JP2021155580A - Anion exchange membrane and method for producing the same - Google Patents
Anion exchange membrane and method for producing the same Download PDFInfo
- Publication number
- JP2021155580A JP2021155580A JP2020057931A JP2020057931A JP2021155580A JP 2021155580 A JP2021155580 A JP 2021155580A JP 2020057931 A JP2020057931 A JP 2020057931A JP 2020057931 A JP2020057931 A JP 2020057931A JP 2021155580 A JP2021155580 A JP 2021155580A
- Authority
- JP
- Japan
- Prior art keywords
- anion exchange
- group
- exchange membrane
- polyolefin
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920000098 polyolefin Polymers 0.000 claims abstract description 58
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000002759 woven fabric Substances 0.000 claims abstract description 38
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 31
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 239000000806 elastomer Substances 0.000 claims abstract description 29
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 24
- 230000002378 acidificating effect Effects 0.000 claims abstract description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 91
- 239000000178 monomer Substances 0.000 claims description 63
- 238000005349 anion exchange Methods 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 36
- -1 polyethylene Polymers 0.000 claims description 22
- 239000004793 Polystyrene Substances 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000003505 polymerization initiator Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 229920001577 copolymer Polymers 0.000 description 21
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- 229920005989 resin Polymers 0.000 description 18
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
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- 239000012528 membrane Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 9
- 239000003014 ion exchange membrane Substances 0.000 description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
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- 239000004700 high-density polyethylene Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
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- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
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- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 4
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- 229920000915 polyvinyl chloride Polymers 0.000 description 4
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- 150000003440 styrenes Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229920000428 triblock copolymer Polymers 0.000 description 4
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical group C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical group CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JXCAHDJDIAQCJO-UHFFFAOYSA-N (1-tert-butylperoxy-2-ethylhexyl) hydrogen carbonate Chemical compound CCCCC(CC)C(OC(O)=O)OOC(C)(C)C JXCAHDJDIAQCJO-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
- OTMBZPVYOQYPBE-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclododecane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCCCCCCCC1 OTMBZPVYOQYPBE-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- XIRPMPKSZHNMST-UHFFFAOYSA-N 1-ethenyl-2-phenylbenzene Chemical group C=CC1=CC=CC=C1C1=CC=CC=C1 XIRPMPKSZHNMST-UHFFFAOYSA-N 0.000 description 1
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
- FCMUPMSEVHVOSE-UHFFFAOYSA-N 2,3-bis(ethenyl)pyridine Chemical compound C=CC1=CC=CN=C1C=C FCMUPMSEVHVOSE-UHFFFAOYSA-N 0.000 description 1
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
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- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 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
- 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Description
本発明は、アニオン交換膜及びその製造方法に関するものである。 The present invention relates to an anion exchange membrane and a method for producing the same.
アニオン交換膜は、アニオン交換樹脂を特定の基材に保持させた構造を有している。アニオン交換樹脂単独で膜を形成した場合には、強度が低く、また、液中に浸漬して使用する際に生じる膨潤による形態変化が大きいため、実用に適さない。このため、所定の強度を有し、膨潤による形態変化がなく、しかもアニオン交換樹脂に特有のアニオン交換能を損なわない基材に対し、アニオン交換樹脂を保持させたものがアニオン交換膜として使用される。 The anion exchange membrane has a structure in which an anion exchange resin is held on a specific base material. When the film is formed by the anion exchange resin alone, the strength is low and the morphological change due to swelling that occurs when the anion exchange resin is immersed in the liquid is large, so that it is not suitable for practical use. Therefore, a substrate having an anion exchange resin retained on a base material having a predetermined strength, not changing its morphology due to swelling, and not impairing the anion exchange ability peculiar to the anion exchange resin is used as an anion exchange membrane. NS.
上記のようなアニオン交換膜において、従来は、基材としてポリ塩化ビニル製の織布が広く使用されていたが、ポリ塩化ビニルを基材とするアニオン交換膜は耐熱性や耐薬品性が低いという欠点がある。そこで、最近では、ポリエチレンやポリプロピレンなどのポリオレフィンを基材とするアニオン交換膜が広く検討されている。 In the above-mentioned anion exchange membranes, conventionally, a woven fabric made of polyvinyl chloride has been widely used as a base material, but an anion exchange membrane based on polyvinyl chloride has low heat resistance and chemical resistance. There is a drawback. Therefore, recently, an anion exchange membrane based on a polyolefin such as polyethylene or polypropylene has been widely studied.
ところで、ポリオレフィンを基材とするアニオン交換膜は、ポリ塩化ビニルを基材とするものに比して耐熱性や耐薬品が極めて高いのであるが、該ポリオレフィン基材とアニオン交換樹脂との接着性に乏しい。これに伴い、膨潤や乾燥（収縮）が繰り返されたときにアニオン交換樹脂と基材との剥離を生じ易く、その結果、隔膜としての機能低下を生じてしまい、透水性が悪化し、電流効率が低下してしまうという問題がある。さらには、ポリオレフィン基材とアニオン交換樹脂との接着性の低さは、当然、耐久性の低さにも通じている。 By the way, the anion exchange membrane based on polyolefin has extremely high heat resistance and chemical resistance as compared with the one using polyvinyl chloride as a base material, but the adhesiveness between the polyolefin base material and the anion exchange resin is extremely high. Is scarce. Along with this, when swelling and drying (shrinkage) are repeated, peeling of the anion exchange resin and the base material is likely to occur, and as a result, the function as a diaphragm is deteriorated, the water permeability is deteriorated, and the current efficiency is deteriorated. There is a problem that is reduced. Furthermore, the low adhesiveness between the polyolefin base material and the anion exchange resin naturally leads to the low durability.
ポリオレフィン基材とアニオン交換樹脂との接着性を向上するための手段としては、ポリオレフィン基材表面を電子線照射やコロナ処理する手法が通常考えられるが、かかる手法は装置が大がかりなものとなってしまうばかりか、ポリオレフィン基材の強度を損なうという問題があるため、実用化が困難である。また、ポリオレフィン基材にアニオン交換樹脂の前駆体であるモノマーを塗布して重合させる際に、重合温度をポリオレフィンの融点より少し高くすることによりポリオレフィンの一部を溶融させてイオン交換樹脂との密着性を高めることも行われているが、ポリオレフィン基材の強度が低下するため、あらかじめ基材厚みを大きくすることが行われているが、イオン交換膜の電気抵抗が大きくなってしまい、時間経過とともに密着性も低下してしまう。このため、種々の接着性向上手段が提案されている。 As a means for improving the adhesiveness between the polyolefin base material and the anion exchange resin, a method of irradiating the surface of the polyolefin base material with an electron beam or corona treatment is usually considered, but such a method requires a large-scale device. Not only that, there is a problem that the strength of the polyolefin base material is impaired, so that it is difficult to put it into practical use. Further, when a monomer which is a precursor of an anion exchange resin is applied to a polyolefin base material and polymerized, a part of the polyolefin is melted by raising the polymerization temperature slightly higher than the melting point of the polyolefin to adhere to the ion exchange resin. Although the properties have been improved, the thickness of the base material has been increased in advance because the strength of the polyolefin base material decreases, but the electrical resistance of the ion exchange film increases and the time elapses. At the same time, the adhesion is also reduced. Therefore, various means for improving adhesiveness have been proposed.
例えば、特許文献１には、アニオン交換樹脂形成用の重合組成物の粘度を上げるために、含有されるモノマーに可溶性の種々の線状高分子化合物を配合することが記載されている（００１６段落）。ここで示されている線状高分子化合物の中で、スチレン-ブタジエン共重合体、スチレン-エチレン-ブチレン共重合体、スチレン-エチレン-プロピレン共重合体、スチレン-イソプレン共重合体等のいわゆるスチレン系熱可塑性樹脂エラストマーは、アニオン交換基が導入されず、かつ基材の素材樹脂との親和性を有する性状を有しており、各種樹脂基材との密着性をかなり向上させるものである。特にこれらスチレン系熱可塑性樹脂エラストマーは、前記例示のように、スチレンと、ブタジエンやイソプレン等の共役ジオレフィンとの共重合体が汎用的であるところ、これらに存在する不飽和結合は化学的安定性を低下させるため、これを水素添加処理により消失させた共重合体は、前記基材との接着性の向上効果に一層優れていることが知られている（特許文献２）。 For example, Patent Document 1 describes that various soluble linear polymer compounds are blended with the monomer contained in order to increase the viscosity of the polymerization composition for forming an anion exchange resin (paragraph 0016). ). Among the linear polymer compounds shown here, so-called styrenes such as styrene-butadiene copolymers, styrene-ethylene-butylene copolymers, styrene-ethylene-propylene copolymers, and styrene-isoprene copolymers. The based thermoplastic resin elastomer has a property that an anion exchange group is not introduced and has an affinity with the material resin of the base material, and the adhesion with various resin base materials is considerably improved. In particular, as described above, these styrene-based thermoplastic resin elastomers are generally copolymerized with a copolymer of styrene and a conjugated diolefin such as butadiene or isoprene, and the unsaturated bonds present in these are chemically stable. It is known that a copolymer obtained by eliminating this by hydrogenation treatment is more excellent in the effect of improving the adhesiveness with the base material in order to reduce the property (Patent Document 2).
