JP7488183B2 - Polyvinyl alcohol polymer and molded body using same - Google Patents
Polyvinyl alcohol polymer and molded body using same Download PDFInfo
- Publication number
- JP7488183B2 JP7488183B2 JP2020531269A JP2020531269A JP7488183B2 JP 7488183 B2 JP7488183 B2 JP 7488183B2 JP 2020531269 A JP2020531269 A JP 2020531269A JP 2020531269 A JP2020531269 A JP 2020531269A JP 7488183 B2 JP7488183 B2 JP 7488183B2
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- Prior art keywords
- mol
- polyvinyl alcohol
- based polymer
- terminal
- polymerization
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims description 98
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 82
- 238000006116 polymerization reaction Methods 0.000 claims description 58
- 229920000642 polymer Polymers 0.000 claims description 55
- 238000007127 saponification reaction Methods 0.000 claims description 33
- 150000007942 carboxylates Chemical group 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 150000001735 carboxylic acids Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 74
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000000178 monomer Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 17
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 16
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 229920001567 vinyl ester resin Polymers 0.000 description 16
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 15
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 9
- 229920001290 polyvinyl ester Polymers 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- -1 2-ethylhexyl Chemical group 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 7
- 238000010557 suspension polymerization reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000009825 accumulation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 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
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000005456 alcohol based solvent Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000000457 gamma-lactone group Chemical group 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004334 sorbic acid Substances 0.000 description 2
- 229940075582 sorbic acid Drugs 0.000 description 2
- 235000010199 sorbic acid Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 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 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- NXVGUNGPINUNQN-UHFFFAOYSA-N 2-phenylpropan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C1=CC=CC=C1 NXVGUNGPINUNQN-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- DBUPOCYLUHVFHU-UHFFFAOYSA-N carboxyoxy 2,2-diethoxyethyl carbonate Chemical compound CCOC(OCC)COC(=O)OOC(O)=O DBUPOCYLUHVFHU-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- GDEBSAWXIHEMNF-UHFFFAOYSA-O cupferron Chemical compound [NH4+].O=NN([O-])C1=CC=CC=C1 GDEBSAWXIHEMNF-UHFFFAOYSA-O 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 235000010981 methylcellulose Nutrition 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 239000002002 slurry Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical class [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004448 titration Methods 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F118/00—Homopolymers 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
- C08F118/02—Esters of monocarboxylic acids
- C08F118/04—Vinyl esters
- C08F118/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Description
本発明は、フィルム等の成形体とした際に、高強度を発現するポリビニルアルコール系重合体に関する。 The present invention relates to a polyvinyl alcohol-based polymer that exhibits high strength when molded into a film or other molded body.
ポリビニルアルコール系重合体(以下、「PVA」と略記することがある。)は、繊維、フィルム又はゲルのような様々な強度が要求される成形体に使用されている。PVAは、一般的に重合度が高いほど高強度を発現し易いことから、高重合度のPVAを得るための方法が各種提案されている。例えば、ポリビニルアルコールの前駆体である高重合度のポリビニルエステルの製法として、低温懸濁重合(特許文献1参照)、低温乳化重合(特許文献2参照)、低温光乳化重合(特許文献3参照)等が報告されている。Polyvinyl alcohol-based polymers (hereinafter sometimes abbreviated as "PVA") are used for molded articles requiring various strengths, such as fibers, films, and gels. Generally, the higher the degree of polymerization of PVA, the easier it is for PVA to exhibit high strength, and therefore various methods have been proposed for obtaining PVA with a high degree of polymerization. For example, low-temperature suspension polymerization (see Patent Document 1), low-temperature emulsion polymerization (see Patent Document 2), low-temperature photoemulsion polymerization (see Patent Document 3), and the like have been reported as methods for producing polyvinyl esters with a high degree of polymerization, which are precursors of polyvinyl alcohol.
しかしながら、これらの手法では高強度の発現が十分でない場合やPVAの生産が困難である場合等の問題があった。例えば、乳化重合に関しては、反応速度が速く効率的であるが、ポリマーと水とを分離するのが困難であるため、加工性の良いペレット状や粉末状の樹脂を得る手法としては適していない。However, these methods have problems such as insufficient strength and difficulty in producing PVA. For example, emulsion polymerization has a fast reaction rate and is efficient, but because it is difficult to separate the polymer and water, it is not suitable as a method for obtaining easily processable pelletized or powdered resins.
本発明は、フィルム又はゲルのような成形体とした際に高強度を発現するポリビニルアルコール系重合体を提供することを目的とする。 The present invention aims to provide a polyvinyl alcohol-based polymer that exhibits high strength when molded into a molded body such as a film or gel.
このような目的は、下記に例示される(1)~(6)の本発明により達成される。
(1)鹸化度が98モル%以上であるポリビニルアルコール系重合体であって、以下の式(I)に示す末端カルボン酸及び/又は末端カルボン酸塩構造を前記ポリビニルアルコール系重合体中に、0.003モル%以上、0.015モル%以下の割合で有することを特徴とするポリビニルアルコール系重合体。
(1) A polyvinyl alcohol-based polymer having a degree of saponification of 98 mol % or more, characterized in that the polyvinyl alcohol-based polymer has a terminal carboxylic acid and/or a terminal carboxylate structure represented by the following formula (I) in a proportion of 0.003 mol % or more and 0.015 mol % or less.
(2)前記ポリビニルアルコール系重合体において、以下の式(II)に示す末端ヒドロキシ構造の占める割合が、前記ポリビニルアルコール系重合体中に0.003モル%以上、0.030モル%以下である(1)に記載のポリビニルアルコール系重合体。
(3)前記ポリビニルアルコール系重合体は、主鎖中に以下の(III)に示す主鎖1、2-グリコール構造の占める割合が、前記ポリビニルアルコール系重合体中に0.90モル%以上、1.50モル%以下である上記(1)又は(2)に記載のポリビニルアルコール系重合体。
(4)前記ポリビニルアルコール系重合体は、前記ポリビニルアルコール系重合体中に、以下の式(IV)に示す末端1、2-グリコール構造の占める割合が、0.10モル%以上、0.20モル%以下である上記(1)乃至(3)のいずれか一項に記載のポリビニルアルコール系重合体。
(5)前記ポリビニルアルコール系重合体の粘度平均重合度が、5.5×103以上1.5×104以下である上記(1)乃至(4)のいずれか一項に記載のポリビニルアルコール系重合体。
(6)(1)乃至(5)のいずれか一項に記載のポリビニルアルコール系重合体を含有する成形体。
(5) The polyvinyl alcohol-based polymer according to any one of (1) to (4), wherein the polyvinyl alcohol-based polymer has a viscosity-average degree of polymerization of 5.5 × 10 3 or more and 1.5 × 10 4 or less.
(6) A molded article comprising the polyvinyl alcohol-based polymer according to any one of (1) to (5).
本発明によれば、フィルム、ゲル状の成形体とした際に高強度を発現するポリビニルアルコール系重合体を得ることができる。 According to the present invention, a polyvinyl alcohol-based polymer can be obtained that exhibits high strength when molded into a film or gel-like body.
