WO2024014269A1 - 陽イオン交換樹脂、陽イオン交換膜、電解質膜、電極触媒層形成用バインダーおよび電池電極触媒層 - Google Patents

陽イオン交換樹脂、陽イオン交換膜、電解質膜、電極触媒層形成用バインダーおよび電池電極触媒層 Download PDF

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WO2024014269A1
WO2024014269A1 PCT/JP2023/023602 JP2023023602W WO2024014269A1 WO 2024014269 A1 WO2024014269 A1 WO 2024014269A1 JP 2023023602 W JP2023023602 W JP 2023023602W WO 2024014269 A1 WO2024014269 A1 WO 2024014269A1
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group
cation exchange
divalent
hydrophobic
carbon
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French (fr)
Japanese (ja)
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健治 宮武
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University of Yamanashi NUC
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University of Yamanashi NUC
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Priority to US18/993,519 priority Critical patent/US20260001983A1/en
Priority to EP23839443.1A priority patent/EP4556509A1/en
Priority to JP2024533616A priority patent/JPWO2024014269A1/ja
Publication of WO2024014269A1 publication Critical patent/WO2024014269A1/ja
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    • 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
    • C08J5/2225—Synthetic macromolecular compounds containing fluorine
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • 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
    • H01M8/1039—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
    • 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
    • C08G2261/124—Copolymers alternating
    • 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
    • C08G2261/14—Side-groups
    • C08G2261/141—Side-chains having aliphatic units
    • C08G2261/1412—Saturated aliphatic units
    • 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
    • C08G2261/14—Side-groups
    • C08G2261/145—Side-chains containing sulfur
    • C08G2261/1452—Side-chains containing sulfur containing sulfonyl or sulfonate-groups
    • 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
    • C08G2261/14—Side-groups
    • C08G2261/146—Side-chains containing halogens
    • 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
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/415—Sonogashira / Hagihara reactions
    • 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
    • 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
    • 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 cation exchange resin, a cation exchange membrane, an electrolyte membrane, a binder for forming an electrode catalyst layer, and a battery electrode catalyst layer.
  • the cation exchange resin described in Patent Document 1 has succeeded in improving chemical properties (durability, solubility, gas permeation suppressing effect) and mechanical properties (flexibility), but further chemical properties Improvement in properties (especially gas permeability) is desired.
  • the binder for forming the electrode catalyst layer is required to adjust and control the gas diffusivity, considering the use of the cation exchange resin described in Patent Document 1 as the binder for forming the electrode catalyst layer, further improvement is required. Improvement in gas permeability is desired.
  • the present invention produces cation exchange membranes, electrolyte membranes, binders for forming electrode catalyst layers, and battery electrode catalyst layers that have excellent electrical properties (cation conductivity) and chemical properties (gas permeability and water content).
  • a cation exchange resin a cation exchange membrane formed from the cation exchange resin, a binder for forming an electrolyte membrane and an electrode catalyst layer, and a battery electrode catalyst layer formed from the binder for forming the electrode catalyst layer.
  • the cation exchange resin of the present invention has the following features:
  • the hydrophobic unit (a), the hydrophobic unit (b), and the hydrophilic unit are bonded to each other via an ether bond, a thioether bond, or a carbon-carbon bond.
  • Alk is the same or different from each other and represents an alkyl group or an aryl group
  • R represents a divalent hydrocarbon group forming an alicyclic structure
  • a, b, c, and d are (Indicates an integer from 0 to 4, which are the same or different from each other.)
  • the hydrophobic group (a) contains a bisphenol residue represented by the following formula (1').
  • the hydrophobic group (b) contains a bisphenol residue represented by the following formula (2).
  • Alk' is the same or different from each other and represents an alkyl group or an aryl group
  • a', b', c', and d' are the same or different from each other and represent an integer of 0 to 4.
  • l' indicates an integer of 1 or more.
  • the hydrophobic group (b) contains a bisphenol residue represented by the following formula (2').
