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WO2009110052A1 - Membrane électrolytique polymère, son utilisation et son procédé de fabrication - Google Patents

Membrane électrolytique polymère, son utilisation et son procédé de fabrication Download PDF

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Publication number
WO2009110052A1
WO2009110052A1 PCT/JP2008/053741 JP2008053741W WO2009110052A1 WO 2009110052 A1 WO2009110052 A1 WO 2009110052A1 JP 2008053741 W JP2008053741 W JP 2008053741W WO 2009110052 A1 WO2009110052 A1 WO 2009110052A1
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group
polymer electrolyte
polymer
electrolyte membrane
general formula
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Japanese (ja)
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北村　幸太
坂口　佳充
裕樹 山口
全広 山下
佐々井　孝介
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Toyobo Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04197—Preventing means for fuel crossover
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C08J2365/02—Polyphenylenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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

Definitions

  • the present invention relates to a polymer electrolyte membrane, and more particularly to a polymer electrolyte membrane suitable for a fuel cell having low methanol permeability and excellent proton conductivity.
  • polymer electrolyte membranes exhibit methanol permeability as well as proton conductivity.
  • methanol has a high affinity with water, and thus easily permeates the polymer electrolyte membrane.
  • a membrane containing a perfluorocarbon sulfonic acid polymer widely used as a polymer electrolyte membrane for fuel cells has high methanol permeability. For this reason, there may be a problem that the concentration of the aqueous methanol solution in the fuel cannot be increased and the power generation efficiency cannot be increased.
  • hydrocarbon polymer electrolyte membranes that use polymers with ionic groups such as sulfonic acid groups introduced into heat-resistant polymers such as polyimide and polysulfone are compared to perfluorocarbon sulfonic acid polymer polymer electrolyte membranes. Because of its low methanol permeability, it is expected to be used for methanol fuel cells (see, for example, Patent Document 1).
  • Patent Document 5 it is already known to add a compound containing a hydroxyl group to the polymer electrolyte membrane.
  • a compound containing a hydroxyl group examples thereof include a polymer electrolyte membrane containing polyvinyl alcohol (see Patent Document 5) and a polymer electrolyte membrane containing a compound having a phenolic hydroxyl group (see Patent Document 6 or 7).
  • Patent Document 2 also describes that a phenol resin can be blended with the polymer electrolyte.
  • the output voltage was plotted against the current density (showing the output characteristics of the polymer electrolyte membrane).
  • the output is plotted against the current density (showing the output characteristics of the polymer electrolyte membrane).
  • the present invention has been made against the background of the problems of the prior art, and is intended to suppress methanol permeability without significantly lowering proton conductivity, and has low methanol permeability and high proton conductivity.
  • a molecular electrolyte membrane is to be provided.
  • the inventors of the present invention minimize the decrease in proton conductivity by adding a polymer of a specific phenolic hydroxyl group-containing compound to the polymer electrolyte.
  • the present inventors found that methanol permeability can be greatly suppressed. It has been found that a polymer of a phenolic hydroxyl group-containing compound that is insoluble in methanol is one of the preferred embodiments of the polymer of a phenolic hydroxyl group-containing compound, and among them, a phenol aralkyl resin is a particularly preferred embodiment. Moreover, it discovered that a phenol cycloalkyl resin was also one of the preferable aspects.
  • the present invention (1) One or more phenolic hydroxyl group-containing resins having a solubility in methanol at 25 ° C. of 1% by weight or less and a solubility in N-methyl-2-pyrrolidone at 25 ° C.
  • a polymer electrolyte membrane comprising 2 to 100% by weight of an electrolyte.
  • a polymer electrolyte comprising a film containing 2 to 100% by weight of one or more resins selected from the group consisting of phenol aralkyl resins and phenol cycloalkyl resins with respect to the polymer electrolyte film.
  • Ar 1 represents one or more groups selected from the group consisting of the following general formulas (2) to (4)
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and one or more groups selected from the group consisting of groups represented by the following general formula (5), or a cyclic hydrocarbon group R 2 and the number of carbon together are 3 ⁇
  • R 2 is hydrogen
  • R 3 is a hydrogen atom and One or more groups selected from the group consisting of methyl groups
  • R 4 is one or more groups selected from the group consisting of hydrogen atoms and methyl groups
  • m is an integer from 0 to 2
  • n is from 1 to 100,000. Each represents an integer.
  • R 5 represents one or more groups selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms
  • p1 represents an integer of 0 to 4.
  • R 6 represents one or more groups selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms
  • p2 represents an integer of 0 to 6.
  • R 7 represents one or more groups selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms
  • R 8 represents a hydrogen atom and an alkyl having 1 to 20 carbon atoms.
  • One or more groups selected from the group consisting of groups, p3 represents an integer of 0 to 3, and p4 represents an integer of 0 to 4, respectively.
  • R 9 represents a direct bond between benzene rings, a sulfonyl group, a sulfone group, a carbonyl group, a methylene group, an isopropylidene group, a hexafluoroisopropylidene group, a phenylene group, a cyclohexylidene group, One or more groups selected from the group consisting of bis (isopropylidene) phenyl group, oxygen atom, sulfur atom, bis (oxy) phenyl group, and bis (thio) phenyl group, R 10 represents a hydrogen atom, a hydroxyl group, and One or more groups selected from the group consisting of alkoxy groups having 1 to 10 carbon atoms, R 11 is one or more groups selected from the group consisting of hydrogen atoms and alkyl groups having 1 to 20 carbon atoms, q Represents an integer of 0 to 4, respectively. ]
  • R 12 represents one or more groups selected from the group consisting of a hydrogen atom and a methyl group
  • R 13 represents one or more groups selected from the group consisting of a hydrogen atom and a methyl group
  • R 14 represents one or more groups selected from the group consisting of a hydrogen atom and a methyl group
  • n1 represents an integer of 1 to 100,000.
  • R 15 represents one or more groups selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a group represented by the following general formula (5); 16 and the cyclic hydrocarbon groups together form a carbon number of 3 to 20
  • R 16 is one or more groups selected from the group consisting of a hydrogen atom and alkyl groups having 1 to 20 carbon atoms, or an R 1
  • R 17 is a cycloalkylene group having 4 to 20 carbon atoms
  • m2 is an integer of 0 to 2
  • n2 is an integer of 1 to 100,000, Represent each.
  • R 9 represents a direct bond between benzene rings, a sulfonyl group, a sulfone group, a carbonyl group, a methylene group, an isopropylidene group, a hexafluoroisopropylidene group, a phenylene group, a cyclohexylidene group, One or more groups selected from the group consisting of bis (isopropylidene) phenyl group, oxygen atom, sulfur atom, bis (oxy) phenyl group, and bis (thio) phenyl group, R 10 represents a hydrogen atom, a hydroxyl group, and One or more groups selected from the group consisting of alkoxy groups having 1 to 10 carbon atoms, R 11 is one or more groups selected from the group consisting of hydrogen atoms and alkyl groups having 1 to 20 carbon atoms, q Represents an integer of 0 to 4, respectively. ]
  • R 18 represents one or more groups selected from the group consisting of a hydrogen atom and a methyl group, and n3 represents an integer of 1 to 100,000, respectively.
  • R 18 ′ represents one or more groups selected from the group consisting of alkyl groups having 1 to 20 carbon atoms
  • R 18 ′′ represents a methylene group, and 2 to 10 carbon atoms.
  • One or more phenolic hydroxyl group-containing resins selected from the group consisting of phenol aralkyl resins and phenol cycloalkyl resins have a solubility in methanol at 25 ° C. of 10% by weight or less and N-methyl- at 25 ° C.
  • the hydrocarbon polymer electrolyte contains a sulfonic acid group and includes at least one selected from the group consisting of polysulfone, polyethersulfone, polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfide sulfone, and polyether ketone polymer.
  • the polymer electrolyte membrane according to claim 10, comprising any one of a polyarylene ether compound, a polyarylene sulfide compound and a polyarylene compound as a constituent component and having an ion exchange capacity of 0.5 to 3.0 meq / g. .
  • X represents a —S ( ⁇ O) 2 — group or —C ( ⁇ O) — group
  • Y represents H or a monovalent cation
  • R 19 represents the number of carbon atoms.
  • R 20 and R 21 may contain a sulfur atom or an oxygen atom;
  • a method for producing a polymer electrolyte membrane comprising a polymer electrolyte having an acidic group and a phenolic hydroxyl group-containing resin, wherein the acidic group of the polymer electrolyte comprises an alkali metal ion and a basic compound
  • the polymer electrolyte and a polymer of a phenolic hydroxyl group-containing compound are mixed to form a film, and then the acidic group of the obtained film
  • a method for producing a polymer electrolyte membrane comprising the step of converting the acid into a free acid by acid treatment.
  • the phenolic hydroxyl group-containing resin has 0.001 to 0.01 mol / g of phenolic hydroxyl group in the molecule, has a solubility in methanol of 1% by weight or less at 25 ° C., and N— at 25 ° C.
  • the polymer electrolyte membrane according to the present invention can greatly suppress methanol permeability while minimizing a decrease in proton conductivity. In particular, a remarkable effect is exhibited when the polymer electrolyte is a hydrocarbon polymer electrolyte. Therefore, since the polymer electrolyte membrane according to the present invention is excellent in proton conductivity and can suppress methanol permeability, when used in a fuel cell using methanol as a fuel, the output can be improved or a high-concentration methanol solution can be used. Is used as a fuel to increase the energy density and improve the power generation capacity. Further, since the bondability with the electrode at the time of manufacturing the membrane / electrode assembly is improved, the resistance is reduced and the output can be improved.
  • the weight in this invention means mass.
  • the first aspect of the polymer electrolyte membrane in the present invention is a phenol having a solubility in methanol at 25 ° C. of 1% by weight or less and a solubility in N-methyl-2-pyrrolidone at 25 ° C. of 1% by weight or more.
  • the phenolic hydroxyl group-containing resin is a polymer having a phenolic hydroxyl group-containing compound as a constituent component, and a phenolic hydroxyl group, that is, a compound residue having a hydroxyl group directly bonded to an aromatic ring is directly or by another group.
  • a polymer having a linked structure can be shown as an example, but is not limited thereto.
  • Examples of the group linking a compound residue having a hydroxyl group include a methylene group, an ethylene group, an alkylene group having 3 or more carbon atoms, an alkenylene group, an aralkylene group, a sulfide group, an ether group, a carbonyl group, a sulfonyl group, and a sulfone group. However, it is not limited to these.
  • the number of atoms substantially contributing to the linkage is preferably 1 (for example, methylene group, 1,1-ethylene group, 2,2-propylene).
  • the phenolic hydroxyl group-containing compound is linked with an ethylene group
  • the phenolic hydroxyl group-containing compound is preferably bonded to the same carbon atom.
  • the linking group is an alkylene group having 3 or more carbon atoms
  • the alkyl group preferably has a cyclic structure.
  • the phenolic hydroxyl group-containing compound is preferably bonded with a cyclic alkylene group or an aralkylene group.