しかしながら、前記スチレン系熱可塑性樹脂エラストマーは、たとえ特許文献２の水素添加体を用いても、前記基材がポリオレフィン製である場合には、その接着性向上効果は十分ではなく、基材とアニオン交換樹脂との間の隙間の形成を実用上満足できるだけ高度に防止することができなかった。特に低抵抗や高選択性が求められる電気透析に好適なアニオン交換膜においては、高いアニオン交換基密度が必要となる。この場合アニオン交換樹脂がより極性が高くより膨潤が大きくなるため、更にポリオレフィン基材との密着性が悪化する。従って、得られるアニオン交換膜は透水度が十分でなく、特には、アニオン交換樹脂が膨潤・収縮を過度に繰り返すと、前記基材とアニオン交換樹脂との間の隙間が増大し、該透水度は顕著に悪化し、結果として電流効率も低くなる問題があった。 However, even if the hydrogenated material of Patent Document 2 is used, the styrene-based thermoplastic resin elastomer does not have a sufficient effect of improving the adhesiveness when the base material is made of polyolefin, and the base material and the anion are not sufficient. The formation of a gap between the exchange resin and the resin could not be prevented as highly as practically satisfactory. In particular, an anion exchange membrane suitable for electrodialysis, which requires low resistance and high selectivity, requires a high density of anion exchange groups. In this case, the anion exchange resin has a higher polarity and a larger swelling, so that the adhesion to the polyolefin base material is further deteriorated. Therefore, the obtained anion exchange membrane does not have sufficient water permeability. In particular, when the anion exchange resin repeatedly expands and contracts, the gap between the base material and the anion exchange resin increases, and the water permeability increases. Has a problem that the current efficiency is lowered as a result.
本発明は、かかる点に鑑みてなされたものであり、その目的とするところは、ポリオレフィン系織布とアニオン交換樹脂との密着性が高いアニオン交換膜を提供することにある。 The present invention has been made in view of the above points, and an object of the present invention is to provide an anion exchange membrane having high adhesion between a polyolefin-based woven fabric and an anion exchange resin.
本発明のアニオン交換膜は、ポリオレフィン系基材と、アニオン交換樹脂とを備えたアニオン交換膜であって、さらに酸性基または酸無水物基により変性されたスチレン系熱可塑性樹脂エラストマーが含有されている構成を有している。 The anion exchange membrane of the present invention is an anion exchange membrane provided with a polyolefin-based substrate and an anion exchange resin, and further contains a styrene-based thermoplastic resin elastomer modified with an acidic group or an acid anhydride group. Has a configuration that
前記酸性基はカルボキシ基であることが好ましく、酸無水物基はカルボン酸無水物基であることが好ましい。 The acidic group is preferably a carboxy group, and the acid anhydride group is preferably a carboxylic acid anhydride group.
前記酸性基または酸無水物基により変性された前記スチレン系熱可塑性樹脂エラストマーは、ポリスチレン−ポリ共役ジオレフィン−ポリスチレン共重合体又はその水素添加物の前記酸性基また前記は酸無水物基による変性体であってもよく、さらに、前記ポリスチレン−ポリ共役ジオレフィン−ポリスチレン共重合体はポリスチレン−ポリブタジエン−ポリスチレン共重合体であってもよい。 The styrene-based thermoplastic resin elastomer modified with the acidic group or the acid anhydride group is modified with the acidic group or the acid anhydride group of the polystyrene-polyconjugated diolefin-polystyrene copolymer or its hydrogenated product. It may be a body, and further, the polystyrene-polyconjugate diolefin-polystyrene copolymer may be a polystyrene-polybutadiene-polystyrene copolymer.
前記ポリオレフィン系基材はポリエチレン系織布であってもよく、さらに、前記ポリエチレン系織布はポリエチレンのモノフィラメント織布であってもよい。 The polyolefin-based base material may be a polyethylene-based woven fabric, and the polyethylene-based woven fabric may be a polyethylene monofilament woven fabric.
本発明のアニオン交換膜の製造方法は、アニオン交換基を導入可能な官能基又はアニオン交換基を有する単量体と架橋性単量体とを含む単量体成分、及び重合開始剤を含有するアニオン交換樹脂形成用の重合性組成物に酸性基または酸無水物基により変性されたスチレン系熱可塑性樹脂エラストマーを加えて、ポリオレフィン系基材に浸漬させる浸漬工程と、前記浸漬工程の後に、前記単量体成分を共重合させる工程とを含む構成を有している。ここで、前記ポリオレフィン系基材はポリエチレン系織布であってもよい。また、アニオン交換基を導入可能な官能基又はアニオン交換基を有する前記単量体は、アニオン交換基を導入可能な官能基又はアニオン交換基を有するスチレン系単量体であってもよい。 The method for producing an anion exchange film of the present invention contains a monomer component containing a functional group into which an anion exchange group can be introduced or a monomer having an anion exchange group and a crosslinkable monomer, and a polymerization initiator. A styrene-based thermoplastic resin elastomer modified with an acidic group or an acid anhydride group is added to a polymerizable composition for forming an anion-exchange resin, and the mixture is immersed in a polyolefin-based substrate. It has a structure including a step of copolymerizing a monomer component. Here, the polyolefin-based base material may be a polyethylene-based woven fabric. Further, the monomer having a functional group into which an anion-exchange group can be introduced or an anion-exchange group may be a styrene-based monomer having a functional group into which an anion-exchange group can be introduced or an anion-exchange group.
本発明に係るアニオン交換膜は、酸性基または酸無水物基により変性されたスチレン系熱可塑性樹脂エラストマーが含有されているので、それによってアニオン交換樹脂とポリオレフィン系基材との密着性が高度に向上する。 Since the anion exchange film according to the present invention contains a styrene-based thermoplastic resin elastomer modified with an acidic group or an acid anhydride group, the adhesion between the anion exchange resin and the polyolefin-based base material is highly improved. improves.
以下、本発明の実施形態を詳細に説明する。以下の好ましい実施形態の説明は、本質的に例示に過ぎず、本発明、その適用物或いはその用途を制限することを意図するものではない。 Hereinafter, embodiments of the present invention will be described in detail. The following description of preferred embodiments is merely exemplary and is not intended to limit the invention, its applications or its uses.
背景技術及び発明が解決しようとする課題の欄で述べたように、安価なポリオレフィン系織布を基材とするアニオン交換膜を製造する場合、アニオン交換膜の強度を高く保ち、電気抵抗は低くし、さらにポリオレフィン系織布とアニオン交換樹脂との密着性を十分に大きくすることは困難であるところ、本願発明者らは様々な検討を行って、本願発明に想到するに至った。 As described in the column of background techniques and problems to be solved by the invention, when producing an anion exchange membrane based on an inexpensive polyolefin-based woven fabric, the strength of the anion exchange membrane is kept high and the electrical resistance is low. However, since it is difficult to sufficiently increase the adhesion between the polyolefin-based woven fabric and the anion exchange resin, the inventors of the present application have conducted various studies and came up with the invention of the present application.
（実施形態１）
実施形態１に係るアニオン交換膜は、ポリオレフィン系織布からなる基材と、アニオン交換基として４級アンモニウム基を有するアニオン交換樹脂とを備えたアニオン交換膜であって、基材以外の部分には、酸性基または酸無水物基により変性されたスチレン系熱可塑性樹脂エラストマーが含有されている構成を有している。
(Embodiment 1)
The anion exchange film according to the first embodiment is an anion exchange film comprising a base material made of a polyolefin-based woven fabric and an anion exchange resin having a quaternary ammonium group as an anion exchange group, and is formed on a portion other than the base material. Has a structure containing a styrene-based thermoplastic resin elastomer modified with an acidic group or an acid anhydride group.
＜ポリオレフィン系織布＞
ポリオレフィンとしては、エチレン、プロピレン、１−ブテン、４−メチル−１−ペンテン等のα−オレフィンの単独重合体またはこれらのランダムあるいはブロック共重合体が挙げられる。具体的には、低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、ポリ１−ブテン、ポリ４−メチル−１−ペンテンが挙げられる。中でも、低密度ポリエチレン、高密度ポリエチレン、ポリプロピレンが好ましく、入手の容易さやアニオン交換樹脂との親和性の点から低密度ポリエチレンや高密度ポリエチレンなどのポリエチレン系重合体が最も好ましい。
<Polyolefin-based woven fabric>
Examples of the polyolefin include homopolymers of α-olefins such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and random or block copolymers thereof. Specific examples thereof include low-density polyethylene, high-density polyethylene, polypropylene, poly1-butene, and poly4-methyl-1-pentene. Among them, low-density polyethylene, high-density polyethylene, and polypropylene are preferable, and polyethylene-based polymers such as low-density polyethylene and high-density polyethylene are most preferable from the viewpoint of easy availability and affinity with anion exchange resin.
ポリオレフィン系基材は、織布、不織布、多孔質フィルム等任意の形態を有するものであってよいが、強度の観点から織布が好ましい。織布の開口率は２０％以上７０％以下が好ましく、３５％以上５５％以下がさらに好ましい。織布の単糸は、マルチフィラメントとモノフィラメントのいずれでも使用することができるが、モノフィラメントの方が密着性の観点から好ましい。また、用途に応じて適宜選択すれば良いが、強度と膜抵抗をバランスさせる点で、ポリオレフィン系織布の厚さは６０μｍ以上１９０μｍ以下が好ましく、単糸の線径は１〜７０デニール（１０〜１００μｍ）が好ましい。 The polyolefin-based base material may have any form such as a woven fabric, a non-woven fabric, and a porous film, but a woven fabric is preferable from the viewpoint of strength. The opening ratio of the woven fabric is preferably 20% or more and 70% or less, and more preferably 35% or more and 55% or less. The single yarn of the woven fabric can be either multifilament or monofilament, but monofilament is preferable from the viewpoint of adhesion. The thickness of the polyolefin woven fabric is preferably 60 μm or more and 190 μm or less, and the wire diameter of the single yarn is 1 to 70 denier (10) from the viewpoint of balancing the strength and the film resistance. ~ 100 μm) is preferable.
＜酸性基または酸無水物基により変性されたスチレン系熱可塑性樹脂エラストマー＞
スチレン系熱可塑性樹脂エラストマーは、脂肪族炭化水素系単量体から導かれる単量体単位とスチレン系単量体単位との共重合物からなる熱可塑性の弾性樹脂である。 その弾性樹脂はＩＳＯ５２７に従い測定した引張弾性率が０．０１ＭＰa以上、より好適には０．１ＭＰa以上１０００ＭＰa以下のものが好ましい。
<Styrene-based thermoplastic resin elastomer modified with an acidic group or an acid anhydride group>
The styrene-based thermoplastic resin elastomer is a thermoplastic elastic resin composed of a copolymer of a monomer unit derived from an aliphatic hydrocarbon-based monomer and a styrene-based monomer unit. The elastic resin preferably has a tensile elastic modulus of 0.01 MPa or more, more preferably 0.1 MPa or more and 1000 MPa or less as measured according to ISO527.