以下に本発明を実施するための形態について詳細に説明する。尚、以下に記載する実施形態は、本発明を説明するための例示であり、必ずしも実施形態に限定されるものでない。The following describes in detail the form for implementing the present invention. Note that the embodiments described below are examples for explaining the present invention, and are not necessarily limited to the embodiments.
本発明は、鹸化度が98モル%以上であるポリビニルアルコール系重合体であって、前記ポリビニルアルコール系重合体中に、下記式(I)に示す末端カルボン酸及び/又は末端カルボン酸塩構造の占める割合が0.003モル%以上、0.015モル%以下であるポリビニルアルコール系重合体である。本発明によるポリビニルアルコール系重合体を用いて得られる成形体は、従来よりも高強度となり、例えば、より薄膜化したフィルムや、亀裂の入りにくいフィルムの作製が可能である。また、高強度、高弾性なゲル成形体等の作製も可能になる。下記式(I)に示す末端カルボン酸又は末端カルボン酸塩構造の占める割合は、好ましくは0.005モル%以上、0.012モル%以下であり、より好ましくは0.008モル%以上、0.010モル%以下である。
Xとしては、溶解性の観点からアルカリ金属が好ましく、その中でもナトリウムが好ましい。 From the standpoint of solubility, alkali metals are preferred as X, and sodium is particularly preferred.
好ましい実施形態においては、以下の式(II)に示す末端ヒドロキシ構造の占める割合が、前記ポリビニルアルコール系重合体中に0.003モル%以上、0.030モル%以下であり、当該割合は0.005モル%以上、0.020モル%以下であることがより好ましい。
好ましい実施形態においては、前記ポリビニルアルコール系重合体において、主鎖中に以下の(III)に示す主鎖1、2-グリコール構造の占める割合が0.90モル%以上、1.50モル%以下である。当該割合は1.10モル%以上、1.40モル%以下であることがより好ましい。
好ましい実施形態においては、前記ポリビニルアルコール系重合体において、以下の式(IV)に示す末端1、2-グリコール構造の占める割合が、0.10モル%以上、0.20モル%以下である。当該割合は0.12モル%以上、0.18モル%以下であることがより好ましい。
前記鹸化度が98モル%以上であるポリビニルアルコール系重合体の合成方法は、特に限定されるものでなく、一般的に用いられる方法により合成でき、例えば、ビニルエステルモノマーと重合開始剤を用いて、所定の温度で反応させることで、ポリビニルエステルを得て、得られたポリビニルエステルを水酸化ナトリウムのメタノール溶液などのアルカリ溶液で鹸化することによって得ることができる。ポリビニルアルコール系重合体の鹸化度は、好ましくは99モル%以上である。
なお、ポリビニルエステルの合成はビニルエステルと共重合可能なビニルエステル以外のモノマーを混合して用いても良い。
The method for synthesizing the polyvinyl alcohol-based polymer having a saponification degree of 98 mol% or more is not particularly limited, and the polymer can be synthesized by a commonly used method, for example, by reacting a vinyl ester monomer with a polymerization initiator at a predetermined temperature to obtain a polyvinyl ester, and then saponifying the obtained polyvinyl ester with an alkaline solution such as a methanol solution of sodium hydroxide. The saponification degree of the polyvinyl alcohol-based polymer is preferably 99 mol% or more.
In addition, in the synthesis of polyvinyl ester, a monomer other than vinyl ester which is copolymerizable with vinyl ester may be mixed and used.
本発明で用いられるビニルエステルモノマーとしては、特に限定されるものでなく、例えば、ギ酸ビニル、酢酸ビニル、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、ピバリン酸ビニル等が挙げられる。これらの中で重合のし易さの観点から、酢酸ビニルが好ましい。The vinyl ester monomer used in the present invention is not particularly limited, and examples thereof include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, etc. Among these, vinyl acetate is preferred from the viewpoint of ease of polymerization.
ビニルエステルモノマーと共重合可能なビニルエステル以外の単量体としては、例えば、エチレン、プロピレン等のα-オレフィン単量体、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸2-エチルヘキシル等の(メタ)アクリル酸アルキルエステル単量体、(メタ)アクリルアミド、N-メチロールアクリルアミド等の不飽和アミド単量体、(メタ)アクリル酸、クロトン酸、マレイン酸、イタコン酸、フマル酸等の不飽和カルボン酸単量体、不飽和カルボン酸のアルキル(メチル、エチル、プロピル等)エステル単量体、無水マレイン酸等の不飽和カルボン酸の無水物、不飽和カルボン酸のナトリウム、カリウム、アンモニウム等との塩、アリルグリシジルエーテル、グリシジル(メタ)アクリレート等のグリシジル基含有単量体、2-アクリルアミド-2-メチルプロパンスルホン酸等のスルホン酸基含有単量体又はその塩、アシッドホスホオキシエチル(メタ)アクリレート、アシッドホスホオキシプロピル(メタ)アクリレート等のリン酸基含有単量体、アルキルビニルエーテル単量体等が挙げられる。 Examples of monomers other than vinyl esters that can be copolymerized with vinyl ester monomers include α-olefin monomers such as ethylene and propylene, (meth)acrylic acid alkyl ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, unsaturated amide monomers such as (meth)acrylamide and N-methylolacrylamide, unsaturated carboxylic acid monomers such as (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, and fumaric acid, and alkyl (meth)acrylate monomers of unsaturated carboxylic acids. methyl, ethyl, propyl, etc.) ester monomers, anhydrides of unsaturated carboxylic acids such as maleic anhydride, salts of unsaturated carboxylic acids with sodium, potassium, ammonium, etc., glycidyl group-containing monomers such as allyl glycidyl ether and glycidyl (meth)acrylate, sulfonic acid group-containing monomers such as 2-acrylamide-2-methylpropanesulfonic acid or salts thereof, phosphoric acid group-containing monomers such as acid phosphooxyethyl (meth)acrylate and acid phosphooxypropyl (meth)acrylate, and alkyl vinyl ether monomers.
ビニルエステルモノマーを重合する重合方法としては、溶液重合、懸濁重合、バルク重合等の既知の重合方法が採用可能であるが、懸濁重合が好ましい。溶液重合においては、一般的にはメタノール等のアルコール系の溶媒が使用され、溶媒への連鎖移動により得られるPVAの重合度が低下する、またバルク重合においては、反応液の粘度上昇によりハンドリングが困難となる問題点がある。As a polymerization method for polymerizing vinyl ester monomers, known polymerization methods such as solution polymerization, suspension polymerization, and bulk polymerization can be used, but suspension polymerization is preferred. In solution polymerization, an alcohol-based solvent such as methanol is generally used, and the degree of polymerization of the resulting PVA decreases due to chain transfer to the solvent. In addition, in bulk polymerization, there is a problem that the viscosity of the reaction liquid increases, making it difficult to handle.
懸濁重合の際に使用する水性溶媒としては、イオン交換等により十分に精製した水を用いることが好ましいが、事前に使用に問題が無いことを確認出来れば、工業用水等でも使用することができる。
また、水性溶媒中には、pHを調整するための緩衝剤や、泡立ちを抑えるための消泡剤等を加えることも可能である。
As the aqueous solvent used in the suspension polymerization, it is preferable to use water that has been sufficiently purified by ion exchange or the like. However, industrial water or the like can also be used as long as it is confirmed in advance that there are no problems with its use.
