JP2008071706A - Method of manufacturing electrolyte membrane - Google Patents
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- JP2008071706A JP2008071706A JP2006251516A JP2006251516A JP2008071706A JP 2008071706 A JP2008071706 A JP 2008071706A JP 2006251516 A JP2006251516 A JP 2006251516A JP 2006251516 A JP2006251516 A JP 2006251516A JP 2008071706 A JP2008071706 A JP 2008071706A
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- electrolyte membrane
- liquid
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- vinyl monomer
- crosslinking agent
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- 239000012528 membrane Substances 0.000 title claims abstract description 62
- 239000003792 electrolyte Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 35
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 35
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 23
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 24
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical group OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 8
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000446 fuel Substances 0.000 abstract description 29
- 230000035699 permeability Effects 0.000 abstract description 19
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 229920000642 polymer Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000008961 swelling Effects 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FLCWLOFMVFESNI-UHFFFAOYSA-N acridine-9(10H)-thione Chemical compound C1=CC=C2C(=S)C3=CC=CC=C3NC2=C1 FLCWLOFMVFESNI-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 238000003221 volumetric titration Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Conductive Materials (AREA)
- Fuel Cell (AREA)
Abstract
Description
本発明は、燃料電池、特に固体高分子型燃料電池及び直接液体燃料型燃料電池に関する。 The present invention relates to a fuel cell, and more particularly to a polymer electrolyte fuel cell and a direct liquid fuel fuel cell.
燃料電池用電解質膜として、スルホン酸基をはじめとする、プロトン解離性基を有するポリマーからなる電解質膜が知られている。なかでも、（ｉ）燃料電池内で生成する水や、メタノールなどの液体燃料への膨潤や溶解が抑制され、（ｉｉ）燃料透過性が抑制され、（ｉｉｉ）高いプロトン伝導性を有する電解質膜へのニーズが高い。
近年、上記（ｉ）〜（ｉｉｉ）を解決する目的で、ポリオレフィンやポリイミドを基材とする、水や液体燃料に実質的に膨潤、溶解することのない、疎水性の多孔質基材にプロトン解離性官能基含有ポリマーを充填した電解質膜が開発されている。なかでも、充填するプロトン解離性官能基含有ポリマーの水や液体燃料への膨潤や溶解を分子レベルで抑え、より一層上記（ｉ）〜（ｉｉｉ）を向上させる目的で、プロトン解離性官能基とともに架橋構造を有するポリマーが充填された電解質膜が開発されている。
As an electrolyte membrane for a fuel cell, an electrolyte membrane made of a polymer having a proton dissociable group such as a sulfonic acid group is known. Among them, (i) swelling and dissolution in liquid fuel such as water and methanol generated in the fuel cell are suppressed, (ii) fuel permeability is suppressed, and (iii) an electrolyte membrane having high proton conductivity. The need for is high.
In recent years, for the purpose of solving the above (i) to (iii), a proton is applied to a hydrophobic porous substrate which is based on polyolefin or polyimide and does not substantially swell or dissolve in water or liquid fuel. An electrolyte membrane filled with a dissociative functional group-containing polymer has been developed. Among them, together with the proton-dissociating functional group, for the purpose of suppressing the swelling and dissolution of the proton-dissociable functional group-containing polymer to be filled in water or liquid fuel at the molecular level and further improving the above (i) to (iii) An electrolyte membrane filled with a polymer having a crosslinked structure has been developed.