  • the linking group is an aralkylene group, it is preferably bonded to the phenolic hydroxyl group-containing compound by a methylene group bonded to an aromatic group or a methylene group substituted with an alkyl group.
  • the solubility in methanol increases, and the polymer electrolyte membrane In some cases, it is impossible to achieve the problem of suppressing methanol permeability.
  • a 1,2-ethylene group for example, poly (4-hydroxystyrene)
  • the phenolic hydroxyl group-containing resin examples include a phenol aralkyl resin, a phenol cycloalkyl resin, an alkyl phenol resin, a phenol terpene resin, an aralkyl group-substituted phenol resin, a phenyl group-substituted phenol resin, and a phenoxy group-substituted phenol resin.
  • the alkylphenol resin is one of these preferable resins because of its excellent solubility and mixing properties. When these resins are used, there is a secondary effect that the softening temperature of the polymer electrolyte is lowered and the workability is improved, such as bonding with an electrode by hot pressing.
  • the phenolic hydroxyl group-containing resin it is essential to select and use one having a solubility in methanol at 25 ° C. of 1% by weight or less. More preferred are those having a solubility in methanol of 0.5% by weight or less, and even more preferred that they are substantially insoluble in methanol. A high solubility in methanol is not preferable because the permeability of the aqueous methanol solution increases. Further, it is essential that the phenolic hydroxyl group-containing resin has a solubility in N-methyl-2-pyrrolidone at 25 ° C. of 1% by weight or more. The solubility in N-methyl-2-pyrrolidone is preferably 10% by weight or more, and more preferably 20% by weight.
  • the solubility of the polymer electrolyte, which is a polar compound, in N-methyl-2-pyrrolidone, which is a good solvent, is a measure of the affinity between the phenolic hydroxyl group-containing resin and the polymer electrolyte membrane.
  • the phenolic hydroxyl group-containing resin and the polymer electrolyte membrane can be dissolved and mixed in a solvent such as N-methyl-2-pyrrolidone, or can be mixed by melting without using a solvent.
  • the phenolic hydroxyl group content of the phenolic hydroxyl group-containing resin is preferably in the range of 0.001 to 0.01 mol / g, and more preferably in the range of 0.005 to 0.01 mol / g.
  • the molecular weight of the phenolic hydroxyl group-containing resin is preferably in the range of 100 to 1000000.
  • the lower the molecular weight the better the miscibility with the polymer electrolyte membrane, which is preferable.
  • the amount of the phenolic hydroxyl group-containing polymer with respect to the polymer electrolyte is preferably in the range of 2 to 50% by weight of the polymer electrolyte, and more preferably in the range of 3 to 20% by weight.
  • the polymer electrolyte is not particularly limited, but a hydrocarbon polymer electrolyte is preferable because of its large methanol permeation suppressing effect, and an aromatic hydrocarbon polymer electrolyte is preferable because of its greater methanol permeation suppressing effect. More preferred.
  • the mechanism by which the methanol permeability of the polymer electrolyte membrane composed of the polymer (resin) containing the phenolic hydroxyl group-containing compound and the polymer electrolyte is suppressed is not clear. It is presumed that the polymer has a low solubility (preferably not dissolved) in methanol, which suppresses methanol permeation in the membrane. Moreover, it is guessed that the phenolic hydroxyl group contributes to affinity with a polymer electrolyte.
  • a polymer electrolyte having an acidic group such as a sulfonic acid group or a phosphonic acid group or a polar group such as a basic group is easily mixed with a highly polar substance, the polymer having a polar phenolic hydroxyl group is It is presumed that it is effective when mixed with a polymer electrolyte. Even if the compound is poorly soluble in methanol, it will be difficult to uniformly disperse in the polymer electrolyte membrane if the affinity to the polymer electrolyte is low, and the methanol permeation suppression effect will not be obtained. In addition, there is a very high possibility that the film will be hindered.
  • a polymer having another polar group for example, a carboxyl group, a sulfonic acid group, a phosphonic acid group, an imino group, etc., instead of the phenolic hydroxyl group, having a solubility in methanol within the above range.
  • a polymer having another polar group for example, a carboxyl group, a sulfonic acid group, a phosphonic acid group, an imino group, etc.
  • the second preferred embodiment of the present invention comprises 2 to 100% by weight of one or more phenolic hydroxyl group-containing resins selected from the group consisting of phenol aralkyl resins and phenol cycloalkyl resins, based on the polymer electrolyte.
  • the phenol aralkyl resin in the present invention is a group having a phenolic hydroxyl group, that is, a group in which a hydroxyl group is bonded to an aromatic group, and an aralkyl group, that is, a group comprising an aromatic group and a non-aromatic hydrocarbon group.
  • the group having a phenolic hydroxyl group is not limited to phenol, phenol derivatives such as cresol, ethylphenol, propylphenol, butylphenol, bisphenol A, bisphenol S, bisphenol B, bisphenol H, biphenol, and their Groups derived from polyphenol compounds such as derivatives and naphthol compounds such as naphthol and naphthdiol are also included.
  • the aralkyl group represents a group having two methylene groups which may have a substituent with respect to the aromatic group, a xylidene group, ⁇ , ⁇ ′-dimethylxylidene group, a naphthalene derivative having a methylene group, Examples thereof include, but are not limited to, biphenyl derivatives having a methylene group.
  • the phenol aralkyl resin in the present invention can be obtained by subjecting the compound having a phenolic hydroxyl group and an aralkyl group compound to a condensation reaction.
  • a compound having a phenolic hydroxyl group an aromatic divinyl compound, an aromatic compound having a vinyl group and a halomethyl group, a bis (halomethyl) aromatic compound, a bis (methoxymethyl) aromatic compound, (Hydroxymethyl) aromatic compounds such as toluenesulfonic acid, hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, maleic acid, etc., aluminum chloride, stannous chloride, zinc chloride, boron trifluoride etherate, It can be obtained by reacting in the presence of a Friedel-Crafts catalyst such as dimethyl sulfate. The reaction temperature can be appropriately selected between 30 ° C.
  • the amount of catalyst is between 0.001 and 5% by weight, and can be appropriately selected according to the type of catalyst, reaction temperature, and raw materials.
  • the raw material may be reacted in a molten state, or in a solvent such as diethyl ketone, methyl ethyl ketone, N, N-dimethylacetamide, N-methyl-2-pyrrolidone.
  • a compound having a phenolic hydroxyl group the vinyl group undergoes addition polymerization at the ⁇ -position with respect to the benzene ring of the compound having a phenolic hydroxyl group.
  • halomethyl groups such as chloromethyl groups are polymerized by eliminating HCl, methoxymethyl groups methanol, and hydroxymethyl groups water.
  • Such a method for producing a phenol aralkyl resin includes, for example, Japanese Patent Publication No. 47-6510, Japanese Patent Publication No. 48-10960, Japanese Patent Publication No. 61-212284, Japanese Patent Publication No. 61-296024, Japanese Patent Publication No. 63-238129, JP-A-5-78457, and JP-A-2000-53740.
  • the resin composition after the reaction may be used as it is, or may be used after removing unreacted substances, oligomers, modified monomers, etc. by distillation under reduced pressure or reprecipitation, or diethyl ketone, methyl ethyl ketone, N, N It may be used by dissolving in a suitable solvent such as -dimethylacetamide and N-methyl-2-pyrrolidone.
  • the phenol cycloalkyl resin in the present invention is a resin in which a group having a phenolic hydroxyl group, that is, a group in which a hydroxyl group is bonded to an aromatic group and a cycloalkyl group are bonded to form a main structural unit.
  • the group having a phenolic hydroxyl group is not limited to phenol, phenol derivatives such as cresol, ethylphenol, propylphenol, butylphenol, bisphenol A, bisphenol S, bisphenol B, bisphenol H, biphenol, and their Groups derived from polyphenol compounds such as derivatives and naphthol compounds such as naphthol and naphthdiol are also included.
  • cycloalkyl group examples include a cyclobutane group, a cyclopentyl group, a cyclohexyl group, a dicycloheptane group, a dicyclononane group, and a tricyclodecyl group.
  • the phenol cycloalkyl resin in the present invention can be obtained by a condensation reaction between the compound having a phenolic hydroxyl group and a cycloalkyl group compound.
  • a compound having a phenolic hydroxyl group dicyclopentadiene, cycloterpene, pinene, cyclobutadiene, cyclopentadiene, cyclohexadiene, dicycloheptadiene, dicyclononadiene, divinyl cycloalkyl compound, vinyl group and
  • a cycloalkyl compound having a halomethyl group, a bis (halomethyl) cycloalkyl compound, a bis (methoxymethyl) cycloalkyl compound, a bis (hydroxymethyl) cycloalkyl compound, etc. are added with toluenesulfonic acid, hydrochloric acid, sulfuric acid, oxalic acid, It can be obtained by reacting in the presence of an acidic substance such
  • the reaction temperature can be appropriately selected between 30 ° C. and 150 ° C. according to the type of raw material and the degree of polymerization.
  • the amount of catalyst is between 0.001 and 5% by weight, and can be appropriately selected according to the type of catalyst, reaction temperature, and raw materials.
  • the raw material may be reacted in a molten state, or in a solvent such as diethyl ketone, methyl ethyl ketone, N, N-dimethylacetamide, N-methyl-2-pyrrolidone.
  • a solvent such as diethyl ketone, methyl ethyl ketone, N, N-dimethylacetamide, N-methyl-2-pyrrolidone.
  • the vinyl group undergoes addition polymerization at the ⁇ -position with respect to the benzene ring of the compound having a phenolic hydroxyl group.
  • halomethyl groups such as chloromethyl groups are polymerized by eliminating HCl, methoxymethyl groups methanol, and hydroxymethyl groups water.
  • a method for producing such a phenol aralkyl resin is described in, for example, US Pat. No. 3,536,734.
  • the resin composition after the reaction may be used as it is, or may be used after removing unreacted substances, oligomers, modified monomers, etc. by distillation under reduced pressure or reprecipitation, or diethyl ketone, methyl ethyl ketone, N, N It may be used by dissolving in a suitable solvent such as -dimethylacetamide and N-methyl-2-pyrrolidone.
  • the phenol aralkyl resin and the phenol cycloalkyl resin preferably have a molecular weight of 100 to 1,000,000. More preferably, it is between 200 and 500,000.
  • the resin is preferably a substantially linear polymer. If the resin has a large number of branched structures or a network structure, the miscibility with the polymer electrolyte may be lowered.
  • the resin is dissolved in a solvent capable of dissolving a general polymer electrolyte, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and diphenyl sulfone. It is preferable to be able to mix with a solution. When the polymer electrolyte and the resin are not mixed in the same solvent, they can be mixed in a molten state.
  • the phenol aralkyl resin and the phenol cycloalkyl resin have a solubility in methanol at 25 ° C. of preferably 10% by weight or less, and more preferably 1% by weight or less. If the solubility in methanol is large, the methanol permeation suppression performance may be reduced.
  • the amount of the resin relative to the polymer electrolyte membrane is preferably 2 to 50% by weight, and more preferably 2 to 20% by weight. If the amount of the resin is less than 2% by weight based on the polymer electrolyte, the effect of suppressing methanol permeation may not be sufficiently obtained, which is not preferable. On the other hand, if it exceeds 100% by weight, the mechanical properties of the polymer electrolyte membrane may deteriorate, which is not preferable.