  • the hydrophobic group (b) contains a bisphenol residue represented by the following formula (3).
  • Alk'' is the same or different from each other and represents an alkyl group or an aryl group
  • a'', b'', c'', and d'' are the same or different from each other, and 0
  • l'' indicates an integer of 1 or more.
  • the hydrophobic group (b) contains a bisphenol residue represented by the following formula (3').
  • the hydrophilic group includes a bisphenol residue represented by the following formula (4).
  • Alk''' is the same or different from each other and represents an alkyl group or an aryl group
  • Ion is the same or different from each other and represents a cation exchange group-containing group
  • R' is the cation exchange group-containing group.
  • c''' and d''' is the same or different and represents an integer from 0 to 4
  • a''', b''' and e''' are the same or different and represent an integer from 0 to 4. and at least one of a''', b''' and e''' indicates 1 or more.
  • the hydrophilic group is an o-, m-, or p-phenylene residue represented by the following formula (5).
  • Alk'''' represents an alkyl group or an aryl group
  • Ion represents a cation exchange group-containing group
  • c'''' represents an integer from 0 to 4
  • a'''' indicates an integer from 1 to 4.
  • the cation exchange membrane of the present invention is characterized by containing the above cation exchange resin.
  • the cation exchange membrane of the present invention is characterized by containing the above cation exchange resin.
  • cation exchange membranes electrolyte membranes, binders for forming electrode catalyst layers, and battery electrode catalyst layers with excellent electrical properties (cation conductivity) and chemical properties (gas permeability and water content) are produced. It is possible to provide a cation exchange resin that can be produced, a cation exchange membrane formed from the cation exchange resin, a binder for forming an electrolyte membrane and an electrode catalyst layer, and a battery electrode catalyst layer formed from the binder for forming the electrode catalyst layer.
  • the cation exchange resin of the present invention consists of a divalent hydrophobic group (a), a divalent hydrophobic group (b), and a divalent hydrophilic group.
  • examples of the divalent hydrophobic group (a) include those containing a bisphenol residue represented by the following formula (1).
  • Alk is the same or different from each other and represents an alkyl group or an aryl group
  • R represents a divalent hydrocarbon group forming an alicyclic structure
  • a, b, c, and d are (Indicates an integer from 0 to 4, which are the same or different from each other.)
  • Alk is the same or different and represents an alkyl group or an aryl group.
  • alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, and octyl group. and cycloalkyl groups having 1 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.
  • aryl group include a phenyl group, a biphenyl group, a naphthyl group, and a fluorenyl group.
  • R represents a divalent hydrocarbon group forming an alicyclic structure.
  • Alicyclic structures include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclo Monocyclic cycloalkane structures such as octadecane, cyclononadecane, and cycloicosane; Monocyclic cycloalkene structures such as cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, and cyclooctene; Polycyclic
  • the alicyclic structure described above may be substituted with an alkyl group, an aryl group, a halogen atom, or the like.
  • the alkyl group include the alkyl groups described above.
  • the aryl group include the above-mentioned aryl groups.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the number of substitutions and the substitution position of the alkyl group or aryl group are appropriately set depending on the purpose and use.
  • a and b are the same or different from each other and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably, a and b both represent 0. show.
  • c and d are the same or different from each other and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably, c and d both represent 0. show.
  • hydrophobic group (a) examples include the following structures.
  • such a hydrophobic group (a) includes a bisphenol residue represented by the following formula (1').
  • l represents an integer of 2 or more, preferably an integer of 3 to 20, more preferably an integer of 5 to 8.
  • the divalent hydrophobic group (b) is one consisting of a single aromatic ring, a divalent hydrocarbon group, a divalent silicon-containing group, or a divalent nitrogen-containing group. group, a divalent phosphorus-containing group, a divalent oxygen-containing group, a divalent sulfur-containing group, or a plurality of (two or more, preferably two) aromatic rings bonded to each other via a carbon-carbon bond.