In addition, a buffering agent for adjusting the pH and an antifoaming agent for suppressing foaming can be added to the aqueous solvent.
ビニルエステルモノマーを懸濁重合するに際しては、一般的に分散安定剤が使用される。この際の分散安定剤としては、特に制限するものではなく、一般的な懸濁重合用の分散安定剤であるポリビニルアルコール類、メチルセルロース類、ポリビニルピロリドン類等が使用可能である。本発明においては、製造するポリビニルアルコール系重合体の構造が類似する構造のポリビニルアルコール類を使用することが好ましい。類似する構造とすることで相溶性がよくなり、フィルムにした際の強度の向上、亀裂の入りにくいフィルムを得ることができる。When vinyl ester monomers are subjected to suspension polymerization, a dispersion stabilizer is generally used. There are no particular limitations on the dispersion stabilizer used in this case, and polyvinyl alcohols, methylcelluloses, polyvinylpyrrolidones, and the like, which are general dispersion stabilizers used in suspension polymerization, can be used. In the present invention, it is preferable to use polyvinyl alcohols having a structure similar to that of the polyvinyl alcohol-based polymer to be produced. By making the structures similar, compatibility is improved, and a film that is stronger and less prone to cracking can be obtained when made into a film.
ビニルエステルモノマーをラジカル重合する際の重合開始剤は、特に限定されるものではないが、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などのアゾ化合物、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などの過酸化物、ジイソプ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ネート、α-クミルパーオキシネオデカネート、t-ブチルパーオキシネオデカネート等のパーエステル化合物等を単独又は組み合わせて使用することができるが、低温で重合する場合はアゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)が好ましい。重合開始剤は、多いと重合速度が速くなって反応熱により系内の温度が上昇してしまい、また、分子量分布が広くなりやすいことから、ラジカル重合するビニルエステルモノマー100質量部に対して0.005~0.05質量部とすることが好ましい。 Polymerization initiators for radical polymerization of vinyl ester monomers are not particularly limited, but include azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis(4-methoxy-2,4-dimethylvaleronitrile), azobisdimethylvaleronitrile, and azobismethoxyvaleronitrile, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, acetylcyclohexylsulfonyl peroxide, and 2,4,4-trimethylpentyl-2-peroxide. Peroxides such as 4-oxyphenoxyacetate, percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, and perester compounds such as t-butyl peroxyneodecanate, α-cumyl peroxyneodecanate, and t-butyl peroxyneodecanate can be used alone or in combination, but azobis(4-methoxy-2,4-dimethylvaleronitrile) is preferred when polymerizing at low temperatures. If the polymerization initiator is used in large amounts, the polymerization rate increases, causing the temperature in the system to rise due to reaction heat, and the molecular weight distribution tends to become broad, so that the amount of the polymerization initiator is preferably 0.005 to 0.05 parts by mass per 100 parts by mass of the vinyl ester monomer to be radically polymerized.
ビニルエステルモノマーをラジカル重合する際の重合禁止剤は特に限定されるものではないが、4-tert-ブチルカテコール等のカテコール化合物、ソルビン酸等の不飽和二重結合を有する化合物、クペロン等のニトロソ化合物、空気等の酸素含有気体等を単独又は組み合わせて使用することができる。これらの化合物の中でも、重合停止能力が高いため4-tert-ブチルカテコールやソルビン酸を用いることが好ましい。重合禁止剤は開始剤の0.01倍~2倍のモル量とすることが好ましい。重合禁止剤の添加量が少なすぎると目標の重合率で反応が停止しない。 The polymerization inhibitor used in the radical polymerization of vinyl ester monomers is not particularly limited, but catechol compounds such as 4-tert-butylcatechol, compounds with unsaturated double bonds such as sorbic acid, nitroso compounds such as cupferron, oxygen-containing gases such as air, etc. can be used alone or in combination. Among these compounds, it is preferable to use 4-tert-butylcatechol or sorbic acid because of their high polymerization termination ability. The polymerization inhibitor is preferably used in a molar amount of 0.01 to 2 times that of the initiator. If the amount of polymerization inhibitor added is too small, the reaction will not stop at the target polymerization rate.
ビニルエステルモノマーの重合温度は、10~50℃であることが好ましく、より好ましくは15~45℃、更に好ましくは20~40℃である。重合温度が10℃未満の場合、重合速度が遅く、実用上問題となる場合がある。また、重合温度が50℃超の場合、得られるPVAの重合度が低下して末端カルボン酸及び/又は末端カルボン酸塩構造及び主鎖及び末端1、2-グリコール構造が増加する。また分岐構造も増加して、末端ヒドロキシ構造が増加する。このため、得られるPVAフィルムの引張強度が低下する。The polymerization temperature of the vinyl ester monomer is preferably 10 to 50°C, more preferably 15 to 45°C, and even more preferably 20 to 40°C. If the polymerization temperature is less than 10°C, the polymerization rate is slow, which may cause practical problems. If the polymerization temperature is more than 50°C, the degree of polymerization of the resulting PVA decreases, and the terminal carboxylic acid and/or terminal carboxylate structures and main chain and terminal 1,2-glycol structures increase. In addition, the branched structure increases, and the terminal hydroxyl structures increase. As a result, the tensile strength of the resulting PVA film decreases.
ビニルエステルモノマーの重合率は、好ましくは60%以下であり、より好ましくは50%以下であり、更に好ましくは40%以下である。重合率が60%超であると、ポリビニルエステルの分岐構造が大きく増加し、溶解性が低下する。また分子量分布が広くなり、末端カルボン酸及び/又は末端カルボン酸塩構造及び主鎖及び末端1、2-グリコール構造が増加する。The polymerization rate of the vinyl ester monomer is preferably 60% or less, more preferably 50% or less, and even more preferably 40% or less. If the polymerization rate exceeds 60%, the branched structure of the polyvinyl ester increases significantly, and the solubility decreases. In addition, the molecular weight distribution becomes broad, and the terminal carboxylic acid and/or terminal carboxylate structure and main chain and terminal 1,2-glycol structure increase.
本発明で云う重合率は、ビニルエステルモノマー及びポリビニルエステル粒子が水中で均一に分散している状態で少量サンプリングし、そのサンプリングした溶液を150℃で30分乾燥させ、重量法から求められる。The polymerization rate referred to in this invention is determined by taking a small amount of a solution in a state where the vinyl ester monomer and polyvinyl ester particles are uniformly dispersed in water, drying the sampled solution at 150°C for 30 minutes, and then using a gravimetric method.