  • the content of the resin can be analyzed by an extraction method, an NMR method, or the like.
  • the amount of phenolic hydroxyl group is preferably in the range of 1 to 10 mmol / g, more preferably 1 to 7.5 mmol / g, still more preferably 2 to 6 mmol / g. g, particularly preferably in the range of 2.5 to 5 mmol / g.
  • the amount of the phenolic hydroxyl group is less than 1 mmol / g, the mixing property with the polymer electrolyte is lowered, and there may be a problem in uniformity as the polymer electrolyte membrane.
  • the amount of the phenolic hydroxyl group can be quantified by an arbitrary method such as an NMR method, a hydroxyl group quantification method using an acid anhydride, or an oxidation-reduction titration method.
  • the polymer electrolyte membrane can be analyzed as it is or after the resin is extracted.
  • a polymer (phenolic hydroxyl group-containing resin) containing a phenolic hydroxyl group-containing compound in the present invention such as a phenol aralkyl resin, a phenol cycloalkyl resin and an alkylphenol resin, has a phenolic hydroxyl group and an acidic group of a polymer electrolyte. It is preferred that substantially no bond is formed. Whether or not a bond is formed can be determined by performing IR measurement or NMR measurement on the polymer electrolyte membrane and confirming the presence or absence of a free hydroxyl group. If the peak or signal derived from OH detected by the resin alone is also detected for the polymer electrolyte membrane, it indicates that no bond is formed.
  • the ion exchange capacity of the polymer electrolyte membrane is measured, and it can be determined whether there is a difference between the theoretical amount (the amount of the polymer electrolyte contained in the polymer electrolyte membrane) and the actual measurement value. If the theoretical amount and the actually measured value are equivalent, it can be determined that there is no coupling. It can also be determined by observing whether the polymer electrolyte membrane is immersed in a solvent capable of dissolving the polymer electrolyte. If the polymer electrolyte membrane dissolves satisfactorily, it can be determined that there is no bond. If the polymer electrolyte membrane does not dissolve and only swells or remains partially gelled, it can be determined that there is a bond. it can.
  • the acidic group of the polymer electrolyte and the phenolic hydroxyl group of the phenolic hydroxyl group-containing resin in the present invention such as phenol aralkyl resin, phenol cycloalkyl resin and alkylphenol resin do not form a bond
  • the acid group of the polymer electrolyte membrane is converted to an acid by acid treatment after being mixed with the resin in the state where the acid group of the polymer electrolyte is converted into a salt and forming into a membrane.
  • the substance that forms a salt with the acidic group of the polymer electrolyte is preferably an alkali metal ion such as Li, K, or Na, a monovalent cation such as an aliphatic or aromatic amine compound, or a quaternary ammonium salt.
  • alkali metal ions such as Li, K, and Na are preferable.
  • the polymer electrolyte having a salt of an acidic group and the resin may be mixed in a solution state or in a molten state, but mixing in a solution with higher mixing property is preferable. Further, instead of converting the acidic group of the polymer electrolyte into a salt, it can be halogenated or esterified.
  • the phenol aralkyl resin is preferable because it can have higher methanol permeability suppression performance than the phenol cycloalkyl resin.
  • the mechanism by which the phenol aralkyl resin, phenol cycloalkyl resin and alkyl phenol resin suppress the methanol permeability of the polymer electrolyte membrane is not clear, but it is merely a compound having a phenolic hydroxyl group (for example, poly (4-hydroxylstyrene).
  • phenolic antioxidants such as a phenol aralkyl resin, an alkylphenol resin, or a phenolcycloalkyl resin, since there is no significant permeation suppression effect, a hydrophobic alkyl group, an aralkyl group, or The cycloalkyl group suppresses methanol permeation, and the phenolic hydroxyl group, which is a polar group, improves the miscibility with the polymer electrolyte, so that the miscibility of the polymer electrolyte and the resin is ensured. Is done.
  • the phenol aralkyl resin in the present invention is preferably composed mainly of a structural unit represented by the following general formula (1).
  • the phenol aralkyl resin in the present invention has at least a structural unit represented by the following general formula (1), and other than the structural unit represented by the following general formula (1), terminal groups, other repeating units, etc. You may have.
  • the proportion of the structural unit represented by the following general formula (1) in the phenol aralkyl resin in the present invention is preferably 50% by weight or more, more preferably 80% by weight or more, and 90% by weight or more. More preferably it is. If it is less than 50% by weight, the effect of suppressing methanol permeation may not be sufficiently obtained, which is not preferable.
  • the structural unit other than the structural unit represented by is preferably a terminal group.
  • the terminal group may be any group that can be introduced into the polymer terminal in the synthesis reaction of the phenol aralkyl resin, but is preferably a group derived from a monomer for obtaining a structural unit of the following general formula.
  • Ar 1 represents one or more groups selected from the group consisting of the following general formulas (2) to (4)
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and one or more groups selected from the group consisting of groups represented by the following general formula (5), or a cyclic hydrocarbon group R 2 and the number of carbon together are 3 ⁇
  • R 2 is hydrogen
  • R 3 is a hydrogen atom and One or more groups selected from the group consisting of methyl groups
  • R 4 is one or more groups selected from the group consisting of hydrogen atoms and methyl groups
  • m is an integer from 0 to 2
  • n is from 1 to 100,000. Each represents an integer.
  • R 5 represents one or more groups selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms
  • p1 represents an integer of 0 to 4.
  • R 6 represents one or more groups selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms
  • p2 represents an integer of 0 to 6.
  • R 7 represents one or more groups selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms
  • R 8 represents a hydrogen atom and an alkyl having 1 to 20 carbon atoms.
  • One or more groups selected from the group consisting of groups, p3 represents an integer of 0 to 3, and p4 represents an integer of 0 to 4, respectively.
  • Ar 1 is a group represented by the general formula (2) because the raw material is often available at a low cost.
  • R 5 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • p1 is 1 because the reactivity becomes high.
  • R 6 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • p2 is 1 because the reactivity becomes high.
  • R 7 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • R 7 is an alkyl group having 1 to 20 carbon atoms, it is preferable that p3 is 1 because the reactivity becomes high.
  • R 8 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • p4 is 1 because the reactivity becomes high.
  • R 1 may be integrated with R 2 to form a cyclic alkyl group having 3 to 20 carbon atoms.
  • R 2 may be positioned at the ortho position of R 1 to form an aromatic ring and form a naphthol group.
  • R 1 is preferably a hydrogen atom, a methyl group, or a group represented by the following chemical formula (5).
  • a methyl group is preferred because side reactions during synthesis are easily suppressed.
  • the group represented by the following chemical formula (5) is preferable because the mixing property with the polymer electrolyte is improved.
  • R 9 represents a direct bond between benzene rings, a sulfonyl group, a sulfone group, a carbonyl group, a methylene group, an isopropylidene group, a hexafluoroisopropylidene group, a phenylene group, a cyclohexylidene group, One or more groups selected from the group consisting of bis (isopropylidene) phenyl group, oxygen atom, sulfur atom, bis (oxy) phenyl group, and bis (thio) phenyl group, R 10 represents a hydrogen atom, a hydroxyl group, and One or more groups selected from the group consisting of alkoxy groups having 1 to 10 carbon atoms, R 11 is one or more groups selected from the group consisting of hydrogen atoms and alkyl groups having 1 to 20 carbon atoms, q Represents an integer of 0 to 4, respectively. ]
  • R 9 is a sulfonyl group, a sulfone group, a carbonyl group, a methylene group, an isopropylidene group, a hexafluoroisopropylidene group, a cyclohexylidene group, an oxygen atom, or a sulfur atom
  • R 11 is preferably a hydrogen atom or a methyl group. In the case of a methyl group, q is preferably 1 or 2.
  • R 10 is preferably a hydrogen atom, a methyl group, or a hydroxyl group, and is preferably a hydroxyl group in terms of miscibility with the polymer electrolyte.
  • R 2 is preferably a hydrogen atom or a methyl group.
  • m is preferably 1 or 2.
  • At least one of R 3 and R 4 is preferably a methyl group.
  • n is preferably in the range of 3 to 1,000,000, more preferably in the range of 10 to 100,000.
  • a structural isomer in which R 3 and R 4 are interchanged The structural unit represented by may be included.
  • a more preferred embodiment is a phenol aralkyl resin mainly composed of a structural unit represented by the following general formula (6).
  • R 12 represents one or more groups selected from the group consisting of a hydrogen atom and a methyl group
  • R 13 represents one or more groups selected from the group consisting of a hydrogen atom and a methyl group
  • R 14 represents one or more groups selected from the group consisting of a hydrogen atom and a methyl group
  • n1 represents an integer of 1 to 100,000.
  • R 12 and R 13 are preferably a methyl group.
  • R 14 is preferably a methyl group.
  • n1 is preferably in the range of 3 to 1,000,000, and more preferably in the range of 10 to 100,000.
  • the bonding position of the methylene group or 1,1-ethylene group to the benzene ring may not be constant.
  • the ortho position is predominant, but it may be bonded to the meta position or para position.
  • the benzene rings in the aralkyl group are bonded to each other so as to be in the meta position or the para position, but may be bonded so as to be in the ortho position.
  • the phenol cycloalkyl resin in the present invention is preferably mainly composed of a structural unit represented by the following general formula (7).
  • the phenol cycloalkyl resin in the present invention has at least a structural unit represented by the following general formula (1), and other than the structural unit represented by the following general formula (1), a terminal group and other repeating units. And so on.
  • the proportion of the structural unit represented by the following general formula (1) in the phenol cycloalkyl resin in the present invention is preferably 50% by weight or more, more preferably 80% by weight or more, and 90% by weight or more. More preferably. If it is less than 50% by weight, the effect of suppressing methanol permeation may not be sufficiently obtained, which is not preferable.
  • the structural unit other than the structural unit represented by is preferably a terminal group.
  • the terminal group may be any group that can be introduced into the polymer terminal in the synthesis reaction of the phenol cycloalkyl resin, but is preferably a group derived from a monomer for obtaining a structural unit of the following general formula.
  • R 15 represents one or more groups selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a group represented by the following general formula (5); 16 and the cyclic hydrocarbon groups together form a carbon number of 3 to 20
  • R 16 is one or more groups selected from the group consisting of a hydrogen atom and alkyl groups having 1 to 20 carbon atoms, or an R 1
  • R 17 is a cycloalkylene group having 4 to 20 carbon atoms
  • m2 is an integer of 0 to 2
  • n2 is an integer of 1 to 100,000, Represent each.