例えば、特許文献１には、スルホン酸基含有ビニルモノマーを含む溶液を多孔性基材に含浸させた後、これを重合する工程を含む電解質膜の製造方法において、前記スルホン酸基含有ビニルモノマーとして、純度９０％以上のビニルスルホン酸及び／又はその塩を８０モル％以上含有するとともに、前記溶液中のビニルスルホン酸及び／又はその塩の濃度を３５重量％以上とすることを特徴とする、電解質膜及びその製造方法が記載されている。しかし、特許文献１において、スルホン酸基含有ビニルモノマー中に使用される、ビニルスルホン酸は、水などの溶媒を必要とするその塩であってもよく、スルホン酸基含有ビニルモノマーをプロトン解離性液状モノマーに限定していないため、燃料透過性を一層改善する余地があると考えられる。また、イオン交換容量の大きいビニルスルホン酸ポリマーが含水膨張するため、多孔質基材、特に実質的に重量平均分子量が５０万以下のポリオレフィンのみからなる多孔質基材を、変形させることにより発生する外観不良を回避する方法については何ら記載がない。
発明者らは、上記の課題を解決すべく検討を行い、均一混合液を形成する、特定の組み合わせの、プロトン解離性液状モノマーと液状架橋剤が、実質的に溶媒を含むことなく容易に疎水性の多孔質基材へ充填、重合され、該多孔質基材内にプロトン解離性液状モノマーと液状架橋剤のコポリマーとして密に充填され、低ＥＷでかつ低含水率の電解質膜が得られ、際立った低燃料透過性と高プロトン伝導性が発現することを見出し、先に特許出願した（特願２００６−９６４８号）。しかしながら、本発明者らが更に検討を進めたところ、前記方法では、電解質の充填時に多孔質基材が変形し外観不良を発生し、得られた電解質膜を燃料電池に使用する際に、電極との接触不良が懸念されるという問題があった。
本発明の目的は外観不良の少ない電解質膜を提供することである。更には、多孔質基材内に電解質が密に充填され、燃料透過性が低く、プロトン伝導性の高い、外観不良の少ない電解質膜を提供することにある。
The inventors have studied to solve the above problems, and a specific combination of proton dissociable liquid monomer and liquid cross-linking agent that form a homogeneous mixed solution is easily hydrophobic without substantially containing a solvent. A porous porous substrate, polymerized, and densely packed into the porous substrate as a copolymer of a proton dissociable liquid monomer and a liquid cross-linking agent to obtain an electrolyte membrane having a low EW and a low water content, It was found that outstanding low fuel permeability and high proton conductivity were developed, and a patent application was filed earlier (Japanese Patent Application No. 2006-9648). However, as a result of further investigation by the present inventors, in the above method, when the electrolyte is filled, the porous base material is deformed to cause poor appearance, and when the obtained electrolyte membrane is used for a fuel cell, an electrode is used. There was a problem that there was a concern about poor contact with.
An object of the present invention is to provide an electrolyte membrane with few appearance defects. It is another object of the present invention to provide an electrolyte membrane in which a porous substrate is densely filled with an electrolyte, fuel permeability is low, proton conductivity is high, and appearance is small.
本発明者等は、上記の課題を解決すべく検討を行った結果、本発明を完成するに至った。
すなわち、本発明は以下の通りである。
（１）液状プロトン解離性ビニルモノマーと、一分子中に少なくとも二つの炭素−炭素二重結合を有する実質的に水に溶解しない架橋剤とを含有する混合液を疎水性多孔質基材に含浸、重合する電解質膜の製造方法であって、該混合液の含水率が０．５％以下であることを特徴とする電解質膜の製造方法。
（２）架橋剤が液状である、上記（１）の電解質膜の製造方法。
（３）液状プロトン解離性ビニルモノマーがビニルスルホン酸である、上記（１）又は（２）の電解質膜の製造方法。
（４）架橋剤が、更にＮ−Ｃ＝Ｏ結合を有する、上記（１）〜（３）いずれかの電解質膜の製造方法。
（５）架橋剤がトリアリルイソシアヌレートである、上記（１）〜（４）いずれかの電解質膜の製造方法。
（６）疎水性多孔質基材が、実質的に、重量平均分子量が５０万以下のポリオレフィンのみからなる、上記（１）〜（５）いずれかの電解質膜の製造方法。
As a result of studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention is as follows.
(1) A hydrophobic porous substrate is impregnated with a mixed solution containing a liquid proton-dissociable vinyl monomer and a crosslinking agent having at least two carbon-carbon double bonds in one molecule and not substantially soluble in water. A method for producing an electrolyte membrane to be polymerized, wherein the water content of the mixed solution is 0.5% or less.
(2) The method for producing an electrolyte membrane according to (1), wherein the cross-linking agent is liquid.
(3) The method for producing an electrolyte membrane according to (1) or (2) above, wherein the liquid proton dissociable vinyl monomer is vinyl sulfonic acid.
(4) The method for producing an electrolyte membrane according to any one of (1) to (3), wherein the crosslinking agent further has an N—C═O bond.
(5) The method for producing an electrolyte membrane according to any one of (1) to (4), wherein the crosslinking agent is triallyl isocyanurate.
(6) The method for producing an electrolyte membrane according to any one of the above (1) to (5), wherein the hydrophobic porous substrate is substantially composed only of a polyolefin having a weight average molecular weight of 500,000 or less.
本発明の電解質膜の製造方法により、プロトン解離性液状モノマーと架橋剤のコポリマーが該多孔質基材内に密に充填され、際立った低燃料透過性と高プロトン伝導性を備えた電解質膜を、外観不良を発生させることなく製造することが可能となる。本発明の製造方法により得られた電解質膜は、燃料電池、特に固体高分子型燃料電池や、直接メタノール型燃料電池をはじめとする直接燃料型燃料電池に好適に使用可能である。 By the electrolyte membrane production method of the present invention, a proton dissociable liquid monomer and a cross-linking agent copolymer are closely packed in the porous substrate, and an electrolyte membrane having outstanding low fuel permeability and high proton conductivity is obtained. Thus, it is possible to manufacture without causing appearance defects. The electrolyte membrane obtained by the production method of the present invention can be suitably used for fuel cells, particularly solid polymer fuel cells and direct fuel fuel cells including direct methanol fuel cells.