これらスチレン系熱可塑性樹脂エラストマーは、スチレン系単量体単位部分がアニオン交換樹脂（特にポリスチレン系のアニオン交換樹脂）との親和性が高く、脂肪族炭化水素系単量体単位部分がポリオレフィン系基材との親和性が高いため、アニオン交換樹脂とポリオレフィン系基材との密着性を向上させる働きがある。 In these styrene-based thermoplastic resin elastomers, the styrene-based monomer unit portion has a high affinity with the anion exchange resin (particularly polystyrene-based anion exchange resin), and the aliphatic hydrocarbon-based monomer unit portion is a polyolefin-based group. Since it has a high affinity with the material, it has a function of improving the adhesion between the anion exchange resin and the polyolefin-based base material.
こうしたスチレン系熱可塑性樹脂エラストマーは、スチレン−エチレン−ブチレン共重合体、スチレン−エチレン−プロピレン共重合体等であって良いが、通常は、重合のし易さ等から、スチレンと、ブタジエンやイソプレン等の共役ジオレフィンとの共重合体が好ましく用いられる。これらはスチレンと共役ジオレフィンとの共重合体には、前記共役ジオレフィンに起因して不飽和結合が存在するところ、これがアニオン交換膜に残存すると化学的安定性を低下させ、引いてはアニオン交換樹脂とポリオレフィン系基材との密着性も低下させる。従って、スチレン系熱可塑性樹脂エラストマーは、共重合体を構成した状態において、上記脂肪族炭化水素系単量体単位中に不飽和結合を有さないものが好ましい。具体的には、前記スチレンと共役ジオレフィンとの共重合体であれば、水素添加処理して不飽和結合を消失させたものが好ましい。なお、斯様に水素添加処理する場合においても、共重合体には若干の不飽和結合が残存しても良い。通常、こうした残存する不飽和結合の数は、水素添加処理を行う前の全不飽和結合の数に対して１０％以内好ましくは５％以内とするのが望ましい。 Such a styrene-based thermoplastic resin elastomer may be a styrene-ethylene-butylene copolymer, a styrene-ethylene-propylene copolymer, or the like, but usually, styrene and butadiene or isoprene are used because of ease of polymerization and the like. A copolymer with a conjugated diolefin such as the above is preferably used. These are the copolymers of styrene and conjugated diolefins, which have unsaturated bonds due to the conjugated diolefins, and if they remain on the anion exchange membrane, they reduce the chemical stability, which in turn reduces the anion. It also reduces the adhesion between the exchange resin and the polyolefin-based substrate. Therefore, it is preferable that the styrene-based thermoplastic resin elastomer does not have an unsaturated bond in the above-mentioned aliphatic hydrocarbon-based monomer unit in the state of forming the copolymer. Specifically, in the case of a copolymer of the styrene and the conjugated diolefin, a copolymer in which the unsaturated bond is eliminated by hydrogenation treatment is preferable. Even in the case of such hydrogenation treatment, some unsaturated bonds may remain in the copolymer. Generally, the number of such residual unsaturated bonds is preferably within 10% and preferably within 5% of the number of total unsaturated bonds before the hydrogenation treatment.
上記脂肪族炭化水素系単量体単位とスチレン系単量体単位との共重合体において、各構成単位の含有量は、特に制限されるものではないが、アニオン交換基の導入に適した官能基を有する単量体との相溶性や得られる共重合体の柔軟性等を勘案すれば、スチレン系単量体単位が共重合体の全質量に対して１０〜８０質量％とするのが好ましい。脂肪族炭化水素系単量体単位は、共重合体の全質量に対して９０〜２０質量％とするのが好ましい。 In the above-mentioned copolymer of the aliphatic hydrocarbon-based monomer unit and the styrene-based monomer unit, the content of each structural unit is not particularly limited, but is a functional suitable for introducing an anion exchange group. Considering the compatibility with the monomer having a group and the flexibility of the obtained copolymer, the styrene-based monomer unit should be 10 to 80% by mass based on the total mass of the copolymer. preferable. The aliphatic hydrocarbon-based monomer unit is preferably 90 to 20% by mass with respect to the total mass of the copolymer.
脂肪族炭化水素系単量体単位は前記共役ジオレフィンが用いられるのが一般的であるが、水素添加処理後の共役ジオレフィンと同一化学構造を持つエチレン、プロピレン、ブチレン、ペンテン等のエチレン性不飽和二重結合を有する肪族炭化水素系単量体を用いても良い。前記共役ジオレフィンを用いる場合において、その一部をエチレン、プロピレン等のエチレン性不飽和二重結合を有する肪族炭化水素系単量体としても良く、その好適な含有量は、共役ジオレフィンの１００質量部に対して３０質量部％以下、より好適には１０質量部以下である。 The conjugated diolefin is generally used as the aliphatic hydrocarbon-based monomer unit, but it is ethylenically such as ethylene, propylene, butylene, and penten having the same chemical structure as the conjugated diolefin after the hydrogenation treatment. A aliphatic hydrocarbon-based monomer having an unsaturated double bond may be used. When the conjugated diolefin is used, a part thereof may be a aliphatic hydrocarbon-based monomer having an ethylenically unsaturated double bond such as ethylene or propylene, and a suitable content thereof is the conjugated diolefin. It is 30 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass.
共重合体の分子量は、特に制限されるものではないが、通常、１，０００〜１，０００，０００好ましくは５０，０００〜５００，０００の範囲とするのが好適である。 The molecular weight of the copolymer is not particularly limited, but is usually preferably in the range of 1,000 to 1,000,000, preferably 50,000 to 500,000.
共重合の形態としては、いわゆるＡ−Ｂ型のジブロックタイプ、Ａ−Ｂ−Ａ型のトリブロックタイプ、またはランダムタイプなど如何なるものであっても良い。前記スチレン系単量ブタジエン、イソプレン等の共役ジオレフィン体単位部分のアニオン交換樹脂との親和性向上効果、及び脂肪族炭化水素系単量体単位部分のポリオレフィン系基材との親和性向上効果をより高く発揮させるためには、スチレン系単量体単位Ａと脂肪族炭化水素系単量体単位Ｂとのブロックタイプであるのが好ましく、特に、Ａ−Ｂ−Ａ型のトリブロックタイプが好ましい。 The form of copolymerization may be any form such as a so-called AB type diblock type, an ABA type triblock type, or a random type. The effect of improving the affinity of the conjugated diolefin unit portion such as styrene-based single-quantity butadiene and isoprene with the anion exchange resin, and the effect of improving the affinity of the aliphatic hydrocarbon-based monomer unit portion with the polyolefin-based substrate. In order to exert higher performance, it is preferable to use a block type of a styrene-based monomer unit A and an aliphatic hydrocarbon-based monomer unit B, and in particular, an ABA type triblock type is preferable. ..
以上から本発明において、特に好ましいスチレン系熱可塑性樹脂エラストマーは、ポリスチレン−（ポリ共役ジオレフィン）−ポリスチレン共重合体であり、最も好ましいのはその水素添加物である。 From the above, in the present invention, a particularly preferable styrene-based thermoplastic resin elastomer is a polystyrene- (polyconjugate diolefin) -polystyrene copolymer, and the most preferable is a hydrogenated product thereof.
本願発明者らはこのスチレン系熱可塑性樹脂エラストマーに関して種々検討を行った結果、酸性基または酸無水物基により変性を行うことで、さらにアニオン交換樹脂とポリオレフィン系基材との密着性を向上させることができることを見出した。即ち、酸性基を導入したポリマーはカチオン交換機能を有している。他方、酸無水物基も水の存在下で容易に加水分解するため、該酸無水物基を導入したポリマーを、イオン交換膜の製造環境や使用環境におくと、これは上記酸性基に変換され、係るポリマーはカチオン交換機能を有するものになる。従って、このようなポリマーをアニオン交換樹脂に添加するとアニオン交換機能が低下する危惧もある。このような理由で酸性基を導入したポリマーをアニオン交換樹脂に添加してアニオン交換膜を作成しようとは通常は考えない。 As a result of various studies on this styrene-based thermoplastic resin elastomer, the inventors of the present application further improve the adhesion between the anion exchange resin and the polyolefin-based base material by modifying it with an acidic group or an acid anhydride group. I found that I could do it. That is, the polymer into which an acidic group has been introduced has a cation exchange function. On the other hand, since the acid anhydride group is also easily hydrolyzed in the presence of water, when the polymer into which the acid anhydride group is introduced is placed in the production environment or use environment of the ion exchange membrane, it is converted into the above acidic group. The polymer will have a cation exchange function. Therefore, when such a polymer is added to the anion exchange resin, there is a concern that the anion exchange function may be deteriorated. For this reason, it is usually not considered to add an acidic group-introduced polymer to an anion exchange resin to form an anion exchange membrane.