  • R 9 represents a direct bond between benzene rings, a sulfonyl group, a sulfone group, a carbonyl group, a methylene group, an isopropylidene group, a hexafluoroisopropylidene group, a phenylene group, a cyclohexylidene group, One or more groups selected from the group consisting of bis (isopropylidene) phenyl group, oxygen atom, sulfur atom, bis (oxy) phenyl group, and bis (thio) phenyl group, R 10 represents a hydrogen atom, a hydroxyl group, and One or more groups selected from the group consisting of alkoxy groups having 1 to 10 carbon atoms, R 11 is one or more groups selected from the group consisting of hydrogen atoms and alkyl groups having 1 to 20 carbon atoms, q Represents an integer of 0 to 4, respectively. ]
  • R 15 may be integrated with R 16 to form a cyclic alkyl group having 3 to 20 carbon atoms.
  • R 16 may be positioned at the ortho position of R 15 to form an aromatic ring and form a naphthol group.
  • R 15 is preferably a hydrogen atom, a methyl group, or a group represented by the following chemical formula (5).
  • a methyl group is preferred because side reactions during synthesis are easily suppressed.
  • the group represented by the following chemical formula (5) is preferable because the mixing property with the polymer electrolyte is improved.
  • R 9 represents a direct bond between benzene rings, a sulfonyl group, a sulfone group, a carbonyl group, a methylene group, an isopropylidene group, a hexafluoroisopropylidene group, a phenylene group, a cyclohexylidene group, One or more groups selected from the group consisting of bis (isopropylidene) phenyl group, oxygen atom, sulfur atom, bis (oxy) phenyl group, and bis (thio) phenyl group, R 10 represents a hydrogen atom, a hydroxyl group, and One or more groups selected from the group consisting of alkoxy groups having 1 to 10 carbon atoms, R 11 is one or more groups selected from the group consisting of hydrogen atoms and alkyl groups having 1 to 20 carbon atoms, q Represents an integer of 0 to 4, respectively. ]
  • R 9 is a sulfonyl group, a sulfone group, a carbonyl group, a methylene group, an isopropylidene group, a hexafluoroisopropylidene group, a cyclohexylidene group, an oxygen atom, or a sulfur atom
  • R 11 is preferably a hydrogen atom or a methyl group. In the case of a methyl group, q is preferably 1 or 2.
  • R 10 is preferably a hydrogen atom, a methyl group, or a hydroxyl group, and is preferably a hydroxyl group in terms of miscibility with the polymer electrolyte.
  • R 17 is preferably a cyclobutane group, a cyclopentyl group, a cyclohexyl group, a dicycloheptane group, a dicyclononane group, or a tricyclodecyl group.
  • a cyclohexyl group, a dicycloheptane group, a dicyclononane group, and a tricyclodecyl group are preferable, and a tricyclodecyl group is more preferable.
  • n2 is preferably in the range of 3 to 1,000,000, and more preferably in the range of 10 to 100,000.
  • a further preferred embodiment of the phenol cycloalkyl resin in the present invention is a phenol cycloalkyl resin mainly composed of a structural unit represented by the following general formula (8).
  • R 18 represents one or more groups selected from the group consisting of a hydrogen atom and a methyl group, and n3 represents an integer of 1 to 100,000, respectively.
  • the bonding position between the tricyclodecyl group and the benzene ring having a phenolic hydroxyl group is not particularly limited, and a resin having a different structure can be produced even if the same raw material is used.
  • the structure represented by the following general formula (8 ') can also be regarded as substantially equivalent.
  • n3 is preferably in the range of 3 to 1,000,000, and more preferably in the range of 10 to 100,000.
  • examples of the compound having a phenolic hydroxyl group may include the following compounds, but are not limited thereto, Any compound can be used as long as it can synthesize a phenol aralkyl resin and a phenol cycloalkyl resin suitable for the conditions.
  • examples of the compound to be reacted with the compound having a phenolic hydroxyl group include the following compounds, but are not limited thereto, and are phenols that meet the above conditions. Any compound that can synthesize an aralkyl resin can be used.
  • p-divinylbenzene, o-divinylbenzene, a mixture of p-divinylbenzene and o-divinylbenzene divinylnaphthalene, divinylbiphenol, divinylanthracene, 1,4-bis (methoxymethyl) benzene, 1,3-bis ( Methoxymethyl) benzene, bis (methoxymethyl) naphthalene, 4,4′-bis (methoxymethyl) biphenyl, bis (methoxymethyl) anthracene, 1,4-bis (chloromethyl) benzene, 1,4-bis (bromomethyl) Benzene, 1,4-bis (fluoromethyl) benzene, 1,4-bis (iodomethyl) benzene, 1,3-bis (chloromethyl) benzene, 1,3-bis (bromomethyl) benzene, 1,3-bis ( Fluoromethyl) benzene, 1,
  • examples of the compound to be reacted with the compound having a phenolic hydroxyl group include the following compounds, but are not limited thereto, and conform to the above conditions. Any compound can be used as long as it can synthesize a phenol cycloalkyl resin.
  • alkylphenol resin in the present invention examples include o- or p-cresol novolak resin, dimethylphenol novolak resin, tertiary butylphenol novolak resin, cresol resol resin and the like.
  • the cresol novolac resin can be obtained, for example, by dehydrating condensation by heating o- or p-cresol and formaldehyde in the presence of an acidic catalyst.
  • the alkylphenol resin can be obtained by reacting a phenol derivative having an alkyl group as a substituent with a condensing agent such as formaldehyde.
  • Alkyl-substituted phenols for obtaining alkylphenol resins include o-cresol, p-cresol, m-cresol, dimethylphenol, trimethylphenol, ethylphenol, diethylphenol, triethylphenol, propylphenol, isopropylphenol, butylphenol, and tertiary. Examples include but are not limited to butylphenol.
  • Examples of the condensing agent to be reacted with the alkyl-substituted phenol include, but are not limited to, formaldehyde and hexamethylenetetramine.
  • Examples of the acidic compound used for the catalyst include strong acids such as hydrochloric acid, sulfuric acid, toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, phosphoric acid, alkylphosphonic acid, and vinylphosphonic acid.
  • the alkyl-substituted phenol, the condensing agent, and the catalyst can be reacted by heating under reflux conditions in the presence or absence of a solvent such as methyl ethyl ketone, cyclohexanone, diethyl ketone, tetrahydrofuran, or dioxane. Unreacted compounds and solvents can be removed by reprecipitation, dialysis, distillation, vacuum distillation or the like. It is preferable to remove unreacted compounds as much as possible.
  • the substituted phenol resins such as aralkyl group-substituted phenol resin, phenyl group-substituted phenol resin, and phenoxy group-substituted phenol resin in the present invention are substituted phenols such as aralkyl group-substituted phenol, phenyl group-substituted phenol, and phenoxy group-substituted phenol, and formaldehyde and the like. It can be obtained by reacting with a condensing agent. These resins can be synthesized in the same manner as the above alkyl-substituted phenol resins.
  • phenol compound that can be used as a raw material examples include 2- (4-hydroxyphenyl) -2-phenylpropane, methylphenylphenol, phenylphenol (hydroxybiphenyl), and phenoxyphenol (hydroxydiphenyl ether). It is not limited to.
  • the phenol aralkyl resin and the phenol cycloalkyl resin are obtained by reacting an excess of a compound having a phenolic hydroxyl group and dehydrating and condensing an oligomer, which is a compound having a phenolic hydroxyl group at the terminal, with a dialdehyde compound such as formaldehyde. Can also be manufactured.
  • the polymer electrolyte in the present invention preferably has an ion exchange capacity of 0.1 to 5.0 meq / g, more preferably 0.5 to 2.5 meq / g. Further, it preferably has an ion exchange capacity of 0.5 to 1.5 meq / g, and more preferably has an ion exchange capacity of 0.7 to 1.3 meq / g.
  • a polymer electrolyte having a smaller ion exchange capacity tends to have better miscibility with a phenol aralkyl resin, an alkylphenol resin, or a phenolcycloalkyl resin. The higher the ion exchange capacity, the higher the proton conductivity.
  • the polymer electrolyte membrane of the present invention preferably has an ion exchange capacity of 0.1 to 3.0 meq / g, more preferably 0.5 to 2.0 meq / g. Further, it preferably has an ion exchange capacity of 0.5 to 1.5 meq / g, and more preferably has an ion exchange capacity of 0.7 to 1.3 meq / g.
  • the polymer electrolyte in the polymer electrolyte membrane of the present invention is preferably a hydrocarbon polymer electrolyte.
  • Hydrocarbon polymer electrolyte membranes have advantages such as being free of halogens, having less harmful emissions, and being able to reduce costs compared to fluorine polymer electrolyte membranes. This is because the dimensional stability is poor.
  • a hydrocarbon-based polymer electrolyte membrane can overcome the above-mentioned drawbacks by compounding with a titanate fiber.
  • the hydrocarbon polymer electrolyte is mainly composed of a hydrocarbon polymer which may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, and has a sulfonic acid group or a phosphonic acid group. , And having an acidic ionic group such as a sulfonimide group, a phosphoric acid group, and a carboxyl group.
  • a strong acid group such as a sulfonic acid group or a sulfonimide group is preferable because proton conductivity increases, and a phosphonic acid group or a phosphoric acid group exhibits proton conductivity even under high temperature and low humidity conditions. preferable.
  • polysulfone examples include polyethersulfone, polyphenylsulfone, polyetherketone, polyetheretherketone, polyimide, polybenzazole, polyetherimide, polyamide, polyamideimide, and the like. Absent.
  • polyarylene ether polyarylene ether, polyarylene sulfide, polyarylene ether sulfide, polyarylene ether nitrile, polyarylene ether nitrile sulfide, polysulfone, polyethersulfone, polyphenylsulfone, polyetherketone, polyetheretherketone are more preferable examples. It can be mentioned, but is not limited to these.
  • the hydrocarbon-based polymer electrolyte in the present invention is preferably mainly composed of an aromatic polymer, but may partially have an aliphatic group.
  • at least part of the side chain or main chain may be composed of an aliphatic group.
  • the hydrocarbon-based polymer electrolyte in the present invention contains a sulfonic acid group, and includes a polysulfone, a polyethersulfone, a polyphenylene oxide, a polyphenylene sulfide, a polyphenylene sulfide sulfone and a polyether ketone-based polymer. It is preferable that any one of an arylene ether compound, a polyarylene sulfide compound, and a polyarylene compound is used as a constituent component. This is because these polymers are easy to synthesize, have good solubility in solvents, and are excellent in heat resistance and mechanical properties.
  • the hydrocarbon-based polymer electrolyte in the present invention preferably has an ion exchange capacity of 0.5 to 3.0 meq / g, more preferably 0.5 to 2.5 meq / g, It is more preferable to have an ion exchange capacity of 0.5 to 1.5 meq / g, and it is more preferable to have an ion exchange capacity of 0.7 to 1.3 meq / g.
  • a preferred embodiment of the hydrocarbon-based polymer electrolyte in the present invention is one selected from one or more structures selected from the structure represented by the following general formula (9) and a structure represented by the following general formula (10). It is a hydrocarbon-based polymer electrolyte composed of one or more kinds of polymers selected from the group consisting of polymers having at least one kind of structure.
  • X represents a —S ( ⁇ O) 2 — group or —C ( ⁇ O) — group
  • Y represents H or a monovalent cation
  • R 19 represents the number of carbon atoms. Any one of 1 to 10 alkylene group, oxyalkylene group, aryl group and direct bond (of —SO 3 Y group), R 20 and R 21 each independently contains a sulfur atom or an oxygen atom.