以下本発明を具体的に説明する。本発明において、電解質膜は、液状プロトン解離性ビニルモノマーと、一分子中に少なくとも二つの炭素―炭素二重結合を有する実質的に水に溶解しない架橋剤とを含有する、含水率が０．５％以下の混合液を作成し、これを疎水性多孔質基材に含浸、重合することにより製造される。
本発明において、液状プロトン解離性ビニルモノマーは、分子内に少なくとも一つの炭素−炭素二重結合（Ｃ＝Ｃ結合）と、例えばスルホン酸基、ホスホン酸基、硫酸基、リン酸基、カルボン酸基から選択される、少なくとも一つプロトン解離性官能基を有する液状のビニルモノマーである。
The present invention will be specifically described below. In the present invention, the electrolyte membrane contains a liquid proton dissociable vinyl monomer and a cross-linking agent that has at least two carbon-carbon double bonds in one molecule and is substantially insoluble in water, and has a water content of 0. It is produced by preparing a mixed solution of 5% or less, impregnating and polymerizing this into a hydrophobic porous substrate.
In the present invention, the liquid proton dissociable vinyl monomer includes at least one carbon-carbon double bond (C═C bond) in the molecule, such as a sulfonic acid group, a phosphonic acid group, a sulfuric acid group, a phosphoric acid group, and a carboxylic acid. It is a liquid vinyl monomer having at least one proton dissociable functional group selected from the group.
本発明において、液状とは、３０℃で液状であることをいう。該液状プロトン解離性ビニルモノマーの粘度は、均一混合液として使用される際に、該電解質膜前駆体への良好な含浸性を保つため、４０℃で１０００００ｃＰ以下、より好ましくは１００００ｃＰ以下、更に好ましくは１０００ｃＰ以下であることが好ましい。ここで、粘度は円錐平板型回転粘度計（Ｅ型回転粘度計、ローター回転数５０ｒｐｍ）により測定されるものである。
このような液状解離性ビニルモノマーの例として、ビニルスルホン酸、ビニルホスホン酸、アクリル酸、メタクリル酸、ビニル酢酸等が好ましく用いられる。中でも、プロトン解離性官能基あたりの分子量が小さく、かつプロトン解離性官能基のプロトンが解離しやすい、ビニルスルホン酸を使用すると、イオン交換容量が大きく、高いプロトン伝導性を有する電解質膜が得られるので、特に好ましい。
In the present invention, “liquid” means liquid at 30 ° C. The viscosity of the liquid proton dissociable vinyl monomer is 100000 cP or less, more preferably 10000 cP or less, more preferably 10,000 cP or less at 40 ° C. in order to maintain good impregnation to the electrolyte membrane precursor when used as a homogeneous mixed solution. Is preferably 1000 cP or less. Here, the viscosity is measured by a conical plate type rotational viscometer (E type rotational viscometer, rotor rotational speed 50 rpm).
As examples of such liquid dissociable vinyl monomers, vinyl sulfonic acid, vinyl phosphonic acid, acrylic acid, methacrylic acid, vinyl acetic acid and the like are preferably used. In particular, when vinyl sulfonic acid is used, which has a small molecular weight per proton-dissociable functional group and protons of the proton-dissociable functional group are easily dissociated, an electrolyte membrane having a large ion exchange capacity and high proton conductivity can be obtained. Therefore, it is particularly preferable.
