WO2011145748A1 - Copolymère à blocs de polyarylène, procédé pour le produire et électrolyte polymère - Google Patents

Copolymère à blocs de polyarylène, procédé pour le produire et électrolyte polymère Download PDF

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WO2011145748A1
WO2011145748A1 PCT/JP2011/061921 JP2011061921W WO2011145748A1 WO 2011145748 A1 WO2011145748 A1 WO 2011145748A1 JP 2011061921 W JP2011061921 W JP 2011061921W WO 2011145748 A1 WO2011145748 A1 WO 2011145748A1
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group
carbon atoms
substituent
ion exchange
block copolymer
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Japanese (ja)
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中村　大輔
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住友化学株式会社
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8668—Binders
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • 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
    • C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
    • 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
    • H01M8/10—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
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    • 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]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/122—Copolymers statistical
    • C—CHEMISTRY; METALLURGY
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/145—Side-chains containing sulfur
    • C08G2261/1452—Side-chains containing sulfur containing sulfonyl or sulfonate-groups
    • C—CHEMISTRY; METALLURGY
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/146—Side-chains containing halogens
    • C—CHEMISTRY; METALLURGY
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
    • C08G2261/3444—Polyethersulfones
    • C—CHEMISTRY; METALLURGY
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C08G2261/516—Charge transport ion-conductive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • 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
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Polymers having proton conductivity that is, polymer electrolyte membranes
  • diaphragms for electrochemical devices such as primary batteries, secondary batteries, and fuel cells.
  • a fluorine-based polymer electrolyte membrane such as Nafion (registered trademark of DuPont)
  • Nafion registered trademark of DuPont
  • the fluorine-based polymer electrolyte membranes are expensive, have low heat resistance, have high disposal costs, and have low membrane strength and are not practical unless they are reinforced.
  • hydrocarbon-based polymer electrolyte membranes that can replace the fluorine-based polymer electrolyte membranes has recently been activated and studied.
  • hydrocarbon-based polymer electrolyte membrane include a block copolymer composed of a block having an ion exchange group whose main chain has a polyarylene structure and a block having no ion exchange group, and the ion exchange group A polyarylene block copolymer is described in which all of the aromatic rings constituting the main chain of the block it has have a sulfo group in the side chain.
  • the polymer electrolyte described in Japanese Patent Application Laid-Open No. 2004-137444 tends to decrease the dimensional stability during water absorption swelling when the ion exchange capacity is increased in order to improve proton conductivity. As a conductive film, it was poor in practicality.
  • An object of the present invention is to provide a polyarylene-based block copolymer capable of obtaining a proton conductive membrane that exhibits high proton conductivity and excellent dimensional stability during water absorption swelling when used as a polymer electrolyte membrane. There is to do.
  • a copolymer comprising a block substantially free of ion exchange groups, wherein the sequence of the block having ion exchange groups and the ion exchange capacity and the sequence of blocks having no ion exchange groups are specified
  • a polyarylene-based block copolymer comprising:
  • the first block includes a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2)
  • the second block includes a structural unit represented by the following formula (3)
  • the polyarylene block copolymer is characterized in that the ion exchange capacity of the first block is 3.5 to 6.0 meq / g.
  • Ar 1 is an arylene group constituting the first main chain, and the arylene group has at least one ion-exchange group bonded directly or indirectly, and includes a fluorine atom, a substituent, An optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, and an optionally substituted aryl having 6 to 20 carbon atoms Group, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, an acyl group having 2 to 20 carbon atoms which may have a substituent, and a carbon number which may have a substituent 6 arylsulfonyl group to 20, .Ar 1 which may have one or more groups selected from the group consisting of an alkylsulfonyl group, and a cyano group substituents to 1 carbon atoms which may have a 20, When there are multiple, these are the same or different In it may be.
  • Ar 2 is an arylene group constituting the first main chain, the arylene group, a fluorine atom, substituent optionally good having 1 to 20 carbon atoms include An alkyl group, an optionally substituted alkoxy group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted carbon number An aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms which may have a substituent, an arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent, and a substituent; It may have at least one group selected from the group consisting of an alkylsulfonyl group having 1 to 20 carbon atoms and a cyano group, provided that the arylene group does not have an ion exchange group.
  • Ar 3 is a divalent aromatic group constituting the second main chain, the divalent aromatic group optionally having fluorine atom, a substituent
  • arylsulfonyl group, .Ar 3 which may have one or more groups selected from the group consisting of an alkylsulfonyl group, and a cyano group substituents to 1 carbon atoms which may have a 20, when there are a plurality of These may be the same or different.
  • X 1 represents O (oxygen) or S (sulfur).
  • the present invention provides the following [2] to [11] as preferred embodiments according to the polyarylene block copolymer.
  • the ratio of the number of structural units represented by the above formula (2) to the number of structural units represented by the above formula (1) is 10: 1 to 1: 2.
  • the ion exchange group possessed by Ar 1 is one or more acid groups selected from the group consisting of a sulfo group, a phosphone group, a carboxyl group and a sulfonimide group [1] to [5] ]
  • the polyarylene-type block copolymer in any one.
  • An aryl group having 6 to 20 carbon atoms which may be substituted, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an acyl group having 2 to 20 carbon atoms which may have a substituent Represents an arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms which may have a substituent, or a cyano group, k being 0 to 3; Represents an integer, p represents an integer of 1 or 2, and k + p is an integer of 4 or less. When k is 2 or 3, a plurality of R may be the same or different from each other.
  • An aryl group having 6 to 20 carbon atoms which may be substituted, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an acyl group having 2 to 20 carbon atoms which may have a substituent Represents an arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms which may have a substituent, or a cyano group, k being 0 to 4; Represents an integer, and when k ′ is 2 to 4, a plurality of R may be the same or different from each other.
  • the polyarylene block copolymer according to any one of [1] to [9], wherein the ion exchange capacity is 3.1 to 5.6 meq / g. Furthermore, the present invention provides the following [11] to [13] as suitable production methods for the polyarylene block copolymer.
  • [11] A method for producing a polyarylene-based block copolymer having a main chain, the monomer represented by the following formula (1-h), the monomer represented by the following formula (2-i), A method comprising copolymerizing a polymer having substantially no ion exchange group represented by the formula (7).
  • Ar 10 is an arylene group constituting the main chain or a biphenylylene group constituting the main chain, and the arylene group or the biphenylylene group is at least one bonded directly or indirectly.
  • Ar 11 is an arylene group constituting the main chain or a biphenylylene group constituting the main chain, and the arylene group or the biphenylylene group is a carbon atom optionally having a fluorine atom or a substituent.
