TWI491438B - 陰離子交換膜及其製造方法 - Google Patents
陰離子交換膜及其製造方法 Download PDFInfo
- Publication number
- TWI491438B TWI491438B TW099108669A TW99108669A TWI491438B TW I491438 B TWI491438 B TW I491438B TW 099108669 A TW099108669 A TW 099108669A TW 99108669 A TW99108669 A TW 99108669A TW I491438 B TWI491438 B TW I491438B
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- Prior art keywords
- anion exchange
- exchange membrane
- group
- general formula
- polymer block
- Prior art date
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- 239000003011 anion exchange membrane Substances 0.000 title claims description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920001400 block copolymer Polymers 0.000 claims description 61
- 229920000642 polymer Polymers 0.000 claims description 60
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 48
- 125000002091 cationic group Chemical group 0.000 claims description 38
- -1 dialdehyde compound Chemical class 0.000 claims description 34
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 238000004132 cross linking Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000005342 ion exchange Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 238000007127 saponification reaction Methods 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000005349 anion exchange Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims 3
- 239000000178 monomer Substances 0.000 description 40
- 239000012528 membrane Substances 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 24
- 239000003014 ion exchange membrane Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 18
- 125000003396 thiol group Chemical group [H]S* 0.000 description 16
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical class OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 15
- 238000000909 electrodialysis Methods 0.000 description 15
- 238000011109 contamination Methods 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
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- 238000013508 migration Methods 0.000 description 9
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- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
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- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 238000003756 stirring Methods 0.000 description 6
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- 239000007788 liquid Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- LBIHNTAFJVHBLJ-UHFFFAOYSA-N 3-(triethoxymethyl)undec-1-ene Chemical compound C(=C)C(C(OCC)(OCC)OCC)CCCCCCCC LBIHNTAFJVHBLJ-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- LWJHSQQHGRQCKO-UHFFFAOYSA-N 1-prop-2-enoxypropane Chemical compound CCCOCC=C LWJHSQQHGRQCKO-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 2
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 2
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 2
- VZMJQFZZUNSSNA-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid prop-2-en-1-amine Chemical compound NCC=C.CC(C)CS(O)(=O)=O VZMJQFZZUNSSNA-UHFFFAOYSA-N 0.000 description 2