本発明では、必要に応じて、これらの液状プロトン解離性ビニルモノマーを複数種類併用してもよい。また、必要に応じて、液状プロトン解離性ビニルモノマーに、例えば、アクリルアミド−２−メチルプロパンスルホン酸に例示される固体プロトン解離性ビニルモノマーを、液状プロトン解離性ビニルモノマーに溶解しうる範囲内で少量併用してもよい。
本発明において、架橋剤は、分子内に少なくとも二つの炭素―炭素二重結合（Ｃ＝Ｃ結合）を有し、実質的に水に溶解しない架橋剤である。架橋剤は、３０℃で液状であることが好ましく、粘度は、均一混合液として使用される際に、疎水性多孔質基材への良好な含浸性を保つため、４０℃で１０００００ｃＰ以下、より好ましくは１００００ｃＰ以下、更に好ましくは１０００ｃＰ以下の液状であることが好ましい。ここで、粘度は前述の方法により測定される。該架橋剤は、該液状プロトン解離性ビニルモノマーと均一混合液を形成し、かつ実質的に水に溶解しないものであれば特に限定されるものではない。架橋剤は、疎水性多孔質基材に単独でぬれ性を有することが好ましい。例えば、該液状プロトン解離性ビニルモノマーとして、好ましい例であるビニルスルホン酸を使用する場合、好ましくは分子内に少なくとも二つのＣ＝Ｃ二重結合と、Ｎ−Ｃ＝Ｏ結合を有する液状架橋剤、より好ましくはトリアリルイソシアヌレートが使用可能である。
In the present invention, if necessary, a plurality of these liquid proton dissociable vinyl monomers may be used in combination. Further, if necessary, in the liquid proton dissociable vinyl monomer, for example, a solid proton dissociable vinyl monomer exemplified by acrylamide-2-methylpropanesulfonic acid may be dissolved in the liquid proton dissociable vinyl monomer. A small amount may be used together.
In the present invention, the crosslinking agent is a crosslinking agent having at least two carbon-carbon double bonds (C═C bond) in the molecule and substantially not soluble in water. The cross-linking agent is preferably liquid at 30 ° C., and the viscosity is 100000 cP or less at 40 ° C. in order to maintain good impregnation into the hydrophobic porous substrate when used as a homogeneous mixed solution. The liquid is preferably 10000 cP or less, more preferably 1000 cP or less. Here, the viscosity is measured by the method described above. The crosslinking agent is not particularly limited as long as it forms a uniform mixed solution with the liquid proton dissociable vinyl monomer and does not substantially dissolve in water. The cross-linking agent preferably has wettability alone on the hydrophobic porous substrate. For example, when vinyl sulfonic acid which is a preferred example is used as the liquid proton dissociable vinyl monomer, a liquid crosslinking agent preferably having at least two C═C double bonds and N—C═O bonds in the molecule. More preferably, triallyl isocyanurate can be used.
混合液中の液状プロトン解離性ビニルモノマーと液状架橋剤の量比は、該電解質膜の膜燃料透過性やプロトン伝導性に影響する、該電解質膜のイオン交換容量及び含水率や、該電解質膜を製造する際に液状プロトン解離性ビニルモノマーと液状架橋剤が均一混合液を形成しうる混合比で決まるもので、特に限定されるものではない。例えば、該液状プロトン解離性ビニルモノマーとして、好ましい例であるビニルスルホン酸を使用する場合、該液状架橋剤として、好ましい例であるトリアリルイソシアヌレートを使用する場合、該ビニルモノマーと該架橋剤の混合重量比は、混合液の均一性、疎水性多孔質基材への含浸性の点から、好ましくは４０／６０〜７０／３０である。 The quantity ratio of the liquid proton dissociable vinyl monomer and the liquid crosslinking agent in the mixed solution affects the membrane fuel permeability and proton conductivity of the electrolyte membrane, the ion exchange capacity and water content of the electrolyte membrane, and the electrolyte membrane. The liquid proton dissociable vinyl monomer and the liquid cross-linking agent are determined by a mixing ratio capable of forming a uniform mixed solution, and are not particularly limited. For example, when vinyl sulfonic acid which is a preferred example is used as the liquid proton dissociable vinyl monomer, when triallyl isocyanurate which is a preferred example is used as the liquid crosslinking agent, the vinyl monomer and the crosslinking agent The mixing weight ratio is preferably 40/60 to 70/30 from the viewpoint of the uniformity of the mixed solution and the impregnation property to the hydrophobic porous substrate.