  • Ar 21 is a divalent aromatic group constituting the main chain, and the divalent aromatic group is a fluorine atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, An optionally substituted alkoxy group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted carbon group having 6 to 20 carbon atoms Aryloxy group, which has a substituent An acyl group having 2 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms which may have a substituent, and cyano.
  • the plurality of Ar 21 may be the same as or different from each other.
  • X 11 represents O (oxygen) or S (sulfur).
  • the plurality of X 11 may be the same as or different from each other.
  • q represents an integer of 2 or more.
  • Y represents a leaving group. A plurality of Y may be the same as or different from each other.
  • a catalyst composition comprising the polymer electrolyte according to [14] and a catalyst component.
  • a membrane electrode assembly including a polymer electrolyte membrane and a catalyst layer provided on the polymer electrolyte membrane, wherein the polymer electrolyte membrane is the polymer described in [15] or [16] A membrane electrode assembly, wherein the membrane electrode assembly is an electrolyte membrane and / or the catalyst layer is a layer formed from the catalyst composition described in [17].
  • a polymer electrolyte fuel cell comprising the membrane electrode assembly according to [18].
  • the polyarylene-based block copolymer of the present invention has a first main chain having a polyarylene structure and a first block having an ion exchange group, a second main chain, and an ion exchange.
  • the second block includes a structural unit represented by the following formula (3), and the ion exchange capacity (IEC) of the first block is 3.5 to 6.0 meq / g. It is characterized by being.
  • Ar 1 Is an arylene group constituting the first main chain, and the arylene group has at least one ion-exchange group bonded directly or indirectly and may have a fluorine atom or a substituent.
  • Ar 1 Are present, they may be the same or different.
  • Ar 2 Is an arylene group constituting the first main chain, and the arylene group may have a fluorine atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or a substituent. It has an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and a substituent.
  • Ar 3 Are present, they may be the same or different.
  • the “main chain” refers to the longest chain forming a polymer. This chain is composed of carbon atoms bonded to each other by a covalent bond. In this case, this chain may be interrupted by a nitrogen atom, an oxygen atom, a sulfur atom, or the like.
  • the polyarylene structure is a structure in which substantially all aromatic rings constituting the main chain are directly bonded to each other.
  • the block having an ion-exchange group of the present invention (that is, the first block) includes an aromatic ring in which the main chains are directly bonded to each other, and the aromatic rings constituting the polymer main chain The larger the ratio of direct bonds to the total number of bonds, the better the water resistance and proton conductivity.
  • the polyarylene structure is preferably a structure having a direct bond ratio of 80% or more and a structure of 90% or more when the total number of bonds between the aromatic rings is 100%. More preferably, the structure is 95% or more, more preferably 100%.
  • the “ion exchange group” represents a group related to ion exchange.
  • Examples of the ion exchange group include a phosphone group (—PO 3 H 2 ), Carboxyl group (—COOH), sulfo group (—SOOH) 3 H), sulfonimide group (-SO 2 -NH-SO 2 -R.
  • R represents a monovalent substituent such as an alkyl group or an aryl group.
  • Phenolic hydroxyl group (—OH), hydroxyl group (—OH), mercapto group (—SH), primary amino group (—NH) 2 ), Secondary amino group (—NHR, R is as defined above), tertiary amino group (—NRR ′, where R is as defined above), quaternary ammonium group (—N + RR'R ''.
  • the “block copolymer” is a molecular structure in which a polymer having an ion exchange group and a polymer having substantially no ion exchange group are linked by a covalent bond to form a long chain.
  • the polymer is referred to as “block”.
  • a block is a combination of three or more repeats having the same skeleton. Preferably, 5 or more of 1 type of repeating units are connected.
  • the skeleton means a main chain constituting a polymer and containing no substituent.
  • the block “having an ion exchange group” means that the ion exchange group is a block containing an average of 0.3 or more per repeating unit, and per repeating unit. And an average of 0.5 or more is more preferable.
  • the phrase “substantially having no ion exchange group” means that the block has an average number of ion exchange groups of less than 0.3 per repeating unit, and per repeating unit. The average is more preferably 0.1 or less, and the average is more preferably 0.05 or less.
  • the ratio of the number of both structural units is controlled by the monomer charge ratio when producing the polyarylene block copolymer described later.
  • the polyarylene-based block copolymer is prepared by a production method described later using a monomer having at least one selected from the group consisting of an ion exchange group and an ion exchange group precursor. When manufacturing a polymer, the following method is used.
  • the molecular weight obtained by weighted averaging from the molecular weight and the substance amount is used as the molecular weight of the structural unit of the block having an ion exchange group.
  • the ion exchange capacity of the block having an ion exchange group is 3.5 meq / g or more and 6.0 meq / g or less. More preferably, it is 4.0 meq / g or more and 5.9 meq / g or less, More preferably, it is 4.5 meq / g or more and 5.8 meq / g or less.
  • the ion exchange capacity is 3.5 meq / g or more because proton conductivity becomes higher and functions as a polymer electrolyte for a fuel cell are more excellent.
  • an ion exchange capacity of 6.0 meq / g or less is preferable because water resistance and dimensional stability during water absorption swelling become better.
  • the ion exchange capacity is controlled by the monomer structure and the monomer ratio when a polyarylene block copolymer described later is produced.
  • the polyarylene block copolymer is prepared by the production method described later using a monomer having at least one selected from the group consisting of an ion exchange group and an ion exchange group precursor.
  • the following method calculates from the charged substance amount ratio of the monomer represented by the following formula (1-h) and the monomer represented by the following formula (2-i) used for copolymerization. Moreover, after obtaining a copolymer beforehand, an ion exchange group is introduce
  • Ar in the above formula (1) 1 Is an arylene group constituting the first main chain, and the arylene group has at least one ion-exchange group bonded directly or indirectly. That is, the ion exchange group may be directly bonded to the aromatic ring of the arylene group constituting the main chain, or may be indirectly bonded via a group of the arylene group constituting the main chain. Good. When the ion exchange group is indirectly bonded to the arylene group, the group bonding the ion exchange group and the arylene group is referred to as a linking group.
  • arylene group examples include a monocyclic aromatic group such as a phenylene group, a condensed aromatic group such as a naphthalenediyl group, an aromatic heterocyclic group such as a pyridinediyl group, a quinoxalinediyl group, and a thiophenediyl group. Is mentioned. Among them, in the production of the polyarylene block copolymer of the present invention described later, a raw material that can be easily obtained industrially can be used. From the viewpoint that a raw material that is easy to produce can be used, the following formula (ca ) To (cj) are preferred.
  • Phenolic hydroxyl groups (—OH), hydroxyl groups (—OH), mercapto groups (—SH) and other acid groups, primary amino groups (—NH) 2 ), Secondary amino group (—NHR, R is as defined above), tertiary amino group (—NRR ′, where R is as defined above), quaternary ammonium group (—N + RR'R ''. R is as defined above.
