various types of polymerization cans, such as the large polymerization cans that have been used in recent years. That is, vinyl resin particles with non-uniform particle diameters increase the adhesion of scale, or vinyl resin particles with strong dispersing power but poor protective colloid properties are obtained and become coarse, resulting in a decrease in workability. Since vinyl resin particles have poor dispersing power and low plasticizer absorbability, and there are problems such as low bulk specific gravity despite being fine vinyl resin particles, the performance required by users is stably satisfied It was insufficient to stably obtain vinyl resin particles.
そこで、本発明は、一実施形態において、塩化ビニルのようなビニル系化合物を懸濁重合するに際して、微細で粒度の均一性が高く、粗大化した粒子が少なく、かさ比重が高い樹脂粒子を得るのに適した分散安定剤として有用な変性ポリビニルアルコール系重合体を含有する樹脂組成物を提供することを課題の一つとする。
Therefore, in one embodiment of the present invention, when a vinyl compound such as vinyl chloride is subjected to suspension polymerization, resin particles that are fine and highly uniform in particle size, have few coarse particles, and have a high bulk specific gravity are obtained. An object of the present invention is to provide a resin composition containing a modified polyvinyl alcohol-based polymer useful as a dispersion stabilizer suitable for
本発明者等は、上記の課題を解決すべく鋭意研究を重ねた結果、ポリビニルアルコールの主鎖中にジカルボン酸単量体単位と共役二重結合を有する変性ポリビニルアルコール系重合体と、ポリビニルアルコールのホモポリマーと、を含有する樹脂組成物であって、前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーの合計100質量%中の、前記ポリビニルアルコールのホモポリマーの質量割合が5質量%以下である樹脂組成物を使用することが有効であることを見出した。
As a result of intensive studies to solve the above problems, the present inventors have found a modified polyvinyl alcohol polymer having a dicarboxylic acid monomer unit and a conjugated double bond in the main chain of polyvinyl alcohol, and polyvinyl alcohol wherein the homopolymer of polyvinyl alcohol accounts for 5% by mass of the total 100% by mass of the modified polyvinyl alcohol-based polymer and the homopolymer of polyvinyl alcohol We have found that it is effective to use the following resin composition.
特許文献2には、不飽和二重結合が導入された変性PVAにおいて、未変性PVAの含有量が25質量%以下であるのが好ましいことが記載されている。しかし、特許文献2では、未変性PVAの含有量が最も低い実施例においても10質量%である。特許文献2には未変性PVAの含有量を5質量%以下とするための方法、及び、それによって得られる分散安定剤としての有利な効果について何れも記載されていない。
Patent Document 2 describes that in modified PVA into which unsaturated double bonds are introduced, the content of unmodified PVA is preferably 25% by mass or less. However, in Patent Literature 2, even the lowest content of unmodified PVA is 10% by mass. Patent document 2 does not describe a method for reducing the content of unmodified PVA to 5% by mass or less, nor does it describe an advantageous effect as a dispersion stabilizer obtained thereby.
本発明は一側面において、主鎖中に一般式(I)に示す構成単位を有する変性ポリビニルアルコール系重合体と、ポリビニルアルコールのホモポリマーと、を含有する樹脂組成物であって、前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーの合計100質量%中の、前記ポリビニルアルコールのホモポリマーの質量割合が0~5質量%である樹脂組成物である。
(式中、XとYは炭素数1~12の低級アルキル基、水素原子又は金属原子を表し、同一でも異なっていてもよい。Zは繰り返し単位数を表し、0~3の整数である。)
In one aspect of the present invention, there is provided a resin composition containing a modified polyvinyl alcohol-based polymer having a structural unit represented by general formula (I) in the main chain and a polyvinyl alcohol homopolymer, wherein the modified polyvinyl In the resin composition, the proportion by mass of the homopolymer of polyvinyl alcohol is 0 to 5% by mass in the total 100% by mass of the alcohol-based polymer and the homopolymer of polyvinyl alcohol.
(Wherein, X and Y represent a lower alkyl group having 1 to 12 carbon atoms, a hydrogen atom or a metal atom, and may be the same or different. Z represents the number of repeating units and is an integer of 0 to 3. )
本発明に係る樹脂組成物の一実施形態においては、0.2質量%水溶液の波長280nm、光路長10mmにおけるUV吸光度(Abs)が0.1以上5.0以下である。
In one embodiment of the resin composition according to the present invention, the UV absorbance (Abs) of a 0.2% by mass aqueous solution at a wavelength of 280 nm and an optical path length of 10 mm is 0.1 or more and 5.0 or less.
本発明に係る樹脂組成物の別の一実施形態においては、0.2質量%水溶液の波長325nm、光路長10mmにおけるUV吸光度(Abs)が0.01以上1.0以下である。
In another embodiment of the resin composition according to the present invention, the UV absorbance (Abs) of a 0.2% by mass aqueous solution at a wavelength of 325 nm and an optical path length of 10 mm is 0.01 or more and 1.0 or less.
本発明に係る樹脂組成物の更に別の一実施形態においては、前記樹脂組成物のケン化度が65~99.9モル%である。
In still another embodiment of the resin composition according to the present invention, the resin composition has a saponification degree of 65 to 99.9 mol%.
本発明に係る樹脂組成物の更に別の一実施形態においては、前記樹脂組成物が、ジカルボン酸単量体単位を0.1~5.0モル%含むものである。
In still another embodiment of the resin composition according to the present invention, the resin composition contains 0.1 to 5.0 mol % of dicarboxylic acid monomer units.
本発明は別の一側面において、本発明に係る樹脂組成物の製造方法であって、ビニルエステル系単量体と、一般式(I)に示すジカルボン酸単量体単位を誘導する不飽和単量体とを共重合して変性ビニルエステル系重合体を得る工程と、得られた変性ビニルエステル系重合体をケン化する工程とを含み、変性ビニルエステル系重合体の最終重合率に対して、90%以上の重合率になるまでジカルボン酸単量体を断続的又は連続的に添加することを含む製造方法である。
In another aspect of the present invention, there is provided a method for producing a resin composition according to the present invention, comprising a vinyl ester monomer and an unsaturated monomer deriving a dicarboxylic acid monomer unit represented by general formula (I) a step of obtaining a modified vinyl ester polymer by copolymerizing with a monomer, and a step of saponifying the obtained modified vinyl ester polymer. , intermittently or continuously adding a dicarboxylic acid monomer until a conversion of 90% or more is achieved.
本発明は更に別の一側面において、本発明に係る樹脂組成物を含有する懸濁重合用分散安定剤である。
Another aspect of the present invention is a dispersion stabilizer for suspension polymerization containing the resin composition according to the present invention.
本発明は更に別の一側面において、懸濁重合用分散安定剤を用いて、ビニル系化合物単量体、又はビニル系化合物単量体とそれに共重合し得る単量体との混合物を水中に分散させて懸濁重合を行うことを含むビニル系樹脂の製造方法である。
In still another aspect of the present invention, a vinyl compound monomer or a mixture of a vinyl compound monomer and a monomer copolymerizable therewith is added to water using a dispersion stabilizer for suspension polymerization. A method for producing a vinyl-based resin including dispersion and suspension polymerization.
本発明の懸濁重合用分散安定剤を用いてビニル系化合物の懸濁重合を行った場合には、粗大粒子の形成が少なく、粒子径の均一性が高い樹脂粒子が得られる。粗大粒子の形成が少ないために重合時のブロック化が抑制され、粒子径の均一性が高い粒子が得られることからスケール付着が低減する。また、高いかさ比重の樹脂が得られ、樹脂加工時の生産性が向上する。このように、本発明の懸濁重合用分散安定剤は従来技術では達成することが難しかった要求性能を兼備することができる。
When suspension polymerization of a vinyl compound is carried out using the dispersion stabilizer for suspension polymerization of the present invention, resin particles with high uniformity in particle size are obtained with little formation of coarse particles. Since the formation of coarse particles is small, blocking during polymerization is suppressed, and particles having a highly uniform particle size are obtained, thereby reducing scale adhesion. Moreover, a resin having a high bulk specific gravity can be obtained, and the productivity at the time of resin processing is improved. Thus, the dispersion stabilizer for suspension polymerization of the present invention can have the required properties that have been difficult to achieve with the prior art.
本発明の懸濁重合用分散安定剤は一実施形態において、ポリビニルアルコールの主鎖中に下記の一般式(I)に示す構成単位、すなわちジカルボン酸単量体単位に共役二重結合をもつ炭素鎖が連結した構成単位を有する変性ポリビニルアルコール系重合体(変性PVA)と、ポリビニルアルコールのホモポリマー(未変性PVA)と、を含有する樹脂組成物であって、前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーの合計100質量%中の、前記ポリビニルアルコールのホモポリマーの質量割合が0~5質量%である樹脂組成物を含有する。
In one embodiment of the dispersion stabilizer for suspension polymerization of the present invention, a carbon having a conjugated double bond in a structural unit represented by the following general formula (I), that is, a dicarboxylic acid monomer unit in the main chain of polyvinyl alcohol A resin composition containing a modified polyvinyl alcohol polymer (modified PVA) having chain-linked structural units and a polyvinyl alcohol homopolymer (unmodified PVA), wherein the modified polyvinyl alcohol polymer and It contains a resin composition in which the homopolymer of polyvinyl alcohol accounts for 0 to 5% by mass of the total 100% by mass of the homopolymer of polyvinyl alcohol.
一般式(I)におけるジカルボン酸単量体単位を誘導する不飽和単量体は、特に限定されるものではないが、マレイン酸ジメチル、マレイン酸モノメチル、マレイン酸ジエチル、マレイン酸モノエチル、マレイン酸ジプロピル、マレイン酸モノプロピル、マレイン酸ジブチル、マレイン酸モノブチル、マレイン酸ジペンチル、マレイン酸モノペンチル、マレイン酸ジヘキシル、マレイン酸モノヘキシル、マレイン酸ジオクチル、マレイン酸モノオクチル、フマル酸ジメチル、フマル酸モノメチル、フマル酸ジエチル、フマル酸モノエチル、フマル酸ジブチル、フマル酸モノブチル、フマル酸ジペンチル、フマル酸モノペンチル、フマル酸ジヘキシル、フマル酸モノヘキシル、フマル酸ジヘプチル、フマル酸モノヘプチル、フマル酸ジオクチル、フマル酸モノオクチル、マレイン酸、無水マレイン酸、フマル酸等が挙げられる。
The unsaturated monomer from which the dicarboxylic acid monomer unit in general formula (I) is derived is not particularly limited, but dimethyl maleate, monomethyl maleate, diethyl maleate, monoethyl maleate, and dipropyl maleate. , monopropyl maleate, dibutyl maleate, monobutyl maleate, dipentyl maleate, monopentyl maleate, dihexyl maleate, monohexyl maleate, dioctyl maleate, monooctyl maleate, dimethyl fumarate, monomethyl fumarate, fumaric acid Diethyl, monoethyl fumarate, dibutyl fumarate, monobutyl fumarate, dipentyl fumarate, monopentyl fumarate, dihexyl fumarate, monohexyl fumarate, diheptyl fumarate, monoheptyl fumarate, dioctyl fumarate, monooctyl fumarate, maleic acid , maleic anhydride, fumaric acid and the like.
一般式(I)において、Zは0~3が好ましく、1~3がより好ましく、1~2がさらに好ましい。
In general formula (I), Z is preferably 0 to 3, more preferably 1 to 3, even more preferably 1 to 2.