本発明に係る鹸化度が98モル%以上であるポリビニルアルコール系重合体の合成方法は、特に限定されないが、例えば、上記ポリビニルエステルを鹸化することで、本発明の鹸化度が98モル%以上であるポリビニルアルコール系重合体を得ることが出来る。鹸化反応は、常法により実施可能であるが、ポリビニルエステルをアルコール系溶媒に溶解し、アルカリ触媒により鹸化する方法が簡便であり、好ましい。使用するアルコール系溶媒としては、特に限定されないが、メタノール、エタノール、ブタノール等が挙げられ、メタノールの使用が好ましい。メタノールを用いると溶媒の回収が容易で、回収したメタノールを再利用することで製造コストを下げることができる。アルコール系溶媒中の重合体の濃度は、2~50質量%の範囲が好ましく、より好ましくは3~40質量%、更に好ましくは5~30質量%である。 The method for synthesizing the polyvinyl alcohol-based polymer having a saponification degree of 98 mol% or more according to the present invention is not particularly limited, but for example, the polyvinyl ester can be saponified to obtain the polyvinyl alcohol-based polymer having a saponification degree of 98 mol% or more according to the present invention. The saponification reaction can be carried out by a conventional method, but a method in which the polyvinyl ester is dissolved in an alcohol-based solvent and saponified with an alkali catalyst is simple and preferable. The alcohol-based solvent used is not particularly limited, but examples include methanol, ethanol, butanol, etc., and methanol is preferably used. The use of methanol makes it easy to recover the solvent, and the production cost can be reduced by reusing the recovered methanol. The concentration of the polymer in the alcohol-based solvent is preferably in the range of 2 to 50% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass.
鹸化度が98モル%以上であるポリビニルアルコール系重合体であって、前記ポリビニルアルコール系重合体中に、上記式(I)に示す末端カルボン酸又は末端カルボン酸塩構造の占める割合が0.003モル%以上、0.015モル%以下であるビニルアルコール系重合体の合成方法は、特に限定されないが、鹸化反応時にアルカリ触媒を用いることができる。アルカリ触媒としては、特に限定されないが、例えば、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アルコール塩や、マグネシウム、カルシウムなどを用いた金属水酸化物を用いることができる。
本発明のポリビニルアルコール系重合体の式(I)のXは、酸の状態又はイオン化された状態であれば良く、ポリビニルアルコール系重合体中に、上記式(I)に示す末端カルボン酸又は末端カルボン酸塩構造の占める割合が0.003モル%以上、0.015モル%以下であることで、フィルムにしたときの強度が上がる。Xは、水素であっても、アルカリ金属であっても、アルカリ土類金属であってもフィルムにした場合の強度は向上する。
The method for synthesizing a polyvinyl alcohol-based polymer having a degree of saponification of 98 mol% or more, in which the proportion of the terminal carboxylic acid or terminal carboxylate structure represented by the above formula (I) in the polyvinyl alcohol-based polymer is 0.003 mol% or more and 0.015 mol% or less, is not particularly limited, but an alkali catalyst can be used during the saponification reaction. The alkali catalyst is not particularly limited, but for example, an alcohol salt of an alkali metal such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, or potassium methylate, or a metal hydroxide using magnesium, calcium, or the like can be used.
X in formula (I) of the polyvinyl alcohol polymer of the present invention may be in an acid state or an ionized state, and the strength of the film formed by forming the polyvinyl alcohol polymer is improved by the proportion of the terminal carboxylic acid or terminal carboxylate structure represented by formula (I) being 0.003 mol % or more and 0.015 mol % or less. The strength of the film is improved whether X is hydrogen, an alkali metal, or an alkaline earth metal.
また、アルカリ触媒の替わりに酸触媒を使用しても鹸化することが可能である。酸触媒としては、特に限定されないが、例えば、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。これらアルカリ若しくは酸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必要である。
鹸化反応温度には、特に制限はないが、通常10~70℃であり、好ましくは30~50℃である。反応は通常15~180分間に渡って行われる。
Also, saponification can be performed using an acid catalyst instead of an alkali catalyst. The acid catalyst is not particularly limited, but for example, an aqueous solution of an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as p-toluenesulfonic acid can be used. The amount of the alkali or acid catalyst used must be 1 to 100 millimole equivalents relative to the vinyl ester monomer.
The saponification reaction temperature is not particularly limited, but is usually 10 to 70° C., preferably 30 to 50° C. The reaction is usually carried out for 15 to 180 minutes.
上記の式(II)に示す末端ヒドロキシ構造の占める割合が0.003モル%以上、0.030モル%以下であるポリビニルアルコール系重合体の合成方法は、特に限定されないが、例えば、以下の合成方法が挙げられる。まず、酢酸ビニルモノマーを懸濁重合法により、重合温度、開始剤及び重合禁止剤を調整することで酢酸ビニル樹脂を得る。次に、得られた酢酸ビニル樹脂を水酸化ナトリウムのメタノール溶液などのアルカリ溶液で鹸化する。重合温度、開始剤及び重合禁止剤を調整することで、式(II)に示す末端ヒドロキシ構造の占める割合を0.003モル%以上、0.030モル%以下に容易に調整することができる。このようにして得られたポリビニルアルコール系重合体は、メタノール中で重合する場合に比べ、高分子量で、分岐が少なく、分子量分布の狭いものとなる。The synthesis method of the polyvinyl alcohol-based polymer in which the proportion of the terminal hydroxy structure shown in the above formula (II) is 0.003 mol % or more and 0.030 mol % or less is not particularly limited, but examples thereof include the following synthesis method. First, vinyl acetate monomer is subjected to a suspension polymerization method to obtain a vinyl acetate resin by adjusting the polymerization temperature, initiator, and polymerization inhibitor. Next, the obtained vinyl acetate resin is saponified with an alkaline solution such as a methanol solution of sodium hydroxide. By adjusting the polymerization temperature, initiator, and polymerization inhibitor, the proportion of the terminal hydroxy structure shown in formula (II) can be easily adjusted to 0.003 mol % or more and 0.030 mol % or less. The polyvinyl alcohol-based polymer obtained in this manner has a high molecular weight, less branching, and a narrow molecular weight distribution compared to the case of polymerization in methanol.
主鎖中において、上記の式(III)に示す主鎖1、2-グリコール構造の占める割合が0.90モル%以上、1.50モル%以下であるポリビニルアルコール系重合体の合成方法は、特に限定されないが、例えばビニルエステルモノマーを重合温度10~50℃で重合し、鹸化することで、主鎖中において、式(III)に示す主鎖1、2-グリコール構造の占める割合を0.90モル%以上、1.50モル%以下に容易に調整することができる。上記の範囲とすることで、上記ポリビニルアルコール系重合体を用いて得られるフィルムは、結晶性を維持し、高強度なものとなる。 The method for synthesizing a polyvinyl alcohol-based polymer in which the proportion of the main chain 1,2-glycol structure shown in the above formula (III) in the main chain is 0.90 mol % or more and 1.50 mol % or less is not particularly limited, but for example, by polymerizing a vinyl ester monomer at a polymerization temperature of 10 to 50°C and saponifying it, the proportion of the main chain 1,2-glycol structure shown in formula (III) in the main chain can be easily adjusted to 0.90 mol % or more and 1.50 mol % or less. By setting it in the above range, the film obtained using the above polyvinyl alcohol-based polymer maintains its crystallinity and has high strength.