本発明では、液状プロトン解離性ビニルモノマーと架橋剤の混合液の含水率が０．５％以下である。含水率が０．５％以下であることにより、（ｉ）単独では親水性が強く疎水性多孔質基材に含浸されない該液状プロトン解離性ビニルモノマーを、電解質膜形成後脱落すると考えられる、溶媒や界面活性剤を併用することなく疎水性多孔質基材に含浸させることができ、液状プロトン解離性ビニルモノマーと架橋剤の緻密な電解質重合体を形成し、結果得られる電解質膜の水素透過性やメタノール透過性を抑制できる効果だけでなく、（ｉｉ）該液状プロトン解離性ビニルモノマーと該架橋剤が重合後、含水膨張により疎水性多孔質基材、特に実質的に重量平均分子量が５０万以下のポリオレフィンのみからなる疎水性多孔質基材が変形破壊し、得られる電解質膜に外観不良が発生するのを防止する効果があると考えられる。含水率は好ましくは０．４％以下である。 In the present invention, the water content of the liquid mixture of the liquid proton dissociable vinyl monomer and the crosslinking agent is 0.5% or less. A solvent that has a water content of 0.5% or less, and (i) the liquid proton-dissociable vinyl monomer, which is highly hydrophilic by itself and not impregnated in the hydrophobic porous substrate, is considered to drop off after the formation of the electrolyte membrane. Can be impregnated into a hydrophobic porous substrate without using a surfactant or a surfactant, forming a dense electrolyte polymer of a liquid proton dissociable vinyl monomer and a crosslinking agent, and the resulting electrolyte membrane's hydrogen permeability And (ii) after the polymerization of the liquid proton-dissociable vinyl monomer and the cross-linking agent, the hydrous expansion causes a hydrophobic porous substrate, particularly a weight average molecular weight of substantially 500,000. It is considered that the hydrophobic porous substrate made of only the following polyolefin is deformed and broken, and has an effect of preventing the appearance failure of the resulting electrolyte membrane. The water content is preferably 0.4% or less.
混合液の均一性は、液状プロトン解離性ビニルモノマーと架橋剤の組み合わせを工夫することにより、一層向上できる。例えば、先述の通り、該液状プロトン解離性ビニルモノマーとして、好ましい例であるビニルスルホン酸を使用する場合、架橋剤として、好ましい例であるＮ−Ｃ＝Ｏ結合を有する液状のトリアリルイソシアヌレートを使用することが好ましい。また必要に応じて、混合液の含水率が０．５％以下の範囲で、該液状プロトン解離性ビニルモノマーに溶解可能な、少なくとも一つの炭素−炭素二重結合（Ｃ＝Ｃ結合）を有する非解離性モノマーや、固体状プロトン解離性ビニルモノマーを、非解離性モノマーが解離性液状モノマーの重量を超えない範囲で混合液に少量溶解させ、共重合して併用してもよい。 The uniformity of the mixed liquid can be further improved by devising a combination of a liquid proton dissociable vinyl monomer and a crosslinking agent. For example, as described above, when vinyl sulfonic acid which is a preferable example is used as the liquid proton dissociable vinyl monomer, a liquid triallyl isocyanurate having an N—C═O bond which is a preferable example is used as a crosslinking agent. It is preferable to use it. Further, if necessary, it has at least one carbon-carbon double bond (C═C bond) that is soluble in the liquid proton-dissociable vinyl monomer within a range where the water content of the mixed liquid is 0.5% or less. A small amount of a non-dissociable monomer or a solid proton-dissociable vinyl monomer may be dissolved in a mixed solution in a range in which the non-dissociable monomer does not exceed the weight of the dissociable liquid monomer, and copolymerized and used together.
混合液は、液状プロトン解離性ビニルモノマーと架橋剤を主成分とすることが好ましく、５０ｗｔ％以上含有すること、更には８０ｗｔ％以上、更に好ましくは９０ｗｔ％以上含有することが好ましい。
混合液は、得られる電解質膜のメタノール透過性を低く保つため、実質的に水以外のアルコール類をはじめとする有機溶剤等の溶媒を含有しないことが好ましい。
本発明において、疎水性多孔質基材は、例えば、ポリオレフィン、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリイミド等の、水や液体燃料に実質的に膨潤、溶解することのない、疎水性のポリマーからなり、三次元網目構造を有する通気性の多孔質基材である。好ましくは、ポリエチレン、ポリプロピレンに代表されるポリオレフィン系ポリマー及びコポリマーや、ポリフッ化ビニリデンポリマー及びコポリマーを主成分とするものである。得られる電解質膜のハンドリング性と、プロトン伝導性を燃料電池用電解質膜として好ましい範囲に保つため、疎水性多孔質基材の厚みは、好ましくは５〜１００μｍ、より好ましくは１０〜６０μｍであり、気孔率は好ましくは、２５〜７０％が好ましく、より好ましくは３０〜５５％であり、厚み２５μｍ換算透気度は好ましくは２００〜９００秒／１００ｃｃ、より好ましくは３００〜８００秒／１００ｃｃである。含浸重合させる液状プロトン解離性ビニルモノマーと架橋剤のコポリマーの含水膨張を抑えるために、多孔質膜を構成するポリマーの重量平均分子量が２５万以上であり、二軸方向に３×３〜１０×１０倍、更には５×５〜１０×１０倍延伸処理がなされた強度の高いものであることが好ましい。更に、重量平均分子量が２５万以上５０万以下のポリオレフィンのみからなることが、疎水性多孔質基材の生産性や、得られる電解質膜のプロトン伝導性やメタノール透過性の安定性などの観点から好ましい。
The mixed solution preferably contains a liquid proton-dissociable vinyl monomer and a crosslinking agent as main components, preferably 50 wt% or more, more preferably 80 wt% or more, and still more preferably 90 wt% or more.