  • basic groups such as nitrogen-containing heterocyclic groups such as pyridine, pyrrole and imidazole.
  • the ion exchange group is preferably an acid group, and the acid group is preferably a phosphone group, a carboxyl group, a sulfo group, a sulfonimide group, or the like.
  • a strong acid acid group such as a sulfo group or a sulfonimide group is preferable, and a sulfo group is particularly preferable.
  • the acid group of the strong acid is converted into a super strong acid by the effect of the electron withdrawing group.
  • the arylene group includes a fluorine atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, and an optionally substituted substituent having 1 to 20 carbon atoms.
  • an alkoxy group, an optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted carbon Selected from an acyl group having 2 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent, an alkylsulfonyl group having 1 to 20 carbon atoms which may have a substituent, and a cyano group Group.
  • Preferable groups include an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted group.
  • Examples thereof include an acyl group having 2 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent, and a cyano group.
  • a polyarylene block copolymer having such a group is preferable because it has high hydrolysis resistance.
  • Particularly preferred groups include an acyl group having 2 to 20 carbon atoms which may have a substituent.
  • a polyarylene block copolymer having such a group is preferable because of excellent water resistance.
  • the two structural units having the acyl group are adjacent to each other, and the acyl groups in the two structural units are bonded to each other. May occur.
  • the group after bonding (after the rearrangement reaction) has an alkyl group having 1 to 20 carbon atoms and a substituent which may have a substituent.
  • a case where it corresponds to any of the acyl groups having 2 to 20 carbon atoms which may have a group is included in the polymer of the present invention.
  • alkyl group having 1 to 20 carbon atoms which may have a substituent for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group N-pentyl group, 2,2-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, 2-methylpentyl group, 2-ethylhexyl group, nonyl group, dodecyl group, hexadecyl group, octadecyl group, icosyl group
  • alkyl groups having 1 to 20 carbon atoms and these alkyl groups are
  • Examples of the substituent include an alkyl group having a total carbon number of 20 or less.
  • Examples of the optionally substituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, sec-butyloxy group, tert.
  • -Butyloxy group isobutyloxy group, n-pentyloxy group, 2,2-dimethylpropyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, 2-methylpentyloxy group, 2-ethylhexyloxy group, Alkoxy groups having 1 to 20 carbon atoms such as dodecyloxy group, hexadecyloxy group, icosyloxy group, etc., and the total carbon number of these groups having one or more substituents selected from the following substituent group is 20 or less. And an alkoxy group.
  • an acyl group having 20 or less total carbon atoms each having ⁇ 20 acyl groups and one or more substituents selected from the following substituent group.
  • substituent group Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, 2,2-dimethylpropyl group, cyclopentyl group, n- C1-C18 alkyl groups such as hexyl group, cyclohexyl group, 2-methylpentyl group, 2-ethylhexyl group, nonyl group, dodecyl group, etc., these alkyl groups are hydroxyl group, cyano group, amino group, phenyl group, An alkyl group having a naphthyl group or the like as a substituent and a total carbon number of 18 or less, and a hydroxyl group,
  • substituent group Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, 2,2-dimethylpropyl group, cyclopentyl group, n- C1-C14 alkyl groups such as hexyl group, cyclohexyl group, 2-methylpentyl group, 2-ethylhexyl group, nonyl group, dodecyl group, etc., these alkyl groups are hydroxyl group, cyano group, amino group, phenyl group, An alkyl group having a naphthyl group or the like as a substituent and having a total carbon number of 14 or less, and a hydroxyl
  • the structural unit represented by the formula (1) When the ion exchange group is directly bonded to the aromatic ring constituting the first main chain of the structural unit represented by the formula (1), the structural unit represented by the formula (1) There is a tendency to be superior in water resistance as compared with the case where it is bonded to an aromatic ring constituting the main chain of 1 by an appropriate linking group.
  • the ion exchange groups in the structural unit represented by the formula (1) When the proportion of ion exchange groups directly bonded to the aromatic ring constituting the main chain is larger, even if the ion exchange capacity is increased, a proton conductive membrane having excellent water resistance can be obtained.
  • the main chain of the block having an ion exchange group (that is, the first main chain of the first block) preferably has a polyparaphenylene structure.
  • the main chain When the main chain has a rigid polyparaphenylene structure, it tends to be more excellent in dimensional stability during water absorption and water resistance than when it contains a bending component having a metaphenylene structure or the like.
  • the structural unit represented by the above formula (1) include a structural unit represented by the following formula (4).
  • the block having such a structural unit can use a raw material that can be easily obtained industrially, or a raw material that is easy to manufacture.
  • a polyarylene block copolymer including a block having such a structural unit is preferable because it is excellent in water resistance when used as a polymer electrolyte membrane.
  • R is a fluorine atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, or a substituent.
  • It represents an acyl group, an optionally substituted arylsulfonyl group having 6 to 20 carbon atoms, an optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms, or a cyano group.
  • the number k of the substituents is preferably 0 or 1, and particularly preferably k is 0, that is, a repeating unit having no substituent.
  • p is preferably 1.
  • the structural unit represented by the above formula (4) include a structural unit represented by the following formula (5). (In the formula, R is as defined above, and k represents an integer of 0 to 3.)
  • Ar in the above formula (2) 2 Is an arylene group constituting the first main chain, and Ar 1 It represents an arylene group that does not have an ion exchange group as the arylene group has, but may have a substituent other than the ion exchange group.
  • the arylene group has a fluorine atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, and a substituent.
  • the weight of the monomer represented by (2-i) used for the copolymerization was calculated from the amount of the substance at the position, and the weight of the monomer represented by the following formula (2-i) used for the obtained copolymerization; And the weight of the polymer substantially not having an ion exchange group represented by the following formula (7) used for copolymerization.
  • the molecular weight obtained by weighted averaging from the molecular weight and the substance amount is used as the molecular weight of the structural unit of the block having an ion exchange group.
  • the arylene group or biphenylene group may have one or more selected from the group consisting of an ion exchange group and an ion exchange group precursor, directly and / or indirectly.
  • Q represents a leaving group, and two Qs may be the same or different.