  • aromatic rings include monocyclic or polycyclic compounds having 6 to 14 carbon atoms, such as benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, and phenanthrene ring, and azole, oxole, Examples include heterocyclic compounds such as thiophene, oxazole, thiazole, and pyridine.
  • the aromatic ring is preferably a monocyclic aromatic hydrocarbon having 6 to 14 carbon atoms, and more preferably a benzene ring.
  • the aromatic ring may be substituted with a substituent such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide, if necessary.
  • a substituent such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide, if necessary.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • pseudohalides include trifluoromethyl group, -CN, -NC, -OCN, -NCO, -ONC, -SCN, -NCS, -SeCN, -NCSe, -TeCN, -NCTe, -N3 .
  • the alkyl group include the alkyl groups described above.
  • the aryl group include the above-mentioned aryl groups.
  • an aromatic ring is substituted with a substituent such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide
  • a substituent such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide
  • the number and position of the substituent such as a halogen atom, alkyl group, aryl group, or pseudohalide, etc. is set as appropriate depending on the purpose and use.
  • the aromatic ring substituted with halogen atoms includes, for example, a benzene ring substituted with 1 to 4 halogen atoms (e.g., a benzene ring substituted with 1 to 4 fluorine atoms, a benzene ring substituted with 1 to 4 fluorine atoms, a benzene ring substituted with 1 to 4 fluorine atoms, 1 to 4 halogen atoms may be the same or different, such as a benzene ring substituted with ), etc.
  • a benzene ring substituted with 1 to 4 halogen atoms e.g., a benzene ring substituted with 1 to 4 fluorine atoms, a benzene ring substituted with 1 to 4 fluorine atoms, 1 to 4 halogen atoms may be the same or different, such as a benzene ring substituted with ), etc.
  • divalent hydrocarbon groups examples include methylene (-CH 2 -), ethylene, propylene, i-propylene (-C(CH 3 ) 2 -), butylene, i-butylene, sec-butylene, pentylene (pentene), ), i-pentylene, sec-pentylene, hexylene (hexamethylene), 3-methylpentene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, i-decylene, dodecylene, tetradecylene, hexadecylene, octadecylene, etc., carbon Examples include 1 to 20 divalent saturated hydrocarbon groups.
  • the divalent hydrocarbon group is preferably a divalent saturated hydrocarbon group having 1 to 3 carbon atoms, specifically methylene (-CH 2 -), ethylene, propylene, i-propylene (-C(CH 3 ) 2 -), more preferably methylene (-CH 2 -) and isopropylene (-C(CH 3 ) 2 -), particularly preferably i-propylene (-C(CH 3 ) ) 2 -).
  • the divalent hydrocarbon group may be substituted with a monovalent residue in the aromatic ring described above.
  • hydrophobic group (b) examples include bisphenol residues represented by the following formula (2) and bisphenol residues represented by the following formula (3).
  • Alk' is the same or different from each other and represents an alkyl group or an aryl group
  • a', b', c', and d' are the same or different from each other and represent an integer of 0 to 4.
  • l' indicates an integer of 1 or more.
  • Alk'' is the same or different from each other and represents an alkyl group or an aryl group
  • a'', b'', c'', and d'' are the same or different from each other, and 0
  • l'' indicates an integer of 1 or more.
  • Alk' is the same or different and represents an alkyl group or an aryl group.
  • alkyl group include the alkyl groups described above.
  • aryl group include the above-mentioned aryl groups.
  • a' and b' are the same or different from each other and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably, a' and b' are , both indicate 0.
  • c' and d' are the same or different from each other and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably, c' and d' are , both indicate 0.
  • l' represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 2 to 6.
  • Alk'' are the same or different and represent an alkyl group or an aryl group.
  • alkyl group include the alkyl groups described above.
  • aryl group include the above-mentioned aryl groups.