本発明に係る樹脂組成物において、ポリビニルアルコールの主鎖中に下記の一般式(I)に示す構成単位を有する変性ポリビニルアルコール系重合体(変性PVA)の含有量は多い方が好ましい。具体的には、前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーの合計100質量%中の前記変性ポリビニルアルコール系重合体の質量割合(「変性PVA含有量」ともいう。)は好ましくは95質量%以上であり、より好ましくは96質量%以上であり、更に好ましくは97質量%以上であり、更により好ましくは98質量%以上である。
In the resin composition according to the present invention, it is preferable that the content of the modified polyvinyl alcohol-based polymer (modified PVA) having the structural unit represented by the following general formula (I) in the polyvinyl alcohol main chain is large. Specifically, the mass ratio of the modified polyvinyl alcohol polymer in the total 100% by mass of the modified polyvinyl alcohol polymer and the polyvinyl alcohol homopolymer (also referred to as "modified PVA content") is preferably It is 95% by mass or more, more preferably 96% by mass or more, still more preferably 97% by mass or more, and even more preferably 98% by mass or more.
本発明に係る樹脂組成物において、ポリビニルアルコールのホモポリマー、すなわち一般式(I)に示すような構成単位及び、その他共重合可能な単量体由来の構成単位の何れも含まれていない未変性ポリビニルアルコール(未変性PVA)は不純物であり、その含有量は少ないことが望ましい。具体的には、前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーの合計100質量%中の前記ホモポリマーの質量割合(「ホモポリマー含有量」ともいう。)は好ましくは5質量%以下であり、より好ましくは4質量%以下であり、更に好ましくは3質量%以下である。ポリビニルアルコールとは、ビニルエステル系重合体を完全にケン化した完全ケン化ポリビニルアルコールと部分的にビニルエステル単位が残存する部分ケン化ポリビニルアルコールの両方を含む。上記ホモポリマー含有量が5質量%超の場合、保護コロイド性が低い成分が多くなるため、ビニル系樹脂の粗大化した粒子が多くなることがある。なお、上記ホモポリマー含有量の下限には特に制限はなく、0質量%でもよいが、精製コストの観点から、典型的に0.1質量%以上、より典型的に0.3質量%以上である。本発明に係る樹脂組成物が上記ホモポリマーを含有するとき、前記樹脂組成物は、一般式(I)に示す構成単位を有する変性ポリビニルアルコール系重合体及びポリビニルアルコールのホモポリマーの混合物である。
In the resin composition according to the present invention, a homopolymer of polyvinyl alcohol, i.e., an unmodified structural unit that does not contain structural units such as those represented by the general formula (I) and structural units derived from other copolymerizable monomers Polyvinyl alcohol (unmodified PVA) is an impurity, and its content is desirably small. Specifically, the mass ratio of the homopolymer (also referred to as "homopolymer content") in the total 100% by mass of the modified polyvinyl alcohol-based polymer and the polyvinyl alcohol homopolymer is preferably 5% by mass or less. , more preferably 4% by mass or less, and still more preferably 3% by mass or less. Polyvinyl alcohol includes both completely saponified polyvinyl alcohol obtained by completely saponifying a vinyl ester polymer and partially saponified polyvinyl alcohol in which vinyl ester units partially remain. If the homopolymer content is more than 5% by mass, the content of components with low protective colloid properties increases, and thus the vinyl-based resin particles may increase in size. The lower limit of the homopolymer content is not particularly limited, and may be 0% by mass, but from the viewpoint of purification cost, it is typically 0.1% by mass or more, more typically 0.3% by mass or more. be. When the resin composition according to the present invention contains the above homopolymer, the resin composition is a mixture of a modified polyvinyl alcohol-based polymer having a structural unit represented by general formula (I) and a homopolymer of polyvinyl alcohol.
本発明に係る樹脂組成物において、前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーの合計100質量%中の前記ホモポリマーの質量割合は以下の手順で測定する。前記樹脂組成物をケン化度99.95モル%以上に完全にケン化した後、十分にメタノール洗浄を行い、分析用の樹脂組成物を作製する。作製した分析用の樹脂組成物を純水に溶解し、HPLC(高速液体クロマトグラフ)で測定する。得られたHPLC結果のピーク面積比を基準に前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーの合計100質量%中の前記ホモポリマー含有量を算出する。例えば、下記の条件又はこれと同等の条件でHPLCを測定した場合、変性ポリビニルアルコール系重合体は3.5~7.0分にピークが検出され、ホモポリマーは7.5~10.0分にピークが検出されるため、これらのピーク面積比からホモポリマーの質量割合を算出する。具体的には3.5~7.0分のピーク面積及び7.5~10.0分のピーク面積の合計に対する7.5~10.0分のピーク面積の割合(%)を、前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーの合計100質量%中の前記ホモポリマーの質量割合(質量%)とする。また、3.5~7.0分のピーク面積及び7.5~10.0分のピーク面積の合計に対する3.5~7.0分のピーク面積の割合(%)を、前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーの合計100質量%中の前記変性ポリビニルアルコール系重合体の質量割合(質量%)とする。
<HPLC測定条件>
カラム:MCI(登録商標) GEL CK08EH(三菱ケミカル株式会社製)
溶離液:純水
移動相流速:0.6ml/min
温度:40℃
注入濃度:0.01wt%
注入量:20μL
検出器:RI In the resin composition according to the present invention, the mass ratio of the homopolymer in the total 100% by mass of the modified polyvinyl alcohol-based polymer and the homopolymer of the polyvinyl alcohol is measured by the following procedure. After completely saponifying the resin composition to a degree of saponification of 99.95 mol % or more, it is sufficiently washed with methanol to prepare a resin composition for analysis. The prepared resin composition for analysis is dissolved in pure water and measured by HPLC (high performance liquid chromatograph). Based on the peak area ratio of the obtained HPLC results, the content of the homopolymer in the total 100% by mass of the modified polyvinyl alcohol-based polymer and the homopolymer of the polyvinyl alcohol is calculated. For example, when HPLC is measured under the following conditions or equivalent conditions, a modified polyvinyl alcohol polymer shows a peak at 3.5 to 7.0 minutes, and a homopolymer at 7.5 to 10.0 minutes. Since peaks are detected in , the mass ratio of the homopolymer is calculated from these peak area ratios. Specifically, the ratio (%) of the peak area of 7.5 to 10.0 minutes to the total of the peak area of 3.5 to 7.0 minutes and the peak area of 7.5 to 10.0 minutes, the denaturation It is the mass ratio (% by mass) of the homopolymer in the total 100% by mass of the polyvinyl alcohol-based polymer and the homopolymer of the polyvinyl alcohol. Also, the ratio (%) of the peak area of 3.5 to 7.0 minutes to the total of the peak area of 3.5 to 7.0 minutes and the peak area of 7.5 to 10.0 minutes, the modified polyvinyl alcohol It is defined as the mass ratio (% by mass) of the modified polyvinyl alcohol polymer in the total 100% by mass of the poly(vinyl alcohol) polymer and the homopolymer of the polyvinyl alcohol.
<HPLC measurement conditions>
Column: MCI (registered trademark) GEL CK08EH (manufactured by Mitsubishi Chemical Corporation)
Eluent: pure water Mobile phase flow rate: 0.6 ml/min
Temperature: 40°C
Injection concentration: 0.01 wt%
Injection volume: 20 μL
Detector: RI
<HPLC測定条件>
カラム:MCI(登録商標) GEL CK08EH(三菱ケミカル株式会社製)
溶離液:純水
移動相流速:0.6ml/min
温度:40℃
注入濃度:0.01wt%
注入量:20μL
検出器:RI In the resin composition according to the present invention, the mass ratio of the homopolymer in the total 100% by mass of the modified polyvinyl alcohol-based polymer and the homopolymer of the polyvinyl alcohol is measured by the following procedure. After completely saponifying the resin composition to a degree of saponification of 99.95 mol % or more, it is sufficiently washed with methanol to prepare a resin composition for analysis. The prepared resin composition for analysis is dissolved in pure water and measured by HPLC (high performance liquid chromatograph). Based on the peak area ratio of the obtained HPLC results, the content of the homopolymer in the total 100% by mass of the modified polyvinyl alcohol-based polymer and the homopolymer of the polyvinyl alcohol is calculated. For example, when HPLC is measured under the following conditions or equivalent conditions, a modified polyvinyl alcohol polymer shows a peak at 3.5 to 7.0 minutes, and a homopolymer at 7.5 to 10.0 minutes. Since peaks are detected in , the mass ratio of the homopolymer is calculated from these peak area ratios. Specifically, the ratio (%) of the peak area of 7.5 to 10.0 minutes to the total of the peak area of 3.5 to 7.0 minutes and the peak area of 7.5 to 10.0 minutes, the denaturation It is the mass ratio (% by mass) of the homopolymer in the total 100% by mass of the polyvinyl alcohol-based polymer and the homopolymer of the polyvinyl alcohol. Also, the ratio (%) of the peak area of 3.5 to 7.0 minutes to the total of the peak area of 3.5 to 7.0 minutes and the peak area of 7.5 to 10.0 minutes, the modified polyvinyl alcohol It is defined as the mass ratio (% by mass) of the modified polyvinyl alcohol polymer in the total 100% by mass of the poly(vinyl alcohol) polymer and the homopolymer of the polyvinyl alcohol.
<HPLC measurement conditions>
Column: MCI (registered trademark) GEL CK08EH (manufactured by Mitsubishi Chemical Corporation)
Eluent: pure water Mobile phase flow rate: 0.6 ml/min
Temperature: 40°C
Injection concentration: 0.01 wt%
Injection volume: 20 μL
Detector: RI
本発明に係る樹脂組成物は一実施形態において、前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーの合計質量割合が90質量%以上であり、典型的には95質量%以上であり、より典型的には98質量%以上である。本明細書においては、当該合計質量割合(「樹脂組成物中の変性PVAと未変性PVAの合計含有量」ともいう。)は、上述したHPLCによる測定の際に、0~20分のピーク面積の合計に対する、3.5~7.0分のピーク面積及び7.5~10.0分のピーク面積の合計の割合(%)として定義する。
In one embodiment of the resin composition according to the present invention, the total mass ratio of the modified polyvinyl alcohol-based polymer and the homopolymer of polyvinyl alcohol is 90% by mass or more, typically 95% by mass or more, More typically, it is 98% by mass or more. In the present specification, the total mass ratio (also referred to as "the total content of modified PVA and unmodified PVA in the resin composition") is measured by HPLC as described above, and the peak area of 0 to 20 minutes It is defined as the ratio (%) of the sum of the peak area from 3.5 to 7.0 minutes and the peak area from 7.5 to 10.0 minutes to the total of .
本発明に係る樹脂組成物は、光路長10mmの石英セルを使用して測定した0.2質量%水溶液の波長280nmにおけるUV吸光度(Abs)が0.1以上5.0以下であることが好ましい。UV吸光度(Abs)はより好ましくは0.3以上3.0以下であり、更に好ましくは0.5以上2.0である。この波長280nmのUV吸収は共役二重結合の二連鎖(Z=1)に相当し、このUV吸光度(Abs)が0.1未満の場合、炭素-炭素二重結合が不足し、保護コロイド性が低下したりするため、結果として適度な粒子径を有するビニル系樹脂を得にくい。また、このUV吸光度(Abs)が5.0を超える場合、着色が顕著になり、分散剤として使用した際、得られるビニル系樹脂の着色に影響を与えることがある。また、化学的に不安定となり、水溶液の粘度が高くなったり、ゲル化したりする場合がある。
The resin composition according to the present invention preferably has a UV absorbance (Abs) of 0.1 or more and 5.0 or less at a wavelength of 280 nm of a 0.2% by mass aqueous solution measured using a quartz cell with an optical path length of 10 mm. . The UV absorbance (Abs) is more preferably 0.3 or more and 3.0 or less, and still more preferably 0.5 or more and 2.0. This UV absorption at a wavelength of 280 nm corresponds to a double chain of conjugated double bonds (Z = 1). As a result, it is difficult to obtain a vinyl resin having an appropriate particle size. Moreover, when this UV absorbance (Abs) exceeds 5.0, coloring becomes conspicuous, and when used as a dispersant, the coloring of the resulting vinyl resin may be affected. In addition, it may become chemically unstable, resulting in an increase in the viscosity of the aqueous solution or gelation.