  • sulfonic acid ester group examples include a sulfonic acid methyl ester group, a sulfonic acid ethyl ester group, a sulfonic acid n-propyl ester group, a sulfonic acid isopropyl ester group, a sulfonic acid n-butyl ester group, a sulfonic acid sec-butyl ester group, Sulfonic acid tert-butyl ester group, sulfonic acid n-pentyl ester group, sulfonic acid neopentyl ester group, sulfonic acid n-hexyl ester group, sulfonic acid cyclohexyl ester group, sulfonic acid n-heptyl ester group, sulfonic acid n-octyl Ester group, sulfonic acid n-nonyl ester group, sulfonic acid
  • Sulfonamide group di-n-propylsulfonamide group, N-isopropylsulfonamide group, N, N-diisopropylsulfonamide group, Nn-butylsulfonamide group, N, N-di-n-butylsulfonamide group N-sec-butylsulfonamide group, N, N-di-sec-butylsulfonamide group, N-tertbutylsulfonamide group, N, N-di-tert-butylsulfonamide group, Nn-pentylsulfone Amide group, N-neopentylsulfonamide group, Nn-hexylsulfonamide group, N-cycl Hexylsulfonamide group, Nn-heptylsulfonamide group, Nn-octylsulfonamide group, Nn-nonylsulfonamide group, Nn-
  • the arylene group or biphenylene group has neither an ion exchange group nor an ion exchange group precursor. That is, the arylene group or biphenylene group is bonded directly to the directly bonded ion exchange group, directly bonded ion exchange group precursor, or indirectly bonded ion exchange group via the linking group. And no ion exchange group precursor.
  • Q represents a leaving group, and two Qs may be the same or different.
  • the arylene group or biphenylene group is Ar. 2
  • the arylene group constituting can have the same group as the specific examples of the substituent which can be included.
  • the leaving group represents a group that is eliminated during the condensation reaction. Specific examples thereof include, for example, a halogen atom such as a chlorine atom, a bromine atom, and an iodine atom, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, Examples include sulfonyloxy groups such as a trifluoromethanesulfonyloxy group.
  • monomers represented by the formula (2-i) include 1,4-dichlorobenzene, 1,4-dichloro-3-methoxybenzene, 4,4′-dichlorobiphenyl, 4,4′-dichloro- 3,3′-dimethylbiphenyl, 4,4′-dichloro-3,3′-dimethoxybiphenyl, 1,4-dichloronaphthalene, 1,5-dichloronaphthalene, 2,6-dichloronaphthalene, 2,7-dichloronaphthalene 2,5-dichlorobenzophenone.
  • a monomer in which a halogen atom such as a bromine atom or an iodine atom, a sulfonyloxy group such as a p-toluenesulfonyloxy group, a methanesulfonyloxy group, or a trifluoromethanesulfonyloxy group is substituted for a chlorine atom in these monomers Can be used.
  • a polymer which does not have an ion exchange group substantially it is preferable that it is a polymer represented by following formula (7).
  • Ar 21 Is a divalent aromatic group constituting the main chain, and the divalent aromatic group has neither a group represented by -O- nor a group represented by -S-. That is, the divalent aromatic group Ar 21 One and the group X represented by —O— or —S— bonded thereto 11 In combination with one, it is regarded as one structural unit.
  • a plurality of Ar 21 May be the same or different.
  • the divalent aromatic group includes a fluorine atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, and a substituent.
  • X 11 Represents a group represented by -O- or a group represented by -S-. Multiple X 11 May be the same or different.
  • Y represents a leaving group.
  • b represents a molar composition ratio
  • b is preferably 0.50 or more.
  • b is preferably 0.90 or less, more preferably 0.70 or less, and further preferably 0.60 or less.
  • b is 0.50.
  • b is controlled by the monomer ratio in producing the polymer substantially having no ion exchange group.
  • Q is as defined above.
  • the weight-average molecular weight in terms of polystyrene of the polymer substantially having no ion exchange group represented by the above formula (7) is preferably 1000 to 21000, more preferably 2000 to 16000, and more preferably 3000 to 10,000.
  • a zero-valent nickel complex and a zero-valent palladium complex are preferably used, and a zero-valent nickel complex is more preferably used.
  • the zerovalent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), and tetrakis (triphenylphosphine) nickel.
  • bis (1,5-cyclooctadiene) nickel (0) is preferably used from the viewpoints of reactivity, yield of the obtained polymer and the like, and increase in the molecular weight of the obtained polymer and the like.
  • Examples of the zero-valent palladium complex include tetrakis (triphenylphosphine) palladium (0).
  • these zerovalent transition metal complexes those synthesized as described above may be used, or commercially available products may be used.
  • Examples of the method for synthesizing the zero-valent transition metal complex include known methods such as a method in which the transition metal compound is made zero-valent with a reducing agent such as zinc or magnesium. The synthesized zero-valent transition metal complex may be used after being taken out or may be used in situ without being taken out.
  • a zero-valent transition metal compound can be used as the transition metal compound used, but it is usually preferable to use a divalent one.
  • divalent nickel compounds and divalent palladium compounds are preferred.
  • the divalent nickel compound include nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel acetylacetonate, nickel chloride bis (triphenylphosphine), nickel bromide bis (triphenylphosphine), nickel iodide bis ( Triphenylphosphine).
  • the added amount of the ligand is usually about 0.2 to 10 mole times, preferably about 1 to 5 mole times based on the transition metal atom in the zero-valent transition metal complex.
  • the amount of the zero-valent transition metal complex used is the total of the monomer represented by the formula (1-h), the monomer represented by the formula (2-i), and the polymer represented by the formula (7) used for the production of polymers and the like. It is 0.1 mol times or more with respect to the molar amount (hereinafter referred to as “total molar amount of all monomers”).
  • the reaction temperature is usually about 0 ° C. to 200 ° C., preferably about 10 ° C. to 100 ° C.
  • the reaction time is usually about 0.5 to 48 hours.
  • a zero-valent transition metal complex is mixed with a monomer represented by the formula (1-h), a monomer represented by the formula (2-i), and a polymer represented by the formula (7), which are used for production of a polymer or the like.
  • the method may be a method of adding a zero-valent transition metal complex to a substrate or a method of simultaneously adding a zero-valent transition metal complex and a substrate to a reaction vessel.
  • the condensation reaction is usually carried out in the presence of a solvent.
  • solvents examples include aprotic compounds such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide and the like.
  • aprotic compounds such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide and the like.
  • Polar solvents such as toluene, xylene, mesitylene, benzene, n-butylbenzene; ether solvents such as tetrahydrofuran, 1,4-dioxane, dibutyl ether, tert-butyl methyl ether; ethyl acetate, Examples include ester solvents such as butyl acetate and methyl benzoate; and alkyl halide solvents such as chloroform and dichloroethane.
  • aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, benzene, n-butylbenzene
  • ether solvents such as tetrahydrofuran, 1,4-dioxane, dibutyl ether, tert-butyl methyl ether
  • ethyl acetate examples include ester solvents such as butyl acetate and methyl benzoate; and alkyl halide
  • a solvent in which the polymer etc. is sufficiently dissolved In order to further increase the molecular weight of the polymer to be produced, it is desirable to use a solvent in which the polymer etc. is sufficiently dissolved. Therefore, tetrahydrofuran, 1,4-dioxane, DMF, DMAc, which are good solvents for the polymer to be produced, etc.