さらに、主鎖中において、上記の式(IV)に示す末端1、2-グリコール構造の占める割合が0.10モル%以上、0.20モル%以下であるポリビニルアルコール系重合体の合成方法は、懸濁重合にて重合温度10~50℃で重合し、鹸化することで、主鎖中に式(IV)に示す末端1、2-グリコール構造の占める割合が0.10モル%以上、0.20モル%以下に容易に調整することができる。上記ポリビニルアルコール系重合体を用いて得られるフィルムは、結晶性を維持し、高強度なものとなる。 Furthermore, a method for synthesizing a polyvinyl alcohol-based polymer in which the proportion of the terminal 1,2-glycol structure shown in the above formula (IV) in the main chain is 0.10 mol % or more and 0.20 mol % or less can be achieved by polymerization at a polymerization temperature of 10 to 50°C by suspension polymerization and saponification, which allows the proportion of the terminal 1,2-glycol structure shown in formula (IV) in the main chain to be easily adjusted to 0.10 mol % or more and 0.20 mol % or less. A film obtained using the above polyvinyl alcohol-based polymer maintains its crystallinity and has high strength.
本発明のポリビニルアルコール系重合体の鹸化度は好ましくは98モル%以上であり、より好ましくは99モル%であり、更に好ましくは99.4モル%以上である。鹸化度を98モル%以上とすることで、ポリビニルアルコール系重合体を成形体とした際に高強度を発現する。鹸化度が98モル%未満の場合、成形体の強度が大きく低下する。The degree of saponification of the polyvinyl alcohol-based polymer of the present invention is preferably 98 mol% or more, more preferably 99 mol%, and even more preferably 99.4 mol% or more. By making the degree of saponification 98 mol% or more, the polyvinyl alcohol-based polymer exhibits high strength when molded into a molded article. If the degree of saponification is less than 98 mol%, the strength of the molded article is significantly reduced.
本発明で云うポリビニルアルコール系重合体の鹸化度は、JIS-K6726:1994に従った方法にて測定される。すなわち、JIS-K8951:2006に規定されているN/10の硫酸とJIS-K8576:2019に規定されているN/10の水酸化ナトリウム溶液を用いた逆滴定から求められる。The degree of saponification of the polyvinyl alcohol polymer referred to in the present invention is measured by a method according to JIS-K6726:1994. That is, it is determined by back titration using N/10 sulfuric acid as specified in JIS-K8951:2006 and N/10 sodium hydroxide solution as specified in JIS-K8576:2019.
本発明のポリビニルアルコール系重合体の粘度平均重合度は好ましくは5.5×103以上、1.5×104以下である。より好ましくは、8.0×103以上、1.2×104以下である。粘度平均重合度が1.5×104を超えると、鹸化前のポリビニルエステルの粘度が高く、ハンドリングが困難となり、5.5×103未満の場合は、強度が低下する場合がある。 The viscosity average degree of polymerization of the polyvinyl alcohol polymer of the present invention is preferably 5.5×10 3 or more and 1.5×10 4 or less, and more preferably 8.0×10 3 or more and 1.2×10 4 or less. If the viscosity average degree of polymerization exceeds 1.5×10 4 , the viscosity of the polyvinyl ester before saponification becomes high and handling becomes difficult, and if it is less than 5.5×10 3 , the strength may decrease.
本発明の鹸化度が98モル%以上であるポリビニルアルコール系重合体の粘度平均重合度は、JIS-K6726:1994に準拠する方法にて測定される。すなわち、ビニルアルコール系重合体を完全に鹸化し、精製した後、30℃の水中で測定して得られた相対粘度から算出した極限粘度[η]から求める。The viscosity average degree of polymerization of the polyvinyl alcohol-based polymer of the present invention having a degree of saponification of 98 mol% or more is measured by a method conforming to JIS-K6726:1994. That is, after the vinyl alcohol-based polymer is completely saponified and purified, it is determined from the limiting viscosity [η] calculated from the relative viscosity obtained by measuring in water at 30°C.
本発明の鹸化度が98モル%以上であるポリビニルアルコール系重合体は、特定の末端構造を特定の比率で有することが好ましい。特定の末端構造を特定の比率とすることでより高強度を発現することができ、特定の末端構造を特定の比率を有することで、得られたフィルムは、より薄膜化したフィルムや、亀裂の入りにくいフィルムの作製が可能である。また、高強度なゲル成形体等の作製も可能になる。これら末端構造の定量は、網屋繁俊,「PVAの微細構造」,高分子加工,38(8),P388-396,1989年に記載されている通り1H-NMRのピーク位置及びその積分値から同定及び定量可能である。 The polyvinyl alcohol polymer of the present invention having a degree of saponification of 98 mol% or more preferably has a specific terminal structure in a specific ratio. By having a specific terminal structure in a specific ratio, higher strength can be achieved, and by having a specific terminal structure in a specific ratio, it is possible to produce a thinner film or a film that is less susceptible to cracking. It is also possible to produce a gel molded body with high strength. The amount of these terminal structures can be identified and quantified from the peak position and its integral value of 1 H-NMR as described in Shigetoshi Amiya, "Microstructure of PVA", Polymer Processing, 38(8), pp. 388-396, 1989.
上記の式(I)に示す末端カルボン酸又は末端カルボン酸塩構造、上記の式(II)に示す末端ヒドロキシ構造、上記の式(III)に示す主鎖1、2-グリコール構造及び、上記の式(IV)に示す末端1、2-グリコール構造の測定手順について説明する。The measurement procedures for the terminal carboxylic acid or terminal carboxylate structure shown in the above formula (I), the terminal hydroxyl structure shown in the above formula (II), the main chain 1,2-glycol structure shown in the above formula (III), and the terminal 1,2-glycol structure shown in the above formula (IV) are described below.
鹸化度が98モル%以上であるポリビニルアルコール系重合体に対して、1H-NMR(例:日本電子株式会社製「ECX-400」)を用いて測定を行う。 A polyvinyl alcohol polymer having a degree of saponification of 98 mol % or more is measured using 1 H-NMR (eg, "ECX-400" manufactured by JEOL Ltd.).
上記の式(I)に示す末端カルボン酸又は末端カルボン酸塩構造を分析する場合、作製した分析用のポリビニルアルコール系重合体を重水に溶解し、更にNaOH重水溶液を数滴加えpH14にし、末端カルボン酸をすべて末端カルボン酸ナトリウム構造とした後、1H-NMR(例:日本電子株式会社製「ECX-400」)を用いて、400MHz、測定温度80℃、積算回数1024の条件にて、1H-NMRスペクトルを得て、構造を同定する。 When analyzing the terminal carboxylic acid or terminal carboxylate structure shown in the above formula (I), the prepared polyvinyl alcohol polymer for analysis is dissolved in heavy water, and several drops of a heavy water solution of NaOH are added to adjust the pH to 14, and all the terminal carboxylic acids are converted to sodium terminal carboxylate structures. Then, a 1H -NMR spectrum is obtained using a 1H -NMR (e.g., "ECX-400" manufactured by JEOL Ltd.) under conditions of 400 MHz, measurement temperature 80°C, and accumulation count 1024, and the structure is identified.
上記の式(IV)に示す末端1、2-グリコール構造を分析する場合、作製した分析用の鹸化度が98モル%以上であるポリビニルアルコール系重合体を重水に溶解し、更にNaOH重水溶液を数滴加えpH14にした後、400MHzの1H-NMR(例:日本電子社の「ECX-400」)を用いて、測定温度80℃、積算回数1024の条件にて、1H-NMRスペクトルを得て、構造を同定する。 When analyzing the terminal 1,2-glycol structure shown in the above formula (IV), the prepared polyvinyl alcohol polymer for analysis having a degree of saponification of 98 mol % or more is dissolved in deuterium oxide, and a few drops of a heavy water solution of NaOH are added to adjust the pH to 14. Then, a 1H -NMR spectrum is obtained using a 400 MHz 1H -NMR (e.g., JEOL's "ECX-400") at a measurement temperature of 80°C and an accumulation count of 1024 to identify the structure.