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 2
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- 102000004310 Ion Channels Human genes 0.000 description 2
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- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
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- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 2
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- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical group IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 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
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 2
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 2
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- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
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- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
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- DCFJTMOYYVXKID-UHFFFAOYSA-M (3-ethenylphenyl)methyl-triethylazanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC(C=C)=C1 DCFJTMOYYVXKID-UHFFFAOYSA-M 0.000 description 1
- ZDEQQWGIEVYLSQ-UHFFFAOYSA-M (3-ethenylphenyl)methyl-trimethylazanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC(C=C)=C1 ZDEQQWGIEVYLSQ-UHFFFAOYSA-M 0.000 description 1
- LZYWFGSAWORGPW-UHFFFAOYSA-M (3-ethenylphenyl)methyl-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC(C=C)=C1 LZYWFGSAWORGPW-UHFFFAOYSA-M 0.000 description 1
- DSPYSSAIDMDPIQ-UHFFFAOYSA-M (4-ethenylphenyl)methyl-dimethyl-propylazanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)CC1=CC=C(C=C)C=C1 DSPYSSAIDMDPIQ-UHFFFAOYSA-M 0.000 description 1
- BPFFRLYERCFJGN-UHFFFAOYSA-M (4-ethenylphenyl)methyl-ethyl-dimethylazanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CC1=CC=C(C=C)C=C1 BPFFRLYERCFJGN-UHFFFAOYSA-M 0.000 description 1
- VXKYXLCPIZSXPI-UHFFFAOYSA-N (4-ethenylphenyl)methyl-ethylazanium chloride Chemical compound [Cl-].C(C)[NH2+]CC1=CC=C(C=C1)C=C VXKYXLCPIZSXPI-UHFFFAOYSA-N 0.000 description 1
- VYYHGIIMGCZIIS-UHFFFAOYSA-M (4-ethenylphenyl)methyl-trimethylazanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=C(C=C)C=C1 VYYHGIIMGCZIIS-UHFFFAOYSA-M 0.000 description 1
- TVXNKQRAZONMHJ-UHFFFAOYSA-M (4-ethenylphenyl)methyl-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=C(C=C)C=C1 TVXNKQRAZONMHJ-UHFFFAOYSA-M 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- IBTLFDCPAJLATQ-UHFFFAOYSA-N 1-prop-2-enoxybutane Chemical compound CCCCOCC=C IBTLFDCPAJLATQ-UHFFFAOYSA-N 0.000 description 1
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- YNOYMZQUEXKLSI-UHFFFAOYSA-M 2-(4-ethenylphenyl)ethyl-diethyl-methylazanium;acetate Chemical compound CC([O-])=O.CC[N+](C)(CC)CCC1=CC=C(C=C)C=C1 YNOYMZQUEXKLSI-UHFFFAOYSA-M 0.000 description 1
- XISCORVELQXNAT-UHFFFAOYSA-M 2-(4-ethenylphenyl)ethyl-diethyl-methylazanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CCC1=CC=C(C=C)C=C1 XISCORVELQXNAT-UHFFFAOYSA-M 0.000 description 1