  • Ar 2 is a divalent aromatic group having an electron-withdrawing group
  • Z or Z ′ represents either an oxygen atom or a sulfur atom
  • m4 and m5 each represents an integer of 1 to 1000 in terms of the number of moles of each structural unit in the polymer molecule.
  • the hydrocarbon-based polymer electrolyte in the present invention may contain a plurality of structural units within the range of the structural unit represented by the general formula (9) or (10).
  • bonding mode of the structural unit represented by General formula (9) and the structural unit represented by General formula (10) is not specifically limited, You may couple
  • the structural unit represented by general formula (9) and the structural unit represented by general formula (10) may be combined alternately. It may be.
  • X in the general formula (9) is preferably a —S ( ⁇ O) 2 — group because solubility in a solvent is improved. It is preferable that X is a —C ( ⁇ O) — group because the softening temperature of the polymer can be lowered to enhance the bonding property with the electrode, or the photocrosslinking property can be imparted to the electrolyte membrane.
  • Y is preferably an H atom. However, if Y is an H atom, it is easily decomposed by heat or the like.
  • Y is set as an alkali metal salt such as Na or K, and Y is converted to H atom by acid treatment after processing.
  • a polymer electrolyte membrane can also be obtained by conversion.
  • Z is preferably O because it has advantages such as little polymer coloring and easy availability of raw materials.
  • Z is preferably S because oxidation resistance is improved.
  • R 19 in the general formula (9) represents any one of an alkylene group having 1 to 10 carbon atoms, an oxyalkylene group, an aryl group, and a direct bond, and an alkylene group is preferable because proton conductivity is improved.
  • a direct bond in which a sulfonic acid group and a benzene ring are directly bonded is more preferable because stability of the sulfonic acid group with respect to heat, radicals, and the like is increased and proton conductivity is excellent.
  • the alkylene group is preferably a straight chain rather than a branched one.
  • the alkylene group preferably has 1 to 5 carbon atoms, more preferably 3 to 4 carbon atoms.
  • an n-propylene group and an n-butylene group are preferable.
  • the number of carbon atoms in the oxyalkylene group is more preferably 1 to 5, and more preferably 3 to 4.
  • an oxy-n-propylene group and an oxy-n-butylene group are preferable.
  • the aryl group include an oxyphenylene group and a phenylene group.
  • partial structure represented by examples include those in which part and all of the sulfonic acid groups form a monovalent cation.
  • Chemical Formulas 11A, 11B, 11C, and 11D are more preferable, and Chemical Formulas 11A and 11B are more preferable.
  • R 20 and R 21 in the general formulas (9) and (10) are each independently an alkylene group, an aralkyl group or an aromatic group having 2 to 20 carbon atoms which may contain a sulfur atom or an oxygen atom.
  • R 20 and R 21 include aromatic rings such as a benzene ring and a pyridine ring, condensed polycyclic aromatic groups such as a naphthalene ring and an anthracene ring, an aromatic group having a direct bond, an aliphatic group, a sulfone group, Examples include, but are not limited to, a group connected by an aliphatic group including an ether group, a sulfide group, a perfluoroalkyl group and an aromatic group, an aliphatic group, and an aliphatic group including an aromatic group. It is not something.
  • R 20 and R 21 in the general formulas (9) and (10) may have a plurality of structures.
  • R 20 and R 21 in the general formulas (9) and (10) are shown below, but are not limited thereto.
  • the structural units represented by the chemical formulas 12E and 12AV are preferable because they suppress swelling of the polymer electrolyte membrane.
  • structures such as chemical formulas 12F, 12G, 12N, 12O, 12U, and 12Y are preferable because they lower the softening temperature of the polymer electrolyte membrane and improve the bondability with the electrode catalyst layer.
  • the structures represented by the chemical formulas 12AX and 12AY are also preferable because the softening temperature of the polymer electrolyte membrane is lowered, so that the bondability with the electrode catalyst layer is improved.
  • the structures represented by the chemical formulas 12AY to 12BN are preferable for improving the bondability with the electrode catalyst layer and improving the durability, and the structures represented by the chemical formulas 12AO, 12AI, 12AN, 12AQ, and 12X are This is preferable because methanol permeability is suppressed.
  • the structures represented by the chemical formulas 12I, 12J, and 12K are preferable because they suppress flooding in the fuel cell.
  • the structure represented by the chemical formula 12BO is preferable because it improves the durability of the polymer electrolyte membrane.
  • Z and Z ′ in the general formulas (9) and (10) are sulfur atoms.
  • o represents an integer of 2 to 10.
  • R 20 and R 21 in the general formulas (9) and (10) may be composed of a plurality of groups, but as a preferable combination, a structure represented by the chemical formula 12E and a chemical formula 12F, 12G, 12N, 12O , 12U, 12Y, 12AX, 12AY, a combination with one or more structures selected from the group consisting of structures represented by 12AY to 12BN, from structures represented by chemical formulas 12F, 12G, 12N, 12O, 12U, 12Y
  • one or more structures selected from the group consisting of one or more structures selected from the group consisting of: 12AY to 12BN The combination of the concrete is preferred.
  • a flooding suppression effect is obtained by further combining chemical formulas 12I, 12J, and 12K with the preferred structure and the preferred structure combination
  • Ar 2 in the general formula (10) is preferably a divalent aromatic group having an electron-withdrawing group.
  • the electron-withdrawing group include a sulfone group, a sulfonyl group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid amide group, a sulfonic acid imide group, a carboxyl group, a carbonyl group, a carboxylic acid ester group, a cyano group, a halogen group, Although a trifluoromethyl group, a nitro group, etc. can be mentioned, it is not limited to these, What is necessary is just a well-known arbitrary electron withdrawing group.
  • a preferred structure of Ar 2 in the general formula (10) is a structure represented by the chemical formulas 13A to 13D.
  • a structure represented by the chemical formulas 13C and 13D is more preferable, and a structure represented by the chemical formula 13D is more preferable.
  • the structure of Chemical Formula 13A is preferable because it can increase the solubility of the polymer.
  • the structure of the chemical formula 13B is preferable because it lowers the softening temperature of the polymer to enhance the bondability with the electrode or impart photocrosslinkability.
  • the structure of the chemical formula 13C or 13D is preferable because the swelling of the polymer can be reduced, and the structure of the chemical formula 13D is more preferable.
  • Ar 2 in the general formula (10) may be composed of a plurality of structures, and when composed of a plurality of structures, two or more structures selected from the group consisting of the chemical formulas 13A to 13D, or a chemical formula 13A A combination of at least one structure selected from the group consisting of ⁇ 13D and at least one structure selected from the group consisting of chemical formulas 13E to 13P is preferable.
  • the polymer constituting the polymer electrolyte in the present invention includes, for example, two or more compounds selected from the group consisting of aromatic dihalogen compounds and aromatic dinitro compounds activated with an electron-withdrawing group, bisphenol compounds, bisthiols.
  • One or more compounds selected from the group consisting of phenol compounds and alkyldithiol compounds can be polymerized by an aromatic nucleophilic substitution reaction by heating in the presence of a basic compound.
  • the monovalent cation species may be sodium, potassium, other metal species, various amines, or the like, but is not limited thereto.
  • Examples of compounds in which the sulfonic acid group is a salt include sodium 3,3′-disulfonate-4,4′-dichlorodiphenylsulfone, sodium 3,3′-disulfonate-4,4′-difluorodiphenylsulfone Sodium 3,3′-disulfonate-4,4′-dichlorodiphenyl ketone, sodium 3,3′-disulfonate-4,4′-difluorodiphenyl sulfone, sodium 3,3′-disulfonate-4,4 ′ -Difluorodiphenyl ketone, potassium 3,3'-disulfonate 4,4'-dichlorodiphenyl sulfone, potassium 3,3'-disulfonate 4,4'-dichlorodiphenyl sulfone, potassium 3,3'-disulfonate 4,4'-dichlorodiphenyl sulfone,
  • the activated aromatic dihalogen compound containing no ionic group includes 2,6-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2,4-difluorobenzonitrile, 4, 4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, decafluorobiphenyl, 3,3'-bis (trifluoromethyl) -4, 4'-dichlorobiphenyl, 3,3'-bis (trifluoromethyl) -p-terphenyl, and the like, but not limited thereto, other aromatics active in aromatic nucleophilic substitution reaction Dihalogen compounds, aromatic dinitro compounds, aromatic dicyano compounds and the like can also be used.
  • 2,6-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, 2,6-difluorobenzonitrile and 2,4-difluorobenzonitrile are preferable, and 2,6-dichlorobenzonitrile, 2,6 -Difluorobenzonitrile is more preferred.
  • bisphenol compounds or bisthiophenol compounds examples include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 4,4′-biphenol, 4 , 4'-dimercaptobiphenyl, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) Methane, 2,2-bis (4-hydroxyphenyl) butane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4 -Hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-2,5-dimethylpheny ) Methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-
  • alkyldithiol compounds include 1,2-ethanedithiol, 1,3-propanedithiol, 1,2-propanedithiol, 1,4-butanedithiol, 2,3-dihydroxy-1,4-butanedithiol, , 5-pentanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,11-undecanedithiol, 1, 12-dodecanedithiol, 1,13-tridecanedithiol, 1,14-tetradecanedithiol, 1,15-pentadecanedithiol, 1,16-hexadecanedithiol, 1,17-heptadecanedithiol, 1,18-octadecanedithiol, 1 , 19-
  • polymer electrolyte used in the present invention is polymerized by an aromatic nucleophilic substitution reaction
  • a polymer can be obtained by adding one or more compounds selected from the group consisting of a phenol compound and an alkyldithiol compound and reacting by heating in the presence of a basic compound.
  • the degree of polymerization of the resulting polymer can be adjusted. Is from 0.8 to 1.2, more preferably from 0.9 to 1.1, even more preferably from 0.95 to 1.05, and a polymer having the highest degree of polymerization when 1 is obtained. Can do.
  • Polymerization can be carried out in the temperature range of 0 to 350 ° C., but a temperature of 50 to 250 ° C. is preferred. When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and when the temperature is higher than 350 ° C., the polymer tends to be decomposed.
  • the reaction can be carried out in the absence of a solvent, but is preferably carried out in a solvent.
  • the solvent examples include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenyl sulfone, sulfolane, and the like. And any solvent that can be used as a stable solvent in the aromatic nucleophilic substitution reaction. These organic solvents may be used alone or as a mixture of two or more.
  • a bisphenol compound, a bisthiophenol compound, and an alkyldithiol compound are reacted with an isocyanate compound such as phenyl isocyanate without using a basic compound, and an activated dihalogen aromatic A compound or a dinitroaromatic compound can also be directly reacted.
  • Examples of basic compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc., but those capable of converting aromatic diols and aromatic dimercapto compounds into active phenoxide structures If it is, it can be used without being limited to these.