本発明に係る樹脂組成物は、光路長10mmの石英セルを使用して測定した0.2質量%水溶液の波長325nmにおけるUV吸光度(Abs)が0.01以上1.0以下であることが好ましい。波長325nmにおけるUV吸光度(Abs)はより好ましくは0.03以上0.5以下であり、更に好ましくは0.05以上0.25以下である。この波長325nmのUV吸収は共役二重結合の三連鎖(Z=2)に相当し、このUV吸光度(Abs)が0.01未満の場合、炭素-炭素二重結合が不足し、保護コロイド性が低下したりするため、結果として適度な粒子径を有するビニル系樹脂を得にくい。また、このUV吸光度(Abs)が1.0を超える場合、着色が顕著になり、分散剤として使用した際、得られるビニル系樹脂の着色に影響を与えることがある。また、化学的に不安定となり、水溶液の粘度が高くなったり、ゲル化したりする場合がある。
The resin composition according to the present invention preferably has a UV absorbance (Abs) of 0.01 or more and 1.0 or less at a wavelength of 325 nm of a 0.2% by mass aqueous solution measured using a quartz cell with an optical path length of 10 mm. . The UV absorbance (Abs) at a wavelength of 325 nm is more preferably 0.03 or more and 0.5 or less, and still more preferably 0.05 or more and 0.25 or less. This UV absorption at a wavelength of 325 nm corresponds to a triple chain of conjugated double bonds (Z = 2). As a result, it is difficult to obtain a vinyl resin having an appropriate particle size. Moreover, when this UV absorbance (Abs) exceeds 1.0, coloring becomes conspicuous, and when used as a dispersant, the coloring of the obtained vinyl resin may be affected. In addition, it may become chemically unstable, resulting in an increase in the viscosity of the aqueous solution or gelation.
本発明の樹脂組成物のケン化度は、水溶性を高くして取り扱いを容易にする観点から65モル%以上が好ましく、68モル%以上がより好ましく、70モル%以上であることが更に好ましい。また、本発明の樹脂組成物のケン化度は、ビニル系化合物を懸濁重合した際に得られる粒子のポロシティを高めて可塑剤吸収性を高めるために、99.9モル%以下であることが好ましく、90モル%以下であることがより好ましく、80モル%以下であることが更により好ましい。
The degree of saponification of the resin composition of the present invention is preferably 65 mol% or more, more preferably 68 mol% or more, and even more preferably 70 mol% or more, from the viewpoint of improving water solubility and facilitating handling. . In addition, the degree of saponification of the resin composition of the present invention should be 99.9 mol % or less in order to increase the porosity of the particles obtained when the vinyl compound is subjected to suspension polymerization to increase the absorbability of the plasticizer. is preferred, 90 mol % or less is more preferred, and 80 mol % or less is even more preferred.
本発明の樹脂組成物のケン化度は、JIS K6726:1994に準拠して測定される。すなわち、水酸化ナトリウムで試料中の残存酢酸基(モル%)を定量し、100から差し引くことで求めることができる。
The degree of saponification of the resin composition of the present invention is measured according to JIS K6726:1994. That is, it can be obtained by quantifying the remaining acetic acid group (mol%) in the sample with sodium hydroxide and subtracting it from 100.
本発明の樹脂組成物のジカルボン酸単量体単位は0.1~5.0モル%であることが好ましく、0.3~3.0モル%であることがより好ましく、0.5~2.0モル%であることが更に好ましい。0.1モル%未満の場合、ジカルボン酸単量体単位に連結する共役二重結合部分(-C=CH-(CH=CH)z-)が減少するため、結果として適度な粒子径を有するビニル系樹脂を得ることが難しい。また、かさ密度の低いビニル系樹脂となってしまう。また、5.0モル%を超える場合、pHの変化により物性が大きく変わるためビニル系化合物の懸濁重合時の保護コロイド性が低下したり、化学的に不安定となって、不溶化したり、ゲル化したりする場合がある。
The dicarboxylic acid monomer unit of the resin composition of the present invention is preferably 0.1 to 5.0 mol%, more preferably 0.3 to 3.0 mol%, and 0.5 to 2 0 mol % is more preferred. If it is less than 0.1 mol%, the conjugated double bond portion (-C=CH-(CH=CH)z-) linked to the dicarboxylic acid monomer unit is reduced, resulting in a moderate particle size. It is difficult to obtain a vinyl resin. Moreover, it becomes a vinyl-type resin with a low bulk density. If it exceeds 5.0 mol %, the physical properties change greatly with changes in pH, so that the protective colloid property of the vinyl compound during suspension polymerization decreases, or it becomes chemically unstable and insoluble. It may gel.
本発明の樹脂組成物のジカルボン酸単量体単位の含有量は、実質的に、前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーを構成する単量体単位の全モル数に対するジカルボン酸単量体のモル数の割合(モル%)に等しい。ジカルボン酸単量体単位の含有量を求める方法は特に限定されず、酸価等で求めることができるが、カーボンNMR(13C-NMR)で求めるのが簡便である。具体的には、樹脂組成物をケン化度99.95モル%以上に完全にケン化した後、十分にメタノール洗浄を行い、分析用の樹脂組成物を作製する。作製した分析用の樹脂組成物を重水に溶解し、更にNaOH重水溶液を数滴加えてpH=14にした後、80℃で測定し13C-NMRを測定する。得られたスペクトルの樹脂組成物のメチレン基(25~50ppm)のピークの積分値を基準とし、カルボキシル基の炭素原子である178~185ppmのピークから算出する。例えば、樹脂組成物のメチレン基の積分値をbとし、カルボキシル基の炭素原子の積分値をaとすると、ジカルボン酸単量体単位の含有量は(a/2)/(a/2+b)×100(モル%)と計算される。例えば、a=2、b=99の場合は、1.0モル%と計算される。
The content of dicarboxylic acid monomer units in the resin composition of the present invention is substantially equal to the total number of moles of monomer units constituting the modified polyvinyl alcohol-based polymer and the polyvinyl alcohol homopolymer. It is equal to the ratio (mole %) of the number of moles of the monomer. The method for determining the content of dicarboxylic acid monomer units is not particularly limited, and it can be determined by acid value or the like, but it is convenient to determine by carbon NMR ( 13 C-NMR). Specifically, the resin composition is completely saponified to a degree of saponification of 99.95 mol % or more, and then thoroughly washed with methanol to prepare a resin composition for analysis. The prepared resin composition for analysis is dissolved in heavy water, and several drops of NaOH heavy aqueous solution are added to adjust the pH to 14. Then, the pH is measured at 80° C. and 13 C-NMR is measured. Based on the integrated value of the methylene group (25 to 50 ppm) peak of the resin composition in the obtained spectrum, the peak is calculated from the 178 to 185 ppm peak of the carbon atom of the carboxyl group. For example, if the integrated value of the methylene group in the resin composition is b and the integrated value of the carbon atom of the carboxyl group is a, the content of the dicarboxylic acid monomer unit is (a/2)/(a/2+b)× Calculated as 100 (mol%). For example, when a=2 and b=99, it is calculated as 1.0 mol %.
本発明の樹脂組成物の粘度平均重合度は、ビニル系樹脂を懸濁重合する際の分散安定性を高めるために400以上であることが好ましく、500以上であることがより好ましい。また、粘度平均重合度は分散力を低下させないために4000以下であることが好ましく、3000以下であることがより好ましく、2000以下であることが更により好ましく、1500以下であることが更により好ましい。
The viscosity-average degree of polymerization of the resin composition of the present invention is preferably 400 or more, more preferably 500 or more, in order to improve the dispersion stability during suspension polymerization of the vinyl resin. Further, the viscosity average degree of polymerization is preferably 4000 or less, more preferably 3000 or less, even more preferably 2000 or less, and even more preferably 1500 or less so as not to reduce the dispersing power. .
粘度平均重合度は、JIS K6726:1994に準拠して測定される。すなわち、樹脂組成物を完全にケン化し、精製した後、30℃のジメチルスルホキシド(DMSO)中で測定した極限粘度[η]から求める。
The viscosity average degree of polymerization is measured according to JIS K6726:1994. That is, it is obtained from the intrinsic viscosity [η] measured in dimethyl sulfoxide (DMSO) at 30° C. after completely saponifying and purifying the resin composition.
本発明に係る樹脂組成物の製造方法は特に制限されないが、酢酸ビニルに代表されるビニルエステル系単量体と、一般式(I)に示すジカルボン酸単量体単位を誘導する不飽和単量体とを共重合して変性ビニルエステル系重合体を得る工程と、得られた変性ビニルエステル系重合体をケン化する工程とを含む製造方法が容易で経済的であり、好適に用いられる。ビニルエステル系単量体としては、酢酸ビニルの他、蟻酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、ピバリン酸ビニル及びバーサティック酸ビニル等が挙げられる。一般式(I)に示すジカルボン酸単量体単位を誘導する不飽和単量体は先述した通りである。
The method for producing the resin composition according to the present invention is not particularly limited. A production method comprising a step of copolymerizing a modified vinyl ester polymer with a polymer and a step of saponifying the resulting modified vinyl ester polymer is easy and economical, and is preferably used. Vinyl ester monomers include vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate and vinyl versatate. is mentioned. The unsaturated monomer from which the dicarboxylic acid monomer unit represented by formula (I) is derived is as described above.
必要であればビニルエステル系単量体と共重合可能な単量体、例えばアクリル酸、メタクリル酸、クロトン酸等の不飽和モノカルボン酸或いはこれら不飽和モノカルボン酸のアルキルエステル、フマル酸、イタコン酸等の不飽和ジカルボン酸或いはこれら不飽和ジカルボン酸のアルキルエステル、アクリロニトリル、メタクリロニトリル、アクリルアミド、メタクリルアミド等のニトリル又はアミド、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸等のオレフィンスルホン酸或いはこれらの塩、ビニルエーテル、ビニルケトン、α-オレフィン、ハロゲン化ビニル、ハロゲン化ビニリデン等を単独又は組み合わせて共重合させることも可能である。共重合可能な単量体の混合割合はビニルエステル系単量体及び一般式(I)に示す構成単位を誘導する不飽和単量体の合計モル数に対して合計10モル%以下、好ましくは合計5モル%以下が適当である。
If necessary, monomers copolymerizable with vinyl ester monomers, such as unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, or alkyl esters of these unsaturated monocarboxylic acids, fumaric acid, and itacones. Unsaturated dicarboxylic acids such as acids or alkyl esters of these unsaturated dicarboxylic acids, nitriles or amides such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, olefin sulfonic acids such as ethylenesulfonic acid, allylsulfonic acid, methallylsulfonic acid Alternatively, these salts, vinyl ethers, vinyl ketones, α-olefins, vinyl halides, vinylidene halides, etc. can be copolymerized singly or in combination. The mixing ratio of the copolymerizable monomers is a total of 10 mol% or less, preferably less than the total number of moles of the vinyl ester monomers and the unsaturated monomers from which the structural units represented by the general formula (I) are derived. A total of 5 mol % or less is appropriate.