- PGMMQIGGQSIEGH-UHFFFAOYSA-N 2-ethenyl-1,3-oxazole Chemical class C=CC1=NC=CO1 PGMMQIGGQSIEGH-UHFFFAOYSA-N 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
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- 239000013535 sea water Substances 0.000 description 1
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- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- NCDYOSPPJZENCU-UHFFFAOYSA-M triethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCOC(=O)C=C NCDYOSPPJZENCU-UHFFFAOYSA-M 0.000 description 1
- YYDPXUCJQLEUHK-UHFFFAOYSA-N triethyl-[2-(2-methylprop-2-enoylamino)ethyl]azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCNC(=O)C(C)=C YYDPXUCJQLEUHK-UHFFFAOYSA-N 0.000 description 1
- PLEPDIIXZWQNEP-UHFFFAOYSA-M triethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCCOC(=O)C(C)=C PLEPDIIXZWQNEP-UHFFFAOYSA-M 0.000 description 1
- IACHBBYPUKLZPO-UHFFFAOYSA-N triethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CCCNC(=O)C=C IACHBBYPUKLZPO-UHFFFAOYSA-N 0.000 description 1
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- CCVMLEHYQVSFOM-UHFFFAOYSA-N trimethyl-[2-(prop-2-enoylamino)ethyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCNC(=O)C=C CCVMLEHYQVSFOM-UHFFFAOYSA-N 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- XYAHMUGLVOAFIU-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCNC(=O)C=C XYAHMUGLVOAFIU-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Description
本發明係關於陰離子交換膜,其含有之主成分係將乙烯醇系聚合物嵌段(A)及具有陽離子性基之聚合物嵌段(B)作為構成成分、且施行交聯處理而得者。更詳細來講,係關於膜電阻小、且膜的有機汙染少之對電透析有用的陰離子交換膜。
離子交換膜係在海水濃縮、飲料水用地下鹹水之除鹽或硝酸鹽氮(Nitrate Nitrogen)之去除、於食品製造工程中之鹽分去除或醫藥品之有效成分的濃縮等、於現在的各式各樣用途中、使用作為電透析法、擴散透析法等之離子的分離膜。使用於此之有用的離子交換膜主要為苯乙烯-二乙烯苯系之均相離子交換膜(homogeneous ion exchange membrane),經一價與二價之離子選擇、特定離子之選擇性提升、低膜電阻化等種種技術之開發,達到能夠在工業上有用之分離。
一般而言,於上述之食品、醫藥品、農藥等領域之有機物的合成步驟中,有產生許多鹽類副產物之情形。許多時候係經由電透析來分離所使用的有機物中所含之鹽類。電透析之鹽類分離係藉由交互配列陽離子交換膜與陰離子交換膜、流通直流電流,自陽離子交換膜之陰極側將陽離子排除、自陰離子交換膜之陽極側將陰離子排除,從而,於夾在陰極側之陽離子交換膜與陽極側之陰離子交換膜間形成之室,自濃縮的電解質液把鹽取出去除,而實現除鹽。於經由電透析對處理液進行除鹽之情形,被處理液中之有機汙染物質,特別是具有電荷之巨大分子(以下稱為巨大有機離子)附著於離子交換膜,降低膜之性能,即,產生稱為膜的有機汙染之問題。
特別是由於陰離子交換膜容易被有機汙染,於進行透析循環的同時,膜性能慢慢惡化,於汙染明顯之情形下,在相對較短的期間內有膜顯著的膨潤、破損之情況。
作為抑制有機汙染之陰離子交換膜,過去已知防止巨大有機離子對膜內之浸入的陰離子交換膜。此係在膜表面形成中性、兩性或與離子交換基相反電荷之薄層而成者。此陰離子交換膜於膜為緻密構造、或巨大有機離子之分子量大時,其效果顯著。例如具有陰離子交換基之樹脂膜的表層部導入相對電荷之磺酸基、以抑制陰離子性之巨大有機離子對膜內之浸入的陰離子交換膜(專利文獻1)。亦有研究陰離子交換基之陰離子對的構造、以改善有機汙染性之陰離子交換膜(專利文獻2)。
專利文獻1日本特公昭51-40556號公報
專利文獻2日本特開平3-146525號公報
專利文獻3日本特開昭59-189113號公報
專利文獻4日本特開昭59-187003號公報
但是,上述進行防止巨大有機離子對膜內的浸入之陰離子交換膜,雖能發揮一定程度之耐有機汙染性,但由於設置於前述樹脂膜之表層部的相對電荷層之形成,而有膜電阻顯著增大之缺點。又,研究陰離子交換基之陰離子對之構造的陰離子交換膜亦無法滿足耐有機汙染性。
從而,本發明之目的為提供抑制有機汙染、且於膜電阻或離子選擇性等之基礎性質優良、於電透析亦有用之離子交換膜。
本發明人為了實現上述目的不斷專心研究。其結果,將乙烯醇系聚合物嵌段(A)及具有陽離子性基之聚合物嵌段(B)作為構成成分的嵌段共聚物(P),施行交聯處理而成者作為主成分來含有之陰離子交換膜,係發現不降低膜電阻或離子遷移數等之基礎性質、顯現於電透析有用之優良耐有機汙染性,而完成本發明。
於上述嵌段共聚物(P)之聚合物嵌段(B)較佳為下述一般式(2)~(7)之重複單元。
(式中,R1
係表示氫原子或碳數1~4之烷基;R2
、R3
、R4
係各自獨立表示氫原子、亦可具有取代基或亦可連結形成飽和或不飽和環狀構造之碳數1~18之烷基、芳基或芳烷基。Z係表示-O-或NH-;Y係表示亦可帶有雜原子之總碳數1~8之二價連結基;X-