また、上記の式(II)に示す末端ヒドロキシ構造及び、上記の式(III)に示す主鎖1、2-グリコール構造を分析する場合、作製した分析用のビニルアルコール系重合体を重DMSOに溶解し、400MHzの1H-NMR(例:日本電子社の「ECX-400」)を用いて、測定温度60℃、積算回数1024の条件にて、1H-NMRスペクトルを得て、構造を同定する。 In addition, when analyzing the terminal hydroxy structure shown in the above formula (II) and the main chain 1,2-glycol structure shown in the above formula (III), the prepared vinyl alcohol polymer for analysis is dissolved in deuterated DMSO, and a 1H -NMR spectrum is obtained using a 400 MHz 1H -NMR (e.g., JEOL's "ECX-400") at a measurement temperature of 60°C and an accumulation count of 1024 to identify the structure.
何れの末端及び主鎖の含有量(モル%)も鹸化度が98モル%以上であるポリビニルアルコール系重合体の主鎖のメチレン基(1.2~2.0ppm)のピークの積分値を基準として、各末端又は主鎖を示すピークの積分値から算出する(上記の式(I)に示す末端カルボン酸ナトリウム構造:2.2~2.3ppm、上記の式(III)に示す主鎖1、2-グリコール構造:3.2~3.3ppm、上記の式(IV)に示す末端1、2グリコール構造:1.0~1.1ppm)。具体的には、各末端測定用の1H-NMRスペクトルにおいて、PVAの主鎖のメチレン基のピークの積分値をbとし、末端カルボン酸ナトリウム構造のピークの積分値をaとすると、各々のピークに由来する炭素上のプロトン数を考慮し算出する。式(I)に示す構造の含有率A(モル%)は、末端カルボン酸ナトリウム構造はメチレン基(プロトン数=2)を分析しているので、A=(a/2)/(b/2)×100と計算できる。同様に、(III)に示す構造の含有率B(モル%)は、主鎖1、2-グリコール構造のピークの積分値をcとすると、B=(c/2)/(b/2)×100と計算でき、(IV)に示す構造の含有率C(モル%)は、末端1、2グリコール構造のピークの積分値をdとすると、C=(d/3)/(b/2)×100と計算できる。
上記の式(II)に示す末端ヒドロキシ構造の場合においては、3.4~3.5ppm付近のピークの積分値(e)から末端量を算出するが、3.4~3.5ppm付近のピークには、上記の式(II)に示す末端ヒドロキシ構造、上記の式(III)に示す主鎖1、2-グリコール構造、及び上記の式(IV)に示す末端1、2-グリコール構造のプロトンに由来するピークも含まれている。ただし、上記の式(III)に示す主鎖1、2-グリコール構造は、3.2~3.3ppmのピークの積分値(c)から算出でき、また上記の式(IV)に示す末端1、2-グリコール構造は、1.0~1.1ppmのピークの積分値(d)から算出できるので、上記の式(II)に示す末端ヒドロキシ構造含有率D(%)はD=(e-c-(d/3))/2×100と計算される。
The contents (mol%) of each terminal and main chain are calculated from the integral value of the peak representing each terminal or main chain, based on the integral value of the peak of the methylene group (1.2 to 2.0 ppm) of the main chain of a polyvinyl alcohol polymer having a degree of saponification of 98 mol% or more (terminal sodium carboxylate structure shown in the above formula (I): 2.2 to 2.3 ppm, main chain 1,2-glycol structure shown in the above formula (III): 3.2 to 3.3 ppm, terminal 1,2-glycol structure shown in the above formula (IV): 1.0 to 1.1 ppm). Specifically, in the 1 H-NMR spectrum for measuring each terminal, the integral value of the peak of the methylene group of the main chain of PVA is b, and the integral value of the peak of the terminal sodium carboxylate structure is a, and the calculation is performed taking into consideration the number of protons on carbon originating from each peak. The content A (mol %) of the structure shown in formula (I) can be calculated as A = (a/2)/(b/2) x 100 because the terminal sodium carboxylate structure is analyzed as a methylene group (number of protons = 2). Similarly, the content B (mol %) of the structure shown in (III) can be calculated as B = (c/2)/(b/2) x 100 when the integral value of the peak of the main chain 1,2-glycol structure is c, and the content C (mol %) of the structure shown in (IV) can be calculated as C = (d/3)/(b/2) x 100 when the integral value of the peak of the terminal 1,2-glycol structure is d.
In the case of the terminal hydroxy structure shown in formula (II) above, the amount of terminals is calculated from the integral value (e) of the peak in the vicinity of 3.4 to 3.5 ppm, but the peak in the vicinity of 3.4 to 3.5 ppm also includes peaks derived from the protons of the terminal hydroxy structure shown in formula (II) above, the main chain 1,2-glycol structure shown in formula (III) above, and the terminal 1,2-glycol structure shown in formula (IV) above. However, since the main chain 1,2-glycol structure shown in formula (III) above can be calculated from the integral value (c) of the peak at 3.2 to 3.3 ppm, and the terminal 1,2-glycol structure shown in formula (IV) above can be calculated from the integral value (d) of the peak at 1.0 to 1.1 ppm, the terminal hydroxy structure content D (%) shown in formula (II) above is calculated as D = (e-c-(d/3))/2 x 100.
なお、末端カルボン酸構造はγ-ラクトン構造と化学平衡にある。NMRの測定は上述の通りpH14で行うため、PVA中にγ-ラクトン構造が存在していた場合でもすべて末端カルボン酸ナトリウム構造に平衡が偏る。このため、本発明において末端カルボン酸ナトリウム構造の含有量は末端カルボン酸構造、末端カルボン酸塩構造及びγ-ラクトン構造の合計含有量を意味することになる。 The terminal carboxylic acid structure is in chemical equilibrium with the γ-lactone structure. Since the NMR measurement is performed at pH 14 as described above, even if a γ-lactone structure is present in the PVA, the equilibrium is biased entirely towards the terminal sodium carboxylate structure. For this reason, in the present invention, the content of terminal sodium carboxylate structures means the total content of terminal carboxylic acid structures, terminal carboxylate salt structures, and γ-lactone structures.
本発明のポリビニルアルコール系重合体は、高強度を発現することから、フィルム、繊維、ゲル等の成形体の原材料として好適に使用可能であるが、これら以外にも接着剤、増粘剤、バインダー等の原材料としても優れた特性を発揮する。 The polyvinyl alcohol-based polymer of the present invention exhibits high strength and can therefore be suitably used as a raw material for molded bodies such as films, fibers, and gels, but also exhibits excellent properties as a raw material for adhesives, thickeners, binders, etc.
以下に、本発明を実施例に基づいて具体的に説明するが、本発明はこれに限定されるものではない。尚、特に断りがない限り、「部」及び、「%」は「質量部」及び「質量%」を意味する。The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass".