しかしながら本願発明者らが検討を行ったところ、たとえ酸性基や酸無水物基を有していたとしても、分子量の大きいポリマーの形態であれば、アニオン交換の機能はさほど低下せずにアニオン交換樹脂とポリオレフィン系基材との密着性が向上することを見出したのである。酸性基はスルホ基やホスホ基、カルボキシ基など特に限定されないが、カルボキシ基が好ましい。他方、酸無水物基は、上記カルボキシ基を無水物化した基が好ましく、具体的には、環状酸無水物基であれば、無水マレイン酸基、無水フタル酸基、無水コハク酸基、無水グルタル酸基等が挙げられ、非環状酸無水物基であれば、無水酢酸基、無水プロピオン酸基、無水安息香酸基等が挙げられる。最も好ましい変成させる基は無水マレイン酸基である。スチレン系熱可塑性樹脂エラストマーに対する、酸性基または酸無水物基の変性量は、特に制限されるものではないが、重合体に対して０．１〜２０質量％、好ましくは、０．２〜１０質量％、さらに好ましくは、０．２〜５重量％が望ましい。 However, as a result of studies by the inventors of the present application, even if it has an acidic group or an acid anhydride group, if it is in the form of a polymer having a large molecular weight, the anion exchange function is not significantly reduced and the anion exchange is performed. They found that the adhesion between the resin and the polyolefin-based base material was improved. The acidic group is not particularly limited, such as a sulfo group, a phospho group, and a carboxy group, but a carboxy group is preferable. On the other hand, the acid anhydride group is preferably an anhydrideized group of the above carboxy group. Specifically, if it is a cyclic acid anhydride group, it is a maleic anhydride group, a phthalic anhydride group, a succinic anhydride group, or a glutal anhydride. Acid groups and the like can be mentioned, and examples of the acyclic acid anhydride group include an acetate group anhydride, a propionic anhydride group, a benzoic anhydride group and the like. The most preferred modifying group is a maleic anhydride group. The amount of modification of the acidic group or acid anhydride group with respect to the styrene-based thermoplastic resin elastomer is not particularly limited, but is 0.1 to 20% by mass, preferably 0.2 to 10% by mass with respect to the polymer. It is preferably by mass, more preferably 0.2 to 5% by mass.
環状酸無水物基は、例えば、無水マレイン酸基、無水フタル酸基、無水コハク酸基、無水グルタル酸基が挙げられ、非環状酸無水物基は、例えば、無水酢酸基、無水プロピオン酸基、無水安息香酸基が挙げられる。 Examples of the cyclic acid anhydride group include a maleic anhydride group, a phthalic anhydride group, a succinic anhydride group, and a glutaric anhydride group. Examples of the non-cyclic acid anhydride group include an acetic anhydride group and a propionic anhydride group. , Anhydrous benzoic acid group.
変性したスチレン系熱可塑性樹脂エラストマーは未変性のものと比べ極性が高くイオン交換樹脂との密着性が向上すると考えられるが、酸変性の場合は酸性基がアニオン交換基と強く相互作用するため、密着性が特に大きく向上する。 The modified styrene-based thermoplastic resin elastomer has a higher polarity than the unmodified one and is considered to improve the adhesion to the ion exchange resin. However, in the case of acid modification, the acidic group strongly interacts with the anion exchange group. Adhesion is particularly greatly improved.
ここで、前記変性されたスチレン系熱可塑性樹脂エラストマーの配合量は、特に制限されるものではないが、後述するアニオン交換樹脂形成用の重合性組成物に含まれる単量体成分１００質量部に対して０．５質量部以上５０質量部以下であるのが好ましい。０．５質量部よりも少ないと密着性の向上効果が不十分なおそれがあり、５０質量部を超えるとアニオン交換の機能が低下してしまうおそれがある。配合量は３質量部以上３０質量部以下であることがより好ましい。 Here, the blending amount of the modified styrene-based thermoplastic resin elastomer is not particularly limited, but is 100 parts by mass of the monomer component contained in the polymerizable composition for forming an anion exchange resin described later. On the other hand, it is preferably 0.5 parts by mass or more and 50 parts by mass or less. If it is less than 0.5 parts by mass, the effect of improving the adhesion may be insufficient, and if it exceeds 50 parts by mass, the function of anion exchange may be deteriorated. The blending amount is more preferably 3 parts by mass or more and 30 parts by mass or less.
＜アニオン交換樹脂＞
アニオン交換膜を形成するアニオン交換樹脂は、それ自体公知のもの、例えば、骨格を形成する樹脂にアニオン交換基が導入されたものである。骨格を形成する樹脂としては、例えば、ビニル系、スチレン系、アクリル系等のエチレン系不飽和二重結合を有する単量体を重合して得られるポリマー及びその共重合ポリマー、並びに、ポリスルホン、ポリフェニレンスルフィド、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリエーテルイミド、ポリフェニレンオキサイド、ポリエーテルスルホン、ポリベンズイミダゾールなどの主鎖に芳香環を含有するポリマーなどの炭化水素系の樹脂が挙げられる。その中でも骨格を形成する樹脂としてスチレン系の単量体を主としたスチレン系アニオン交換樹脂が好ましい。
<Anion exchange resin>
The anion exchange resin that forms the anion exchange membrane is a resin that is known per se, for example, a resin that forms a skeleton with an anion exchange group introduced therein. Examples of the resin forming the skeleton include a polymer obtained by polymerizing a monomer having an ethylene-based unsaturated double bond such as vinyl-based, styrene-based, and acrylic-based, a copolymer polymer thereof, and polysulfone and polyphenylene. Examples thereof include hydrocarbon-based resins such as polymers containing an aromatic ring in the main chain such as sulfide, polyether ketone, polyether ether ketone, polyetherimide, polyphenylene oxide, polyethersulfone, and polybenzimidazole. Among them, a styrene-based anion exchange resin mainly composed of a styrene-based monomer is preferable as the resin forming the skeleton.
また、アニオン交換基は、水溶液中で正の電荷となり得る反応基なら特に制限されるものではない。例えば、アニオン交換基としては、１〜３級アミノ基、４級アンモニウム基、ピリジル基、イミダゾール基、４級ピリジニウム基等が挙げられ、一般的に、強塩基性基である４級アンモニウム基や４級ピリジニウム基が好適である。 Further, the anion exchange group is not particularly limited as long as it is a reactive group that can be positively charged in an aqueous solution. For example, examples of the anion exchange group include a 1-3-amino group, a quaternary ammonium group, a pyridyl group, an imidazole group, a quaternary pyridinium group and the like, and generally, a quaternary ammonium group which is a strongly basic group and a quaternary ammonium group and the like. A quaternary pyridinium group is suitable.
＜アニオン交換膜の製造＞
本実施形態に係るアニオン交換膜は、以下のように製造される。
<Manufacturing of anion exchange membrane>
The anion exchange membrane according to this embodiment is manufactured as follows.
アニオン交換基を有する単量体、架橋性単量体、重合開始剤等のアニオン交換樹脂形成用重合硬化性成分と酸性基により変性されたスチレン系熱可塑性樹脂エラストマーとを混合して重合性組成物を調整する。かかる重合性組成物を、基材であるポリオレフィン系織布に浸漬させて当該織布の空隙に充填せしめた後、重合性組成物を重合硬化せしめてアニオン交換樹脂を生成する。これにより、目的とする基材アニオン交換膜を得ることができる。 Polymerizable composition by mixing a polymerization curable component for forming an anion exchange resin such as a monomer having an anion exchange group, a crosslinkable monomer, and a polymerization initiator with a styrene-based thermoplastic resin elastomer modified with an acidic group. Adjust things. The polymerizable composition is dipped in a polyolefin-based woven fabric as a base material to fill the voids of the woven fabric, and then the polymerizable composition is polymerized and cured to produce an anion exchange resin. Thereby, the target base material anion exchange membrane can be obtained.
重合硬化温度は、基材の強度を低下させないようにポリオレフィン系織布の融点を下回る温度に設定される。ポリオレフィンや重合硬化性成分の種類、重合硬化時間にもよるが、重合硬化温度の上限は、基材を構成するポリオレフィンの融点よりも２０℃以上低い温度とすることが好ましい。具体的には、重合硬化温度は４０℃以上１２０℃未満が好ましく、より好ましくは５０℃以上１００℃未満である。過度に低温で重合をおこなうと、モノマーの重合が充分に進行せず未重合分が増加し、溶出するために空隙が生じ、電流効率の低下や透水量の増加につながる虞がある。一方、過度に高温にすると、ポリオレフィンの融点を超えることで、ポリオレフィン系樹脂製基材の強度が低下する虞がある。 The polymerization curing temperature is set to a temperature lower than the melting point of the polyolefin-based woven fabric so as not to reduce the strength of the base material. Although it depends on the type of polyolefin and the polymerization curable component and the polymerization curing time, the upper limit of the polymerization curing temperature is preferably 20 ° C. or more lower than the melting point of the polyolefin constituting the base material. Specifically, the polymerization curing temperature is preferably 40 ° C. or higher and lower than 120 ° C., more preferably 50 ° C. or higher and lower than 100 ° C. If the polymerization is carried out at an excessively low temperature, the polymerization of the monomer does not proceed sufficiently and the unpolymerized content increases, and voids are generated due to elution, which may lead to a decrease in current efficiency and an increase in water permeability. On the other hand, if the temperature is excessively high, the melting point of the polyolefin may be exceeded, and the strength of the polyolefin-based resin base material may decrease.
重合硬化性成分におけるアニオン交換基を有する単量体は、アニオン交換樹脂を製造するために従来から使用されているもので良い。例えば、ビニルベンジルトリメチルアンモニウム、ビニルベンジルトリエチルアンモニウム等の芳香族アンモニウム系単量体、２−（メタ）アクリロイルオキシエチルトリメチルアンモニウムクロライド、２−（メタ）アクリロイルオキシエチルトリエチルアンモニウムクロライド等の４級アンモニウム基を有する（メタ）アクリル酸誘導体系単量体、ビニルピリジン、ビニルイミダゾール等の含窒素複素環系単量体、それらの塩類およびエステル類等を挙げることができる。これらの単量体は、１種単独で使用してもよいし、或いは互いに共重合可能である２種以上を組み合わせて使用することもできる。この中でもスチレン系の単量体を用いることが好ましい。 The monomer having an anion exchange group in the polymerization curable component may be one conventionally used for producing an anion exchange resin. For example, aromatic ammonium-based monomers such as vinylbenzyltrimethylammonium and vinylbenzyltriethylammonium, and quaternary ammonium groups such as 2- (meth) acryloyloxyethyltrimethylammonium chloride and 2- (meth) acryloyloxyethyltriethylammonium chloride. Examples thereof include (meth) ammonium acid derivative-based monomers having (meth), nitrogen-containing heterocyclic monomers such as vinylpyridine and vinylimidazole, and salts and esters thereof. These monomers may be used alone or in combination of two or more copolymerizable with each other. Of these, it is preferable to use a styrene-based monomer.