In order to keep the methanol permeability of the obtained electrolyte membrane low, the mixed solution preferably does not substantially contain a solvent such as an organic solvent including alcohols other than water.
In the present invention, the hydrophobic porous substrate is made of a hydrophobic polymer that does not substantially swell or dissolve in water or liquid fuel, such as polyolefin, polyvinylidene fluoride, polytetrafluoroethylene, and polyimide. It is a breathable porous substrate having a three-dimensional network structure. Preferably, the main component is a polyolefin polymer or copolymer represented by polyethylene or polypropylene, or a polyvinylidene fluoride polymer or copolymer. The thickness of the hydrophobic porous substrate is preferably 5 to 100 μm, more preferably 10 to 60 μm, in order to keep the handling property and proton conductivity of the obtained electrolyte membrane in a preferable range as an electrolyte membrane for a fuel cell. The porosity is preferably 25 to 70%, more preferably 30 to 55%, and the 25 μm-thickness air permeability is preferably 200 to 900 seconds / 100 cc, more preferably 300 to 800 seconds / 100 cc. . In order to suppress the hydrous expansion of the copolymer of the liquid proton dissociable vinyl monomer and the crosslinking agent to be impregnated, the polymer constituting the porous membrane has a weight average molecular weight of 250,000 or more, and 3 × 3 to 10 × in the biaxial direction. It is preferable that it is a thing with high intensity | strength in which the extending | stretching process was made 10 times, and also 5 * 5-10 * 10 times. Furthermore, it consists only of polyolefin having a weight average molecular weight of 250,000 or more and 500,000 or less from the viewpoint of productivity of the hydrophobic porous substrate, stability of proton conductivity and methanol permeability of the obtained electrolyte membrane, and the like. preferable.
本発明において、混合液は、例えば、（Ｉ）高エネルギー線を照射された電解質膜前駆体に直接、あるいは、（ＩＩ）さらにラジカル重合開始剤が溶解した均一混合液として、該疎水性多孔質基材に含浸、重合されることにより、該液状プロトン解離性ビニルモノマーと、該液状架橋剤の重合体となり、該疎水性多孔質基材に充填される。
（Ｉ）法で使用可能な高エネルギー線として、例えば、プラズマ、紫外線、電子線、γ線等、公知の高エネルギー線が使用可能である。これらの高エネルギー線は、該電解質膜前駆体を励起させ、反応開始点を生成させ、これと該モノマー液が反応するため、重合開始剤を使用しなくても、該モノマー液の重合体が形成される。
In the present invention, the hydrophobic liquid is, for example, (I) the hydrophobic porous material directly in the electrolyte membrane precursor irradiated with high energy rays, or (II) as a homogeneous mixed liquid in which a radical polymerization initiator is further dissolved. By impregnating and polymerizing the base material, a polymer of the liquid proton dissociable vinyl monomer and the liquid cross-linking agent is formed, and the hydrophobic porous base material is filled.
As the high energy rays that can be used in the method (I), known high energy rays such as plasma, ultraviolet rays, electron beams, and γ rays can be used. These high energy rays excite the electrolyte membrane precursor to generate a reaction initiation point, which reacts with the monomer liquid, so that the polymer of the monomer liquid can be obtained without using a polymerization initiator. It is formed.
（ＩＩ）法で使用可能なラジカル重合開始剤として、公知のラジカル重合法の技術を使用することができる。具体例としては、熱開始重合、紫外線等の光開始重合等が挙げられる。熱開始重合のラジカル重合開始剤の具体例とし、一般的に熱開始重合に利用されている、過酸エステル、ベンゾイルパーオキサイド、ジ−ｔ−ブチルパーオキサイド等の有機過酸化物等が挙げられる。
ラジカル系光重合開始剤の具体例としては、一般に紫外線重合に利用されている、ベンゾインエーテル系開始剤、アセトフェノン系開始剤、ベンゾフェノン系開始剤、チオキサントン系開始剤、ベンジル、キノン、チオアクリドンおよびこれらの誘導体等が挙げられる。これらラジカル重合開始剤は、単独で用いてもよく、また、二種類以上を併用してもよい。重合開始剤は、重合開始剤を含めた均一混合液の含水率を０．５％以下に抑えるために、均一混合液へ直接溶解できることが好ましい。また、重合開始剤の使用量は、均一混合液中の、液状プロトン解離性ビニルモノマーと架橋剤の合計１００重量部に対して、０．００１〜５ｗｔ％、更には０．０１〜３ｗｔ％の必要最小限量であることが好ましい。
As a radical polymerization initiator usable in the method (II), a known radical polymerization technique can be used. Specific examples include heat-initiated polymerization and photoinitiated polymerization such as ultraviolet rays. Specific examples of radical polymerization initiators for thermal initiation polymerization include organic peroxides such as peroxide esters, benzoyl peroxide, and di-t-butyl peroxide, which are generally used for thermal initiation polymerization. .