  • the basic compound can be polymerized satisfactorily by using an amount of 100 mol% or more as an alkali metal with respect to the hydroxyl group and mercapto group of the bisphenol compound, bisthiophenol compound and alkyldithiol compound, preferably bisphenol The range of 105 to 125 mol% as an alkali metal with respect to the hydroxyl group and mercaptite group of the compound, bisthiophenol compound, and alkyldithiol compound.
  • An excessive amount of the basic compound is not preferable because it causes side reactions such as decomposition.
  • water may be generated as a by-product.
  • water can be removed from the system as an azeotrope by coexisting toluene or the like in the reaction system.
  • a water absorbing material such as molecular sieve can also be used.
  • the amount is more than 50% by weight, the viscosity of the reaction system becomes too high and the post-treatment of the reaction product tends to be difficult.
  • the solvent is removed from the reaction solution by evaporation, and the residue is washed as necessary to obtain the desired polymer.
  • the polymer can be obtained by precipitating the polymer as a solid by adding the reaction solution in a solvent having low polymer solubility, and collecting the precipitate by filtration.
  • a polymer solution can be obtained by removing by-product salts by filtration.
  • the polymer electrolyte used for the polymer electrolyte membrane of the present invention preferably has a logarithmic viscosity of 0.1 dL / g or more measured by a method described later.
  • the logarithmic viscosity is more preferably 0.3 dL / g or more.
  • the logarithmic viscosity exceeds 5 dL / g, problems in processability such as difficulty in dissolving the polymer occur, which is not preferable.
  • polar organic solvents such as N-methylpyrrolidone and N, N-dimethylacetamide can be generally used. If the solubility is low, concentrated sulfuric acid is used. It can also be measured.
  • the polymer constituting the polymer electrolyte has a phenylene group in which one or more atoms selected from the group consisting of an oxygen atom and a sulfur atom are bonded to both ends
  • a polymer having a phenolic hydroxyl group is contained. This is preferable because the miscibility with the coalesce is improved.
  • Such a structure has 4,4′-dihydroxydiphenyl ether, 4,4′-thiobisbenzenethiol, 4,4′-thiobisphenol, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dichloro as raw materials.
  • the compound can be introduced into the polymer by using a compound such as diphenyl ether, 4,4′-dichlorodiphenyl sulfide, 4,4′-diaminodiphenyl ether, or 4,4′-diaminodiphenyl sulfide.
  • the polymer electrolyte membrane of the present invention can have any thickness, but if it is less than 10 ⁇ m, it may be difficult to satisfy predetermined characteristics, and therefore it is preferably 10 ⁇ m or more, and preferably 20 ⁇ m or more. Is more preferable. Moreover, since manufacture may become difficult when it exceeds 300 micrometers, it is preferable that it is 300 micrometers or less.
  • the polymer electrolyte membrane of the present invention may contain other polymers.
  • polymers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyamides such as nylon 6, nylon 66, nylon 610, and nylon 12, polymethyl methacrylate, polymethacrylates, poly Acrylate resins such as methyl acrylate and polyacrylates, polyacrylic acid resins, polymethacrylic acid resins, polyethylene, polypropylene, various polyolefins including polystyrene and diene polymers, polyurethane resins, cellulose acetate, ethyl cellulose, etc.
  • a resin composition with a basic polymer such as polybenzimidazole or polyvinylpyridine can be said to be a preferable combination for improving the polymer dimensionality, and when a sulfonic acid group is further introduced into these basic polymers, The processability of the composition becomes more preferable.
  • the polymer electrolyte membrane of the present invention preferably contains 50% by weight or more and less than 100% by weight of the proton conductive polymer. More preferably, it is 70 weight% or more and less than 100 weight%. If it is less than 50% by weight, the sulfonic acid group concentration of the polymer electrolyte membrane tends to be low, and good ionic conductivity tends to be not obtained, and the unit containing the sulfonic acid group becomes a discontinuous phase and conducts. Ion mobility tends to decrease.
  • the polymer electrolyte membrane of the present invention can be used as necessary, for example, an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a crosslinking agent, a viscosity modifier, an antistatic agent, an antibacterial agent, and an antifoaming agent.
  • Various additives such as an agent, a dispersant, and a polymerization inhibitor may be included.
  • the average value of the contact angle on both sides of a 5 mol / L aqueous methanol solution in an atmosphere of 20 ° C. and 65% relative humidity is 65 ° or more, and a hydrocarbon polymer electrolyte is used as the electrolyte.
  • a polymer electrolyte membrane When the hydrocarbon electrolyte membrane has a large contact angle with respect to the aqueous methanol solution, methanol permeation can be suppressed.
  • One or more resins selected from the group consisting of resins and a hydrocarbon polymer electrolyte, particularly an aromatic hydrocarbon polymer electrolyte may be mixed to form a film. Since the fluorine-based polymer electrolyte membrane represented by Nafion (registered trademark) has an ion channel structure in the membrane, methanol permeation may increase even if the contact angle is high.
  • the contact angle may differ depending on the surface.
  • the polymer electrolyte membrane solution is cast on a substrate such as glass and dried to form a film. In such a case, it is preferable that the difference between the contact angles on both sides is as small as possible and that the average value thereof is high.
  • the polymer electrolyte membrane of the present invention comprises one or more polymer electrolytes and at least one polymer selected from the group consisting of a polymer of the specific phenol compound, a phenol aralkyl resin, an alkylphenol resin, and a phenol cycloalkyl resin. It can be obtained by molding from a composition containing a resin by any method such as extrusion, rolling or casting. As the composition, a solution composition containing a solvent is preferable. From the solution composition, the polymer electrolyte membrane can be obtained by removing the solvent using any known method. For example, the solvent can be removed by heating, drying under reduced pressure, polymer electrolyte membrane, and immersion of the resin in a non-solvent.
  • the solution composition may contain other compounds as necessary. Compounds having similar dissolution behavior are preferred in that good molding can be achieved.
  • the sulfonic acid group of the obtained polymer electrolyte membrane may form a salt with a cationic species, it can be converted to a free sulfonic acid group by acid treatment as necessary.
  • the solution composition is, for example, the above-mentioned specific phenol compound polymer, phenol aralkyl resin, with respect to a solvent capable of dissolving the polymer electrolyte or a solvent miscible with the polymer electrolyte solution, It can be obtained by mixing a polymer electrolyte solution with a solution obtained by dissolving one or more resins selected from the group consisting of alkylphenol resins and phenolcycloalkyl resins. Alternatively, the polymer electrolyte and one or more resins selected from the group consisting of the specific phenol compound polymer, the phenol aralkyl resin, the alkylphenol resin, and the phenol cycloalkyl resin can be simultaneously dissolved in the same solvent.
  • the method for obtaining the solution composition is not limited to these methods.
  • a stirrer, a stirring blade, a mixer, an extruder, or the like can be used.
  • the solution may be heated at a temperature not higher than the boiling point of the solvent.
  • the solvent that can be mixed in the polymer electrolyte solution include water, methanol, acetone, methyl ethyl ketone, dibutyl ketone, ethyl acetate, methyl acetate, diethyl ether, tetrahydrofuran, and dioxane, but are not limited thereto. It is not something.
  • Solvents that can be used in the solution composition for producing the polymer electrolyte membrane of the present invention include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2 -Aprotic organic polar solvents such as pyrrolidone, dimethyl sulfoxide, hexamethylphosphonamide, N-morpholine oxide, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone, ether solvents such as diethyl ether, etc. Examples include, but are not limited to, polar solvents, mixtures of these organic solvents, and mixtures with water.
  • the concentration of the polymer electrolyte in the solution composition is preferably in the range of 0.1 to 50% by weight, more preferably in the range of 5 to 50% by weight, and still more preferably in the range of 10 to 40% by weight.
  • the most preferable method for forming the polymer electrolyte membrane of the present invention is casting from a solution composition, and the polymer electrolyte membrane can be obtained by removing the solvent from the cast solution composition as described above. .
  • the removal of the solvent is preferably by drying in view of the uniformity of the polymer electrolyte membrane.
  • it can also dry at the lowest temperature possible under reduced pressure.
  • the viscosity of a solution composition is high, when a board
  • the thickness of the solution composition at the time of casting is not particularly limited, but is preferably 10 to 2000 ⁇ m. More preferably, it is 50 to 1500 ⁇ m. When the thickness of the solution composition is less than 10 ⁇ m, the form as a polymer electrolyte membrane tends not to be maintained, and when it is more than 2000 ⁇ m, a non-uniform film tends to be easily formed.
  • a known method can be used as a method for controlling the cast thickness of the solution composition. For example, the thickness can be controlled by the amount and concentration of the solution by making the thickness constant using an applicator, a doctor blade or the like, or making the cast area constant using a glass petri dish or the like. The cast solution composition can obtain a more uniform film by adjusting the solvent removal rate.
  • the evaporation rate can be reduced by lowering the temperature in the first stage.
  • the coagulation rate of the compound can be adjusted by leaving the solution composition in air or an inert gas for an appropriate time.
  • the sulfonic acid group in the proton conductive polymer forms a salt with a cation because stability is improved.
  • it can be converted to free sulfonic acid by an appropriate acid treatment. In this case, it is effective to immerse the membrane in an aqueous solution of sulfuric acid, hydrochloric acid, etc. with or without heating.
  • the membrane / electrode assembly of the present invention can be obtained by bonding the polymer electrolyte membrane of the present invention to an electrode catalyst layer.
  • a manufacturing method of this joined body it can be performed using a conventionally known method, for example, a method of applying an adhesive on the electrode surface and bonding the polymer electrolyte membrane and the electrode, a polymer electrolyte membrane, A method of heating and pressing an electrode catalyst layer prepared by applying a paste containing a catalyst to an electrode in advance, a method of attaching an electrode after transferring a catalyst layer prepared on another sheet to a polymer electrolyte membrane, There are methods such as, but not limited to, a method in which the surface of the molecular electrolyte membrane is coated with a dispersion containing a catalyst and conductive particles by spraying, printing, or the like, and then the electrodes are joined.
  • a known material such as a Nafion (trade name) solution may be used, or an adhesive mainly composed of the same polymer composition as that of the polymer constituting the polymer electrolyte in the present invention may be used. Those having other hydrocarbon proton conductive polymers as a main component may also be used.
  • a catalyst such as platinum or platinum-ruthenium alloy necessary for the electrode reaction can be obtained by dispersing the catalyst supported on conductive particles such as carbon in the adhesive. .
  • the fuel cell of the present invention can be produced using the polymer electrolyte membrane or the membrane / electrode assembly of the present invention.
  • the fuel cell of the present invention includes, for example, an oxygen electrode, a fuel electrode, a polymer electrolyte membrane sandwiched between the electrodes, an oxidant flow path provided on the oxygen electrode side, and a fuel electrode side.
  • the fuel flow path is provided.
  • a fuel cell stack can be obtained by connecting such unit cells with a conductive separator.
  • the polymer electrolyte membrane of the present invention is suitable for a solid polymer fuel cell.