係表示陰離子。)
(式中,R5
係表示氫原子或甲基。R2
、R3
、R4
、X-
係與一般式(2)同義。)
(式中,R2
、R3
、X-
係與一般式(2)同義。)
(式中,n係表示0或1、R2
、R3
、R4
、X-
係與一般式(2)同義。)
又,本發明之陰離子交換膜之離子交換容量較佳為0.30meq/g以上。
又,藉由陰離子交換膜含有之主成分係將乙烯醇系聚合物嵌段(A)及具有陽離子性基之聚合物嵌段(B)作為構成成分之嵌段共聚物(P)、與聚合度200~8000、皂化度80莫耳%以上之乙烯醇系聚合物(Q)之混合物、其中嵌段共聚物(P)與乙烯醇系聚合物(Q)之質量比為3/97以上、施行交聯處理而成者,亦可解決上述課題。此情形中,於嵌段共聚物(P)之聚合物嵌段(B)較佳為上述一般式(2)~(7)之重複單元。又,離子交換容量較佳為、0.30meq/g以上。
又,本發明之製造方法,藉由將得自嵌段共聚物(P)的溶液之皮膜、或得自嵌段共聚物(P)與乙烯醇系聚合物(Q)之混合物的溶液之皮膜以100℃以上之溫度熱處理後,於水、醇或其混合溶劑中、於酸性條件下藉由二醛化合物進行交聯處理,接著進行水洗處理,來提供上述本發明之陰離子交換膜。
本發明之陰離子交換膜具有高親水性、高耐有機汙染性、膜電阻小。此外,因嵌段共聚物能抑制起因於濕度之膜的膨潤,膜強度亦高,而可進行長期間效率良好、安定之電透析。
本發明之陰離子交換膜係設置有、將乙烯醇系聚合物嵌段(A)及具有陽離子性基之聚合物嵌段(B)作為構成成分之嵌段共聚物(P),施行交聯處理而成者作為主成分之陰離子交換層。
本發明之陰離子交換膜的特徵係將將乙烯醇系聚合物嵌段(A)與具有陽離子性基之聚合物嵌段(B)作為構成成分之嵌段共聚物(P)作為主成分。陰離子交換膜之最重要的性質係陰離子傳輸性(陰離子之流動性)。此處膜中之陰離子係如何形成通過路徑(離子通道)為重要的。本發明之嵌段共聚物係由乙烯醇系聚合物嵌段(A)與具有陽離子性基之聚合物嵌段(B)所構成,藉由負責陰離子交換膜整體支強度、形狀保持、及耐有機汙染性之乙烯醇系聚合物嵌段(A)與展現陰離子傳輸性之聚合物嵌段(B)的角色分擔,成功並立了離子傳輸性、膜強度或寸法安定性、及耐有機汙染性。
接著,因可容易的控制單純之混合物與不同之乙烯醇系聚合物嵌段(A)與聚合物嵌段(B)之微相分離構造,而有能容易的控制作為離子通道之功能的聚合物嵌段(B)之連續相的半徑或構造之優點。
構成嵌段共聚物(P)之聚合物嵌段的數目無特別限定,只要是乙烯醇系聚合物嵌段(A)及聚合物嵌段(B)的二嵌段共聚物,即可有效發揮各嵌段之功能。
又,乙烯醇系聚合物嵌段(A)與聚合物嵌段(B)之重複單元數的比較佳為99:1~50:50之範圍、更佳為98:2~60:40之範圍、進一步更佳為95:5~70:30之範圍。
此處,於嵌段共聚物(P)中之聚合物嵌段(B)的重複單元無特別限定,舉例為以下述一般式(2)~(7)表示之重複單元。
(式中,R1
係表示氫原子或碳數1~4之烷基;R2
、R3
、R4
係各自獨立表示氫原子、亦可具有取代基或亦可連結形成飽和或不飽和環狀構造之碳數1~18之烷基、芳基或芳烷基。Z係表示-O-或NH-;Y係表示亦可帶有雜原子之總碳數1~8之二價連結基;X-
係表示陰離子。)
(式中,R5
係表示氫原子或甲基。R2
、R3
、R4
、X-
係與一般式(2)同義。)
(式中,R2
、R3
、X-
係與一般式(2)同義。)
(式中,n係表示0或1、R2
、R3
、R4
、X-
係與一般式(2)同義。)
本發明之陰離子交換膜的特徵係將將乙烯醇系聚合物嵌段(A)與具有陰離子交換性基之聚合物嵌段(B)作為構成成分之嵌段共聚物(P)作為主成分。陰離子交換膜之重要性質係膜中的電荷密度,例如使用於電透析之情形,電荷密度對離子之遷移數有很大之影響為眾所皆知的事實。此處,在膜中之電荷量增加之狀態,如何抑制膨潤度為重要的。
如上所述,本發明之陰離子交換膜之主成分的嵌段共聚物係由乙烯醇系聚合物嵌段(A)與具有陰離子交換性基之聚合物嵌段(B)所構成。乙烯醇系聚合物嵌段(A)在具有高親水性的同時,於陰離子交換膜整體之強度、膨潤度之抑制及形狀保持做出貢獻。如此之乙烯醇系聚合物嵌段(A)與展現離子交換性的聚合物嵌段(B)藉由角色分擔,於陰離子交換膜成功維持高電荷密度與、膨潤度之抑制及尺寸安定性的並立。又,如此之本發明的離子交換膜係膜電阻小、耐有機汙染性優良。接著,於本發明中由於使用單純之混合物與不同之嵌段共聚物,因可以容易的控制乙烯醇系聚合物嵌段(A)與聚合物嵌段(B)之微相分離構造,而有能容易的控制作為離子交換部位之功能的聚合物嵌段(B)之連續相的半徑或構造之優點。
本發明陰離子交換膜之主成分的嵌段共聚物(P)係已施予交聯處理。嵌段聚合物(P)之製造方法主要大致分為下面2種方法。即,(1)製造使用具有陽離子性基之至少1個單體與其它單體之嵌段共聚物的方法、及(2)製造嵌段共聚物後、導入陽離子性基之方法。其中,針對(1),藉由對在末端具有巰基之乙烯醇系聚合物(嵌段(A))、以含有陽離子性基之至少1種單體進行自由基聚合來製造嵌段共聚物之方法,由於在工業上為容易的,而較佳。又,針對(2),舉例為對末端含有巰基之乙烯醇系聚合物(嵌段(A))以1種或複數種之單體進行嵌段共聚合,而得到嵌段共聚物,接著對此嵌段共聚物倒入陽離子性基,而得到含有具陽離子性基之聚合物嵌段(B)之嵌段共聚物(P)的方法。此等方法中,特別是乙烯醇系聚合物嵌段(A)與具有陽離子性基之聚合物嵌段(B)之各成分的種類或量,由於可輕易控制,較佳為對末端具有巰基之乙烯醇系聚合物(嵌段(A))以具有陽離子性基之至少1種單體進行自由基聚合來製造嵌段共聚物之方法。
以下,針對較佳用於本發明之用來製造所期望嵌段共聚物(P)之方法進行說明,其中嵌段共聚物(P)係使用具有陽離子性基的至少1種單體。於末端具有巰基之乙烯醇系聚合物可藉由例如記載於專利文獻4等之方法得到。即,舉例為在硫羥酸的存在下、將乙烯酯單體,例如乙酸乙烯酯,作為主體之乙烯系單體進行自由基聚合所得到之乙烯酯系聚合物進行皂化之方法。
於末端具有巰基之乙烯醇系聚合物的皂化度無特別限制,較佳為40~99.9莫耳%。一旦皂化度小於40莫耳%,因乙烯醇系聚合物嵌段(A)的結晶性降低,陰離子交換膜之強度有不足的可能。上述皂化度更佳為60莫耳%以上、進一步更佳為80莫耳%以上。又,於末端具有巰基之乙烯醇系聚合物的皂化度通常為99.9莫耳%以下。聚乙烯醇之皂化度係依據JIS K6726測定而得值。
於末端含有巰基之乙烯醇系聚合物的聚合度較佳為100以上、3500以下,更佳為200以上3000以下,進一步更佳為250以上、2500以下。於聚合度小於100之情形,將最終所得到之嵌段共聚物(P)作為主成分之陰離子交換膜的膜強度有不足的可能性。另一方面,於聚合度超過3500之情形,由於導入至該乙烯醇系聚合物之巰基不足,而有無法有效率得到嵌段聚合物(P)之可能性。又,聚乙烯醇的黏度平均聚合度係依據JIS K6726測定而得的值。