  • the use of NMP, DMSO, toluene is preferred. These may be used in combination of two or more. Among these, at least one solvent selected from the group consisting of DMF, DMAc, NMP, and DMSO, or a mixture of two or more solvents selected from these is preferably used.
  • the amount of the solvent is not particularly limited, but if the reaction system is too low, it may be difficult to recover the produced polymer or the like, and if the reaction system is too high, stirring may be difficult. Therefore, a monomer selected from a solvent and monomers used for production of a polymer (monomer represented by formula (1-h), monomer represented by formula (2-i), and polymer represented by formula (7))
  • the amount of the solvent to be used is determined so as to be 1 to 999 times, more preferably 3 to 199 times the weight. Thus, although a polymer etc. are obtained, the produced
  • the polymer can be precipitated by adding a poor solvent, and the target product can be taken out by filtration or the like. Moreover, it can also refine
  • Conversion of an ion exchange group precursor in a form in which an ion exchange group is protected by forming an ester or amide into an ion exchange group in the form of a free acid is carried out by hydrolysis with an acid / base, a halide It is possible by deprotection reaction by.
  • a base When a base is used, it is possible to obtain an ion exchange group in the form of a free acid by washing the acidic solution as described above.
  • the acid / base used include hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, and potassium hydroxide.
  • the amount of ion exchange groups introduced into the entire polyarylene block copolymer is preferably 3.1 meq / g or more, more preferably 3.5 meq / g or more, and 4.0 meq / g or more in terms of ion exchange capacity. Further preferred is 4.4 meq / g or more. Moreover, 5.6 meq / g or less is preferable, 5.2 meq / g or less is more preferable, and 5.0 meq / g or less is further more preferable. It is preferable that the ion exchange capacity indicating the amount of introduced ion exchange groups is 3.1 meq / g or more because proton conductivity becomes higher and functions as a polymer electrolyte for a fuel cell are more excellent.
  • the ion exchange capacity indicating the amount of introduced ion exchange groups is 5.6 meq / g or less because the water resistance becomes better.
  • the ion exchange capacity is measured by acid-base titration.
  • the polyarylene block copolymer of the present invention has a molecular weight of preferably 100,000 to 2,000,000, more preferably 150,000 to 1,000,000, and more preferably 200,000 to 1,000,000, expressed as a weight average molecular weight in terms of polystyrene. It is particularly preferred that The weight average molecular weight is measured by gel permeation chromatography (GPC). Any of the polyarylene block copolymers of the present invention can be suitably used as a member for a fuel cell.
  • the polyarylene block copolymer of the present invention is preferably used as a polymer electrolyte of an electrochemical device such as a fuel cell, and particularly preferably used as a polymer electrolyte membrane.
  • the polymer electrolyte membrane will be mainly described.
  • the polymer electrolyte of the present invention is converted into a membrane form.
  • film forming method film forming method
  • solution casting method solution casting method formed into a film from a solution state.
  • the solution casting method is a method that has been widely used in the art as a polymer electrolyte membrane production, and is particularly useful industrially.
  • the polymer electrolyte of the present invention is dissolved in an appropriate solvent to prepare a polymer electrolyte solution, the polymer electrolyte solution is cast on a support substrate, and the solvent is removed to form a film. Is done.
  • a supporting substrate include glass plates and plastic films such as polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI).
  • the solvent (cast solvent) used in the solution casting method is not particularly limited as long as it can sufficiently dissolve the polymer electrolyte of the present invention and can be removed thereafter.
  • NMP, DMAc, DMF, 1, 3 -Aprotic polar solvents such as dimethyl-2-imidazolidinone (DMI) and DMSO; Chlorinated solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and dichlorobenzene; Alcohols such as methanol, ethanol and propanol
  • An alkylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferably used. These can be used singly, but two or more solvents can be mixed and used as necessary.
  • NMP, DMAc, DMF, and DMI are preferable because the polymer electrolyte of the present invention has high solubility and a polymer electrolyte membrane having high water resistance can be obtained.
  • the thickness of the polymer electrolyte membrane thus obtained is not particularly limited, but is preferably 5 to 300 ⁇ m in a practical range as a polymer electrolyte membrane (a diaphragm) for a fuel cell.
  • a film having a film thickness of 5 ⁇ m or more is preferable because of its practical strength, and a film having a film thickness of 300 ⁇ m or less is preferable because the film resistance itself tends to be small.
  • the film thickness can be controlled by the weight concentration of the solution and the coating thickness of the coating film on the support substrate.
  • additives such as plasticizers, stabilizers, mold release agents and the like used in ordinary polymers are added to the polyarylene block copolymer of the present invention to obtain polymers.
  • An electrolyte may be prepared. It is also possible to prepare a polymer electrolyte by compound-alloying another polymer with the polyarylene block copolymer of the present invention by a method such as co-casting in the same solvent. Thus, when a polymer electrolyte is prepared by combining the polyarylene block copolymer of the present invention with an additive and / or another polymer, the polymer electrolyte is applied to a fuel cell member.
  • the type and amount of additives and / or other polymers are determined so that the desired properties are obtained.
  • inorganic or organic fine particles as a water retention agent in order to facilitate water management. Any of these known methods can be used as long as they are not contrary to the object of the present invention.
  • the polymer electrolyte membrane thus obtained may be subjected to a treatment such as irradiation with an electron beam or radiation for the purpose of improving its mechanical strength.
  • the polymer electrolyte containing the polyarylene block copolymer of the present invention is used as a porous substrate.
  • the porous substrate is not particularly limited as long as it satisfies the above-mentioned purpose of use, and examples thereof include porous membranes, woven fabrics, nonwoven fabrics, fibrils and the like, and they can be used regardless of their shapes and materials.
  • As the material for the porous substrate an aliphatic polymer and an aromatic polymer are preferable in view of heat resistance and the effect of reinforcing physical strength.
  • the thickness of the porous substrate is preferably 1 to 100 ⁇ m, more preferably 3 to 30 ⁇ m, and particularly preferably 5 to 20 ⁇ m. It is.
  • the pore diameter of the porous substrate is preferably 0.01 to 100 ⁇ m, more preferably 0.02 to 10 ⁇ m.
  • the porosity of the porous substrate is preferably 20 to 98%, more preferably 40 to 95%.
  • the filling of the polymer of the present invention becomes easier, and when it is 100 ⁇ m or less, the reinforcing effect is further increased.
  • the porosity is 20% or more, the resistance as the polymer electrolyte membrane becomes smaller, and when it is 98% or less, the strength of the porous substrate itself becomes larger and the reinforcing effect is further improved, which is preferable.