また、架橋性単量体は、アニオン交換樹脂を緻密化し、膨潤抑止性や膜強度等を高めるために使用されるものであり、特に制限されるものでは無いが、例えば、ジビニルベンゼン、ジビニルスルホン、ブタジエン、クロロプレン、ジビニルビフェニル、トリビニルベンゼン類、ジビニルナフタリン、ジアリルアミン、ジビニルピリジン等のジビニル化合物が挙げられる。このような架橋性単量体は、一般に、前述したアニオン交換樹脂形成用の重合性組成物に含まれる単量体成分全体の中の、０．１〜５０質量％が好ましく、さらに好ましくは１〜４０質量％を配合する。 Further, the crosslinkable monomer is used for densifying the anion exchange resin to enhance swelling inhibitory property, film strength and the like, and is not particularly limited, but for example, divinylbenzene and divinylsulfone. , Divinyl compounds such as butadiene, chloroprene, divinylbiphenyl, trivinylbenzenes, divinylnaphthalin, diallylamine, and divinylpyridine. In general, such a crosslinkable monomer is preferably 0.1 to 50% by mass, more preferably 1% of the total monomer components contained in the above-mentioned polymerizable composition for forming an anion exchange resin. -40% by mass is blended.
更に、上述したアニオン交換基を有する単量体及び架橋性単量体の他に、必要に応じてこれらの単量体と共重合可能な他の単量体を添加しても良い。他の単量体としては、例えば、スチレン、クロロメチルスチレン、アクリロニトリル、メチルスチレン、エチルビニルベンゼン、アクロレイン、メチルビニルケトン、ビニルビフェニル等が用いられる。他の単量体の配合量は添加の目的によっても異なるが、一般に、アニオン交換樹脂形成用の重合性組成物に含まれる単量体成分全体の中の、０．１〜６０質量％が配合されることが好ましく、特に可撓性を付与する場合には、１〜５０質量％、特に５〜４０質量％配合されることが好ましい。 Further, in addition to the above-mentioned monomer having an anion exchange group and the crosslinkable monomer, another monomer copolymerizable with these monomers may be added, if necessary. As other monomers, for example, styrene, chloromethylstyrene, acrylonitrile, methylstyrene, ethylvinylbenzene, acrolein, methylvinylketone, vinylbiphenyl and the like are used. The blending amount of the other monomers varies depending on the purpose of addition, but generally, 0.1 to 60% by mass of the total monomer components contained in the polymerizable composition for forming an anion exchange resin is blended. In particular, when flexibility is imparted, it is preferably blended in an amount of 1 to 50% by mass, particularly 5 to 40% by mass.
重合開始剤としては、従来公知のものが特に制限されること無く使用できるが、半減期１０時間を得るための分解温度が１１０℃以下であることが好ましい。具体的には、ｔ−ブチルパーオキシ−２−エチルヘキシルモノカルボネート、ｔ−ブチルパーオキシラウレート、１，１−ビス（ｔ−ブチルパーオキシ）シクロドデカン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−ヘキシルパーオキシ）シクロヘキサン、ジベンゾイルパーオキシド、ｔ−ブチルパーオキシ−２−エチルヘキサネート、ｔ−ヘキシルパーオキシ−２−エチルヘキサネート、２，５−２，５−ジ（２−エチルヘキサノイルパーオキシ）ヘキサン、ジサクシニックアシッドパーオキシド、１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエート、ジラウロイルパーオキシド、ジ（３，３，５−トリメチルヘキサノイル）パーオキシド、ｔ−ブチルパーオキシビバレート、ｔ−ヘキシルパーオキシビバレート、ｔ−ブチルパーオキシネオデカネト、ｔ−ヘキシルパーオキシネオデカネート、ジ（２−エチルヘキシル）パーオキシジカーボネート、１，１，３，３−テトラメチルブチルパーオキシネオデカネート等の有機過酸化物が用いられる。重合開始剤は、アニオン交換樹脂形成用の重合性組成物に含まれる単量体成分１００質量部に対して、０．１〜２０質量部配合することが好ましく、更に好ましくは０．５〜１０質量部を配合する。 As the polymerization initiator, conventionally known ones can be used without particular limitation, but the decomposition temperature for obtaining a half-life of 10 hours is preferably 110 ° C. or lower. Specifically, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxylaurate, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butyl). Peroxy) cyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, dibenzoylperoxide, t-butylperoxy-2-ethylhexanate, t-hexylperoxy-2-ethylhexanate, 2, 5-2,5-di (2-ethylhexanoylperoxy) hexane, disuccinic acid peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dilauroyl peroxide, Di (3,3,5-trimethylhexanoyl) peroxide, t-butylperoxyvivalate, t-hexylperoxybivalate, t-butylperoxyneodekaneto, t-hexylperoxyneodecanate, di ( 2-Ethylhexyl) Peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanate and other organic peroxides are used. The polymerization initiator is preferably blended in an amount of 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the monomer component contained in the polymerizable composition for forming an anion exchange resin. Mix parts by mass.
上記の重合性組成物には、更に、熱可塑性樹脂からなる添加物を含有させてもよい。具体的には熱可塑性樹脂として、ポリエチレン、ポリプロピレンなどのポリオレフィン類、ポリアクリロニトリル類、ブタジエン−アクリロニトリル共重合体およびその水素添加物や変性物、塩素化ポリエチレン、ポリ塩化ビニルなどを好適に挙げることができる。これらの少なくとも１種を重合性組成物１００質量部に対して０．５質量部以上５０質量部以下添加することが好ましい。 The above-mentioned polymerizable composition may further contain an additive made of a thermoplastic resin. Specifically, as the thermoplastic resin, polyolefins such as polyethylene and polypropylene, polyacrylonitrile, butadiene-acrylonitrile copolymers and hydrogenated products and modified products thereof, chlorinated polyethylene, polyvinyl chloride and the like can be preferably mentioned. can. It is preferable to add at least one of these to 100 parts by mass of the polymerizable composition in an amount of 0.5 parts by mass or more and 50 parts by mass or less.
また、上記の重合性組成物には、必要に応じて更に、公知の増粘剤、添加剤等を含有させてもよい。 Further, the above-mentioned polymerizable composition may further contain a known thickener, additive or the like, if necessary.
増粘剤としては、平均粒形１０μｍ以下のポリオレフィン粉末、エチレン−プロピレン共重合体、ポリブチレン等の飽和脂肪族炭化水素系ポリマー、スチレンーブタジエン共重合体等のスチレン系ポリマーが挙げられる。このような増粘剤の使用により、成膜作業に際しての垂れを効果的に防止し得るような範囲に粘度調整を行うことができる。 Examples of the thickener include polyolefin powders having an average grain size of 10 μm or less, ethylene-propylene copolymers, saturated aliphatic hydrocarbon-based polymers such as polybutylene, and styrene-based polymers such as styrene-butadiene copolymers. By using such a thickener, the viscosity can be adjusted within a range that can effectively prevent sagging during the film forming operation.
添加剤としては、ジオクチルフタレート、ジブチルフタレート、リン酸トリブチル、アセチルクエン酸トリブチル、或いは脂肪酸や芳香族酸のアルコールエステル等の可塑剤、スチレンオキシド、エチレングリコールジグリシジルエーテルなどの塩酸捕捉剤などが挙げられる。 添加剤の配合量は添加の目的によっても異なるが、アニオン交換樹脂形成用の重合性組成物に含まれる単量体成分１００質量部に対して、０．１〜５０質量部、特に０．５〜３０質量部配合されることが好ましい。 Examples of the additive include plasticizers such as dioctyl phthalate, dibutyl phthalate, tributyl phosphate, tributyl acetylcitrate, alcohol esters of fatty acids and aromatic acids, and hydrochloric acid scavengers such as styrene oxide and ethylene glycol diglycidyl ether. Be done. The amount of the additive to be blended varies depending on the purpose of addition, but is 0.1 to 50 parts by mass, particularly 0.5 parts by mass, based on 100 parts by mass of the monomer component contained in the polymerizable composition for forming an anion exchange resin. It is preferably blended in an amount of up to 30 parts by mass.
かかる重合性組成物の、ポリオレフィン系織布である基材の空隙への含侵方法には特に制限はない。例えば、前述した重合性組成物が充填された槽内に、ポリオレフィン系基材を浸漬することで行われる。もちろん、浸漬の代わりに、スプレー塗布や、ドクターブレードを用いた塗布などの方法で重合性組成物の含侵を行うこともできる。 The method of impregnating the voids of the base material of the polyolefin-based woven fabric of the polymerizable composition is not particularly limited. For example, it is carried out by immersing a polyolefin-based base material in a tank filled with the above-mentioned polymerizable composition. Of course, instead of dipping, impregnation of the polymerizable composition can be performed by a method such as spray coating or coating using a doctor blade.
上記のようにして、ポリオレフィン系織布に含侵された重合性組成物は、加熱オーブン等の重合装置内で加熱されて共重合されて硬化される。 As described above, the polymerizable composition impregnated in the polyolefin-based woven fabric is heated in a polymerization apparatus such as a heating oven, copolymerized, and cured.
この重合工程では、一般に、重合性組成物が充填されたポリオレフィン系織布をポリエステル等のフィルムに挟んで加圧下で常温から昇温する方法が採用される。加圧は、一般に０．１〜１．０ＭＰａ程度の圧力で、窒素等の不活性ガスやロール等による加圧によって行われる。この加圧によって、ポリオレフィン系織布の外側界面に存在している余剰の重合性組成物がポリオレフィン系織布の空隙内に押し込まれた状態で重合が行われ、樹脂溜りの発生などを効果的に防止することができる。 In this polymerization step, a method of sandwiching a polyolefin-based woven fabric filled with a polymerizable composition between films such as polyester and raising the temperature from room temperature under pressure is generally adopted. The pressurization is generally performed at a pressure of about 0.1 to 1.0 MPa by pressurizing with an inert gas such as nitrogen or a roll. By this pressurization, the excess polymerizable composition existing at the outer interface of the polyolefin-based woven fabric is pressed into the voids of the polyolefin-based woven fabric, and the polymerization is carried out, which is effective in generating resin pools and the like. Can be prevented.