得到使用如此進行所得到之於末端含有巰基的乙烯醇系聚合物與含有陽離子性基之單體的嵌段共聚物(P)之方法,例如舉例為於專利文獻3等記載之方法。即,例如於專利文獻3所記載的、在於末端具有巰基之乙烯醇系聚合物的存在下,藉由自由基聚合具有陽離子性基之單體,可得到嵌段共聚物(P)。此自由基聚合為公知方法,例如可藉由總體聚合、溶液聚合、珠狀聚合、乳化聚合等進行,能溶解在末端含有巰基之乙烯醇系聚合物之溶劑,例如較佳為以水或二甲亞碸作為主體之溶劑進行。又,聚合製程可採用批次法、半連續法、連續法中之任一種。
上述自由基聚合可使用通常之自由基聚合起始劑,例如2,2’-偶氮雙異丁腈、過氧化苯甲醯、過氧化月桂醯、異丙基過氧化二碳酸二異丙酯、過氧硫酸鉀、過氧硫酸銨等之中適於聚合系統者進行,而於水系統之聚合的場合,藉由乙烯醇系聚合物末端之巰基與溴酸鉀、過氧硫酸鉀、過氧硫酸銨、過氧化氫等氧化劑的氧化還原反應亦有開始聚合的可能。
於末端具有巰基之乙烯醇系聚合物的存在下、自由基聚合具有離子交換性基之單體時,期望聚合系統為酸性。此係因為巰基於鹼性下對單體之雙鍵的離子加成消失的速度變快、聚合效率顯著降低。又,若為水系統之聚合,較佳全部的聚合操作係在pH4以下實施。
依據上述方法合成嵌段共聚物(P)時使用之具有陽離子性基之單體,例如舉例為氯化三甲基對乙烯苄基銨、氯化三甲基間乙烯苄基銨、氯化三乙基對乙烯苄基銨、氯化三乙基間乙烯苄基銨、氯化N,N-二甲基-N-乙基-N-對乙烯苄基銨、氯化N,N-二乙基-N-甲基-N-對乙烯苄基銨、氯化N,N-二甲基-N-正丙基-N-對乙烯苄基銨物、氯化N,N-二甲基-N-正辛基-N-對乙烯苄基銨、氯化N,N-二甲基-N-苄基-N-對乙烯苄基銨、氯化N,N-二乙基-N-苄基-N-對乙烯苄基銨、氯化N,N-二甲基-N-(4-甲基)苄基-N-對乙烯苄基銨、氯化N,N-二甲基-N-苯基-N-對乙烯苄基銨、溴化三甲基對乙烯苄基銨、溴化三甲基間乙烯苄基銨、三甲基對乙烯苄基磺酸銨、三甲基間乙烯苄基磺酸銨、三甲基對乙烯苄基乙酸銨、三甲基間乙烯苄基乙酸銨、氯化N,N,N-三乙基-N-2-(4-乙烯苯基)乙基銨、氯化N,N,N-三乙基-N-2-(3-乙烯苯基)乙基銨、氯化N,N-二乙基-N-甲基-N-2-(4-乙烯苯基)乙基銨、N,N-二乙基-N-甲基-N-2-(4-乙烯苯基)乙基乙酸銨、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二乙基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基丙酯、(甲基)丙烯酸N,N-二乙基胺基丙酯、(甲基)丙烯醯胺N,N-二甲基胺基乙酯、(甲基)丙烯醯胺N,N-二乙基胺基乙酯、(甲基)丙烯醯胺N,N-二甲基胺基丙酯、(甲基)丙烯醯胺N,N-二乙基胺基丙酯之經由氯化甲基、氯化乙基、溴化甲基、溴化乙基、碘化甲基或碘化乙基之4級化物、或取代其等之陰離子的磺酸鹽、烷基磺酸鹽、乙酸鹽或烷基羧酸鹽等。
具體來說,例如可舉例為氯化單甲基二烯丙基銨、氯化三甲基-2-(甲基丙烯醯氧基)乙基銨、氯化三乙基-2-(甲基丙烯醯氧基)乙基銨、氯化三甲基-2-(丙烯醯氧基)乙基銨、氯化三乙基-2-(丙烯醯氧基)乙基銨、氯化三甲基-3-(甲基丙烯醯氧基)丙基銨、氯化三乙基-3-(甲基丙烯醯氧基)丙基銨、氯化三甲基-2-(甲基丙烯醯胺基)乙基銨、氯化三乙基-2-(甲基丙烯醯胺基)乙基銨、氯化三甲基-2-(丙烯醯胺基)乙基銨、氯化三乙基-2-(丙烯醯胺基)乙基銨、氯化三甲基-3-(甲基丙烯醯胺基)丙基銨、氯化三乙基-3-(甲基丙烯醯胺基)丙基銨、氯化三甲基-3-(丙烯醯胺基)丙基銨、氯化三乙基-3-(丙烯醯胺基)丙基銨、氯化N,N-二甲基-N-乙基-2-(甲基丙烯醯氧基)乙基銨、氯化N,N-二乙基-N-甲基-2-(甲基丙烯醯氧基)乙基銨、氯化N,N-二甲基-N-乙基-3-(丙烯醯胺基)丙基銨、溴化三甲基-2-(甲基丙烯醯氧基)乙基銨、溴化三甲基-3-(丙烯醯胺基)丙基銨、三甲基-2-(甲基丙烯醯氧基)乙基磺酸銨、三甲基-3-(丙烯醯胺基)丙基銨乙酸銨等。作為其它可能共聚合之單體亦可舉例為N-乙烯基咪唑、N-乙烯基-2-甲基咪唑等。
又,合成上述之嵌段共聚物(P)時,具有陽離子性基之聚合物嵌段(B)為了賦予本發明之陰離子交換膜高離子交換性,期望僅由具有陽離子性基之單體單元構成,但亦可含有不具陽離子性基之單體單元。作為含有不具陽離子性基之單體單元的單體,舉例為乙烯、丙烯、1-丁烯、異丁烯、1-己烯等α-烯烴類;丙烯酸或其鹽、或丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯等丙烯酸酯類;甲基丙烯酸或其鹽、或甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯等甲基丙烯酸酯類;富馬酸、馬來酸、伊康酸、馬來酸酐、伊康酸酐等其它不飽和羧酸或其衍生物;丙烯醯胺、N-甲基丙烯醯胺、N-乙基丙烯醯胺等丙烯醯胺衍生物;甲基丙烯醯胺、N-甲基甲基丙烯醯胺、N-乙基甲基丙烯醯胺等甲基丙烯醯胺衍生物;甲基乙烯基醚、乙基乙烯基醚、正丙基乙烯基醚、異丙基乙烯基醚、正丁基乙烯基醚等乙烯基醚類;乙二醇乙烯基醚、1,3-丙二醇乙烯基醚、1,4-丁二醇乙烯基醚等含有羥基之乙烯基醚類;乙酸烯丙酯、丙基烯丙基醚、丁基烯丙基醚、己基烯丙基醚等烯丙基醚類;具有氧伸烷基之單體;乙酸異丙烯酯、3-丁烯-1-醇、4-戊烯-1-醇、5-己烯-1-醇、7-辛烯-1-醇、9-癸烯-1-醇、3-甲基-3-丁烯-1-醇等含有羥基之α-烯烴類;具有乙烯磺酸、烯丙基磺酸、甲基烯丙基磺酸、2-丙烯醯胺-2-甲基丙烷磺酸等磺酸基之單體;具有乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三乙醯氧基矽烷等矽烷基之單體。於聚合物嵌段(B)中,具有離子交換性基之單體單元的比例為80莫耳%以上、特別較佳為90莫耳%以上。
於上述自由基聚合的反應溫度無特別制限,通常適當為0~200℃。聚合之過程藉追蹤以各種色譜、NMR譜等之殘存單體的定量來判斷聚合反應之停止,可將乙烯醇系聚合物嵌段(A)與聚合物嵌段(B)調製為所期望之比例。聚合反應之停止係經由公知的方法,例如聚合系統之冷却,來停止聚合。
為了在用作為電透析用之陰離子交換膜展現充分的離子交換性,所得到之嵌段共聚物(P)的離子交換容量較佳為0.30meq/g以上、更佳為0.50meq/g以上。關於嵌段共聚物之離子交換容量的上限,一旦離子交換容量變得過大,由於親水性上升、膨潤度之抑制變困難,因此較佳為3.0meq/g以下。
作為製作嵌段共聚物(P)之方法,較佳為首先製造具有可能導入上述乙烯醇系聚合物嵌段(A)與陽離子性基之嵌段的嵌段共聚物,接著於該嵌段導入陽離子性基之方法。可能導入陽離子性基之嵌段共聚物、於製造使用上述之含有巰基的乙烯醇系聚合物與具有陽離子性基的單體之嵌段共聚物(P)的方法中,可除了使用具有可能導入陽離子性基之部位的單體取代具有陽離子性基之單體以外,經由同樣之方法製造。作為具有可能導入陽離子性基之部位的單體,例如舉例為2-乙烯基吡啶、4-乙烯基吡啶、2-甲基-5-乙烯基吡啶等乙烯基吡啶類、乙烯基嘧啶類、乙烯基喹啉類、乙烯基咔唑類、乙烯基咪唑類、鄰、間、對乙烯苯基伸烷基烷基胺類、丙烯酸二烷基胺基烷酯類、丙烯酸二烷基胺基烷酯類。