  • a composite membrane using the polymer electrolyte of the present invention and a polymer electrolyte membrane using the polymer electrolyte of the present invention can be laminated and used as a proton conducting membrane. Next, the fuel cell of the present invention will be described.
  • the membrane electrode assembly of the present invention (hereinafter sometimes referred to as “MEA”), which is a basic unit of a fuel cell, includes the polymer electrolyte membrane of the present invention, the polymer electrolyte of the present invention, and a catalyst. It can manufacture using at least 1 sort (s) chosen from the catalyst composition containing a component. That is, the membrane electrode assembly of the present invention is a membrane electrode assembly including a polymer electrolyte membrane and a catalyst layer provided on the polymer electrolyte membrane, wherein the polymer electrolyte membrane is A membrane electrode assembly, wherein the membrane electrode assembly is a polymer electrolyte membrane and / or the catalyst layer is a layer formed from the catalyst composition.
  • the catalyst component is not particularly limited as long as it can activate the oxidation-reduction reaction with hydrogen or oxygen, and a known component can be used, but platinum or platinum alloy fine particles are used as the catalyst component. It is preferable.
  • the fine particles of platinum or platinum-based alloys are often used by being supported on particulate or fibrous carbon such as activated carbon or graphite.
  • a catalyst obtained by mixing platinum supported on carbon or a platinum-based alloy (carbon-supported catalyst) with the solution of the polymer electrolyte of the present invention and / or the alcohol solution of the perfluoroalkylsulfonic acid resin as the polymer electrolyte.
  • the catalyst layer is obtained by applying and drying the composition to the gas diffusion layer and / or polymer electrolyte membrane.
  • MEA is obtained by forming a catalyst layer on both surfaces of a polymer electrolyte membrane.
  • the obtained MEA is a membrane-electrode having both a gas diffusion layer and a catalyst layer on both sides of a polymer electrolyte membrane.
  • a gas diffusion layer is further formed on the obtained catalyst layer to form a membrane.
  • a known material can be used for the gas diffusion layer, but a porous carbon woven fabric, carbon non-woven fabric or carbon paper is preferable in order to efficiently transport the raw material gas to the catalyst.
  • the fuel cell including the MEA manufactured in this way can be used in various formats using methanol as well as a format using hydrogen gas or reformed hydrogen gas as fuel.
  • Molecular weight measurement The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were measured by gel permeation chromatography (GPC) under the following conditions. The following conditions (A) or (B) were used as GPC analysis conditions.
  • A GPC measurement device Prominence GPC system manufactured by Shimadzu Corporation Column TSKgel GMH manufactured by Tosoh Corporation HR -M Column temperature 40 ° C Mobile phase solvent DMF (LiBr 10 mmol / dm 3 To be added) Solvent flow rate 0.5mL / min Detection Differential refractive index Condition
  • B GPC measuring device HLC-8220 manufactured by TOSOH Column TSKgel GMH manufactured by Tosoh Corporation HR -M Column temperature 40 ° C Mobile phase solvent DMAc (LiBr 10 mmol / dm 3 To be added) Solvent flow rate 0.5mL / min Detection Differential refractive index Measurement of ion exchange capacity (IEC): A polymer film obtained by forming a polymer to be measured by a solution casting method was obtained, and the obtained polymer film was cut to an appropriate weight.
  • IEC ion exchange capacity
  • the dry weight of the cut polymer film was measured using a halogen moisture meter set at a heating temperature of 110 ° C.
  • the polymer membrane thus dried was immersed in 5 mL of a 0.1 mol / L sodium hydroxide aqueous solution, and further 50 mL of ion exchange water was added and left for 2 hours.
  • titration was performed by gradually adding 0.1 mol / L hydrochloric acid to the solution in which the polymer film was immersed, and the neutralization point was determined.
  • the ion exchange capacity (unit: meq / g) of the polymer was calculated from the dry weight of the cut polymer film and the amount of hydrochloric acid required for neutralization.
  • Proton conductivity was measured by the AC method. 1cm 2 Two measurement cells with carbon electrodes pasted on one side of silicon rubber (thickness: 200 ⁇ m) having an opening are arranged so that the carbon electrodes face each other, and impedance measurement is performed directly on the two cells. The device terminals were connected. Next, a polymer electrolyte membrane obtained by converting the ion exchange group obtained by the above method into a proton type is set between the two measurement cells, and the resistance between the two measurement cells is measured at a measurement temperature of 23 ° C. The value was measured. Thereafter, the polymer electrolyte membrane was removed and the resistance value was measured again.
  • the membrane resistance in the film thickness direction of the polymer electrolyte membrane was calculated.
  • the proton conductivity in the film thickness direction of the polymer electrolyte membrane was calculated from the obtained membrane resistance value and film thickness.
  • 1 mol / L dilute sulfuric acid was used as the solution to be brought into contact with both sides of the polymer electrolyte membrane.
  • Measurement of dimensional change rate during water absorption swelling The dimension (Ld) in the surface direction of the membrane dried at 23 ° C. and a relative humidity of 50%, and the dimension in the surface direction of the membrane immediately after the membrane was immersed and swollen in deionized water at 80 ° C.
  • Example 1 A flask equipped with an azeotropic distillation apparatus was charged with 67.3 g (200 mmol) of 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 60.3 g (240 mmol) of 4,4′-dichlorobenzophenone, carbonic acid under an argon atmosphere. 71.9 g (520 mmol) of potassium, 300 mL of N, N-dimethylformamide, and 150 mL of toluene were added, and the mixture was stirred at 140 ° C. for 8 hours while distilling off the generated water and toluene. The bath temperature was raised to 158 ° C., and the mixture was kept warm for 10 hours.
  • the bath temperature was lowered to 50 ° C. and 3.20 g (20.5 mmol) of 2,2′-bipyridyl was added to prepare a nickel-containing solution.
  • 0.95 g of the polymer represented by the above formula (B), 2.84 g (11.3 mmol) of 2,5-dichlorobenzophenone and 170 g of N-methylpyrrolidone were added to the flask and adjusted to 50 ° C.
  • the obtained polymerization solution was put into 1400 g of 6 mol / L hydrochloric acid and stirred at room temperature for 1 hour.
  • the resulting precipitate was collected by filtration, then added to 1400 g of 6 mol / L hydrochloric acid, stirred at room temperature, and then filtered.
  • the collected solid was washed with ion exchange water until the pH of the filtrate exceeded 4.
  • a large amount of methanol was added to the obtained crude polymer, and the operation of stirring at room temperature for 1 hour and collecting by filtration was repeated twice and dried to obtain a sulfonic acid group precursor (sulfonic acid (2,2-dimethyl). 10.9 g of polymer (C) having (propyl) groups) was obtained.