Specific examples of radical photopolymerization initiators include benzoin ether initiators, acetophenone initiators, benzophenone initiators, thioxanthone initiators, benzyl, quinone, thioacridone, and those generally used for ultraviolet polymerization. Derivatives and the like. These radical polymerization initiators may be used alone or in combination of two or more. It is preferable that the polymerization initiator can be directly dissolved in the homogeneous mixed solution in order to suppress the water content of the homogeneous mixed solution including the polymerization initiator to 0.5% or less. The amount of the polymerization initiator used is 0.001 to 5 wt%, further 0.01 to 3 wt% with respect to a total of 100 parts by weight of the liquid proton dissociable vinyl monomer and the crosslinking agent in the uniform mixed solution. The minimum amount is preferable.
下記実施例、比較例にて本発明を説明する。尚本実施例は発明の範囲を限定するものではない。
（１）含水率の測定
容量滴定方式カールフィッシャー水分計（京都電子工業株式会社製）を用いて、カールフィッシャー法により、疎水性多孔質基材に充填する直前の均一混合液の含水率を測定した。
（２）プロトン伝導性の測定
４０℃、水中における膜面方向のプロトン伝導度（Ｓ／ｃｍ）を、４端子法により、電気化学測定システム「１２８０Ｚ」（商標、ソーラトロン社製）を用いて、測定した交流インピーダンスから求め、この値を膜厚み（ｃｍ）で割り、プロトン伝導性（Ｓ／ｃｍ２）とした。
（３）メタノール透過性の測定
フロー式ガス・蒸気・液体透過率測定装置「ＧＴＲ−２０ＸＦＡＣ」（商標、ＧＴＲテック株式会社製）を用いて、膜を４０℃に制御されたチャンバー内のセルにセットし、１．５４ｃｍ２の膜の上面に３０ｗｔ％メタノール水溶液を循環させ、膜の下面に乾燥ヘリウムを流し、メタノールを浸透気化させた。膜下面に流したヘリウムを、ガスサンプラーを設けた六方バルブにより一定間隔でサンプリングし、ガスクロマトグラフでヘリウム中のメタノール量を定量した。メタノール量の経時変化を追跡し、一定になった時点のメタノール量から、メタノール透過性を求めた。
（４）気孔率の測定
１０ｃｍ角のサンプルをとり、その体積と質量から次式を用いて計算した。
気孔率（％）＝（体積（ｃｍ３）−質量（ｇ）／ポリマーの密度）／体積（ｃｍ３）×１００
（５）透気度の測定
ＪＩＳ−Ｐ−８１１７に準拠し、２５℃で測定した。
The following examples and comparative examples illustrate the present invention. Note that this example does not limit the scope of the invention.
(1) Measurement of moisture content Using a volumetric titration Karl Fischer moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd.), measure the moisture content of the homogeneous mixture just before filling the hydrophobic porous substrate by the Karl Fischer method. did.
(2) Measurement of proton conductivity The proton conductivity (S / cm) in the direction of the membrane surface in water at 40 ° C. was measured by the 4-terminal method using an electrochemical measurement system “1280Z” (trademark, manufactured by Solartron). It calculated | required from the measured alternating current impedance, and divided | segmented this value by membrane thickness (cm), and it was set as proton conductivity (S / cm < 2 >).
(3) Measurement of methanol permeability Using a flow type gas / vapor / liquid permeability measuring device “GTR-20XFAC” (trademark, manufactured by GTR Tech Co., Ltd.), the membrane is placed in a cell in a chamber controlled at 40 ° C. A 30 wt% aqueous methanol solution was circulated on the upper surface of the 1.54 cm 2 membrane, and dry helium was allowed to flow through the lower surface of the membrane to vaporize methanol. The helium flowed on the lower surface of the membrane was sampled at regular intervals by a hexagonal valve equipped with a gas sampler, and the amount of methanol in the helium was quantified with a gas chromatograph. The change in the amount of methanol over time was followed, and the methanol permeability was determined from the amount of methanol when the amount became constant.
(4) Measurement of porosity A 10 cm square sample was taken and calculated from its volume and mass using the following formula.