對於將陽離子性基導入至具有可能導入陽離子性基之部位的嵌段共聚物,較佳為以烷基鹵化物之蒸氣或溶液對該嵌段共聚物進行處理、四級化其氮原子。此處使用之烷基鹵化物為以Cp
H2p+1
X或X(CH2
)q
X(p為1~12之整數、q為2至12之整數、X為溴或碘原子)表示之化合物即可。對於將陰離子交換性基導入具有鹵甲基之嵌段部分,較佳為於三烷基胺處反應。
又,本發明之陰離子交換膜較佳為含有之主成分為將如上述進行而得得之嵌段共聚物(P)與聚合度為200~8000(較佳為500~7000)、皂化度80莫耳%以上、(較佳為85莫耳%以上)之乙烯醇系聚合物(Q)的混合物、其質量比(P/Q)為3/97、施行交聯處理而得者的陰離子交換膜。像這樣,藉由於嵌段共聚物(P)合併使用乙烯醇系聚合物(Q),可得到在具有充分之離子交換容量與良好之耐有機汙染性的同時、具有高強度之陰離子交換膜。
乙烯醇系聚合物(Q)亦可為乙烯酯系單體與如以下所揭示之單體的共聚物,其中由乙烯酯系單體所構成之部分的聚合度為200~8000(更佳為500~7000)、同部分之皂化度為80莫耳%以上(更佳為85莫耳%以上)。作為後者之單體,舉例為乙烯、丙烯、1-丁烯、異丁烯、1-己烯等α-烯烴類;富馬酸、馬來酸、伊康酸、馬來酸酐、伊康酸酐等之羧酸或其衍生物;丙烯酸或其鹽、或丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯等丙烯酸酯類;甲基丙烯酸或其鹽、或甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯等甲基丙烯酸酯類;丙烯醯胺、N-甲基丙烯醯胺、N-乙基丙烯醯胺等丙烯醯胺衍生物;甲基丙烯醯胺、N-甲基甲基丙烯醯胺、N-乙基甲基丙烯醯胺等甲基丙烯醯胺衍生物;甲基乙烯基醚、乙基乙烯基醚、正丙基乙烯基醚、異丙基乙烯基醚、正丁基乙烯基醚等乙烯基醚類;乙二醇乙烯基醚、1,3-丙二醇乙烯基醚、1,4-丁二醇乙烯基醚等含有羥基之乙烯基醚類;乙酸烯丙酯、丙基烯丙基醚、丁基烯丙基醚、己基烯丙基醚等烯丙基醚類;具有氧伸烷基之單體;乙酸異丙烯酯、3-丁烯-1-醇、4-戊烯-1-醇、5-己烯-1-醇、7-辛烯-1-醇、9-癸烯-1-醇、3-甲基-3-丁烯-1-醇等含有羥基之α-烯烴類;乙烯磺酸、烯丙基磺酸、甲基烯丙基磺酸、2-丙烯醯胺-2-甲基丙烷磺酸等具有磺酸基之單體;乙烯氧乙基三甲基銨氯化物、乙烯氧丁基三甲基銨氯化物、乙烯氧乙基二甲基胺、乙烯氧甲基二乙基胺、N-丙烯醯胺甲基三甲基銨氯化物、N-丙烯醯胺乙基三甲基銨氯化物、N-丙烯醯胺二甲基胺、烯丙基三甲基銨氯化物、甲基烯丙基三甲基銨氯化物、二甲基烯丙基胺、烯丙基乙基胺等具有陽離子性基之單體;乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三乙醯氧基矽烷等具有矽烷基之單體等。於上述共聚物中乙烯酯系單體單元之比例較佳為80莫耳%以上、更佳為90莫耳%以上。
乙烯醇系聚合物(Q)亦可為於2-巰乙醇、正十二硫醇、巰乙酸、3-巰丙酸等硫醇化合物之存在下,經由皂化將乙烯酯系單體進行自由基聚合所得到之乙烯酯系聚合物,其中所得到之末端改質乙烯醇系聚合物、聚合度為200~8000(更佳為500~7000)、皂化度為80莫耳%以上(更佳為85莫耳%以上)。
於上述混合物中之嵌段共聚物(P)與乙烯醇系聚合物(Q)的比例(P/Q)、質量比較佳為5/95以上、更佳為10/90以上。於二者之比例(P/Q)比3/97還要更小的情形,有所得到之陰離子交換膜的離子交換性不充分、電透析性能無法充分發揮的可能性。
將嵌段共聚物(P)作為主成分之本發明的陰離子交換膜,可經由將得自嵌段共聚物(P)的溶液之皮膜於100℃以上之溫度進行熱處理後、在水、醇或其混合溶劑中、於酸性條件下、藉由二醛化合物進行交聯處理、接著進行水洗處理而得到。又,將嵌段共聚物(P)與乙烯醇系聚合物(Q)之混合物作為主成分之本發明的陰離子交換膜,可經由將得自嵌段共聚物(P)與乙烯醇系聚合物(Q)的溶液之皮膜於100℃以上之溫度進行熱處理後、在水、醇或其混合溶劑中、於酸性條件下、藉由二醛化合物進行交聯處理、接著進行水洗處理而得到。
作為用於嵌段共聚物(P)之溶液或嵌段共聚物(P)與乙烯醇系聚合物(Q)之混合物的溶液之溶劑,通常舉例為水、甲醇、乙醇、1-丙醇、2-丙醇等低級醇、或此等之混合溶劑。皮膜通常可藉經由流延將溶液中的溶劑揮發而得到。製膜時的溫度無特殊限制,適當為室溫~100℃左右之溫度範圍。
本發明之陰離子交換膜,由確保做為電透析用電解質膜之必要性能、膜強度、處理性等之觀點來看,較佳為其膜厚為1~1000μm左右。於膜厚小於1μm之情形,膜的機械強度有變的不充分的傾向。相反的,於膜厚超過1000μm之情形,膜電阻變大,因無法展現充分的離子交換性,變得有電透析效率變低的傾向。膜厚更佳為5~500μm、進一步較佳為7~300μm。
於本發明之陰離子交換膜的製造方法,較佳施行熱處理。經由施行熱處理,形成物理的交聯,所得到之陰離子交換膜的機械強度增大。熱處理之方法無特別限制,一般係使用熱風乾燥機等。熱處理之溫度雖無特殊限制,但較佳為50~250℃。熱處理之溫度一旦小於50℃,則所得到之離子交換膜的機械強度即有可能不足。該溫度更佳為80℃以上、更佳為100℃以上。另一方面,熱處理之溫度一旦超過250℃,結晶性聚合物即有可能熔解。更佳為該溫度為230℃以下、進一步較佳為200℃以下。
於本發明之陰離子交換膜製造方法,較佳施行交聯處理。經由施行交聯處理,所得到之離子交換層的機械強度增大。交聯處理之方法,只要是可經由化學鍵結合聚合物彼此之分子鏈的方法即可,無特別限制。通常,使用浸漬於含交聯處理劑之溶液的方法等。該交聯處理劑例示為甲醛、或乙二醛或戊二醛等二醛化合物。於本發明中,較佳將進行熱處理後之上述皮膜,在酸性條件下、浸漬於將二醛化合物溶解於水、醇或其混合溶劑中而成之溶液中、進行交聯處理。交聯處理劑之濃度,通常相對於溶液,交聯處理劑之體積濃度為0.001~1體積%。
於本發明之陰離子交換膜的製造方法中,可同時進行熱處理與交聯處理、亦可只進行其中之一者。於同時進行熱處理與交聯處理的情形,可於熱處理後進行交聯處理、亦可於交聯處理後進行熱處理,亦可二者同時進行。於熱處理後進行交聯處理,由所得到之陰離子交換膜的機械強度之觀點來看係較佳。
[實施例]
以下舉出實施例以更詳細說明本發明,但本發明並非限定於此等實施例。又,實施例中除非另有說明,「%」及「份」係以重量為基準。
參考例(於分子末端具有巰基之聚乙烯醇系聚合物之合成)
藉由專利文獻4中所記載之方法合成表1所示之於分子末端具有巰基的聚乙烯醇。
實施例、比較例中所示之離子交換膜性質係經由以下方法測定。
1)膜含水率(H)