  • a'' and b'' are the same or different from each other and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably a'' and b'' both indicate 0.
  • c'' and d'' are the same or different and represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably c'' and d'' both indicate 0.
  • l'' represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 2 to 6.
  • hydrophobic group (b) include bisphenol residues represented by the following formula (2') and bisphenol residues represented by the following formula (3').
  • l' has the same meaning as l' in the above formula (2), and represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably 2 to 6. Indicates an integer.
  • l'' has the same meaning as l'' in the above formula (3), and represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably 2 to 20. Indicates an integer of 6.
  • the divalent hydrophilic group consists of a single aromatic ring, a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent a linking group that is a phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group, and/or a plurality of aromatic rings bonded to each other via carbon-carbon bonds, and the linking group or the aromatic Examples include those in which at least one of the rings is bonded to a cation exchange group-containing group.
  • aromatic ring examples include the aromatic rings described above.
  • the aromatic ring is preferably a monocyclic aromatic hydrocarbon having 6 to 14 carbon atoms, and more preferably a benzene ring.
  • the aromatic ring may be substituted with a substituent such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide as described above, if necessary.
  • a substituent such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide
  • the number and position of the substituent such as a halogen atom, alkyl group, aryl group, or pseudohalide, etc. is set as appropriate depending on the purpose and use.
  • divalent hydrocarbon group examples include the divalent hydrocarbon groups described above.
  • the divalent hydrocarbon group may be substituted with a monovalent residue in the aromatic ring described above.
  • the number of aromatic rings bonded to the divalent hydrocarbon group is one or two, preferably two.
  • hydrocarbon group when one more aromatic ring is bonded to a divalent hydrocarbon group, that hydrocarbon group becomes trivalent, and when two more aromatic rings are bonded, the hydrocarbon group becomes trivalent.
  • the hydrocarbon group is tetravalent (if the number of carbon atoms is 1, it is a carbon atom).
  • the aromatic rings when two aromatic rings are bonded to a divalent hydrocarbon group, the aromatic rings may be bonded via, for example, a carbon-carbon bond.
  • the cation exchange group is introduced into the main chain or side chain as a hydrophilic group, and is not particularly limited. Any known cation exchange group such as acid (-COOH) can be employed. From the viewpoint of ease of synthesis and cation conductivity, sulfonic acid groups are preferred.
  • the cation exchange group-containing group may be only a cation exchange group, or may be a residue in which, for example, a divalent hydrocarbon group is bonded to a cation exchange group.
  • the divalent hydrocarbon group is preferably methylene (-(CH 2 )-), ethylene (-(CH 2 ) 2 -), trimethylene (-(CH 2 ) 3 -), tetramethylene (-(CH 2 ) 4 -), pentamethylene (-(CH 2 ) 5 -), hexamethylene (-(CH 2 ) 6 -), heptamethylene (-(CH 2 ) 7 -), octamethylene (-(CH 2 ) Examples include linear saturated hydrocarbon groups such as 8- ).
  • Such a cation exchange group-containing group consists of a single aromatic ring, or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, or a divalent phosphorus-containing group.
  • a linking group that is an oxygen-containing group or a divalent sulfur-containing group, and/or a linking group or aromatic ring of a divalent hydrophilic residue consisting of a plurality of aromatic rings bonded to each other via a carbon-carbon bond. be combined.
  • the cation exchange group-containing group may be bonded to at least one linking group or aromatic ring, may be bonded to multiple linking groups or aromatic rings, and may be bonded to all linking groups or aromatic rings. You can leave it there. Further, a plurality of cation exchange group-containing groups may be bonded to one linking group or aromatic ring.
  • hydrophilic groups include bisphenol residues represented by the following formula (4) and o-, m-, or p-phenylene residues represented by the following formula (5).
  • Alk''' is the same or different from each other and represents an alkyl group or an aryl group
  • Ion is the same or different from each other and represents a cation exchange group-containing group
  • R' is the cation exchange group-containing group.