Porosity (%) = (volume (cm 3 ) −mass (g) / polymer density) / volume (cm 3 ) × 100
(5) Measurement of air permeability It measured at 25 degreeC based on JIS-P-8117.
［実施例１］
液状プロトン解離性モノマーであるビニルスルホン酸（粘度：７ｃＰ）５０重量部、液状架橋剤であるトリアリルイソシアヌレート（粘度：１００ｃＰ）５０重量部、光重合開始剤０．１重量部からなる、実質的に溶媒を含まない均一混合液を作成した。該均一混合液の含水率は０．１％であった。該均一混合液に窒素バブリングを行った後、疎水性の多孔質基材である、ポリエチレン多孔質膜（厚み３８μｍ、気孔率４３％、透気度６１０秒／１００ｃｃ、重量平均分子量２８万）を浸漬し、該均一混合液を該微多孔膜に含浸させた。これを該均一混合液から引き上げ、ポリエチレン袋に密封し、余分な該均一混合液を除き、石英ガラス板ではさんだ後、高圧水銀ランプを１５分間照射し、該微多孔膜中に含浸されたビニルスルホン酸とトリアリルイソシアヌレートを重合させ、さらにこれを５０℃のオーブンに２４時間保管し、重合を完了させた。最後に、得られた膜を取り出し、水洗を行い、膜表面に付着した余分な電解質を取り除くことにより、電解質膜を作成した。本電解質膜のプロトン伝導性は１１Ｓ／ｃｍ２、メタノール透過性は４ｋｇ／ｍ２日で、多孔質基材の変形による外観不良は認められなかった。
[Example 1]
It consists of 50 parts by weight of vinyl sulfonic acid (viscosity: 7 cP) as a liquid proton dissociable monomer, 50 parts by weight of triallyl isocyanurate (viscosity: 100 cP) as a liquid crosslinking agent, and 0.1 part by weight of a photopolymerization initiator. Thus, a uniform mixed solution containing no solvent was prepared. The water content of the homogeneous mixed solution was 0.1%. After nitrogen bubbling was performed on the uniform mixed solution, a porous polyethylene membrane (thickness 38 μm, porosity 43%, air permeability 610 sec / 100 cc, weight average molecular weight 280,000), which is a hydrophobic porous substrate, was obtained. It was immersed and the microporous membrane was impregnated with the uniform mixed solution. This is pulled up from the homogeneous mixture, sealed in a polyethylene bag, removed from the excess homogeneous mixture, sandwiched by a quartz glass plate, irradiated with a high pressure mercury lamp for 15 minutes, and impregnated into the microporous film. The sulfonic acid and triallyl isocyanurate were polymerized and further stored in an oven at 50 ° C. for 24 hours to complete the polymerization. Finally, the obtained membrane was taken out, washed with water, and an excess electrolyte adhered to the membrane surface was removed to prepare an electrolyte membrane. The electrolyte membrane had a proton conductivity of 11 S / cm 2 and a methanol permeability of 4 kg / m 2 days, and no poor appearance due to deformation of the porous substrate was observed.
［実施例２］
均一混合液の含水率を０．４％とする以外は、実施例１と同様の方法で電解質膜を作成した。本電解質膜のプロトン伝導性は１１Ｓ／ｃｍ２、メタノール透過性は５ｋｇ／ｍ２日で、多孔質基材の変形による外観不良は認められなかった。
[Example 2]
An electrolyte membrane was prepared in the same manner as in Example 1 except that the water content of the uniform mixed solution was 0.4%. The electrolyte membrane had a proton conductivity of 11 S / cm 2 and a methanol permeability of 5 kg / m 2 days. No poor appearance due to deformation of the porous substrate was observed.
［比較例１］
均一混合液の含水率を０．６％とする以外は、実施例１と同様の方法で電解質膜を作成した。本電解質膜のプロトン伝導性は１１Ｓ／ｃｍ２、メタノール透過性は５ｋｇ／ｍ２日であったが、多孔質基材の変形による泡状の外観不良が認められた。
[Comparative Example 1]
An electrolyte membrane was prepared in the same manner as in Example 1 except that the water content of the uniform mixed solution was 0.6%. The proton conductivity of the electrolyte membrane was 11 S / cm 2 and the methanol permeability was 5 kg / m 2 days. However, a bubble-like appearance defect due to deformation of the porous substrate was observed.
本発明の架橋電解質膜は燃料電池、特に固体高分子型燃料電池や、直接メタノール型燃料電池をはじめとする直接燃料型燃料電池に好適に使用可能である。 The crosslinked electrolyte membrane of the present invention can be suitably used for fuel cells, particularly solid polymer fuel cells and direct fuel fuel cells including direct methanol fuel cells.
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