  • the sulfonic acid group precursor was converted into a sulfo group as follows. 10.9 g of the polymer (C) having a sulfonic acid group precursor obtained as described above, 21.7 g of ion-exchanged water, 8.29 g (95.5 mmol) of anhydrous lithium bromide and 272 g of N-methylpyrrolidone were added to a flask. And the resulting mixture was heated and stirred at a bath temperature of 126 ° C. for 12 hours to obtain a polymer solution. The obtained polymer solution was put into 1520 g of 6 mol / L hydrochloric acid and stirred for 1 hour.
  • the precipitated crude polymer was collected by filtration, and the operation of immersing and washing with 1086 g of a mixed solution of 10 parts by weight of methanol and 10 parts by weight of 35% by weight hydrochloric acid was repeated three times. Thereafter, the crude polymer was washed with ion exchanged water until the pH of the filtrate exceeded 4. Subsequently, a large amount of ion-exchanged water is added to the obtained polymer, the temperature is raised to 90 ° C. or higher, the mixture is heated and kept for about 30 minutes, collected by filtration, and the obtained polymer is dried to obtain the following formula.
  • 9.23 g of a polyarylene block copolymer (D) containing a block represented by 1.0 g of the resulting polyarylene block copolymer (D) was dissolved in dimethyl sulfoxide to prepare a polymer solution. Thereafter, the obtained polymer solution was cast on a PET film, and the solvent was removed by drying at 80 ° C. under normal pressure, followed by washing with 6 wt% hydrochloric acid and washing with ion-exchanged water. A polymer electrolyte membrane of about 18 ⁇ m was produced.
  • the IEC of the block having an ion exchange group was determined from the following calculation formula.
  • the obtained crude product was dissolved in 95 g of N, N-dimethylformamide, the resulting solution was added to a mixed solution of 1100 g of methanol and 100 g of 35% by weight hydrochloric acid, and the deposited precipitate was collected by filtration, followed by ion exchange.
  • the polymer was washed with water until neutral, washed with 1000 g of methanol, and dried to obtain 25.4 g of a polymer represented by formula (E) below.
  • 6.20 g (28.4 mmol) of anhydrous nickel bromide and 140 g of N-methylpyrrolidone were added to the flask under an argon atmosphere, and the resulting mixture was stirred at a bath temperature of 70 ° C. After confirming that anhydrous nickel bromide was dissolved, the bath temperature was lowered to 50 ° C., and 5.32 g (34.1 mmol) of 2,2′-bipyridyl was added to prepare a nickel-containing solution.
  • the collected solid was washed with ion exchange water until the pH of the filtrate exceeded 4. Ion exchange water and methanol were added to the obtained crude polymer, and the mixture was heated and stirred at a bath temperature of 90 ° C. for 1 hour.
  • the crude polymer was collected by filtration and dried to obtain 20.6 g of a polymer (F) having a sulfonic acid group precursor (sulfonic acid (2,2-dimethylpropyl) group).
  • the sulfonic acid group precursor was converted into a sulfo group as follows.
  • the precipitated crude polymer was collected by filtration, and the operation of immersing and washing with 2062 g of a mixed solution of 5 parts by weight of methanol and 1 part by weight of 35% by weight hydrochloric acid was repeated three times. Thereafter, the crude polymer was washed with ion exchanged water until the pH of the filtrate exceeded 4. Subsequently, a large amount of ion-exchanged water was added to the obtained polymer, the temperature was raised to 90 ° C. or higher, the temperature was kept warm for about 30 minutes, and filtration was repeated twice.
  • the obtained polymerization solution was put into 1600 g of 6 mol / L hydrochloric acid and stirred at room temperature for 30 minutes.
  • the resulting precipitate was collected by filtration, then added to 500 g of 6 mol / L hydrochloric acid, stirred at room temperature for 30 minutes, and then filtered.
  • the collected solid was washed with ion exchange water until the pH of the filtrate exceeded 4.
  • 500 g of ion-exchanged water and 500 g of methanol were added, and the mixture was heated and stirred at a bath temperature of 90 ° C. for 1 hour.
  • the crude polymer was filtered and dried to obtain 19.7 g of a polymer (H) having a sulfonic acid group precursor (sulfonic acid (2,2-dimethylpropyl) group).
  • the sulfonic acid group precursor was converted into a sulfo group as follows. 19.7 g of the polymer (H) having a sulfonic acid group precursor obtained as described above, 43 g of ion-exchanged water, 13.3 g (153 mmol) of anhydrous lithium bromide, and 688 g of N-methylpyrrolidone were added to a flask. The mixture was heated and stirred at a bath temperature of 126 ° C. for 12 hours to obtain a polymer solution.
  • the obtained polymer solution was put into 1870 g of 6 mol / L hydrochloric acid and stirred for 1 hour.
  • the precipitated crude polymer was collected by filtration, and the operation of immersing and washing with 931 g of a mixed solution of 10 parts by weight of methanol and 10 parts by weight of 6 mol / L hydrochloric acid was repeated three times. Thereafter, the crude polymer was washed with ion exchanged water until the pH of the filtrate exceeded 4. Subsequently, a large amount of ion-exchanged water was added to the obtained polymer, the temperature was raised to 90 ° C. or higher, the temperature was kept warm for about 15 minutes, and filtration was repeated three times.
  • a and B represent molar composition ratios.
  • a polyarylene block copolymer (K) containing a block represented by 1.0 g of the obtained polyarylene block copolymer (K) was dissolved in N-methylpyrrolidone to prepare a polymer solution. Thereafter, the obtained polymer solution was cast on a glass plate, and the solvent was removed by drying at 80 ° C. under normal pressure, followed by washing with 6% by weight hydrochloric acid and washing with ion-exchanged water. A polymer electrolyte membrane having a thickness of about 20 ⁇ m was produced. The IEC of the block having an ion exchange group was determined from the following calculation formula.
  • reaction solution After standing to cool, the reaction solution is added to a large excess of a mixed solution of 10 parts by weight of methanol and 10 parts by weight of 35% by weight hydrochloric acid, and the deposited precipitate is collected by filtration and then neutralized with ion-exchanged water. Washed and dried. 49 g of the resulting product was dissolved in 441 g of tetrahydrofuran and insoluble matter was filtered off. The filtrate was added to a large excess of methanol, and the deposited precipitate was collected by filtration, and then 6% by weight hydrochloric acid, ion-exchanged water. And dried to obtain 46.2 g of a polymer substantially having no ion exchange group represented by the following formula (L).
  • L a polymer substantially having no ion exchange group represented by the following formula (L).
  • anhydrous nickel bromide and 130 g of N-methylpyrrolidone were added to the flask, and the resulting mixture was stirred at a bath temperature of 70 ° C.
  • the bath temperature was lowered to 50 ° C., and 1.30 g (8.30 mmol) of 2,2′-bipyridyl was added to prepare a nickel-containing solution.