預先測定離子交換膜之乾燥重量,其後浸漬於去離子水中,於達到膨潤平衡時測定濕潤重量。經由下式算出膜含水率H。
H=[(WW
-DW
)/1.0]/[(WW
-DW
)/1.0+(DW
/1.3)]
此處1.0與1.3係各表示水與聚合物之比重。
‧H:膜含水率[-]
‧DW
:膜之乾燥重量[g]
‧WW
:膜之濕潤重量[g]
2)最大裂斷應力
使用JIS規格之沖壓機,將陰離子交換膜切斷成寬2mm、長3cm之啞鈴狀來製作測定試料。測定係使用島津製作所股份有限公司製小型桌上試驗機「EZ-Test500N」。評價點間距離為2cm、在25℃之溫度下進行測定。從所得到之斷裂點之應力、經由下式計算出最大裂斷應力。
最大裂斷應力[MPa]=裂斷點之應力[MPa]×初期斷面積[m2
]/裂斷斷面積[m2
]
3)陰離子交換容量之測定
將陰離子交換膜浸漬於1mol/l之HCl水溶液10小時以上。其後以1mol/l之NaNO3
水溶液將氯離子型取代為硝酸離子型,以電位差滴定裝置定量(Amol)遊離之氯離子(COMTITE-900;平沼產業股份有限公司製)。
接下來,將同一陰離子交換膜浸漬於1mol/l之HCl水溶液4小時以上,以離子交換水充分水洗後取出膜,於105℃之熱風乾燥機中乾燥16小時,測定乾燥時的重量(W[g])。經由下式計算出離子交換容量。
‧離子交換容量=A×1000/W[meq/g]
4)動態遷移數之測定
陰離子交換膜之動態遷移數係於第1圖所示之具有白金黑電極板的2室槽中挾持離子交換膜、於離子交換膜之兩側填滿0.5mol/L-NaCl溶液、以規定時間(t)、規定電流密度(J=10mAcm-2
)之電流密度進行電透析。有效膜面積為8.0cm2
(2cm×4cm)。其後取出測定溶液,將該溶液於300ml定量瓶稀釋。以導電度計測定稀釋溶液之導電度,經由將得到之導電度代入下式,計算出動態遷移數td+
。
td+
=Δm/Ea
td+
:動態遷移數
Ea
:理論當量=I‧t/F
Δm:移動當量
F:法拉第常數
5)膜電阻之測定
在第2圖所示之具有白金黑電極板的2室槽中挾持陰離子交換膜、於膜的兩側填滿0.5mol/L-NaCl溶液、藉由交流電橋(頻率1000周/秒)於25℃測定電極間之電阻,藉由該電極間電阻與未設置陰離子交換膜之情形的電極間電阻的差來求取膜電阻。於上述測定中所使用的膜係使用預先在0.5mol/L-NaCl溶液中平衡者。
6)耐有機汙染性之測定
調理所得到之陰離子交換膜後,於具有銀、氯化銀電極之二室槽間挾持該離子交換膜,於其陽極室加入0.05mol/L-NaCl溶液,於陰極室加入1000ppm之十二基苯磺酸鈉與0.05mol/L-NaCl的混合溶液。以1500rpm之回轉速度攪拌兩室之液體,以0.2A/dm2
之電流密度進行電透析。此時,於兩膜表面附近固定白金線、測定膜間電壓。於通電中,一旦發生有機汙染,膜間電壓即開始上昇。於通電開始30分鐘後測定膜間電壓,以添加及未添加有機汙染物質之情形的電壓差(ΔE)作為膜之汙染性的標準。
(P-1之合成)
於配備有迴流冷却管、攪拌翼之5L四口可拆式燒瓶(seperable-flask)添加2600g水、344g作為末端有巰基之乙烯醇系聚合物、示於表1的PVA-1,於攪拌下加熱至95℃,於溶解該乙烯醇系聚合物後,冷却至室溫。對該水溶液添加1/2當量之硫酸,將pH調整至3.0。此外,將甲基丙烯醯胺丙基三甲基銨氯化物183g溶解於200g水,將其在攪拌下添加至先前調製之水溶液後加熱至70℃,又,一邊以氮於水溶液中吹泡,一邊在30分鐘間於系統內進行氮取代。氮取代後對上述水溶液以1.5小時逐次添加過氧硫酸鉀之2.5%水溶液121ml,開始嵌段共聚合,進行後將系統內溫度維持在75℃ 1小時、繼續進行聚合,接著冷却,得到固形分濃度15%之氯化PVA-(b)-p-甲基丙烯醯胺丙基三氯化甲基銨嵌段共聚物水溶液。乾燥所得到之水溶液的一部分後,溶解於重水中,以400MHz之1
H-NMR測定的結果,甲基丙烯醯胺丙基三甲基銨單元的改質量為10莫耳%。又,以B型黏度計測定之4%水溶液黏度為18mPa‧s(20℃)。
(P-2~P-5之合成)
除了將含有陽離子性基之單體的種類與添加量、聚合起始劑的使用量等聚合條件變更如表2所示以外,藉由與P-1相同之方法得到P-2~P-5。所得到之聚合物的物性示於表2。
(P-6之合成)
除了將含有陽離子性基之單體的種類與添加量、聚合起始劑的使用量等聚合條件變更如表2所示以外,藉由與P-1相同之方法得到固形分濃度15%之PVA-(b)-乙烯甲醯胺嵌段共聚物水溶液(乾燥所得到之水溶液的一部分後,溶解於重水中,以400MHz之1
H-NMR測定的結果,乙烯甲醯胺單元之改質量為10莫耳%)。
(P-7之合成:P-6之水解)
於P-6之濃度15%的水溶液中添加0.08mol%的氫氧化鈉,藉由在110度加熱1小時來水解,得到固形分濃度14%之PVA-(b)-乙烯胺嵌段共聚物水溶液(乾燥所得到之水溶液的一部分後,溶解於重水中,以400MHz之1
H-NMR測定的結果、乙烯胺單元之改質量為10莫耳%)。又,以B型黏度計測定之4%水溶液黏度為16mPa‧s(20℃)。
(P-8之合成)
除了將含有陽離子性基之單體的種類與添加量、聚合起始劑的使用量等聚合條件變更如表2所示以外,藉由與P-1相同之方法得到固形分濃度15%之PVA-(b)-乙烯基吡啶嵌段共聚物水溶液(乾燥所得到之水溶液的一部分後,溶解於重水中,以400MHz之1
H-NMR測定的結果,乙烯基吡啶單元的改質量為10莫耳%)。
(P-9之合成:P-8之四級化)
將P-8之水溶液倒入長270mm×寬210mm之壓克力製流延板,將過多的液體、氣泡去除後,藉由在50℃之加熱板上乾燥24小時來製作皮膜。將如此進行得到之皮膜於碘甲烷蒸氣中、在室溫下進行10小時處理、四級化乙烯基吡啶部分,得到PVA-(b)-四級化乙烯基吡啶嵌段共聚物之薄膜(將得到之薄膜溶解於重水中,以400MHz之1
H-NMR測定的結果,四級化乙烯基吡啶單元的改質量為10莫耳%)。
又,以B型黏度計測定濃度調整為4%之水溶液,黏度為16mPa‧s(20℃)。
(P-10之合成)
於配備有攪拌機、溫度感應器、滴液漏斗及迴流冷却管之6L可拆式燒瓶中混合乙酸乙烯酯2156g、甲醇644g、及含有25質量%之氯化甲基丙烯醯胺丙基三甲基銨的甲醇溶液126g,於攪拌下對系統內進行氮取代後,將內溫提升至60℃為止。對此系統添加20g含有0.8g之2,2’-偶氮雙異丁腈的甲醇,開始聚合反應。從聚合開始之時間點起,一邊添加含有25質量%之氯化甲基丙烯醯胺丙基三甲基銨物之甲醇溶液400g至系統內,一邊進行4小時的聚合反應後,停止聚合反應。於聚合反應停止的時間點,系統內之固形分濃度、亦即相對於聚合反應漿液整體之固形分的含有率係24質量%。接著,藉由將甲醇蒸氣導入系統內,將未反應之乙酸乙烯酯單體排除,得到含有55質量%乙烯酯共聚物之甲醇溶液。
對含有55質量%此乙烯酯共聚物之甲醇溶液,以相對於該共聚物中的乙酸乙烯酯單元,使氫氧化鈉的莫耳比成為0.025、乙烯酯共聚物之固形分濃度成為30質量%的方式,將甲醇及含有10質量%之氫氧化鈉之甲醇溶液以此順序於攪拌下加入,於40℃開始皂化反應。