一般式(I)に示すような、ジカルボン酸単量体単位及び共役二重結合を含有する構成単位を導入する方法としては、特に限定されないが、(i)カルボニル基を含有するアルデヒドやケトン等の連鎖移動剤の存在下でビニルエステル系単量体を重合して得られた変性ビニルエステル系重合体、又は、(ii)ビニルエステル系単量体とジカルボン酸単量体単位を誘導する不飽和単量体とを共重合して得られた変性ビニルエステル系重合体をケン化した後、乾燥工程で脱水反応又は脱酢酸反応を起こしてポリビニルアルコールの主鎖に共役二重結合を導入する方法が挙げられる。乾燥工程によってさらに共役二重結合を発達させるために、90℃以上で1時間以上、好ましくは100℃以上で1時間以上、より好ましくは120℃以上で2時間以上加熱しながら乾燥を実施することが好ましい。乾燥時の加熱温度に特に上限は設定されないが、ゲル化を防止する観点から、180℃以下、好ましくは160℃以下、より好ましくは150℃以下に加熱しながら乾燥を実施することが望ましい。従って、共役二重結合を乾燥工程によって導入する場合の加熱条件は、例えば90~180℃で1~5時間とするのが好ましく、100~160℃で1~5時間とするのがより好ましい。
The method for introducing a structural unit containing a dicarboxylic acid monomer unit and a conjugated double bond as shown in general formula (I) is not particularly limited, but (i) an aldehyde or ketone containing a carbonyl group, etc. (ii) a modified vinyl ester polymer obtained by polymerizing a vinyl ester monomer in the presence of a chain transfer agent, or (ii) an unsaturated derivative that induces a vinyl ester monomer and a dicarboxylic acid monomer unit After saponifying a modified vinyl ester polymer obtained by copolymerizing with a saturated monomer, a dehydration reaction or deacetic acid reaction is caused in a drying step to introduce a conjugated double bond into the main chain of polyvinyl alcohol. method. In order to further develop conjugated double bonds in the drying step, drying is performed while heating at 90° C. or higher for 1 hour or longer, preferably 100° C. or higher for 1 hour or longer, and more preferably 120° C. or higher for 2 hours or longer. is preferred. Although no upper limit is set for the heating temperature during drying, from the viewpoint of preventing gelation, it is desirable to carry out drying while heating at 180°C or lower, preferably 160°C or lower, more preferably 150°C or lower. Therefore, the heating conditions for introducing the conjugated double bond by the drying process are preferably, for example, 90 to 180° C. for 1 to 5 hours, more preferably 100 to 160° C. for 1 to 5 hours.
本発明に係る樹脂組成物を製造するのに採用される重合方法としては、回分重合、半回分重合、連続重合、半連続重合のいずれでもよい。重合方法としては、塊状重合法、溶液重合法、懸濁重合法、乳化重合法等公知の方法の中から、任意の方法を採用することができる。その中でも、重合粒子径を制御する必要のある懸濁重合法及び乳化重合法ではなく、アルコール系溶媒存在下で重合を行う溶液重合法又は溶媒を用いないで重合を行う塊状重合法が好適に採用される。溶液重合法に用いられるアルコール系溶媒としては、メタノール、エタノール、イソプロパノール等を用いることができるが、これらに限定されるものではない。またこれらの溶媒は単独で使用してもよいし、2種類以上のものを併用することもできる。
Any of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization may be used as the polymerization method employed to produce the resin composition according to the present invention. As the polymerization method, any method can be adopted from known methods such as bulk polymerization method, solution polymerization method, suspension polymerization method and emulsion polymerization method. Among them, a solution polymerization method in which polymerization is performed in the presence of an alcoholic solvent or a bulk polymerization method in which polymerization is performed without using a solvent is preferable, instead of a suspension polymerization method and an emulsion polymerization method that require control of the polymer particle size. Adopted. Methanol, ethanol, isopropanol and the like can be used as the alcoholic solvent used in the solution polymerization method, but the solvent is not limited to these. These solvents may be used alone, or two or more of them may be used in combination.
本発明の樹脂組成物を得る際の重合温度は特に限定されないが、0℃以上200℃以下が好ましく、30℃以上150℃以下がより好ましい。共重合を行う温度が0℃より低い場合は、十分な重合速度が得られないため好ましくない。また、重合を行う温度が200℃より高い場合、目的とする変性ポリビニルアルコール系重合体が得られにくい。共重合を行う際に採用される温度を0℃以上200℃以下に制御する方法としては、水等の適当な熱媒を用いた外部ジャケットにより制御する方法等が挙げられる。
Although the polymerization temperature for obtaining the resin composition of the present invention is not particularly limited, it is preferably 0°C or higher and 200°C or lower, more preferably 30°C or higher and 150°C or lower. If the temperature for copolymerization is lower than 0°C, it is not preferable because a sufficient polymerization rate cannot be obtained. Further, when the polymerization temperature is higher than 200° C., it is difficult to obtain the desired modified polyvinyl alcohol polymer. As a method for controlling the temperature in the range of 0° C. or higher and 200° C. or lower, a method of controlling the temperature by an external jacket using a suitable heat medium such as water can be mentioned.
本発明の樹脂組成物を得る際に使用する重合開始剤は、特に限定するものではないが、アゾビスイソブチロニトリル、アゾビス-2,4-ジメチルバレロニトリル、アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、アゾビスジメチルバレロニトリル、アゾビスメトキシバレロニトリル等のアゾ化合物、アセチルパーオキサイド、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、アセチルシクロヘキシルスルホニルパーオキサイド、2,4,4-トリメチルペンチル-2-パーオキシフェノキシアセテート等の過酸化物、ジイソプロピルパーオキシジカーボネート、ジ-2-エチルヘキシルパーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネート等のパーカーボネート化合物、t-ブチルパーオキシネオデカノエート、α-クミルパーオキシネオデカノエート等のパーエステル化合物等を単独で又は二種以上組み合わせて使用することができる。また、重合速度を一定にする目的で重合開始剤を断続的又は連続的に添加することが好ましい。重合速度を一定にすることは、樹脂組成物中の前記ポリビニルアルコールのホモポリマーの質量割合の低下に寄与する。
The polymerization initiator used in obtaining the resin composition of the present invention is not particularly limited, but azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis(4-methoxy-2, 4-dimethylvaleronitrile), azo compounds such as azobisdimethylvaleronitrile, azobismethoxyvaleronitrile, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl- Peroxides such as 2-peroxyphenoxyacetate, peroxydicarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, t-butyl peroxyneodecanoate , α-cumyl peroxyneodecanoate and the like can be used alone or in combination of two or more. Moreover, it is preferable to add the polymerization initiator intermittently or continuously for the purpose of making the polymerization rate constant. Keeping the polymerization rate constant contributes to lowering the mass ratio of the polyvinyl alcohol homopolymer in the resin composition.
本発明の樹脂組成物を得る際に、ビニルエステル系単量体、ジカルボン酸単量体、その他の共重合可能な単量体を重合初期に全量仕込んで重合することもできるが、前記ホモポリマーの質量割合を5質量%以下にするためには、ジカルボン酸単量体を最初に総添加量の1~30質量%、好ましくは5~20質量%を反応容器に添加しておくと共に、残りのジカルボン酸単量体を重合初期(最終重合率に対して0~1%の重合率にある段階)から断続的又は連続的に添加することが好ましい。さらに、前記ホモポリマーの質量割合を5%以下にするためには、ジカルボン酸単量体の断続的又は連続的な添加は、最終重合率に対して90%以上の重合率になるまで継続することが好ましく、最終重合率に対して93%以上の重合率になるまで継続することがより好ましく、最終重合率に対して95%以上の重合率になるまで継続することが更により好ましい。
When obtaining the resin composition of the present invention, the total amount of vinyl ester monomers, dicarboxylic acid monomers, and other copolymerizable monomers may be charged at the initial stage of polymerization for polymerization. In order to make the mass ratio of 5% by mass or less, the dicarboxylic acid monomer is first added to the reaction vessel in an amount of 1 to 30% by mass, preferably 5 to 20% by mass, and the rest is preferably added intermittently or continuously from the initial stage of polymerization (the stage where the polymerization rate is 0 to 1% with respect to the final polymerization rate). Furthermore, in order to make the mass ratio of the homopolymer 5% or less, the intermittent or continuous addition of the dicarboxylic acid monomer is continued until the final polymerization rate reaches 90% or more. It is preferable to continue until the polymerization rate reaches 93% or more of the final polymerization rate, and it is even more preferable to continue until the polymerization rate reaches 95% or more of the final polymerization rate.
本発明の樹脂組成物を得る際の最終重合率は30質量%~97質量%であることが好ましく、より好ましくは50質量%~94質量%であり、更に好ましくは70質量%~93質量%である。最終重合率が30%未満の場合、未反応の原料を廃棄または回収精製する必要があり、経済的に効率的でない。最終重合率が97質量%を超える場合、変性ビニルエステル系重合体に分岐構造が生成しやすくなり、ビニル系樹脂の粒径が大きくなる場合がある。
The final polymerization rate when obtaining the resin composition of the present invention is preferably 30% by mass to 97% by mass, more preferably 50% by mass to 94% by mass, and still more preferably 70% by mass to 93% by mass. is. If the final polymerization rate is less than 30%, unreacted raw materials must be discarded or recovered and purified, which is not economically efficient. If the final polymerization rate exceeds 97% by mass, the modified vinyl ester polymer tends to have a branched structure, which may increase the particle size of the vinyl resin.
重合率は、重合液5.0gを測り取り、150℃で30分間乾燥させて未反応モノマーや溶媒を揮発された乾固物の質量から重合液の濃度を求めて、重合液の濃度からその時点で重合しているポリマーの質量を算出し、モノマーの全仕込量に対するポリマーの割合から重合率を算出する。
For the polymerization rate, measure 5.0 g of the polymerization liquid, dry it at 150° C. for 30 minutes, and determine the concentration of the polymerization liquid from the mass of the dry matter after volatilization of unreacted monomers and solvent. The mass of the polymer polymerized at that time is calculated, and the rate of polymerization is calculated from the ratio of the polymer to the total charged amount of the monomers.
また、重合を高い温度で行った場合、ビニルエステル系単量体の分解に起因するポリビニルアルコールの着色等が見られることがある。その場合には着色防止の目的で重合系にクエン酸のような酸化防止剤を1ppm以上100ppm以下(ビニルエステル系単量体の質量に対して)程度添加することはなんら差し支えない。
Also, when polymerization is carried out at a high temperature, coloring of polyvinyl alcohol due to decomposition of vinyl ester monomers may be observed. In that case, for the purpose of preventing coloration, an antioxidant such as citric acid may be added to the polymerization system in an amount of 1 ppm or more and 100 ppm or less (based on the weight of the vinyl ester monomer).
本発明に係る本発明の樹脂組成物を製造する際のケン化方法も特に限定されるものではなく、前述した方法で得られた変性ビニルエステル系重合体を、常法に従い、アルコール類を溶媒兼用で用いることが好ましい。アルコールとしてはメタノール、エタノール、ブタノール等が挙げられる。アルコール中の変性ビニルエステル系重合体の濃度は20~50質量%の範囲から選ぶことができる。アルカリ触媒としては水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、ナトリウムエチラート、カリウムメチラート等のアルカリ金属の水酸化物やアルコラートの如きアルカリ触媒を用いることができ、酸触媒としては、塩酸、硫酸等の無機酸水溶液、p-トルエンスルホン酸等の有機酸を用いることができる。これら触媒の使用量はビニルエステル系単量体に対して1~100ミリモル当量にすることが好ましい。ケン化温度は特に制限はないが、通常10~70℃の範囲であり、好ましくは30~50℃の範囲から選ぶのが望ましい。反応は通常0.5~3時間にわたって行われる。
The saponification method for producing the resin composition of the present invention is not particularly limited. It is preferable to use it in combination. Alcohols include methanol, ethanol, butanol, and the like. The concentration of the modified vinyl ester polymer in alcohol can be selected from the range of 20 to 50 mass %. Alkali catalysts such as hydroxides and alcoholates of alkali metals such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate can be used as alkali catalysts, and acid catalysts such as hydrochloric acid, An aqueous inorganic acid solution such as sulfuric acid, and an organic acid such as p-toluenesulfonic acid can be used. The amount of these catalysts used is preferably 1 to 100 millimol equivalents relative to the vinyl ester monomer. Although the saponification temperature is not particularly limited, it is usually in the range of 10 to 70°C, preferably in the range of 30 to 50°C. The reaction is usually carried out over 0.5-3 hours.