  • Water in the system was azeotropically dehydrated by heating and refluxing toluene at a bath temperature of 150 ° C. for 2 hours and 30 minutes. After distilling off the generated water and toluene, 50.0 g (174.1 mmol) of 4,4′-dichlorodiphenylsulfone was added to obtain a mixture. The bath temperature was raised to 180 ° C., and the mixture was stirred for 9 hours and 30 minutes while maintaining the temperature.
  • reaction solution After allowing to cool, the reaction solution is added to a mixed solution of 1500 g of methanol and 250 g of 35 wt% hydrochloric acid, and the deposited precipitate is collected by filtration, washed with ion-exchanged water until neutral, and washed with methanol. , Dried.
  • the obtained crude product was dissolved in 321 g of N-methylpyrrolidone, the resulting solution was added to a mixed solution of 1250 g of methanol and 250 g of 35% by weight hydrochloric acid, and the deposited precipitate was collected by filtration, and then ion-exchanged water.
  • the polymer was washed until neutral and dried to obtain 74.7 g of a polymer represented by the following formula (O).
  • 19.92 g (91.2 mmol) of anhydrous nickel bromide and 350 g of N-methylpyrrolidone were added to the flask under a nitrogen atmosphere, and the resulting mixture was stirred at 65 ° C. After confirming that anhydrous nickel bromide was dissolved, the temperature was lowered to 50 ° C., and 14.24 g (91.2 mmol) of 2,2′-bipyridyl was added to prepare a nickel-containing solution.
  • the obtained polymer solution was cast on a PET film, and the solvent was removed by drying at 80 ° C. under normal pressure, followed by washing with 6 wt% hydrochloric acid and washing with ion-exchanged water.
  • a polymer electrolyte membrane of about 19 ⁇ m was produced.
  • the IEC of the block having an ion exchange group was determined from the following calculation formula.
  • the polyarylene block copolymer of the present invention When used as a polymer electrolyte fuel cell member, particularly as a polymer electrolyte membrane, it exhibits high proton conductivity and excellent dimensional stability during water absorption swelling.
  • the polyarylene block copolymer of the present invention is also suitable for use as a catalyst layer of a polymer electrolyte fuel cell.
  • the polyarylene block copolymer of the present invention when used as a polymer electrolyte membrane in a fuel cell, a fuel cell exhibiting high power generation characteristics and excellent shape stability can be obtained.
  • the polyarylene block copolymer of the present invention exhibits high toughness when used as a polymer electrolyte fuel cell member, particularly as a polymer electrolyte membrane, the polymer electrolyte membrane is used for a fuel cell. If so, it shows high durability. As described above, the polyarylene block copolymer of the present invention is industrially extremely useful particularly in the use of fuel cells.

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Abstract

L'invention concerne un copolymère à blocs de polyarylène caractérisé en ce qu'il comprend un premier bloc qui contient une première chaîne principale ayant une structure polyarylène et également un groupe d'échange d'ions et un deuxième bloc qui comprend une deuxième chaîne principale et ne contient pratiquement pas de groupe d'échange d'ions, le premier bloc contenant un motif structural représenté par la formule (1) et un motif structural représenté par la formule (2), le deuxième bloc comprenant un motif structural représenté par la formule (3), et le premier bloc ayant une capacité d'échange d'ions de 3,5 à 6,0 meq/g. (Dans les formules, Ar1 et Ar2 représentent indépendamment un groupe arylène et Ar3 représente un groupe aromatique bivalent, Ar1 contenant au moins un groupe d'échange d'ions ; et X1 représente O ou S). Le copolymère à blocs permet la production d'un film conducteur de protons présentant une conductivité des protons élevée et une excellente stabilité dimensionnelle après gonflement par absorption d'eau.
PCT/JP2011/061921 2010-05-19 2011-05-18 Copolymère à blocs de polyarylène, procédé pour le produire et électrolyte polymère WO2011145748A1 (fr)

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WO2013018677A1 (fr) * 2011-07-29 2013-02-07 Jsr株式会社 Copolymère aromatique comportant un groupe conducteur de protons et ses applications
CN107887642A (zh) * 2016-09-30 2018-04-06 东丽先端材料研究开发（中国）有限公司 聚合物电解质膜及其制备方法

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JP2013209457A (ja) * 2012-03-30 2013-10-10 Sumitomo Chemical Co Ltd ポリアリーレン及びその製造方法
JP6550695B2 (ja) * 2013-07-18 2019-07-31 東洋紡株式会社 複合高分子電解質膜およびその製造方法ならびにその用途
JP2015165461A (ja) * 2014-03-03 2015-09-17 東洋紡株式会社 複合電解質膜及びその製造方法

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JP2006028414A (ja) * 2004-07-20 2006-02-02 Jsr Corp スルホン化ポリマーおよび固体高分子電解質
JP2007270118A (ja) * 2006-03-07 2007-10-18 Sumitomo Chemical Co Ltd ポリアリーレン及びその製造方法
WO2008029937A1 (fr) * 2006-09-05 2008-03-13 Sumitomo Chemical Company, Limited Polymère, polyélectrolyte, et pile à combustible les utilisant
WO2009142274A1 (fr) * 2008-05-21 2009-11-26 住友化学株式会社 Polymère, copolymère bloc de polyarylène, polyélectrolyte, membrane polyélectrolytique, et pile à combustible
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JP2010013625A (ja) * 2008-06-03 2010-01-21 Jsr Corp 重合体およびプロトン伝導膜
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JP2006028415A (ja) * 2004-07-20 2006-02-02 Jsr Corp スルホン化ポリマーおよび固体高分子電解質
JP2006028414A (ja) * 2004-07-20 2006-02-02 Jsr Corp スルホン化ポリマーおよび固体高分子電解質
JP2007270118A (ja) * 2006-03-07 2007-10-18 Sumitomo Chemical Co Ltd ポリアリーレン及びその製造方法
WO2008029937A1 (fr) * 2006-09-05 2008-03-13 Sumitomo Chemical Company, Limited Polymère, polyélectrolyte, et pile à combustible les utilisant
WO2009142274A1 (fr) * 2008-05-21 2009-11-26 住友化学株式会社 Polymère, copolymère bloc de polyarylène, polyélectrolyte, membrane polyélectrolytique, et pile à combustible
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WO2011062302A1 (fr) * 2009-11-20 2011-05-26 住友化学株式会社 Copolymère séquencé de polyarylène et utilisation associée

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013018677A1 (fr) * 2011-07-29 2013-02-07 Jsr株式会社 Copolymère aromatique comportant un groupe conducteur de protons et ses applications
CN107887642A (zh) * 2016-09-30 2018-04-06 东丽先端材料研究开发（中国）有限公司 聚合物电解质膜及其制备方法

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