在伴隨著皂化反應的進行生成膠凝化物後,緊接著將其自反應系統取出並粉碎,在從膠凝化物生成起經過1小時之時間點,藉由對此粉碎物添加乙酸甲酯以進行中和,得到膨潤狀態之聚(氯化乙烯醇-甲基丙烯醯胺丙基三甲基銨)的陽離子性聚合物。加入相對於此膨潤之陽離子性聚合物之質量基準的6倍量(浴比6倍)之甲醇,於迴流下洗淨1小時,濾取該聚合物。以65℃乾燥該聚合物16小時。將所得到之聚合物溶解於重水,以400MHz之1
H-NMR測定的結果,氯化甲基丙烯醯胺丙基三甲基銨單元之改質量為5莫耳%。又,以B型黏度計測定之4%水溶液黏度為18mPa‧s(20℃)、皂化度為98.5莫耳%。
(實施例1)
(離子交換膜之製作)
將P-1之水溶液倒入長270mm×寬210mm的壓克力製流延板,將過多的液體、氣泡去除後,藉由在50℃加熱板上乾燥24小時來製作皮膜。將如此進行得到之皮膜以140℃進行30分鐘熱處理,形成物理的交聯。接著,將皮膜浸漬於2mol/L之硫酸鈉的電解質水溶液24小時。以使該水溶液之pH成為1的方式加入濃硫酸後,將皮膜浸漬於0.05體積%戊二醛水溶液,於25℃使用攪拌子攪拌24小時進行交聯處理。此處,作為戊二醛水溶液係使用將石津製藥股份有限公司製的「戊二醛」(25體積%)以水稀釋而成者。交聯處理後將皮膜浸漬於去離子水中,途中更換數次去離子水,浸漬皮膜直到達成膨潤平衡,得到陰離子交換膜。
(離子交換膜之評價)
將如此進行製作而成的陰離子交換膜裁剪成所希望大小,製作成測定試料。使用所得到之測定試料以上述方法進行膜含水率、最大裂斷應力、陰離子交換容量、動態遷移數之測定、膜電阻之測定、耐有機汙染性之測定。所得到之結果示於表3。
(實施例2~13)
於實施例1中,除了使用嵌段共聚物(P)與聚乙烯醇PVA124(Kuraray(股)製)的混合比變更為如表3中所示之陰離子交換樹脂、熱處理溫度及交聯條件變更為表3中瑣事之內容以外,與實施例1同樣進行,製作陰離子交換膜、進行評價。所得到之結果示於表3。
(比較例1、3)
於實施例1中,除了陰離子交換樹脂、熱處理溫度、交聯條件變更為表3中所示之內容以外,與實施例1同樣進行,測定陰離子交換膜之膜性質。所得到之測定結果示於表3。
(比較例2)
於實施例1中,除了陰離子交換膜使用NEOSEPTA AM-1(苯乙烯-二乙烯苯系膜;TOKUYAMA(股)製)以外,與實施例1同樣進行,測定離子交換膜之膜性質。所得到之測定結果示於表3。
由表3的結果可知,藉由將乙烯醇系聚合物嵌段及具有陽離子性基之聚合物嵌段作為構成成分之嵌段共聚物、且施行交聯處理而成者作為陰離子交換膜,將膨潤抑制於低,且動態遷移數、膜電阻與耐有機汙染性優良(實施例1~13)。特別是在嵌段共聚物(P)與乙烯醇系聚合物(Q)之質量比(P/Q)為3/97以上的情形,可知得到良好的最大裂斷應力(實施例1~13)。又,於熱處理溫度為100℃以上之情形,可知膨潤度為良好的低(實施例1~5、實施例7~13)。進一步,離子交換容量為0.30meq/g以上即得到與市售離子交
換膜相同水準之動態遷移數,且可知膜電阻低(實施例1~7、9~10)。另一方面,未進行交聯處理則離子交換膜無法測定到顯著之膨潤的膜性質(比較例1)。進一步,疏水性高的市售離子交換膜係耐有機汙染性差(比較例2)。又,隨機共聚合陽離子性基而成之乙烯醇系聚合物係膜電阻高(比較例3)。
A...電源
B...安培計
C...庫侖計
D...伏特計
E...馬達
F...攪拌子
G...陰極電極
H...陽極電極
I...0.5M NaCl水溶液
J...離子交換膜(有效膜面積8.0cm2
)
K...離子交換膜(有效面積1.0cm2
)
L...白金電極
M...NaCl水溶液
N...水浴
O...L CR計
第1圖係可用於測定本發明之陰離子交換膜的動態遷移數之裝置的示意圖。
第2圖係可用於測定本發明之陰離子交換膜的膜電阻之裝置的示意圖。
Claims (13)
- 一種陰離子交換膜,其含有之主成分係將乙烯醇系聚合物嵌段(A)、及具有陽離子性基之聚合物嵌段(B)作為構成成分之嵌段共聚物(P)施行交聯處理而成者;其特徵在於該聚合物嵌段(B)係以下述一般式(3)作為重複單元:
- 如申請專利範圍第1項之陰離子交換膜,其中該聚合物嵌段(B)係進一步具有以下述一般式(2)表示之重複單元:
- 如申請專利範圍第1項之陰離子交換膜,其中該聚合物嵌段(B)係進一步具有以下述一般式(4)及/或(5)表示之重複單元:
- 如申請專利範圍第1項之陰離子交換膜,其中該聚合物嵌段(B)係進一步具有以下述一般式(6)及/或(7)表示之重複單元:
- 如申請專利範圍第1項之陰離子交換膜,其中離子交換容量係0.30meq/g以上。
- 一種陰離子交換膜,其含有之主成分係將乙烯醇系聚合物嵌段(A)及具有陽離子性基之聚合物嵌段(B)作為構成 成分之嵌段共聚物(P)、與聚合度200~8000、皂化度80莫耳%以上之乙烯醇系聚合物(Q)之混合物施行交聯處理而成者,其中嵌段共聚物(P)與乙烯醇系聚合物(Q)之質量比(P/Q)為3/97以上。
- 如申請專利範圍第6項之陰離子交換膜,其中該聚合物嵌段(B)係以下述一般式(2)作為重複單元:
- 如申請專利範圍第6項之陰離子交換膜,其中該聚合物嵌段(B)係以下述一般式(3)作為重複單元:
- 如申請專利範圍第6項之陰離子交換膜,其中該聚合物嵌段(B)係以下述一般式(4)及/或(5)作為重複單元:
- 如申請專利範圍第6項之陰離子交換膜,其中該聚合物嵌段(B)係以下述一般式(6)及/或(7)作為重複單元:
- 如申請專利範圍第6項之陰離子交換膜,其中陰離子交換容量係0.30meq/g以上。
- 一種如申請專利範圍第1至5項中任一項之陰離子交換膜之製造方法,其特徵在於將得自嵌段共聚物(P)之溶液的皮膜以100℃以上之溫度熱處理後,於水、醇或其混合溶劑中,於酸性條件下藉由二醛化合物進行交聯處理,接著進行水洗處理。
- 一種如申請專利範圍第6至11項中任一項之陰離子交換膜之製造方法,其特徵在於將得自嵌段共聚物(P)與乙烯醇系聚合物(Q)之混合物的溶液之皮膜以100℃以上之 溫度熱處理後,於水、醇或其混合溶劑中,於酸性條件下藉由二醛化合物進行交聯處理,接著進行水洗處理。
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US20120035280A1 (en) | 2012-02-09 |
US8716358B2 (en) | 2014-05-06 |
EP2412752A1 (en) | 2012-02-01 |
KR20120002595A (ko) | 2012-01-06 |
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US9321047B2 (en) | 2016-04-26 |
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