本発明の懸濁重合用分散安定剤は、本発明の樹脂組成物単独であってもよく、本発明の趣旨を損なわない範囲で、主鎖中に一般式(I)に示す構成単位を有する前記変性ポリビニルアルコール系重合体、及び前記ポリビニルアルコールのホモポリマー以外のポリビニルアルコール系重合体や、その他の各種添加剤を含有してもよい。該添加剤としては、例えば、アルデヒド類、ハロゲン化炭化水素類、メルカプタン類等の重合調整剤;フェノール化合物、イオウ化合物、N-オキサイド化合物等の重合禁止剤;pH調整剤;架橋剤;防腐剤;防黴剤、ブロッキング防止剤;消泡剤等が挙げられる。本発明の効果を有意に発揮するという観点から、本発明の懸濁重合用分散安定剤は前記変性ポリビニルアルコール系重合体を10質量%以上含有することが好ましく、30質量%以上含有することがより好ましく、70質量%以上含有することが更に好ましい。
The dispersion stabilizer for suspension polymerization of the present invention may be the resin composition of the present invention alone, and has a structural unit represented by general formula (I) in the main chain within a range that does not impair the gist of the present invention. The modified polyvinyl alcohol-based polymer, polyvinyl alcohol-based polymers other than the homopolymer of polyvinyl alcohol, and other various additives may be contained. Examples of such additives include polymerization modifiers such as aldehydes, halogenated hydrocarbons and mercaptans; polymerization inhibitors such as phenol compounds, sulfur compounds and N-oxide compounds; pH adjusters; cross-linking agents; antifungal agents, antiblocking agents; antifoaming agents and the like. From the viewpoint of significantly exhibiting the effects of the present invention, the dispersion stabilizer for suspension polymerization of the present invention preferably contains the modified polyvinyl alcohol polymer in an amount of 10% by mass or more, and preferably 30% by mass or more. More preferably, it is contained in an amount of 70% by mass or more.
本発明の懸濁重合用分散安定剤は、特にビニル系化合物の懸濁重合に好適に用いることができる。従って、本発明の別の一側面によれば、懸濁重合用分散安定剤を用いて、ビニル系化合物単量体、又はビニル系化合物単量体とそれに共重合し得る単量体との混合物を水中に分散させて懸濁重合を行うことを含むビニル系樹脂の製造方法が提供される。
The dispersion stabilizer for suspension polymerization of the present invention can be suitably used particularly for suspension polymerization of vinyl compounds. Therefore, according to another aspect of the present invention, a vinyl compound monomer or a mixture of a vinyl compound monomer and a monomer copolymerizable therewith using a dispersion stabilizer for suspension polymerization is dispersed in water to carry out suspension polymerization.
ビニル系化合物としては、塩化ビニル等のハロゲン化ビニル;酢酸ビニル、プロピオン酸ビニル等のビニルエステル;アクリル酸、メタクリル酸、これらのエステル及び塩;マレイン酸、フマル酸、これらのエステル及び無水物;スチレン、アクリロニトリル、塩化ビニリデン、ビニルエーテル等が挙げられる。これらの中でも、本発明の一実施形態に係る懸濁重合用分散安定剤は、特に好適には塩化ビニルを単独で、又は塩化ビニルを塩化ビニルと共重合することが可能な単量体と共に懸濁重合する際に用いられる。塩化ビニルと共重合することができる単量体としては、酢酸ビニル、プロピオン酸ビニル等のビニルエステル;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル等の(メタ)アクリル酸エステル;エチレン、プロピレン等のα-オレフィン;無水マレイン酸、イタコン酸等の不飽和ジカルボン酸類;アクリロニトリル、スチレン、塩化ビニリデン、ビニルエーテル等が挙げられる。
Vinyl compounds include vinyl halides such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid, methacrylic acid, esters and salts thereof; maleic acid, fumaric acid, esters and anhydrides thereof; Styrene, acrylonitrile, vinylidene chloride, vinyl ether and the like. Among these, the dispersion stabilizer for suspension polymerization according to one embodiment of the present invention is particularly suitably suspended with vinyl chloride alone or with a monomer capable of copolymerizing vinyl chloride with vinyl chloride. Used for turbidity polymerization. Examples of monomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylate esters such as methyl (meth)acrylate and ethyl (meth)acrylate; ethylene, α-olefins such as propylene; unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid; acrylonitrile, styrene, vinylidene chloride, vinyl ether and the like.
本発明の懸濁重合用分散安定剤は、単独でもまた他の安定剤、例えばセルロース系誘導体、界面活性剤等と併用することができる。
The dispersion stabilizer for suspension polymerization of the present invention can be used alone or in combination with other stabilizers such as cellulose derivatives and surfactants.
本発明の懸濁重合用分散安定剤を使用することにより、樹脂粒子のかさ比重が高く、粒径分布が均一で優れた物性の塩化ビニル樹脂が得られる。以下、ビニル系化合物の重合法について例を挙げ具体的に説明するが、これらに限定されるものではない。
By using the dispersion stabilizer for suspension polymerization of the present invention, a vinyl chloride resin having a high bulk specific gravity of resin particles, a uniform particle size distribution, and excellent physical properties can be obtained. Hereinafter, the polymerization method of the vinyl compound will be specifically described with examples, but the method is not limited to these.
塩化ビニル樹脂粒子等のビニル系樹脂粒子を製造する場合には、ビニル系化合物単量体に対し、上述の懸濁重合用分散安定剤を0.01質量%~0.3質量%、好ましくは0.04質量%~0.15質量%添加する。また、ビニル系化合物と水の比は質量比でビニル系化合物:水=1:0.9~1:3とすることができ、好ましくはビニル系化合物:水=1:1~1:1.5である。
When producing vinyl resin particles such as vinyl chloride resin particles, the dispersion stabilizer for suspension polymerization described above is added in an amount of 0.01% by mass to 0.3% by mass, preferably 0.3% by mass, based on the vinyl compound monomer. 0.04% by mass to 0.15% by mass is added. In addition, the ratio of the vinyl compound to water can be vinyl compound:water=1:0.9 to 1:3, preferably vinyl compound:water=1:1 to 1:1. 5.
重合開始剤は、ビニル系化合物の重合に従来使用されているものでよく、これにはジイソプロピルパーオキシジカーボネート、ジ-2-エチルヘキシルパーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネート等のパーカーボネート化合物、t-ブチルパーオキシネオデカノエート、α-クミルパーオキシネオデカノエート等のパーエステル化合物、アセチルシクロヘキシルスルホニルパーオキサイド、2,4,4-トリメチルペンチル-2-パーオキシフェノキシアセテート等の過酸化物、アゾビス-2,4-ジメチルバレロニトリル、アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)等のアゾ化合物、更には過硫酸カリウム、過硫酸アンモニウム、過酸化水素等を単独又は組み合わせて使用することができる。
The polymerization initiator may be one conventionally used for the polymerization of vinyl compounds, including peroxydicarbonate such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate. compounds, perester compounds such as t-butyl peroxyneodecanoate and α-cumyl peroxyneodecanoate, acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate Peroxides, azo compounds such as azobis-2,4-dimethylvaleronitrile and azobis(4-methoxy-2,4-dimethylvaleronitrile), potassium persulfate, ammonium persulfate, hydrogen peroxide, etc. alone or in combination can be used
更に、ビニル系化合物の重合に適宜使用される重合調整剤、連鎖移動剤、ゲル化改良剤、帯電防止剤、PH調整剤等を添加することも任意である。
Furthermore, it is also optional to add polymerization modifiers, chain transfer agents, gelation modifiers, antistatic agents, pH adjusters, etc. that are appropriately used in the polymerization of vinyl compounds.
ビニル系化合物の重合を実施するに当たっての各成分の仕込み割合、重合温度等はビニル系化合物の懸濁重合で従来使用されている条件に準じて定めればよく、特に限定する理由は存在しない。
The charging ratio of each component, the polymerization temperature, etc. in carrying out the polymerization of the vinyl compound may be determined according to the conditions conventionally used in the suspension polymerization of the vinyl compound, and there is no particular reason for limitation.
以下、本発明について実施例を挙げて更に詳しく説明する。
(実施例1)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル1.8g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル16.7gを1時間当たり1.45gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.0gを1時間当たり0.2gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。このときのジカルボン酸単量体の連続添加終了時の重合率、最終重合率、及び、最終重合率に対するジカルボン酸単量体の連続添加終了時の重合率を表1に示す。
次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA1を得た。 Hereinafter, the present invention will be described in more detail with reference to examples.
(Example 1)
1410 g of vinyl acetate, 700 g of methanol, 1.8 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 16.7 g of dimethyl maleate was added at a rate of 1.45 g per hour for 11.5 hours. Simultaneously, 2.0 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.2 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Table 1 shows the polymerization rate at the end of the continuous addition of the dicarboxylic acid monomer, the final polymerization rate, and the polymerization rate at the end of the continuous addition of the dicarboxylic acid monomer relative to the final polymerization rate.
Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA1 was obtained by drying at 110° C. for 2 hours.
(実施例1)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル1.8g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル16.7gを1時間当たり1.45gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.0gを1時間当たり0.2gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。このときのジカルボン酸単量体の連続添加終了時の重合率、最終重合率、及び、最終重合率に対するジカルボン酸単量体の連続添加終了時の重合率を表1に示す。
次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA1を得た。 Hereinafter, the present invention will be described in more detail with reference to examples.
(Example 1)
1410 g of vinyl acetate, 700 g of methanol, 1.8 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 16.7 g of dimethyl maleate was added at a rate of 1.45 g per hour for 11.5 hours. Simultaneously, 2.0 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.2 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Table 1 shows the polymerization rate at the end of the continuous addition of the dicarboxylic acid monomer, the final polymerization rate, and the polymerization rate at the end of the continuous addition of the dicarboxylic acid monomer relative to the final polymerization rate.
Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA1 was obtained by drying at 110° C. for 2 hours.
<変性PVAの特性評価>
得られたPVA1の変性率(ジカルボン酸単量体単位の含有量)、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、及び粘度平均重合度を先述した分析法によって測定した。結果を表1に示す。 <Characteristic evaluation of modified PVA>
Modification rate (dicarboxylic acid monomer unit content), saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, and The viscosity average degree of polymerization was measured by the analytical method previously described. Table 1 shows the results.
得られたPVA1の変性率(ジカルボン酸単量体単位の含有量)、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、及び粘度平均重合度を先述した分析法によって測定した。結果を表1に示す。 <Characteristic evaluation of modified PVA>
Modification rate (dicarboxylic acid monomer unit content), saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, and The viscosity average degree of polymerization was measured by the analytical method previously described. Table 1 shows the results.
光路長10mmの試料容器(石英セル)にPVA1の0.2質量%水溶液を入れ、紫外可視近赤外分光光度計((株)島津製作所製分光光度計UV1800)を用いて、波長280nm、325nmにおける、PVA1の0.2質量%水溶液のUV吸光度を測定した。結果を表1に示す。ここで、波長280nmの吸収は共役二重結合の二連鎖(一般式(I)において、Z=1)を表し、325nmの吸収は共役二重結合の三連鎖(一般式(I)において、Z=2)を表す。
A 0.2% by mass aqueous solution of PVA1 is placed in a sample container (quartz cell) with an optical path length of 10 mm, and an ultraviolet-visible-near-infrared spectrophotometer (spectrophotometer UV1800 manufactured by Shimadzu Corporation) is used to measure wavelengths of 280 nm and 325 nm. , the UV absorbance of a 0.2% by mass aqueous solution of PVA1 was measured. Table 1 shows the results. Here, the absorption at a wavelength of 280 nm represents a double chain of conjugated double bonds (in general formula (I), Z = 1), and the absorption at 325 nm represents a triple chain of conjugated double bonds (in general formula (I), Z = 2).