(実施例1)
還流冷却器、滴下漏斗、攪拌機を備えた重合缶に、酢酸ビニルモノマーを100質量部、水120質量部、開始剤である2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)を0.018質量部及び、主にポリビニルアルコールからなる分散剤(デンカ株式会社製DENKA W-20N)0.1質量部を仕込み、25℃で7時間重合後に重合禁止剤である4-tert-ブチルカテコールを加えて反応を停止した。このときの重合率は21.4%であった。
重合反応終了後、その容器を密閉し、内部を減圧状態に保ちながら、撹拌下70℃で、3時間未反応モノマーの除去を行った。得られた酢酸ビニル樹脂スラリーを冷却、濾過、水洗、脱水し、次いで乾燥器にて35℃にて2時間乾燥処理を行って細粒状の粘度平均重合度が12,560の酢酸ビニル樹脂を得た。なお、粘度平均重合度は、JIS K6725:1977「酢酸ビニルの試験方法」の「3.2平均重合度」に準じて測定した。
Example 1
A polymerization vessel equipped with a reflux condenser, a dropping funnel, and a stirrer was charged with 100 parts by mass of vinyl acetate monomer, 120 parts by mass of water, 0.018 parts by mass of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) as an initiator, and 0.1 parts by mass of a dispersant mainly composed of polyvinyl alcohol (DENKA W-20N manufactured by Denka Co., Ltd.), and polymerization was carried out at 25°C for 7 hours, after which the reaction was stopped by adding 4-tert-butylcatechol as a polymerization inhibitor. The polymerization rate at this time was 21.4%.
After the polymerization reaction was completed, the vessel was sealed, and while the inside was kept in a reduced pressure state, unreacted monomers were removed for 3 hours at 70° C. under stirring. The obtained vinyl acetate resin slurry was cooled, filtered, washed with water, dehydrated, and then dried in a dryer at 35° C. for 2 hours to obtain a fine-grained vinyl acetate resin having a viscosity average degree of polymerization of 12,560. The viscosity average degree of polymerization was measured in accordance with "3.2 average degree of polymerization" of JIS K6725:1977 "Testing methods for vinyl acetate".
上記で得られた酢酸ビニル樹脂をメタノールに溶解し、そこに10%の水酸化ナトリウムのメタノール溶液を添加し(酢酸ビニルに対し水酸化ナトリウムを固形分換算で0.04質量部)、40℃で60分間鹸化反応を行った。酢酸で中和後に、得られた固形分を乾燥器にて120℃で1時間、乾燥処理して、鹸化度99.4%、粘度平均重合度が9,840のPVAを得た。The vinyl acetate resin obtained above was dissolved in methanol, to which a 10% methanol solution of sodium hydroxide was added (0.04 parts by mass of sodium hydroxide relative to vinyl acetate in terms of solid content), and a saponification reaction was carried out at 40°C for 60 minutes. After neutralization with acetic acid, the resulting solid content was dried in a dryer at 120°C for 1 hour, yielding a PVA with a saponification degree of 99.4% and a viscosity average polymerization degree of 9,840.
上記で得られたPVAについて、NMRを用いて、下記に記す条件にて末端及び主鎖構造の定量評価を行ったところ、上記の式(I)に示す末端カルボン酸又は末端カルボン酸塩構造が0.008モル%、上記の式(II)に示す末端ヒドロキシ構造が0.008モル%、上記の式(III)に示す主鎖1、2-グリコール結合構造が1.26モル%、上記の式(IV)に示す末端1、2-グリコール構造が0.18モル%であった。
上記の式(I)に示す末端カルボン酸又は末端カルボン酸塩構造を分析する場合、ポリビニルアルコール系重合体を重水に溶解し、更にNaOH重水溶液を数滴加えpH14にし、末端カルボン酸をすべて末端カルボン酸ナトリウム構造とした後、1H-NMR(日本電子株式会社製「ECX-400」)を用いて、400MHz、測定温度80℃、積算回数1024に条件にて、1H-NMRスペクトルを得て、構造を同定した。
上記の式(IV)に示す末端1、2-グリコール構造を分析する場合、同様にポリビニルアルコール系重合体を重水に溶解し、更にNaOH重水溶液を数滴加えpH14にした後、NMR(日本電子社の「ECX-400」)を用いて、測定温度80℃、積算回数1024に条件にて、1H-NMRスペクトルを得て、構造を同定した。
また、上記の式(II)に示す末端ヒドロキシ構造及び、上記の式(III)に示す主鎖1、2-グリコール構造及を分析する場合、作製した分析用のビニルアルコール系重合体を重DMSOに溶解し、1H-NMR(日本電子社の「ECX-400」)を用いて、測定温度60℃、積算回数1024に条件にて、1H-NMRスペクトルを得て、構造を同定した。
The PVA obtained above was quantitatively evaluated for its terminal and main chain structures using NMR under the conditions described below. The results showed that the terminal carboxylic acid or terminal carboxylate structure shown in formula (I) above was 0.008 mol %, the terminal hydroxy structure shown in formula (II) above was 0.008 mol %, the main chain 1,2-glycol bond structure shown in formula (III) above was 1.26 mol %, and the terminal 1,2-glycol structure shown in formula (IV) above was 0.18 mol %.
When analyzing the terminal carboxylic acid or terminal carboxylate structure shown in the above formula (I), a polyvinyl alcohol-based polymer was dissolved in heavy water, and several drops of a heavy water solution of NaOH were added to adjust the pH to 14, and all the terminal carboxylic acids were converted to sodium terminal carboxylate structures. Then, a 1H -NMR spectrum was obtained using a 1H -NMR ("ECX-400" manufactured by JEOL Ltd.) under conditions of 400 MHz, measurement temperature 80°C, and accumulation number 1024, and the structure was identified.
When analyzing the terminal 1,2-glycol structure shown in the above formula (IV), a polyvinyl alcohol polymer was similarly dissolved in heavy water, and several drops of a heavy water solution of NaOH were added to adjust the pH to 14. Then, a 1H -NMR spectrum was obtained using an NMR (JEOL "ECX-400") at a measurement temperature of 80°C and an accumulation number of 1024, and the structure was identified.
In addition, when analyzing the terminal hydroxy structure shown in the above formula (II) and the main chain 1,2-glycol structure shown in the above formula (III), the prepared vinyl alcohol polymer for analysis was dissolved in deuterated DMSO, and a 1 H-NMR spectrum was obtained using a 1 H-NMR (JEOL Ltd.'s "ECX-400") at a measurement temperature of 60°C and an accumulation number of 1024, to identify the structure.
上記で得られたPVAを水に溶解し、高圧ろ過により異物を除去後、アプリケーターを用いて、上記PVA水溶液をポリエチレンテレフタラートフィルム上に塗布して、乾燥させることによって膜厚15.0±1.0μmのフィルムを得た。なお、上記高圧ろ過は、バンテック社製 ろ紙5A(φ110)を用いて、JIS P3801:1995に従って行った。The PVA obtained above was dissolved in water, and foreign matter was removed by high-pressure filtration. The PVA aqueous solution was then applied to a polyethylene terephthalate film using an applicator and dried to obtain a film with a thickness of 15.0±1.0 μm. The high-pressure filtration was performed in accordance with JIS P3801:1995 using Vantec filter paper 5A (φ110).