その他の重合条件は、重合硬化性成分の種類等によって左右されるものであり、公知の条件より適宜選択して決定すればよい。重合温度は、前述の通り、ポリオレフィン系織布の融点よりも大幅に低い温度（具体的には４０℃以上１２０℃未満）に設定され、また、重合時間は、重合温度等によっても異なるが、一般には、３〜２０時間程度である。重合硬化の完了により、ポリオレフィン系織布に支持されたアニオン交換膜が得られる。 Other polymerization conditions depend on the type of polymerization-curable component and the like, and may be appropriately selected and determined from known conditions. As described above, the polymerization temperature is set to a temperature significantly lower than the melting point of the polyolefin-based woven fabric (specifically, 40 ° C. or higher and lower than 120 ° C.), and the polymerization time varies depending on the polymerization temperature and the like. Generally, it takes about 3 to 20 hours. Upon completion of the polymerization curing, an anion exchange membrane supported by the polyolefin-based woven fabric is obtained.
また、本実施形態においては、アニオン交換樹脂形成用重合硬化性成分に代えて、アニオン交換基を導入可能な反応基を有するアニオン交換樹脂前駆樹脂形成用重合硬化性成分を用いて、アニオン交換膜を形成することもできる。具体的には、前記アニオン交換基を有する単量体に替えて、アニオン交換基導入可能な反応基を有する単量体を重合性組成物に配合して、アニオン交換膜前駆体を製造する。この場合も、後述するアニオン交換基導入工程を追加する点を除き、アニオン交換基を有する単量体を配合する場合と同様にしてアニオン交換膜前駆体を作成すれば良い。 Further, in the present embodiment, instead of the polymerization curable component for forming an anion exchange resin, an anion exchange membrane is used by using a polymerization curable component for forming an anion exchange resin precursor resin having a reactive group into which an anion exchange group can be introduced. Can also be formed. Specifically, instead of the monomer having an anion exchange group, a monomer having a reactive group capable of introducing an anion exchange group is blended into the polymerizable composition to produce an anion exchange membrane precursor. In this case as well, the anion exchange membrane precursor may be prepared in the same manner as in the case of blending the monomer having an anion exchange group, except that the anion exchange group introduction step described later is added.
アニオン交換基導入可能な反応基を有する単量体は、アニオン交換樹脂を製造するために、従来から使用されているもので良い。例えば、ビニルピリジン、メチルビニルピリジン、エチルビニルピリジン、ビニルピロリドン、ビニルカルバゾール、ビニルイミダゾール、アミノスチレン、アルキルアミノスチレン、ジアルキルアミノスチレン、トリアルキルアミノスチレン、クロルメチルスチレン、アクリル酸アミド、アクリルアミド、オキシウム、スチレン、ビニルトルエンなどが好適である。これらの単量体は、１ 種単独で使用してもよいし、或いは互いに共重合可能である２種以上を組み合わせて使用することもできる。 The monomer having a reactive group into which an anion exchange group can be introduced may be one conventionally used for producing an anion exchange resin. For example, vinylpyridine, methylvinylpyridine, ethylvinylpyridine, vinylpyrrolidone, vinylcarbazole, vinylimidazole, aminostyrene, alkylaminostyrene, dialkylaminostyrene, trialkylaminostyrene, chloromethylstyrene, acrylic acid amide, acrylamide, oxime, Styrene, vinyltoluene and the like are suitable. These monomers may be used alone or in combination of two or more copolymerizable with each other.
アニオン交換基導入可能な反応基を有する単量体及び架橋性単量体の他に必要に応じて他の単量体を使用することができる。他の単量体としては、アクリロニトリル、アクロレイン、メチルビニルケトンなどが挙げられる。 In addition to the monomer having a reactive group into which an anion exchange group can be introduced and the crosslinkable monomer, other monomers can be used if necessary. Examples of other monomers include acrylonitrile, acrolein, methyl vinyl ketone and the like.
アニオン交換基導入工程は、重合性組成物を重合硬化してアニオン交換樹脂前駆樹脂の膜を得た後に行う。かかる工程においては、１〜３級アミノ基、４級アンモニウム基、ピリジル基、イミダゾール基、４級ピリジニウム基等を導入するために、得られた前駆樹脂にアニオン交換基導入剤として１〜３級アミン等を作用させたり、アルキル化とアミノ化などの処理を施すことによりアニオン交換基を導入する。これにより、目的とするアニオン交換膜を得ることができる。 The anion exchange group introduction step is performed after the polymerizable composition is polymerized and cured to obtain a film of an anion exchange resin precursor resin. In this step, in order to introduce a 1st to 3rd grade amino group, a quaternary ammonium group, a pyridyl group, an imidazole group, a quaternary pyridinium group and the like, the 1st to 3rd grade as an anion exchange group introduction agent is introduced into the obtained precursor resin. An anion exchange group is introduced by allowing an amine or the like to act on it, or by performing treatments such as alkylation and amination. As a result, the desired anion exchange membrane can be obtained.
また、本実施形態においては、上記のアニオン交換樹脂形成用あるいはアニオン交換樹脂前駆樹脂形成用の重合性組成物を用いる方法に替えて、アニオン交換基含有高分子を溶媒に溶解させた、アニオン交換基含有高分子の溶液をポリオレフィン系織布の空隙に充填することもできる。 Further, in the present embodiment, instead of the method using the above-mentioned polymerizable composition for forming an anion exchange resin or forming an anion exchange resin precursor resin, an anion exchange group-containing polymer is dissolved in a solvent to exchange anions. A solution of the group-containing polymer can also be filled in the voids of the polyolefin-based woven fabric.
上記のようにして製造されるアニオン交換膜の厚みは５０〜３００μｍの範囲にあることが好適である。この厚みがあまり薄いと、交換膜の強度が大きく低下する虞がある。厚みが過度に厚いと、電気抵抗が上昇するなどの不都合を生じる虞がある。 The thickness of the anion exchange membrane produced as described above is preferably in the range of 50 to 300 μm. If this thickness is too thin, the strength of the exchange membrane may be significantly reduced. If the thickness is excessively thick, there is a risk of causing inconvenience such as an increase in electrical resistance.
アニオン交換膜の破裂強度は、厚さにもよるが、０．１ＭＰａ以上２．５ＭＰａ以下となるように、ポリオレフィン系織布のフィラメント径、厚さや重合硬化性成分中の架橋性単量体の配合量などを調整される。 The burst strength of the anion exchange film depends on the thickness, but the filament diameter and thickness of the polyolefin-based woven fabric and the crosslinkable monomer in the polymerization curable component so as to be 0.1 MPa or more and 2.5 MPa or less. The blending amount is adjusted.
このような性状を有する本発明のアニオン交換膜は、製塩や食品分野における脱塩工程などで利用される電気透析用膜や、燃料電池の電解質膜として、また、鉄鋼業などで発生する金属イオンを含んだ酸からの酸回収に用いられる拡散透析用膜など多くの分野で有用に利用できる。 The anion exchange membrane of the present invention having such properties is used as a membrane for electrodialysis used in salt production and desalting processes in the food field, as an electrolyte membrane for fuel cells, and metal ions generated in the steel industry and the like. It can be usefully used in many fields such as membranes for diffusion dialysis used for acid recovery from acids containing.
以下、実施例によって本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の実施例及び比較例において、アニオン交換膜についての各種特性は、次の方法により測定した。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following Examples and Comparative Examples, various characteristics of the anion exchange membrane were measured by the following methods.
１．アニオン交換膜の透水量
円筒状のセルにイオン交換膜を挟み、上部に５０ｍｌの水を入れ、更にその上から０．１ＭＰａで圧力をかけた際に、イオン交換膜を１時間に透過してくる水量Ｗｐｗを測定し、下記式に従って透水量を算出した。この際、膜の有効面積は１２．６ｃｍ２である。
1. 1. Water Permeability of Anion Exchange Membrane When an ion exchange membrane is sandwiched between cylindrical cells, 50 ml of water is put in the upper part, and pressure is applied at 0.1 MPa from above, the ion exchange membrane is permeated in 1 hour. The amount of incoming water Wpw was measured, and the amount of water permeation was calculated according to the following formula. At this time, the effective area of the film is 12.6 cm 2 .
透水量（ｍｌ／（ｍ２×ｈｒ））＝Ｗｐｗ／（Ｓ×ｔ） Permeability (ml / (m 2 x hr)) = Wpw / (S x t)
上記式中、
Ｓ：膜の有効面積（ｍ２）
ｔ：試験時間（ｈｒ）
In the above formula,
S: Effective area of membrane (m 2 )
t: Test time (hr)
さらに、アニオン交換膜の密着性を評価する、透水量の高温（８０℃）加速試験として、アニオン交換膜の一部を８０℃の純水中に２４時間浸漬し、その高温処理膜について、上記透水量の測定を実施した。 Further, as a high temperature (80 ° C.) acceleration test of water permeability for evaluating the adhesion of the anion exchange membrane, a part of the anion exchange membrane was immersed in pure water at 80 ° C. for 24 hours, and the high temperature treated membrane was described above. The water permeability was measured.
アニオン交換膜において上記透水量は、３００ｍｌ／（ｍ２×ｈｒ）以下であることが好ましく、５０ｍｌ／（ｍ２×ｈｒ）以下であることがより好ましい。なお、透水量の下限は０ｍｌ／（ｍ２×ｈｒ）である。 In the anion exchange membrane, the water permeability is preferably 300 ml / (m 2 × hr) or less, and more preferably 50 ml / (m 2 × hr) or less. The lower limit of the water permeation amount is 0 ml / (m 2 × hr).