<塩化ビニルの懸濁重合>
攪拌器を備えた容量30Lのステンレス製オートクレーブ中に攪拌下30℃の水10kg、分散安定剤としてPVA1を5.6g、重合開始剤としてt-ブチルパーオキシネオデカノエートを4.6g、α-クミルパーオキシネオデカノエートを1g仕込んだ。オートクレーブを真空で脱気した後、塩化ビニル単量体を7kg加え、53℃で4時間重合した。なお、この懸濁重合では水に対する塩化ビニル単量体の比率を高くし、且つ、低温で重合することにより、塩化ビニル樹脂の粒子が粗大化しやすい条件とした。 <Suspension polymerization of vinyl chloride>
In a 30 L stainless steel autoclave equipped with a stirrer, 10 kg of water at 30 ° C. is stirred, 5.6 g of PVA1 as a dispersion stabilizer, 4.6 g of t-butyl peroxyneodecanoate as a polymerization initiator, α - 1 g of cumyl peroxyneodecanoate was charged. After the autoclave was degassed by vacuum, 7 kg of vinyl chloride monomer was added and polymerized at 53° C. for 4 hours. In this suspension polymerization, the ratio of the vinyl chloride monomer to water was increased and the polymerization was carried out at a low temperature, so that the particles of the vinyl chloride resin were easily coarsened.
攪拌器を備えた容量30Lのステンレス製オートクレーブ中に攪拌下30℃の水10kg、分散安定剤としてPVA1を5.6g、重合開始剤としてt-ブチルパーオキシネオデカノエートを4.6g、α-クミルパーオキシネオデカノエートを1g仕込んだ。オートクレーブを真空で脱気した後、塩化ビニル単量体を7kg加え、53℃で4時間重合した。なお、この懸濁重合では水に対する塩化ビニル単量体の比率を高くし、且つ、低温で重合することにより、塩化ビニル樹脂の粒子が粗大化しやすい条件とした。 <Suspension polymerization of vinyl chloride>
In a 30 L stainless steel autoclave equipped with a stirrer, 10 kg of water at 30 ° C. is stirred, 5.6 g of PVA1 as a dispersion stabilizer, 4.6 g of t-butyl peroxyneodecanoate as a polymerization initiator, α - 1 g of cumyl peroxyneodecanoate was charged. After the autoclave was degassed by vacuum, 7 kg of vinyl chloride monomer was added and polymerized at 53° C. for 4 hours. In this suspension polymerization, the ratio of the vinyl chloride monomer to water was increased and the polymerization was carried out at a low temperature, so that the particles of the vinyl chloride resin were easily coarsened.
<塩化ビニル樹脂の評価>
得られた塩化ビニル樹脂の平均粒径、250μm以上の粒子の割合、及びかさ比重について以下の方法で評価した。 <Evaluation of vinyl chloride resin>
The average particle size, the ratio of particles having a diameter of 250 μm or more, and the bulk specific gravity of the obtained vinyl chloride resin were evaluated by the following methods.
得られた塩化ビニル樹脂の平均粒径、250μm以上の粒子の割合、及びかさ比重について以下の方法で評価した。 <Evaluation of vinyl chloride resin>
The average particle size, the ratio of particles having a diameter of 250 μm or more, and the bulk specific gravity of the obtained vinyl chloride resin were evaluated by the following methods.
平均粒径の測定はJIS Z8815:1994に準拠して、60メッシュ(目開き250μm)、80メッシュ(目開き180μm)、100メッシュ(目開き150μm)、150メッシュ(目開き106μm)、200メッシュ(目開き75μm)の篩を用いて、累積頻度50%(質量基準)の粒子径(D50)である平均粒径と250μm以上の粒子の質量割合を求めた。
The average particle size was measured in accordance with JIS Z8815: 1994, 60 mesh (250 µm opening), 80 mesh (180 µm opening), 100 mesh (150 µm opening), 150 mesh (106 µm opening), 200 mesh ( Using a sieve with an opening of 75 μm), the average particle diameter (D50) at a cumulative frequency of 50% (based on mass) and the mass ratio of particles of 250 μm or more were determined.
かさ比重は、JIS K6720-2:1999に準拠して測定した。
Bulk specific gravity was measured according to JIS K6720-2:1999.
また、オートクレーブから重合体スラリーを取り出した後、反応器内のスケール付着の状態を目視観察し、スケール付着の度合いを以下の基準で評価した。
A:オートクレーブ内にスケールの付着はほとんどない。
B:オートクレーブ内の撹拌器や内壁に100g以上のスケールが付着しているが、水洗で容易に除去できる。
C:オートクレーブ内の撹拌器や内壁に、水洗では除去しにくい100g以上のスケールが多く付着している。 Further, after taking out the polymer slurry from the autoclave, the state of scale adhesion in the reactor was visually observed, and the degree of scale adhesion was evaluated according to the following criteria.
A: There is almost no adhesion of scale inside the autoclave.
B: 100 g or more of scale adheres to the agitator and inner wall of the autoclave, but can be easily removed by washing with water.
C: A large amount of scale weighing 100 g or more, which is difficult to remove by washing with water, adheres to the agitator and inner wall of the autoclave.
A:オートクレーブ内にスケールの付着はほとんどない。
B:オートクレーブ内の撹拌器や内壁に100g以上のスケールが付着しているが、水洗で容易に除去できる。
C:オートクレーブ内の撹拌器や内壁に、水洗では除去しにくい100g以上のスケールが多く付着している。 Further, after taking out the polymer slurry from the autoclave, the state of scale adhesion in the reactor was visually observed, and the degree of scale adhesion was evaluated according to the following criteria.
A: There is almost no adhesion of scale inside the autoclave.
B: 100 g or more of scale adheres to the agitator and inner wall of the autoclave, but can be easily removed by washing with water.
C: A large amount of scale weighing 100 g or more, which is difficult to remove by washing with water, adheres to the agitator and inner wall of the autoclave.
(実施例2)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル3.1g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル27.9gを1時間当たり2.43gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.4gを1時間当たり0.24gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA2を得た。得られたPVA2の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA2を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 2)
1410 g of vinyl acetate, 700 g of methanol, 3.1 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 27.9 g of dimethyl maleate was added at a rate of 2.43 g per hour for 11.5 hours. Simultaneously, 2.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.24 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA2 was obtained by drying at 110° C. for 2 hours. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA2 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA2 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル3.1g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル27.9gを1時間当たり2.43gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.4gを1時間当たり0.24gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA2を得た。得られたPVA2の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA2を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 2)
1410 g of vinyl acetate, 700 g of methanol, 3.1 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 27.9 g of dimethyl maleate was added at a rate of 2.43 g per hour for 11.5 hours. Simultaneously, 2.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.24 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA2 was obtained by drying at 110° C. for 2 hours. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA2 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA2 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
(実施例3)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル3.1g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり40.0gの速度で11時間かけて連続的に添加し、マレイン酸ジメチル27.9gを1時間当たり2.54gの速度で11時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.4gを1時間当たり0.24gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA3を得た。得られたPVA3の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA3を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 3)
1410 g of vinyl acetate, 700 g of methanol, 3.1 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was added continuously over 11 hours at a rate of 40.0 g per hour, and 27.9 g of dimethyl maleate was added continuously over 11 hours at a rate of 2.54 g per hour. Simultaneously, 2.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.24 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA3 was obtained by drying at 110° C. for 2 hours. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA3 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA3 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル3.1g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり40.0gの速度で11時間かけて連続的に添加し、マレイン酸ジメチル27.9gを1時間当たり2.54gの速度で11時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.4gを1時間当たり0.24gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA3を得た。得られたPVA3の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA3を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 3)
1410 g of vinyl acetate, 700 g of methanol, 3.1 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was added continuously over 11 hours at a rate of 40.0 g per hour, and 27.9 g of dimethyl maleate was added continuously over 11 hours at a rate of 2.54 g per hour. Simultaneously, 2.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.24 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA3 was obtained by drying at 110° C. for 2 hours. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA3 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA3 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
(実施例4)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル4.3g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.15gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル38.7gを1時間当たり3.37gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート3.0gを1時間当たり0.3gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA4を得た。得られたPVA4の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA4を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い得られた塩ビの物性を測定した。結果を表1に示す。 (Example 4)
1410 g of vinyl acetate, 700 g of methanol, 4.3 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.15 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 38.7 g of dimethyl maleate was added at a rate of 3.37 g per hour for 11.5 hours. Simultaneously, 3.0 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.3 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA4 was obtained by drying at 110° C. for 2 hours. The modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA4 were compared with Example 1. It was measured by the same method. In addition, the physical properties of vinyl chloride obtained by carrying out suspension polymerization of vinyl chloride under the same conditions as in Example 1 were measured, except that PVA4 was used. Table 1 shows the results.
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル4.3g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.15gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル38.7gを1時間当たり3.37gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート3.0gを1時間当たり0.3gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA4を得た。得られたPVA4の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA4を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い得られた塩ビの物性を測定した。結果を表1に示す。 (Example 4)
1410 g of vinyl acetate, 700 g of methanol, 4.3 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.15 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 38.7 g of dimethyl maleate was added at a rate of 3.37 g per hour for 11.5 hours. Simultaneously, 3.0 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.3 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA4 was obtained by drying at 110° C. for 2 hours. The modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA4 were compared with Example 1. It was measured by the same method. In addition, the physical properties of vinyl chloride obtained by carrying out suspension polymerization of vinyl chloride under the same conditions as in Example 1 were measured, except that PVA4 was used. Table 1 shows the results.
(実施例5)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル5.6g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.2gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル50.1gを1時間当たり4.36gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート3.6gを1時間当たり0.36gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA5を得た。得られたPVA5の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA5を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 5)
1410 g of vinyl acetate, 700 g of methanol, 5.6 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.2 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 50.1 g of dimethyl maleate was added at a rate of 4.36 g per hour for 11.5 hours. Simultaneously, 3.6 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.36 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA5 was obtained by drying at 110° C. for 2 hours. Modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA5 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA5 was used, and physical properties of the resulting vinyl chloride resin were measured. Table 1 shows the results.
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル5.6g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.2gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル50.1gを1時間当たり4.36gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート3.6gを1時間当たり0.36gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA5を得た。得られたPVA5の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA5を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 5)
1410 g of vinyl acetate, 700 g of methanol, 5.6 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.2 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 50.1 g of dimethyl maleate was added at a rate of 4.36 g per hour for 11.5 hours. Simultaneously, 3.6 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.36 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA5 was obtained by drying at 110° C. for 2 hours. Modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA5 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA5 was used, and physical properties of the resulting vinyl chloride resin were measured. Table 1 shows the results.