  • the polymer electrolyte membrane of the present invention is particularly suitable for direct methanol fuel cells, dimethyl ether fuel cells, formic acid fuel cells, direct ethanol fuel cells and the like because of its low permeability for liquid fuels such as methanol. Since the permeability of the fuel is small, a high output can be obtained with little voltage drop due to the permeated fuel, and a high concentration fuel solution can be used. In addition, the amount of fuel that is wasted is reduced due to the permeation, so that the capacity can be improved and the energy efficiency can be increased.
  • a polymer electrolyte membrane is cut into 1 ⁇ 5 cm, fixed on a slide glass with tape, and 5 mol in an atmosphere of 20 ° C. and 60% relative humidity using a contact angle meter CA-X type manufactured by Kyowa Interface Science Co., Ltd.
  • a contact angle 1 minute after adding a methanol aqueous solution (5M aqueous methanol solution) having a concentration of / L was determined from the left and right ends of the droplet and the position of the apex. For each sample, three points were measured for each of the surface (substrate surface) in contact with the substrate during film formation and the opposite surface (air surface), and the average value was used as the value.
  • the catalyst paste is applied and dried by screen printing on carbon paper TGPH-060 manufactured by Toray Co., which will be a gas diffusion layer, so that the adhesion amount of platinum is 2 mg / cm 2 , thereby producing a carbon paper with an electrode catalyst layer for the anode. did. Further, after adding a small amount of ultrapure water and isopropyl alcohol to a Pt catalyst-supporting carbon (TEC 10V40E manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) Then, the Pt catalyst-carrying carbon and Nafion were added in a weight ratio of 2.5: 1 and stirred to prepare a cathode catalyst paste.
  • TEC 10V40E manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.
  • This catalyst paste was applied to and dried on carbon paper TGPH-060 manufactured by Toray Industries, Ltd., which had been subjected to water repellent treatment, so that the amount of platinum deposited was 1 mg / cm 2 , thereby producing a carbon paper with an electrode catalyst layer for cathode. .
  • This joined body was incorporated into an evaluation fuel cell FC25-02SP manufactured by Electrochem, and a power generation test was performed using a fuel cell power generation tester (manufactured by Toyo Corporation). For power generation, a 5 mol / L methanol aqueous solution (1.5 ml / min) adjusted to 40 ° C. at the cell temperature and a high-purity air gas (80 ml / min) adjusted to 40 ° C. at the cathode, respectively. The output voltage was measured while changing the current density while supplying.
  • Synthesis Example 4 The same procedure as in Synthesis Example 1 was conducted, except that 148.1 g of 1,5-dihydroxynaphthalene was used instead of 100.0 g of p-cresol, and 16.3 g of 1,5-dihydroxynaphthalene was used instead of 11.0 g of p-cresol. A yellowish white polymer was obtained. The weight average molecular weight of the polymer is 20000, and the structure is shown in chemical formula (14D). Indicates that the polymer is composed of the two types of structural units described. In addition, the obtained polymer was insoluble with respect to methanol at 25 ° C., and the solubility was 1% by weight or less.
  • the obtained polymer was insoluble with respect to methanol at 25 ° C., and the solubility was 1% by weight or less. Further, when 2 g of the obtained polymer was mixed in 8 g of N-methyl-2-pyrrolidone at 25 ° C., a transparent and uniform light brown solution was obtained, and the solubility in N-methyl-2-pyrrolidone was 1 % Can be confirmed.
  • the phenolic hydroxyl group content in the resin measured by the acetic anhydride method was 0.0045 mol / g.
  • the obtained polymer was insoluble with respect to methanol at 25 ° C., and the solubility was 1% by weight or less. Further, when 2 g of the obtained polymer was mixed in 8 g of N-methyl-2-pyrrolidone at 25 ° C., a transparent and uniform light brown solution was obtained, and the solubility in N-methyl-2-pyrrolidone was 1 % Can be confirmed.
  • the phenolic hydroxyl group content in the resin by the acetic anhydride method was 0.0053 mol / g.
  • the obtained reaction product was dissolved in 200 g of methyl ethyl ketone, reprecipitated with water, washed twice with 0.1 M aqueous sodium hydroxide solution and 5 times with water, and then dried under reduced pressure at 25 ° C. to give a yellowish white polymer.
  • the weight average molecular weight in terms of polystyrene measured by GPC method was 22,000.
  • the structure of the polymer confirmed by NMR method and IR method is shown in chemical formula (141).
  • the chemical formula (141) shows that the polymer is composed of the two kinds of structural units described.
  • the obtained polymer was insoluble with respect to methanol at 25 ° C., and the solubility was 1% by weight or less.
  • the obtained reaction product was dissolved in 200 g of methyl ethyl ketone, reprecipitated with water, washed twice with 0.1 M aqueous sodium hydroxide solution and 5 times with water, and then dried under reduced pressure at 25 ° C. to give a yellowish white polymer.
  • the weight average molecular weight in terms of polystyrene measured by GPC method was 12,000.
  • the structure of the polymer confirmed by NMR method and IR method is shown in chemical formula (14P).
  • the obtained polymer was insoluble with respect to methanol at 25 ° C., and the solubility was 1% by weight or less.
  • the obtained reaction product was washed 4 times with methanol, dissolved in 200 g of methyl ethyl ketone, reprecipitated with water, washed twice with 0.1 M aqueous sodium hydroxide solution and 5 times with water, and then cooled to 25 ° C. And dried under reduced pressure to obtain a yellowish white polymer.
  • the weight average molecular weight in terms of polystyrene measured by GPC method was 14,000.
  • the structure of the polymer confirmed by the NMR method and IR method was represented by the chemical formula (14Q) as in Synthesis Example 17.
  • the obtained polymer was insoluble with respect to methanol at 25 ° C., and the solubility was 1% by weight or less.
  • the mixture was heated with stirring, heated in an oil bath so that the temperature of the reaction solution became 190 to 200 ° C., and reacted for 16 hours in a state of refluxing with 0.5 L / min of nitrogen. Then, it cooled to room temperature and poured the reaction solution into water, and precipitated in strand form.
  • the obtained polymer was washed twice in boiling water and six times with pure water at room temperature, and then dried at 120 ° C.
  • the logarithmic viscosity of the polymer was 1.21 dL / g.
  • the structure of the obtained polymer was confirmed by NMR method and IR method. The structural formula is shown in Chemical Formula 15A.
  • the weight average molecular weight in terms of polystyrene measured by GPC method was 12,000.
  • the structure of the polymer confirmed by NMR method and IR method is shown in chemical formula (14U).
  • 90 g of methanol was added to 10 g of the polymer obtained in Synthesis Example 28 and stirred for 3 days at 25 ° C. in a glass container, but the polymer obtained in Synthesis Example 1 did not dissolve.
  • Methanol which separated the polymer by filtration was evaporated to dryness, but the presence of solids was not observed. That is, the polymer obtained in Synthesis Example 28 was insoluble in methanol at 25 ° C., and the solubility was 1% by weight or less.
  • the weight average molecular weight in terms of polystyrene measured by GPC method was 12,000.
  • the structure of the polymer confirmed by NMR method and IR method is shown in chemical formula (16A).
  • 10 g of the obtained polymer was dissolved in 90 g of methanol at 25 ° C., and the solubility was 10% by weight or more.
  • the phenolic hydroxyl group content in the resin by the acetic anhydride method was 0.0100 mol / g.
  • Example 1 9 g of the polymer obtained in Synthesis Example 22, 1 g of the polymer obtained in Synthesis Example 1, and 30 g of NMP were put into a 100 mL glass flask and stirred at 60 ° C. for 12 hours in a nitrogen atmosphere.
  • the obtained solution was cast on a glass plate placed on a hot plate to a thickness of about 400 ⁇ m and heated at 80 ° C. for 0.5 hour, 120 ° C. for 0.5 hour, and 150 ° C. for 0.5 hour, and then nitrogen. It dried for 1 hour in 150 degreeC oven of atmosphere, and peeled the film from the glass plate.
  • the obtained film was immersed in pure water at room temperature for 1 day, and then immersed in a 2 mol / L sulfuric acid aqueous solution twice for 1 hour each. After that, the film is washed with pure water until the washing water becomes neutral, the water adhering to the surface is removed with filter paper, both sides are sandwiched with new filter paper, and both sides are further sandwiched with a glass plate.
  • a polymer electrolyte membrane was obtained by applying a load and leaving it in a room at 23 ° C. and a relative humidity of 50% for 2 days to dry. The obtained polymer electrolyte membrane was evaluated.
  • the contact angle of the obtained polymer electrolyte membrane with respect to 5M methanol was 69.0 ° on the substrate surface side and 75.6 ° on the air surface side, and averaged 72.3 °.
  • Examples 2 to 21 A polymer electrolyte membrane was prepared and evaluated in the same manner as in Example 1 except that the polymers obtained in Synthesis Examples 2 to 21 were used in place of the polymer obtained in Synthesis Example 1, respectively.
  • Example 22 A polymer electrolyte membrane was prepared and evaluated in the same manner as in Example 1 except that the amount of the polymer obtained in Synthesis Example 22 was changed to 8 g and the amount of the polymer obtained in Synthesis Example 1 was changed to 2 g.
  • the contact angle of the obtained polymer electrolyte membrane with respect to 5M methanol was 62.4 ° on the substrate surface side and 69.2 ° on the air surface side, and averaged 65.2 °.
  • Example 24 A polymer electrolyte membrane was prepared and evaluated in the same manner as in Example 22 except that the polymer obtained in Synthesis Example 23 was used instead of the polymer obtained in Synthesis Example 22.
  • Example 25 A polymer electrolyte membrane was prepared and evaluated in the same manner as in Example 22 except that the polymer obtained in Synthesis Example 24 was used instead of the polymer obtained in Synthesis Example 22.
  • Example 26 A polymer electrolyte membrane was prepared and evaluated in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 25 was used instead of the polymer obtained in Synthesis Example 22.
  • Example 27 A polymer electrolyte membrane was prepared and evaluated in the same manner as in Example 22 except that the polymer obtained in Synthesis Example 26 was used instead of the polymer obtained in Synthesis Example 22.
  • Example 28 A polymer electrolyte membrane was prepared and evaluated in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 27 was used instead of the polymer obtained in Synthesis Example 22.
  • Example 29 A polymer electrolyte membrane was prepared and evaluated in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 28 was used instead of the polymer obtained in Synthesis Example 22.
  • the obtained solution was cast on a glass plate placed on a hot plate to a thickness of about 400 ⁇ m and heated at 80 ° C. for 0.5 hour, 120 ° C. for 0.5 hour, and 150 ° C. for 0.5 hour, and then nitrogen. It dried for 1 hour in 150 degreeC oven of atmosphere, and peeled the film from the glass plate.
  • the obtained film was immersed in pure water at room temperature for 1 day, and then immersed in a 2 mol / L sulfuric acid aqueous solution twice for 1 hour each.
  • a polymer electrolyte membrane was obtained by applying a load and leaving it in a room at 23 ° C. and a relative humidity of 50% for 2 days to dry. The obtained polymer electrolyte membrane was evaluated.
  • Example 11 A polymer electrolyte membrane was prepared and evaluated in the same manner as in Example 1 except that poly (4-hydroxystyrene) (average molecular weight 8000) was used instead of the polymer obtained in Synthesis Example 1. In addition, 10 g of poly (4-hydroxystyrene) was dissolved in 90 g of methanol at 25 ° C., and the solubility was 10% by weight or more.