２．アニオン交換膜のアニオン交換容量および含水率
アニオン交換膜を１ｍｏｌ／Ｌ−ＨＣｌ水溶液に１０時間以上浸漬する。その後、１ｍｏｌ／Ｌ−ＮａＮＯ３水溶液で対イオンを塩化物イオンから硝酸イオンに置換させ、遊離した塩化物イオンを硝酸銀水溶液を用いて電位差滴定装置（ＡＴ−７１０、京都電子工業株式会社製）で定量した（Ａｍｏｌ）。
2. Anion exchange capacity and water content of the anion exchange membrane The anion exchange membrane is immersed in a 1 mol / L-HCl aqueous solution for 10 hours or more. Then, the counterion is replaced with nitrate ion from chloride ion with 1 mol / L-NaNO3 aqueous solution, and the liberated chloride ion is quantified with a potentiometric titrator (AT-710, manufactured by Kyoto Electronics Industry Co., Ltd.) using silver nitrate aqueous solution. (Amol).
次に、同じイオン交換膜を１ｍｏｌ／Ｌ−ＮａＣｌ水溶液に４時間以上浸漬し、イオン交換水で十分水洗した。その後ティッシュペーパーで表面の水分を拭き取り、湿潤時の膜の質量（Ｗｇ）を測定した。さらに、６０℃で５時間減圧乾燥して乾燥時の重さ（Ｄｇ）を測定した。上記測定値に基づいて、アニオン交換膜のアニオン交換容量および含水率を次式により求めた。 Next, the same ion exchange membrane was immersed in a 1 mol / L- NaCl aqueous solution for 4 hours or more, and thoroughly washed with ion exchange water. Then, the water on the surface was wiped off with a tissue paper, and the mass (Wg) of the film when wet was measured. Further, it was dried under reduced pressure at 60 ° C. for 5 hours, and the weight (Dg) at the time of drying was measured. Based on the above measured values, the anion exchange capacity and water content of the anion exchange membrane were determined by the following equations.
イオン交換容量［ｍｅｑ／ｇ−乾燥質量］＝Ａ×１０００／Ｄ
含水率[％]＝１００×（Ｗ−Ｄ）／Ｄ
Ion exchange capacity [meq / g-dry mass] = A × 1000 / D
Moisture content [%] = 100 × (WD) / D
３．アニオン交換膜の厚さ
アニオン交換膜を０．５ｍｏｌ／Ｌ−ＮａＣｌ溶液に４時間以上浸漬した後、ティッシュペーパーで膜の表面の水分を拭き取り、マイクロメ−タＭＥＤ−２５ＰＪ（株式会社ミツトヨ社製）を用いて測定した。
3. 3. Thickness of anion exchange membrane After immersing the anion exchange membrane in a 0.5 mol / L-NaCl solution for 4 hours or more, wipe off the moisture on the surface of the membrane with tissue paper, and micrometer MED-25PJ (manufactured by Mitutoyo Co., Ltd.). Was measured using.
４．アニオン交換膜の電気抵抗
白金黒電極を有する２室セル中にイオン交換膜を挟み、アニオン交換膜の両側に０．５ｍｏｌ／Ｌ−ＮａＣｌ水溶液を満たし、交流ブリッジ（周波数１０００サイクル／秒）により２５℃における電極間の抵抗を測定し、該電極間抵抗とイオン交換膜を設置しない場合の電極間抵抗との差により電気抵抗（Ω・ｃｍ２）を求めた。なお、上記測定に使用するイオン交換膜は、予め０．５ｍｏｌ／Ｌ−ＮａＣｌ水溶液中で平衡にしたものを用いた。
4. Electrical resistance of anion exchange membrane An ion exchange membrane is sandwiched in a two-chamber cell having a platinum black electrode, both sides of the anion exchange membrane are filled with a 0.5 mol / L-NaCl aqueous solution, and 25 by an AC bridge (frequency 1000 cycles / sec). The resistance between the electrodes at ° C was measured, and the electrical resistance (Ω · cm 2 ) was determined by the difference between the resistance between the electrodes and the resistance between the electrodes when the ion exchange membrane was not installed. The ion exchange membrane used for the above measurement was previously equilibrated in a 0.5 mol / L-NaCl aqueous solution.
アニオン交換膜において上記電気抵抗は、４．０Ω・ｃｍ２以下が好ましく、特に１．０Ω・ｃｍ２以上３．０Ω・ｃｍ２以下であるのが消費電力の観点から有利である。 In the anion exchange membrane, the electric resistance is preferably 4.0 Ω · cm 2 or less, and particularly preferably 1.0 Ω · cm 2 or more and 3.0 Ω · cm 2 or less from the viewpoint of power consumption.
５．アニオン交換膜の電流効率
以下の構成を有する２室セルを使用した。
5. Current efficiency of anion exchange membrane A two-chamber cell having the following configuration was used.
陽極（Ｐｔ板）（１．０ｍｏｌ／Ｌ−硫酸水溶液）／アニオン交換膜／（０．２５ｍｏｌ／Ｌ−硫酸水溶液）陰極（Ｐｔ板） Anode (Pt plate) (1.0 mol / L-sulfuric acid aqueous solution) / Anion exchange film / (0.25 mol / L-sulfuric acid aqueous solution) Cathode (Pt plate)
液温２５℃で電流密度１０Ａ／ｄｍ２で1時間通電した後、陰極側の溶液を回収した。回収した液と初期液の硫酸濃度を、水酸化ナトリウム水溶液を用いて電位差滴定装置（ＡＴ−７１０、京都電子工業株式会社製）により定量し、下記式を用いて電流効率を算出した。 After energizing at a liquid temperature of 25 ° C. and a current density of 10 A / dm2 for 1 hour, the solution on the cathode side was recovered. The sulfuric acid concentrations of the recovered liquid and the initial liquid were quantified by a potentiometric titrator (AT-710, manufactured by Kyoto Denshi Kogyo Co., Ltd.) using an aqueous sodium hydroxide solution, and the current efficiency was calculated using the following formula.
電流効率（％）＝（ＣＢ−ＣＳ）／（Ｉ×ｔ／Ｆ）×１００ Current efficiency (%) = (CB-CS) / (I × t / F) × 100
上記式中、
ＣＢ：初期液の濃度
ＣＳ：通電後に回収した液濃度
Ｉ：電流値（Ａ）
ｔ：通電時間（ｓｅｃ）
Ｆ：ファラデー定数（９６５００Ｃ／ｍｏｌ）
In the above formula,
CB: Concentration of initial liquid CS: Concentration of liquid recovered after energization I: Current value (A)
t: Energizing time (sec)
F: Faraday constant (96500C / mol)
６．イオン交換膜の破裂強度
アニオン交換膜を０．５ｍｏｌ／Ｌ−ＮａＣｌ水溶液に４時間以上浸漬し、イオン交換水で十分水洗した。次いで、膜を乾燥させることなく、ミューレン破裂試験機（東洋精機製）により、ＪＩＳ−Ｐ８１１２に準拠して破裂強度を測定した。
6. Rupture strength of ion exchange membrane The anion exchange membrane was immersed in a 0.5 mol / L-NaCl aqueous solution for 4 hours or more, and thoroughly washed with ion exchange water. Next, the burst strength was measured according to JIS-P8112 by a Murren burst tester (manufactured by Toyo Seiki) without drying the membrane.
＜実施例１＞
下記処方の混合物を調製した。
<Example 1>
A mixture of the following formulations was prepared.
スチレン（Ｓｔ）３３．２質量部
ジビニルベンゼン（ＤＶＢ）（純度５７％、残りはエチルビニルベンゼン）１６．８質量部
クロロメチルスチレン（ＣＭＳ）５０．０質量部
アセチルクエン酸トリブチル（ＡＴＢＣ）２５．０質量部
スチレンオキシド（ＳｔＯ）３．４質量部
ｔ−ブチルパーオキシ−２−エチルヘキサノエート（ＢＰＥ）（日本油脂製パーブチルＯ）３．３質量部
Styrene (St) 33.2 parts by mass Divinylbenzene (DVB) (purity 57%, the rest is ethylvinylbenzene) 16.8 parts by mass Chloromethylstyrene (CMS) 50.0 parts by mass Tributyl acetylcitate (ATBC) 25. 0 parts by mass Styrene oxide (StO) 3.4 parts by mass t-butyl peroxy-2-ethylhexanoate (BPE) (Perbutyl O manufactured by Nippon Oil & Fats Co., Ltd.) 3.3 parts by mass
この混合物に、スチレン系熱可塑性樹脂エラストマーとして、無水マレイン酸変性されている、ポリスチレンの含量が３０質量％である、水素添加されたスチレン−ブタジエントリブロック共重合体（商品名：タフテックＭ１９１３、旭化成製；無水マレイン酸変性量＝２質量％）２０．７質量部を加え、４０℃で２０時間攪拌して均一な重合性組成物を得た。 A hydrogenated styrene-butadiene triblock copolymer (trade name: Toughtec M1913, Asahi Kasei) which has been modified with maleic anhydride as a styrene-based thermoplastic resin elastomer and has a polystyrene content of 30% by mass in this mixture. Manufacture; Maleic anhydride modified amount = 2% by mass) 20.7 parts by mass was added, and the mixture was stirred at 40 ° C. for 20 hours to obtain a uniform polymerizable composition.
次いで、ポリオレフィン系織布として、下記の高密度ポリエチレンモノフィラメント織布（ＰＥ３３Ｄ−１２０）を用意した。 Next, as the polyolefin-based woven fabric, the following high-density polyethylene monofilament woven fabric (PE33D-120) was prepared.