(実施例6)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル7.4g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.25gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル66.8gを1時間当たり5.81gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート4.2gを1時間当たり0.42gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA6を得た。得られたPVA6の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA6を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 6)
1410 g of vinyl acetate, 700 g of methanol, 7.4 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.25 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 66.8 g of dimethyl maleate was added at a rate of 5.81 g per hour for 11.5 hours. Simultaneously, 4.2 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.42 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA6 was obtained by drying at 110° C. for 2 hours. Modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA6 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA6 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル7.4g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.25gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル66.8gを1時間当たり5.81gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート4.2gを1時間当たり0.42gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA6を得た。得られたPVA6の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA6を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 6)
1410 g of vinyl acetate, 700 g of methanol, 7.4 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.25 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 66.8 g of dimethyl maleate was added at a rate of 5.81 g per hour for 11.5 hours. Simultaneously, 4.2 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.42 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA6 was obtained by drying at 110° C. for 2 hours. Modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA6 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA6 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
(実施例7)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル9.3g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.3gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル83.7gを1時間当たり7.28gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート5.4gを1時間当たり0.54gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA7を得た。得られたPVA7の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA7を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 7)
1410 g of vinyl acetate, 700 g of methanol, 9.3 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.3 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 83.7 g of dimethyl maleate was added at a rate of 7.28 g per hour for 11.5 hours. Simultaneously, 5.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.54 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA7 was obtained by drying at 110° C. for 2 hours. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA7 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA7 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル9.3g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.3gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジメチル83.7gを1時間当たり7.28gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート5.4gを1時間当たり0.54gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA7を得た。得られたPVA7の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA7を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 7)
1410 g of vinyl acetate, 700 g of methanol, 9.3 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.3 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 83.7 g of dimethyl maleate was added at a rate of 7.28 g per hour for 11.5 hours. Simultaneously, 5.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.54 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA7 was obtained by drying at 110° C. for 2 hours. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA7 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA7 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
(実施例8)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジエチル3.7g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジエチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジエチル33.3gを1時間当たり2.90gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.4gを1時間当たり0.24gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA8を得た。得られたPVA8の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA8を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 8)
1410 g of vinyl acetate, 700 g of methanol, 3.7 g of diethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, diethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 33.3 g of diethyl maleate was added at a rate of 2.90 g per hour for 11.5 hours. Simultaneously, 2.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.24 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA8 was obtained by drying at 110° C. for 2 hours. Modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA8 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA8 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジエチル3.7g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジエチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり38.3gの速度で11.5時間かけて連続的に添加し、マレイン酸ジエチル33.3gを1時間当たり2.90gの速度で11.5時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.4gを1時間当たり0.24gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA8を得た。得られたPVA8の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA8を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表1に示す。 (Example 8)
1410 g of vinyl acetate, 700 g of methanol, 3.7 g of diethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, diethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was continuously added at a rate of 38.3 g per hour over 11.5 hours, and 33.3 g of diethyl maleate was added at a rate of 2.90 g per hour for 11.5 hours. Simultaneously, 2.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.24 g per hour over 10 hours to effect polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA8 was obtained by drying at 110° C. for 2 hours. Modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA8 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA8 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 1 shows the results.
(比較例1)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル1.8g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり55.0gの速度で8時間かけて連続的に添加し、マレイン酸ジメチル16.7gを1時間当たり2.09gの速度で8時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.0gを1時間当たり0.2gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA9を得た。得られたPVA9の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA9を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative example 1)
1410 g of vinyl acetate, 700 g of methanol, 1.8 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was added continuously over 8 hours at a rate of 55.0 g per hour, and 16.7 g of dimethyl maleate was added continuously over 8 hours at a rate of 2.09 g per hour. At the same time, 2.0 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.2 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA9 was obtained by drying at 110° C. for 2 hours. The modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA9 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA9 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル1.8g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり55.0gの速度で8時間かけて連続的に添加し、マレイン酸ジメチル16.7gを1時間当たり2.09gの速度で8時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.0gを1時間当たり0.2gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA9を得た。得られたPVA9の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA9を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative example 1)
1410 g of vinyl acetate, 700 g of methanol, 1.8 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was added continuously over 8 hours at a rate of 55.0 g per hour, and 16.7 g of dimethyl maleate was added continuously over 8 hours at a rate of 2.09 g per hour. At the same time, 2.0 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.2 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA9 was obtained by drying at 110° C. for 2 hours. The modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA9 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA9 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
(比較例2)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル3.1g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり55.0gの速度で8時間かけて連続的に添加し、マレイン酸ジメチル27.9gを1時間当たり3.49gの速度で8時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.4gを1時間当たり0.24gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA10を得た。得られたPVA10の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA10を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative example 2)
1410 g of vinyl acetate, 700 g of methanol, 3.1 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was added continuously over 8 hours at a rate of 55.0 g per hour, and 27.9 g of dimethyl maleate was added continuously over 8 hours at a rate of 3.49 g per hour. Simultaneously, 2.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.24 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA10 was obtained by drying at 110° C. for 2 hours. The modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA10 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA10 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル3.1g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり55.0gの速度で8時間かけて連続的に添加し、マレイン酸ジメチル27.9gを1時間当たり3.49gの速度で8時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート2.4gを1時間当たり0.24gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA10を得た。得られたPVA10の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA10を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative example 2)
1410 g of vinyl acetate, 700 g of methanol, 3.1 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was added continuously over 8 hours at a rate of 55.0 g per hour, and 27.9 g of dimethyl maleate was added continuously over 8 hours at a rate of 3.49 g per hour. Simultaneously, 2.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.24 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA10 was obtained by drying at 110° C. for 2 hours. The modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA10 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA10 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
(比較例3)
酢酸ビニル1850g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル31.0g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったらジ-2-エチルヘキシルパーオキシジカーボネート2.4gを1時間当たり0.24gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して実施例1と同様の加熱条件で常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA11を得た。得られたPVA11の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA11を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative Example 3)
1850 g of vinyl acetate, 700 g of methanol, 31.0 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., 2.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.24 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate was removed by a conventional method, and a methanol solution of sodium hydroxide was added to the resulting polymer under the same heating conditions as in Example 1, and the polymer was saponified at 40°C for 1 hour. Then, it was neutralized and dried at 110° C. for 2 hours to obtain PVA11. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA11 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA11 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
酢酸ビニル1850g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル31.0g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったらジ-2-エチルヘキシルパーオキシジカーボネート2.4gを1時間当たり0.24gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して実施例1と同様の加熱条件で常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA11を得た。得られたPVA11の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA11を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative Example 3)
1850 g of vinyl acetate, 700 g of methanol, 31.0 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., 2.4 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.24 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate was removed by a conventional method, and a methanol solution of sodium hydroxide was added to the resulting polymer under the same heating conditions as in Example 1, and the polymer was saponified at 40°C for 1 hour. Then, it was neutralized and dried at 110° C. for 2 hours to obtain PVA11. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA11 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA11 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
(比較例4)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル4.3g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.2gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり55.0gの速度で8時間かけて連続的に添加し、マレイン酸ジメチル38.7gを1時間当たり4.84gの速度で8時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート3.0gを1時間当たり0.3gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して実施例1と同様の加熱条件で常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA12を得た。得られたPVA12の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA12を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative Example 4)
1410 g of vinyl acetate, 700 g of methanol, 4.3 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.2 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was added continuously over 8 hours at a rate of 55.0 g per hour, and 38.7 g of dimethyl maleate was added continuously over 8 hours at a rate of 4.84 g per hour. At the same time, 3.0 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.3 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate was removed by a conventional method, and a methanol solution of sodium hydroxide was added to the resulting polymer under the same heating conditions as in Example 1, and the polymer was saponified at 40°C for 1 hour. Then, it was neutralized and dried at 110° C. for 2 hours to obtain PVA12. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA12 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA12 was used, and physical properties of the resulting vinyl chloride resin were measured. Table 2 shows the results.
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル4.3g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.2gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり55.0gの速度で8時間かけて連続的に添加し、マレイン酸ジメチル38.7gを1時間当たり4.84gの速度で8時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート3.0gを1時間当たり0.3gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して実施例1と同様の加熱条件で常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA12を得た。得られたPVA12の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA12を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative Example 4)
1410 g of vinyl acetate, 700 g of methanol, 4.3 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.2 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was added continuously over 8 hours at a rate of 55.0 g per hour, and 38.7 g of dimethyl maleate was added continuously over 8 hours at a rate of 4.84 g per hour. At the same time, 3.0 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.3 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate was removed by a conventional method, and a methanol solution of sodium hydroxide was added to the resulting polymer under the same heating conditions as in Example 1, and the polymer was saponified at 40°C for 1 hour. Then, it was neutralized and dried at 110° C. for 2 hours to obtain PVA12. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA12 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA12 was used, and physical properties of the resulting vinyl chloride resin were measured. Table 2 shows the results.
(比較例5)
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル18.5g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.5gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり55.0gの速度で8時間かけて連続的に添加し、マレイン酸ジメチル167.1gを1時間当たり20.89gの速度で8時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート9.0gを1時間当たり0.9gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA13を得た。得られたPVA13の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA13を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative Example 5)
1410 g of vinyl acetate, 700 g of methanol, 18.5 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.5 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was added continuously over 8 hours at a rate of 55.0 g per hour, and 167.1 g of dimethyl maleate was added continuously over 8 hours at a rate of 20.89 g per hour. At the same time, 9.0 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.9 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA13 was obtained by drying at 110° C. for 2 hours. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA13 were compared with Example 1. It was measured by the same method. Further, the physical properties of the vinyl chloride resin obtained by suspension polymerization of vinyl chloride under the same conditions as in Example 1 were measured, except that PVA13 was used. Table 2 shows the results.
酢酸ビニル1410g、メタノール700g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル18.5g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.5gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、マレイン酸ジメチル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり55.0gの速度で8時間かけて連続的に添加し、マレイン酸ジメチル167.1gを1時間当たり20.89gの速度で8時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート9.0gを1時間当たり0.9gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA13を得た。得られたPVA13の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA13を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative Example 5)
1410 g of vinyl acetate, 700 g of methanol, 18.5 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 0.5 g of di-2-ethylhexylperoxydicarbonate were charged in a polymerization vessel, and the system was purged with nitrogen for 30 minutes. It was replaced and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, dimethyl maleate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 g of vinyl acetate was added continuously over 8 hours at a rate of 55.0 g per hour, and 167.1 g of dimethyl maleate was added continuously over 8 hours at a rate of 20.89 g per hour. At the same time, 9.0 g of di-2-ethylhexylperoxydicarbonate was continuously added at a rate of 0.9 g per hour over 10 hours to carry out polymerization. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA13 was obtained by drying at 110° C. for 2 hours. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA13 were compared with Example 1. It was measured by the same method. Further, the physical properties of the vinyl chloride resin obtained by suspension polymerization of vinyl chloride under the same conditions as in Example 1 were measured, except that PVA13 was used. Table 2 shows the results.