  • Example 1 is the same as Example 1 except that Irganox (trade name) 1010 (trade name, manufactured by Ciba Specialty Chemicals), which is a phenolic antioxidant having a phenolic hydroxyl group, was used instead of the polymer obtained in Synthesis Example 1. Similarly, a polymer electrolyte membrane was prepared and evaluated. 2 g of Irganox (trade name) 1010 was dissolved in 98 g of methanol at 25 ° C., and the solubility was 2% by weight or more.
  • Irganox (trade name) 1010 trade name, manufactured by Ciba Specialty Chemicals
  • a polymer electrolyte membrane was prepared and evaluated. 2 g of Irganox (trade name) 1010 was dissolved in 98 g of methanol at 25 ° C., and the solubility was 2% by weight or more.
  • a polymer electrolyte membrane was prepared in the same manner as in Comparative Example 1 except that the polymer obtained in Synthesis Example 22 was used instead of the polymer obtained in Comparative Synthesis Example 6.
  • the obtained polymer electrolyte membrane had an ion exchange capacity of 1.03 meq / g.
  • the contact angle of the obtained polymer electrolyte membrane with respect to 5M methanol was 62.9 ° on the substrate surface side and 65.5 ° on the air surface side, and averaged 63.7 °.
  • NMP represents N-methyl-2-pyrrolidone
  • the power generation evaluation was performed on the polymer electrolyte membrane obtained in Example 1 and the membrane of Comparative Example 1 having the same ion exchange capacity and membrane resistance.
  • a plot of output voltage against current density is shown in FIG. 1, and a plot of output (power density) against current density is shown in FIG.
  • a preferred first aspect of the present invention which contains a phenolic hydroxyl group having a solubility in methanol at 25 ° C. of 1% by weight or less and a solubility in N-methyl-2-pyrrolidone at 25 ° C. of 1% by weight or more
  • the polymer electrolyte membrane which is a membrane containing 2 to 100% by weight of the polymer electrolyte containing one or more selected from the group consisting of resins, has excellent methanol permeation-preventing properties. It can be seen from the comparison of comparative examples.
  • a polymer electrolyte membrane containing a phenol aralkyl resin or a phenol cycloalkyl resin which is a preferred second embodiment of the present invention, is a polymer electrolyte membrane not containing a phenol aralkyl resin or a phenol cycloalkyl resin, or a phenol aralkyl resin or a phenol cycloalkyl resin. It shows properties superior to those of polymer electrolyte membranes containing compounds other than alkyl resins. For example, according to Tables 1 and 2, when comparing Example 1 with Comparative Example 1 having the same ion exchange capacity and proton conductivity, the polymer electrolyte membrane of Example 1 is the polymer electrolyte membrane of Comparative Example 1.
  • the methanol permeability coefficient is remarkably reduced as compared with FIG. A membrane / electrode assembly of these membranes was prepared, and from the results of evaluation as a direct methanol fuel cell, the polymer electrolyte membrane of Example 1 had a voltage about 20% higher. I understand that The same is apparent from the comparison between Examples 24-28 and Comparative Examples 2-6 corresponding thereto. Further, focusing on Example 25, the methanol permeability is equivalent to that of Comparative Example 1, but the resistance of the membrane is about 1 ⁇ 2, which is a polymer electrolyte membrane useful for producing a fuel cell with high output. I understand that.
  • the polymer electrolyte membranes of Comparative Examples 7 to 10 containing a phenol resin which is neither a phenol aralkyl resin, an alkylphenol resin, nor a phenol cycloalkyl resin, inhibit methanol permeation compared to the polymer electrolyte membrane of Example 1. It is clear that there is almost no effect, and it can be seen that the phenol aralkyl resin, the alkylphenol resin, and the phenol cycloalkyl resin show an important effect for suppressing the permeation of methanol.
  • a polymer electrolyte membrane of Comparative Example 12 using poly (4-hydroxystyrene) as a compound having the same phenolic hydroxyl group, and Irganox (trade name) 1010 which is a phenolic antioxidant having a phenolic hydroxyl group are used. It is clear that the polymer electrolyte membrane of Comparative Example 13 used has almost no effect of suppressing methanol permeation. In addition, when a xylene resin having no phenolic hydroxyl group was used, a good polymer electrolyte membrane could not be obtained, but this is presumed to be due to a problem in compatibility.
  • the phenol aralkyl resin, the alkylphenol resin and the phenolcycloalkyl resin do not suppress methanol permeation merely by having a phenolic hydroxyl group, but have a feature. It is clear that the structure has a significant effect on methanol permeation inhibition when combined with a polyelectrolyte.
  • the polymer electrolyte membrane of Example 29 to which the cresol novolak resin of Synthesis Example 28, which is an alkylphenol resin, was added was more permeable to methanol than the polymer electrolyte membrane of Comparative Example 1 to which the phenol resin of Comparative Synthesis Example 1 was added. It can be seen that is significantly suppressed. This is presumably because the cresol novolak resin of Synthesis Example 28 is insoluble in methanol, whereas the phenol resin of Comparative Synthesis Example 1 is soluble in methanol. From these facts, it is understood that, in the phenolic hydroxyl group-containing resin, the solubility in methanol is a factor that greatly affects the methanol permeation inhibiting property when added to the polymer electrolyte membrane.
  • the polymer electrolyte membrane of the present invention has a slightly higher membrane resistance than the polymer electrolyte membrane made of a commercially available perfluorocarbon sulfonic acid polymer, but has extremely low methanol permeability and can be used for a direct methanol fuel cell. It can be seen that this is a suitable polymer electrolyte membrane.
  • the polymer electrolyte membrane of Comparative Example 15 is a polymer electrolyte membrane consisting only of the polymer electrolyte of Synthesis Example 22.
  • the polymer electrolyte membrane of Example 1 is a polymer electrolyte membrane obtained by adding 1 part by weight of the phenol aralkyl resin of Synthesis Example 1 to 9 parts by weight of the polymer electrolyte of Synthesis Example 22.
  • the calculated ion exchange capacity is 9 of 1.03 meq / g (ion exchange capacity of the polymer electrolyte membrane of Comparative Example 15). Percent, ie 0.93 meq / g. Since the ion exchange capacity of the polymer electrolyte membrane of Example 1 is 0.92 meq / g from Table 1, it agrees with the theoretical value. This indicates that the sulfonic acid group of the polymer electrolyte is not consumed due to bonding with the hydroxyl group.
  • the polymer electrolyte membrane of Comparative Example 1 which is a polymer electrolyte membrane consisting only of a polymer electrolyte that does not contain a phenol aralkyl resin, has an ion exchange capacity equivalent to that of the polymer electrolyte membrane of Example 1, Since proton conductivity is equivalent to that of the polymer electrolyte membrane, in the polymer electrolyte membrane of Example 1, the sulfonic acid group exhibits proton conductivity without being influenced by the phenol aralkyl resin, and has no interaction. It is shown that.
  • the polymer electrolyte is mixed with a phenol aralkyl resin, an alkylphenol resin, or a phenolcycloalkyl resin to form a polymer electrolyte membrane. Furthermore, in the method for producing a polymer electrolyte membrane of the present invention, a phenol aralkyl resin, an alkylphenol resin, or a phenolcycloalkyl resin is mixed in a salt state of the sulfonic acid group, thereby preventing a chemical reaction with the sulfonic acid group from occurring. So it is a better manufacturing method.
  • the polymer electrolyte membrane of the present invention can remarkably suppress methanol permeability without increasing membrane resistance, so that it can be used in a direct methanol fuel cell to improve its output or to enable the use of high-concentration methanol. Can do. Furthermore, the polymer electrolyte membrane of the present invention can be particularly suitably used for fuel cells using liquids such as dimethyl ether and formic acid in addition to methanol. Furthermore, it can be used for any known application as a polymer electrolyte membrane, such as an electrolytic membrane and a separation membrane, and contributes greatly to the industrial world.

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Abstract

L'invention porte sur une membrane électrolytique polymère apte à supprimer la perméabilité au méthanol sans réduire sensiblement la conductivité protonique. La membrane électrolytique polymère contient une résine phénolique qui renferme un groupe hydroxy présentant une solubilité dans le méthanol à 25 °C égale ou inférieure à 1 % en poids et une solubilité dans la N-méthyl-2-pyrrolidone à 25 °C égale ou supérieure à 1 % en poids et en quantité de 0,1 à 100 % en poids, sur la base d'un électrolyte polymère. La membrane électrolytique polymère contient une quantité soit d'une résine phénol aralkyle soit d'une résine phénol cycloalkyle de 2 à 100 % en poids, sur la base d'un électrolyte polymère.
PCT/JP2008/053741 2008-03-03 2008-03-03 Membrane électrolytique polymère, son utilisation et son procédé de fabrication Ceased WO2009110052A1 (fr)

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WO2017170703A1 (fr) * 2016-03-30 2017-10-05 新日鉄住金化学株式会社 Résine polyhydroxy, son procédé de production, résine époxy, composition de résine époxy et produit durci de composition de résine époxy

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JP2006059552A (ja) * 2004-08-17 2006-03-02 Asahi Kasei Chemicals Corp 高温耐久性高分子固体電解質膜
WO2006061993A1 (fr) * 2004-12-07 2006-06-15 Toray Industries, Inc. Element composite d’electrode a couche, procede de fabrication de celui-ci et pile a combustible
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JP2001118591A (ja) * 1999-10-19 2001-04-27 Toyota Central Res & Dev Lab Inc 高耐久性固体高分子電解質
JP2006031970A (ja) * 2004-07-12 2006-02-02 Hitachi Chem Co Ltd プロトン伝導性高分子電解質膜、高分子電解質膜−電極接合体、それらの製造方法及びそれを用いた燃料電池
JP2006059552A (ja) * 2004-08-17 2006-03-02 Asahi Kasei Chemicals Corp 高温耐久性高分子固体電解質膜
WO2006061993A1 (fr) * 2004-12-07 2006-06-15 Toray Industries, Inc. Element composite d’electrode a couche, procede de fabrication de celui-ci et pile a combustible
JP2006176666A (ja) * 2004-12-22 2006-07-06 Toyobo Co Ltd 新規スルホン酸基含有セグメント化ブロック共重合ポリマーおよびその用途
JP2006351401A (ja) * 2005-06-17 2006-12-28 Toyota Motor Corp 燃料電池用電解質膜
JP2007234247A (ja) * 2006-02-27 2007-09-13 Aisin Seiki Co Ltd プロトン伝導性材料及びその製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017170703A1 (fr) * 2016-03-30 2017-10-05 新日鉄住金化学株式会社 Résine polyhydroxy, son procédé de production, résine époxy, composition de résine époxy et produit durci de composition de résine époxy
JPWO2017170703A1 (ja) * 2016-03-30 2019-02-21 日鉄ケミカル＆マテリアル株式会社 多価ヒドロキシ樹脂、その製造方法、エポキシ樹脂、エポキシ樹脂組成物及びその硬化物

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