高密度ポリエチレンモノフィラメント織布（ＰＥ３３Ｄ−１２０）；
縦糸：線径７６μｍ−１インチあたり１２０本（３３デニール）
横糸：線径７６μｍ−１インチあたり１２０本（３３デニール）
厚さ：１３２μｍ
開口率：５４％
High density polyethylene monofilament woven fabric (PE33D-120);
Warp: 120 threads per inch with a wire diameter of 76 μm (33 denier)
Weft: 120 wires per inch with a wire diameter of 76 μm (33 denier)
Thickness: 132 μm
Opening rate: 54%
上記の高密度ポリエチレンモノフィラメント織布（ＰＥ３３Ｄ−１２０）の上に、上記で得られた重合性組成物を塗布し、ポリエステルフィルムを剥離材として両面被覆した後、７０℃で５時間重合を行った。 The polymerizable composition obtained above was applied onto the high-density polyethylene monofilament woven fabric (PE33D-120), coated on both sides with a polyester film as a release material, and then polymerized at 70 ° C. for 5 hours. ..
次いで、得られた膜状高分子体をメタノールに２０時間浸漬し可塑剤および重合残渣を除去したあと、トリメチルアミン５重量％およびアセトン２５重量％水溶液を用いて、３０℃、１６時間のアミノ化反応を行い、アニオン交換膜を得た。アニオン交換膜の構成を表１に示す。また、得られたアニオン交換膜の特性は、表２に示したとおりの次の結果であった。 Next, the obtained film-like polymer was immersed in methanol for 20 hours to remove the plasticizer and the polymerization residue, and then an amination reaction was carried out at 30 ° C. for 16 hours using an aqueous solution of 5% by weight of trimethylamine and 25% by weight of acetone. To obtain an anion exchange membrane. The configuration of the anion exchange membrane is shown in Table 1. The characteristics of the obtained anion exchange membrane were as follows as shown in Table 2.
厚さ：１７６μｍ
イオン交換容量：１．３ｍｅｑ／ｇ−乾燥質量
含水率：２８％
電気抵抗：２．３Ω・ｃｍ２
透水量：８ｍｌ／（ｍ２・ｈｒ）
透水量〔８０℃加速試験〕：２５ｍｌ／（ｍ２・ｈｒ）
電流効率：４３％
破裂強度：１．１ＭＰa
Thickness: 176 μm
Ion exchange capacity: 1.3meq / g-dry mass Moisture content: 28%
Electrical resistance: 2.3Ω ・ cm 2
Water permeability: 8ml / (m 2 · hr )
Water permeability [80 ° C accelerated test]: 25 ml / (m 2 · hr)
Current efficiency: 43%
Burst strength: 1.1MPa
＜比較例１＞
スチレン系熱可塑性樹脂エラストマーとして、酸性基または酸無水物基での変性はされていない、ポリスチレンの含量が３０重量％である水素添加されたスチレン−ブタジエントリブロック共重合体（商品名：タフテックＨ１０４１、旭化成製）を用意した。
<Comparative example 1>
As a styrene-based thermoplastic resin elastomer, a hydrogenated styrene-butadiene triblock copolymer having a polystyrene content of 30% by weight, which has not been modified with an acidic group or an acid anhydride group (trade name: Toughtec H1041). , Asahi Kasei) was prepared.
実施例１において、スチレン系熱可塑性樹脂エラストマーとして、上記スチレン−ブタジエントリブロック共重合体の未変性体を用いた以外は実施例１と同様にして、アニオン交換膜を作成した。得られたアニオン交換膜の膜特性を表２に示した。 An anion exchange film was prepared in the same manner as in Example 1 except that the unmodified styrene-butadiene triblock copolymer was used as the styrene-based thermoplastic resin elastomer in Example 1. The membrane characteristics of the obtained anion exchange membrane are shown in Table 2.
＜実施例２＞
下記処方の混合物を調製した。
<Example 2>
A mixture of the following formulations was prepared.
スチレン（Ｓｔ）１６．６質量部
ジビニルベンゼン（ＤＶＢ）（純度５７％、残りはエチルビニルベンゼン）１６．８質量部
クロロメチルスチレン（ＣＭＳ）６６．６質量部
アセチルクエン酸トリブチル（ＡＴＢＣ）２５．０質量部
スチレンオキシド（ＳｔＯ）３．４質量部
ｔ−ブチルパーオキシ−２−エチルヘキサノエート（ＢＰＥ）（日本油脂製パーブチルＯ）３．３質量部
Styrene (St) 16.6 parts by mass Divinylbenzene (DVB) (purity 57%, the rest is ethylvinylbenzene) 16.8 parts by mass Chloromethylstyrene (CMS) 66.6 parts by mass Tributyl acetylcitate (ATBC) 25. 0 parts by mass Styrene oxide (StO) 3.4 parts by mass t-butyl peroxy-2-ethylhexanoate (BPE) (Perbutyl O manufactured by Nippon Oil & Fats Co., Ltd.) 3.3 parts by mass
この混合物に、無水マレイン酸変性されているポリスチレンの含量が３０重量％である水素添加されたスチレン−ブタジエントリブロック共重合体（商品名：タフテックＭ１９１３、旭化成製）２０．７質量部を加え、４０℃で２０時間攪拌して均一な重合性組成物を得た。 To this mixture, 20.7 parts by mass of hydrogenated styrene-butadiene triblock copolymer (trade name: Toughtec M1913, manufactured by Asahi Kasei) having a content of polystyrene modified with maleic anhydride of 30% by weight was added. Stirring at 40 ° C. for 20 hours gave a uniform polymerizable composition.
上記重合性組成物を用いた以外は実施例１と同様にして、本発明のアニオン交換膜を得た。得られたアニオン交換膜の膜特性を表２に示した。 An anion exchange membrane of the present invention was obtained in the same manner as in Example 1 except that the above polymerizable composition was used. The membrane characteristics of the obtained anion exchange membrane are shown in Table 2.
＜実施例３＞
ポリオレフィン系織布として、下記性状の高密度ポリエチレンモノフィラメント織布（ＰＥ３３Ｄ−１００）
縦糸：線径７６μｍ−１インチあたり１００本（３３デニール）
横糸：線径７６μｍ−１インチあたり１００本（３３デニール）
厚さ：１３２μｍ
を用いた以外は、は実施例１と同様にして、本発明のアニオン交換膜を得た。得られたアニオン交換膜の膜特性を表２に示した。
<Example 3>
As a polyolefin-based woven fabric, a high-density polyethylene monofilament woven fabric having the following properties (PE33D-100)
Warp: Wire diameter 76 μm-1 inch 100 threads (33 denier)
Weft: 100 wires per wire diameter 76 μm-1 inch (33 denier)
Thickness: 132 μm
The anion exchange membrane of the present invention was obtained in the same manner as in Example 1 except that The membrane characteristics of the obtained anion exchange membrane are shown in Table 2.
各実施例で製造されたアニオン交換膜は、電気抵抗が各３．０Ω・ｃｍ２以下の低さであるにもかかわらず、スチレン系熱可塑性樹脂エラストマーとして、無水マレイン酸による変性体が含有されている結果、透水量はいずれも８ｍｌ／（ｍ２×ｈｒ）の優れた値であり、これは８０℃の加速試験後であっても２５ｍｌ／（ｍ２×ｈｒ）に維持されていた。これに対して、比較例１で製造されたアニオン交換膜は、スチレン系熱可塑性樹脂エラストマーは酸変成されていないため、透水量は７６ｍｌ／（ｍ２×ｈｒ）の高さであり、これは８０℃の加速試験後において７５６ｍｌ／（ｍ２×ｈｒ）にまで悪化した。このことから、スチレン系熱可塑性樹脂エラストマーとして、無水マレイン酸により変性体を用いることにより、得られるアニオン交換膜において、アニオン交換樹脂とポリオレフィン系基材との密着性が大きく向上することが確認できた。 The anion exchange membranes produced in each example contain a modified product of maleic anhydride as a styrene-based thermoplastic resin elastomer , although the electrical resistance is as low as 3.0 Ω · cm 2 or less. As a result, the water permeability was an excellent value of 8 ml / (m 2 × hr), which was maintained at 25 ml / (m 2 × hr) even after the acceleration test at 80 ° C. On the other hand, in the anion exchange membrane produced in Comparative Example 1, since the styrene-based thermoplastic resin elastomer was not acid-modified, the water permeability was as high as 76 ml / (m 2 × hr). After the acceleration test at 80 ° C., it deteriorated to 756 ml / (m 2 × hr). From this, it can be confirmed that the adhesion between the anion exchange resin and the polyolefin-based substrate is greatly improved in the obtained anion exchange membrane by using a modified product with maleic anhydride as the styrene-based thermoplastic resin elastomer. rice field.
（その他の実施形態）
上述の実施形態は本願発明の例示であって、本願発明はこれらの例に限定されず、これらの例に周知技術や慣用技術、公知技術を組み合わせたり、一部置き換えたりしてもよい。また当業者であれば容易に思いつく改変発明も本願発明に含まれる。
(Other embodiments)
The above-described embodiment is an example of the present invention, and the present invention is not limited to these examples, and well-known techniques, conventional techniques, and known techniques may be combined or partially replaced with these examples. The invention of the present application also includes modified inventions that can be easily conceived by those skilled in the art.
Claims (10)
さらに酸性基または酸無水物基により変性されたスチレン系熱可塑性樹脂エラストマーが含有されている、アニオン交換膜。 An anion exchange membrane comprising a polyolefin-based substrate and an anion exchange resin.
An anion exchange film further containing a styrene-based thermoplastic resin elastomer modified with an acidic group or an acid anhydride group.
前記浸漬工程の後に、前記単量体成分を共重合させる工程と
を含む、アニオン交換膜の製造方法。 In a polymerizable composition for forming an anion exchange resin containing a monomer component containing a functional group into which an anion exchange group can be introduced or a monomer having an anion exchange group and a crosslinkable monomer, and a polymerization initiator. A dipping step of adding a styrene-based thermoplastic resin elastomer modified with an acidic group or an acid anhydride group and immersing it in a polyolefin-based substrate.
A method for producing an anion exchange membrane, which comprises a step of copolymerizing the monomer component after the dipping step.
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