(比較例6)
酢酸ビニル1670g、メタノール1160g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル2.5g、及びアゾビスイソブチロニトリル2.0gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、メタノール及びマレイン酸ジメチルの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル520gを1時間当たり104gの速度で5時間かけて連続的に添加し、メタノール270gを1時間当たり54gの速度で5時間かけて連続的に添加し、マレイン酸ジメチル23gを1時間当たり4.60gの速度で5時間かけて連続的に添加することで重合を行った。液温が60℃になってから6時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA14を得た。得られたPVA14の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA14を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative Example 6)
1670 g of vinyl acetate, 1160 g of methanol, 2.5 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 2.0 g of azobisisobutyronitrile were charged into a polymerization vessel, and the inside of the system was replaced with nitrogen for 30 minutes. Heating was started. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, methanol and dimethyl maleate was started to carry out polymerization. Specifically, 520 g of vinyl acetate was continuously added over 5 hours at a rate of 104 g per hour, 270 g of methanol was continuously added over 5 hours at a rate of 54 g per hour, and 23 g of dimethyl maleate was added continuously. was added continuously over 5 hours at a rate of 4.60 g per hour. After 6 hours had passed since the liquid temperature reached 60° C., the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA14 was obtained by drying at 110° C. for 2 hours. The modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA14 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA14 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
酢酸ビニル1670g、メタノール1160g、変性種(ジカルボン酸単量体)としてのマレイン酸ジメチル2.5g、及びアゾビスイソブチロニトリル2.0gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル、メタノール及びマレイン酸ジメチルの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル520gを1時間当たり104gの速度で5時間かけて連続的に添加し、メタノール270gを1時間当たり54gの速度で5時間かけて連続的に添加し、マレイン酸ジメチル23gを1時間当たり4.60gの速度で5時間かけて連続的に添加することで重合を行った。液温が60℃になってから6時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムのメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA14を得た。得られたPVA14の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA14を使用したこと以外は、実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative Example 6)
1670 g of vinyl acetate, 1160 g of methanol, 2.5 g of dimethyl maleate as a modified species (dicarboxylic acid monomer), and 2.0 g of azobisisobutyronitrile were charged into a polymerization vessel, and the inside of the system was replaced with nitrogen for 30 minutes. Heating was started. When the liquid temperature reached 60° C., continuous addition of vinyl acetate, methanol and dimethyl maleate was started to carry out polymerization. Specifically, 520 g of vinyl acetate was continuously added over 5 hours at a rate of 104 g per hour, 270 g of methanol was continuously added over 5 hours at a rate of 54 g per hour, and 23 g of dimethyl maleate was added continuously. was added continuously over 5 hours at a rate of 4.60 g per hour. After 6 hours had passed since the liquid temperature reached 60° C., the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, a methanol solution of sodium hydroxide is added to the obtained polymer by a conventional method, saponification is performed at 40° C. for 1 hour, and then neutralization treatment is performed. PVA14 was obtained by drying at 110° C. for 2 hours. The modification rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA14 were compared with Example 1. It was measured by the same method. In addition, suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA14 was used, and physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
(比較例7)
酢酸ビニル1410g、メタノール700g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり55.0gの速度で8時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート1.8gを1時間当たり0.18gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA15を得た。得られたPVA15の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA15を使用したこと以外は実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative Example 7)
1,410 g of vinyl acetate, 700 g of methanol, and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged into a polymerization vessel, the inside of the system was replaced with nitrogen for 30 minutes, and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 grams of vinyl acetate was added continuously over 8 hours at a rate of 55.0 grams per hour while simultaneously adding 1.8 grams of di-2-ethylhexylperoxydicarbonate at 0.8 grams per hour. Polymerization was carried out by continuous addition over 10 hours at a rate of 18 g. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, and a sodium hydroxide methanol solution is added to the obtained polymer by a conventional method, saponified at 40° C. for 1 hour, and then neutralized. C. for 2 hours to obtain PVA15. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA15 were compared with Example 1. It was measured by the same method. Suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA15 was used, and the physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
酢酸ビニル1410g、メタノール700g、及びジ-2-エチルヘキシルパーオキシジカーボネート0.1gを重合缶に仕込み、30分間系内を窒素置換し、昇温を開始した。液温が60℃になったら酢酸ビニル及びジ-2-エチルヘキシルパーオキシジカーボネートの連続的な添加を開始し、重合を行った。具体的には、酢酸ビニル440gを1時間当たり55.0gの速度で8時間かけて連続的に添加し、これと同時に、ジ-2-エチルヘキシルパーオキシジカーボネート1.8gを1時間当たり0.18gの速度で10時間かけて連続的に添加することで重合を行った。液温が60℃になってから12時間経過後、冷却して重合を停止した。次いで常法により未反応の酢酸ビニルを除去し、得られた重合体に対して常法により水酸化ナトリウムメタノール溶液を添加し、40℃で1時間ケン化し、その後、中和処理を行い、110℃で2時間乾燥してPVA15を得た。得られたPVA15の変性率、ケン化度、変性PVA含有量、ホモポリマー含有量、樹脂組成物中の変性PVAと未変性PVAの合計含有量、粘度平均重合度及びUV吸光度を実施例1と同様の方法で測定した。また、PVA15を使用したこと以外は実施例1と同条件で塩化ビニルの懸濁重合を行い、得られた塩化ビニル樹脂の物性を測定した。結果を表2に示す。 (Comparative Example 7)
1,410 g of vinyl acetate, 700 g of methanol, and 0.1 g of di-2-ethylhexylperoxydicarbonate were charged into a polymerization vessel, the inside of the system was replaced with nitrogen for 30 minutes, and the temperature was started to rise. When the liquid temperature reached 60° C., continuous addition of vinyl acetate and di-2-ethylhexylperoxydicarbonate was started to carry out polymerization. Specifically, 440 grams of vinyl acetate was added continuously over 8 hours at a rate of 55.0 grams per hour while simultaneously adding 1.8 grams of di-2-ethylhexylperoxydicarbonate at 0.8 grams per hour. Polymerization was carried out by continuous addition over 10 hours at a rate of 18 g. After 12 hours had passed since the liquid temperature reached 60°C, the polymerization was stopped by cooling. Next, unreacted vinyl acetate is removed by a conventional method, and a sodium hydroxide methanol solution is added to the obtained polymer by a conventional method, saponified at 40° C. for 1 hour, and then neutralized. C. for 2 hours to obtain PVA15. The modified rate, saponification degree, modified PVA content, homopolymer content, total content of modified PVA and unmodified PVA in the resin composition, viscosity average degree of polymerization and UV absorbance of the obtained PVA15 were compared with Example 1. It was measured by the same method. Suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that PVA15 was used, and the physical properties of the obtained vinyl chloride resin were measured. Table 2 shows the results.
比較例1~6は樹脂組成物中のホモポリマー含有量が多いため、塩化ビニル樹脂粒子が粗大化し、粗粒量が多く、スケール付着が多かった。比較例7は一般式(I)に示すような構造を含有していないため、塩化ビニル樹脂粒子が粗大化し、粗粒量が多く、スケール付着が多かった。これに対して、実施例1~8に示した樹脂組成物を使用すると、塩化ビニル樹脂中に粗大粒子の形成が少なく、粒子径の均一性が高い粒子が得られ、かさ比重も高く、スケール付着も少なかった。よって、実施例1~8に係る分散安定剤(PVA1~PVA8)は工業的に極めて有利なものである。
In Comparative Examples 1 to 6, since the homopolymer content in the resin composition was high, the vinyl chloride resin particles were coarsened, the amount of coarse particles was large, and scale adhesion was large. Since Comparative Example 7 did not contain the structure represented by the general formula (I), the vinyl chloride resin particles were coarsened, the amount of coarse particles was large, and scale adhesion was large. On the other hand, when the resin compositions shown in Examples 1 to 8 are used, the formation of coarse particles in the vinyl chloride resin is small, particles having a highly uniform particle size are obtained, the bulk specific gravity is high, and scale Adhesion was also low. Therefore, the dispersion stabilizers (PVA1 to PVA8) according to Examples 1 to 8 are industrially extremely advantageous.
Claims (8)
- 主鎖中に一般式(I)に示す構成単位を有する変性ポリビニルアルコール系重合体と、ポリビニルアルコールのホモポリマーと、を含有する樹脂組成物であって、前記変性ポリビニルアルコール系重合体及び前記ポリビニルアルコールのホモポリマーの合計100質量%中の、前記ポリビニルアルコールのホモポリマーの質量割合が0~5質量%である樹脂組成物。
- 0.2質量%水溶液の波長280nm、光路長10mmにおけるUV吸光度(Abs)が0.1以上5.0以下である請求項1に記載の樹脂組成物。 The resin composition according to claim 1, wherein the UV absorbance (Abs) of a 0.2% by mass aqueous solution at a wavelength of 280 nm and an optical path length of 10 mm is 0.1 or more and 5.0 or less.
- 0.2質量%水溶液の波長325nm、光路長10mmにおけるUV吸光度(Abs)が0.01以上1.0以下である請求項1又は2に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the UV absorbance (Abs) of the 0.2% by mass aqueous solution at a wavelength of 325 nm and an optical path length of 10 mm is 0.01 or more and 1.0 or less.
- 前記樹脂組成物のケン化度が65~99.9モル%である請求項1~3の何れか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the degree of saponification of the resin composition is 65 to 99.9 mol%.
- 前記樹脂組成物が、ジカルボン酸単量体単位を0.1~5.0モル%含むものである請求項1~4の何れか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 4, wherein the resin composition contains 0.1 to 5.0 mol% of dicarboxylic acid monomer units.
- 請求項1~5の何れか一項に記載の樹脂組成物の製造方法であって、ビニルエステル系単量体と、一般式(I)に示すジカルボン酸単量体単位を誘導する不飽和単量体とを共重合して変性ビニルエステル系重合体を得る工程と、得られた変性ビニルエステル系重合体をケン化する工程とを含み、変性ビニルエステル系重合体の最終重合率に対して、90%以上の重合率になるまでジカルボン酸単量体を断続的又は連続的に添加することを含む製造方法。 A method for producing a resin composition according to any one of claims 1 to 5, wherein a vinyl ester monomer and an unsaturated monomer deriving a dicarboxylic acid monomer unit represented by general formula (I) a step of obtaining a modified vinyl ester polymer by copolymerizing with a monomer, and a step of saponifying the obtained modified vinyl ester polymer. , intermittently or continuously adding a dicarboxylic acid monomer until a conversion of 90% or more is achieved.
- 請求項1~5の何れか一項に記載の樹脂組成物を含有する懸濁重合用分散安定剤。 A dispersion stabilizer for suspension polymerization containing the resin composition according to any one of claims 1 to 5.
- 請求項7に記載された懸濁重合用分散安定剤を用いて、ビニル系化合物単量体、又はビニル系化合物単量体とそれに共重合し得る単量体との混合物を水中に分散させて懸濁重合を行うことを含むビニル系樹脂の製造方法。 Using the dispersion stabilizer for suspension polymerization according to claim 7, a vinyl compound monomer or a mixture of a vinyl compound monomer and a monomer copolymerizable therewith is dispersed in water. A method for producing a vinyl-based resin, comprising performing suspension polymerization.
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Citations (8)
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JPS5138753B1 (en) * | 1968-09-21 | 1976-10-23 | ||
JPS59204999A (en) * | 1984-01-23 | 1984-11-20 | 株式会社クラレ | Paper surface sizing agent |
JPS62119202A (en) * | 1985-11-18 | 1987-05-30 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol polymer, production thereof and sizing agent for paper and dispersion stabilizer composed of said polymer |
US5112905A (en) * | 1989-04-05 | 1992-05-12 | Ausidet S.R.L. | Transesterified copolymers of maleic anhydride, particularly useful in the field of detergency |
JP2008116854A (en) * | 2006-11-07 | 2008-05-22 | Denki Kagaku Kogyo Kk | Photosensitive composition and its use |
WO2015019613A1 (en) * | 2013-08-07 | 2015-02-12 | 株式会社クラレ | Dispersion stabilizer for suspension polymerization, and manufacturing method for vinyl resin |
JP2019105008A (en) * | 2017-12-13 | 2019-06-27 | 株式会社クラレ | Paste for fiber |
WO2019181915A1 (en) * | 2018-03-20 | 2019-09-26 | 株式会社クラレ | Dispersion stabilizer for suspension polymerization |
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JPS5138753B1 (en) * | 1968-09-21 | 1976-10-23 | ||
JPS59204999A (en) * | 1984-01-23 | 1984-11-20 | 株式会社クラレ | Paper surface sizing agent |
JPS62119202A (en) * | 1985-11-18 | 1987-05-30 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol polymer, production thereof and sizing agent for paper and dispersion stabilizer composed of said polymer |
US5112905A (en) * | 1989-04-05 | 1992-05-12 | Ausidet S.R.L. | Transesterified copolymers of maleic anhydride, particularly useful in the field of detergency |
JP2008116854A (en) * | 2006-11-07 | 2008-05-22 | Denki Kagaku Kogyo Kk | Photosensitive composition and its use |
WO2015019613A1 (en) * | 2013-08-07 | 2015-02-12 | 株式会社クラレ | Dispersion stabilizer for suspension polymerization, and manufacturing method for vinyl resin |
JP2019105008A (en) * | 2017-12-13 | 2019-06-27 | 株式会社クラレ | Paste for fiber |
WO2019181915A1 (en) * | 2018-03-20 | 2019-09-26 | 株式会社クラレ | Dispersion stabilizer for suspension polymerization |
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