(引張強度評価)
上記で得られたPVAからなるフィルムを、20℃、60%RHで2日間静置後、引張り試験を実施した。引張り試験は(株式会社島津製作所社製「AG-X」型番)を用いた。
PVAフィルムサンプルは幅9.0mm、つかみ器具距離90.0mm、引張り速度50mm/minで行ったところ、フィルムの引張強度は71.2N/mm2であった。
(Tensile strength evaluation)
The PVA film obtained above was left to stand at 20° C. and 60% RH for 2 days, and then subjected to a tensile test. A tensile tester (model “AG-X” manufactured by Shimadzu Corporation) was used for the tensile test.
The PVA film sample had a width of 9.0 mm, a gripper distance of 90.0 mm, and a pulling speed of 50 mm/min. The tensile strength of the film was 71.2 N/ mm2 .
(実施例2~10)
重合温度、重合時間(重合率)をそれぞれ表1に記載したように変えた以外は、実施例1と同様にして高重合度PVAを得て、末端及び主鎖構造の定量評価を行った。また、実施例1と同様にPVAからなるフィルムを作製し、実施例1と同様に引張強度評価を行った。結果を表1に示す。
(Examples 2 to 10)
A highly polymerized PVA was obtained and the terminal and main chain structures were quantitatively evaluated in the same manner as in Example 1, except that the polymerization temperature and polymerization time (polymerization rate) were changed as shown in Table 1. A film made of PVA was also produced in the same manner as in Example 1, and its tensile strength was evaluated in the same manner as in Example 1. The results are shown in Table 1.
(註)
主鎖1,2-Gly:主鎖中に上記の式(III)に示す1、2-グリコール構造の占める割合
末端1,2-Gly:上記の式(IV)に示す末端1、2グリコール構造の占める割合
末端-COOX:上記の式(I)に示す末端カルボン酸又は末端カルボン酸塩構造の占める割合
末端-CH2CH2OH:上記の式(II)に示す末端ヒドロキシ構造の占める割合
(Note)
Main chain 1,2-Gly: the proportion of the 1,2-glycol structure shown in the above formula (III) in the main chain. Terminal 1,2-Gly: the proportion of the terminal 1,2-glycol structure shown in the above formula (IV). Terminal -COOX : the proportion of the terminal carboxylic acid or terminal carboxylate structure shown in the above formula (I). Terminal -CH2CH2OH : the proportion of the terminal hydroxyl structure shown in the above formula (II).
(比較例1~4)
重合温度、重合時間(重合率)をそれぞれ表1に記載したように変えた以外は、実施例1と同様にして、PVAからなるフィルムを作成し、実施例1と同様に引張強度評価を行った。結果を表1に示す。
(Comparative Examples 1 to 4)
A film made of PVA was prepared in the same manner as in Example 1, except that the polymerization temperature and polymerization time (polymerization rate) were changed as shown in Table 1, and the tensile strength was evaluated in the same manner as in Example 1. The results are shown in Table 1.
(比較例5)
還流冷却器、滴下漏斗、攪拌機を備えた重合缶に、酢酸ビニルモノマー100質量部、メタノール65.3質量部、及び重合開始剤としてアゾビスイソブチロニトリルを酢酸ビニルに対して0.022重量部仕込み、窒素気流下で攪拌しながら外温65℃で8時間重合を行った。得られた重合反応溶液中にメタノール蒸気を吹き込んで未反応酢酸ビニルを除去した後、メタノールにて希釈して酢酸ビニル樹脂のメタノール溶液を調整し、粘度平均重合度780の酢酸ビニル樹脂のメタノール溶液を得た。
(Comparative Example 5)
A polymerization vessel equipped with a reflux condenser, a dropping funnel, and a stirrer was charged with 100 parts by mass of vinyl acetate monomer, 65.3 parts by mass of methanol, and 0.022 parts by weight of azobisisobutyronitrile as a polymerization initiator relative to vinyl acetate, and polymerization was carried out for 8 hours with stirring under a nitrogen stream at an external temperature of 65° C. Methanol vapor was blown into the resulting polymerization reaction solution to remove unreacted vinyl acetate, and the solution was then diluted with methanol to prepare a methanol solution of vinyl acetate resin with a viscosity average degree of polymerization of 780.
上記で得られた酢酸ビニル樹脂のメタノール溶液に、水酸化ナトリウムのメタノール溶液を添加し、40℃で45分間鹸化反応を行った。得られた鹸化反応溶液を加熱乾燥して鹸化度96.8モル%、粘度平均重合度が600のPVAを得た。得られたPVAについてNMRを用いて、実施例1と同様の方法で末端及び主鎖構造の定量評価を行った。結果を表1に示す。A methanol solution of sodium hydroxide was added to the methanol solution of the vinyl acetate resin obtained above, and a saponification reaction was carried out at 40°C for 45 minutes. The resulting saponification reaction solution was heated and dried to obtain a PVA with a saponification degree of 96.8 mol% and a viscosity average polymerization degree of 600. The terminal and main chain structures of the obtained PVA were quantitatively evaluated using NMR in the same manner as in Example 1. The results are shown in Table 1.
(引張強度評価)
上記で得られたPVAからなるフィルムを、実施例1と同様に引張試験を行い、引張強度を算出したところ33.8N/mm2であった。結果を表1に示す。
(Tensile strength evaluation)
The PVA film obtained above was subjected to a tensile test in the same manner as in Example 1, and the tensile strength was calculated to be 33.8 N/ mm2 . The results are shown in Table 1.
(比較例6)
メタノールの添加量を20.8質量部に変えた以外は、比較例5と同様にして、鹸化度98.7モル%、粘度平均重合度が1800のPVAを得た。上記で得られたPVAからなるフィルムを作成し、実施例1と同様に引張強度評価を行った。作製したPVAの構造分析結果及び、フィルムの評価結果を表1に示す。
(Comparative Example 6)
A PVA having a degree of saponification of 98.7 mol% and a viscosity average degree of polymerization of 1800 was obtained in the same manner as in Comparative Example 5, except that the amount of methanol added was changed to 20.8 parts by mass. A film made of the PVA obtained above was produced, and its tensile strength was evaluated in the same manner as in Example 1. The results of the structural analysis of the produced PVA and the evaluation results of the film are shown in Table 1.
(比較例7)
メタノールの添加量を5.3質量部に変えた以外は、比較例5と同様にして、鹸化度99.1モル%、粘度平均重合度が3460のPVAを得た。上記で得られたPVAからなるフィルムを作成し、実施例1と同様に引張強度評価を行った。作製したPVAの構造分析結果及び、フィルムの評価結果を表1に示す。
(Comparative Example 7)
A PVA having a degree of saponification of 99.1 mol% and a viscosity average degree of polymerization of 3460 was obtained in the same manner as in Comparative Example 5, except that the amount of methanol added was changed to 5.3 parts by mass. A film made of the PVA obtained above was produced, and its tensile strength was evaluated in the same manner as in Example 1. The results of the structural analysis of the produced PVA and the evaluation results of the film are shown in Table 1.
重合度が高い方が、高いフィルム強度を示し、さらに末端数が少ない方がより高いフィルム強度を示す。 A higher degree of polymerization indicates higher film strength, and a lower number of terminal ends indicates even higher film strength.
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