  • c''' and d''' is the same or different and represents an integer from 0 to 4
  • a''', b''' and e''' are the same or different and represent an integer from 0 to 4. and at least one of a''', b''' and e''' indicates 1 or more.
  • Alk'''' represents an alkyl group or an aryl group
  • Ion represents a cation exchange group-containing group
  • c'''' represents an integer from 0 to 4
  • a'''' indicates an integer from 1 to 4.
  • Alk''' are the same or different and represent an alkyl group or an aryl group.
  • alkyl group include the alkyl groups described above.
  • aryl group include the above-mentioned aryl groups.
  • Ion is the same or different from each other and represents a cation exchange group-containing group.
  • the cation exchange group-containing group include the above-mentioned cation exchange group-containing groups.
  • R' represents a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, or a carbon-carbon bond, and preferably a hydrocarbon group or Indicates a carbon-carbon bond.
  • the hydrocarbon group include the above-mentioned divalent hydrocarbon groups.
  • c''' and d''' are the same or different and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably c''' Both '' and d'' indicate 0.
  • a''', b''' and e''' are the same or different from each other and represent integers from 0 to 4, and a''', b''' and At least one of e''' indicates 1 or more.
  • Alk'''' are the same or different and represent an alkyl group or an aryl group.
  • alkyl group include the alkyl groups described above.
  • aryl group include the above-mentioned aryl groups.
  • Ion is the same or different from each other and represents a cation exchange group-containing group.
  • the cation exchange group-containing group include the above-mentioned cation exchange group-containing groups.
  • c'''' represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
  • a'''' represents an integer from 1 to 4. Note that the substitution position of the cation exchange group-containing group is appropriately set depending on the purpose and use.
  • hydrophilic groups include those having the following structures.
  • Ion represents a cation exchange group-containing substituent or a hydrogen atom, and at least one is a cation exchange group-containing substituent. In addition, multiple Ions are bonded to one benzene ring structure. Also good.
  • hydrophilic groups include p-phenylene groups represented by the following formula (5a) and m-phenylene groups represented by the following formula (5b).
  • the above-mentioned hydrophobic group (a) is composed of a simple substance, or the above-mentioned hydrophobic group (a) is repeated via an ether bond, a thioether bond, or a carbon-carbon bond.
  • a hydrophobic unit (b) consisting of a unit (a) and the above-mentioned hydrophobic group (b) alone, or a hydrophobic unit (b) in which the above-mentioned hydrophobic group (b) is repeated via an ether bond, a thioether bond, or a carbon-carbon bond.
  • hydrophobic unit (a) consists of a single hydrophobic group (a), or that the hydrophobic groups (a) are repeated via carbon-carbon bonds.
  • hydrophobic unit (b) consists of a single hydrophobic group (b), or that the hydrophobic groups (b) are repeated via carbon-carbon bonds.
  • the unit corresponds to a block of a commonly used block copolymer.
  • the hydrophobic unit (a) is a unit formed by bisphenol residues represented by the above formula (1) bonded to each other via a carbon-carbon bond.
  • the bisphenol residue represented by the above formula (1) may be a unit formed by bonding a plurality of types to each other in a random shape, a regular shape such as alternating, or a block shape.
  • Such a hydrophobic unit (a) is represented by the following formula (11), for example.
  • R, Alk, a, b, c, and d have the same meanings as R, Alk, a, b, c, and d in the above formula (1), and q represents 1 to 200. .
  • q represents, for example, 1 to 200, preferably 1 to 50.
  • such hydrophobic unit (a) includes a unit formed by bisphenol residues represented by the above formula (1') bonded to each other via a carbon-carbon bond.
  • Such a hydrophobic unit (a) is represented by the following formula (11'), for example.
  • q represents, for example, 1 to 200, preferably 1 to 50.
  • the hydrophobic unit (b) preferably consists of a single aromatic ring, or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent A divalent hydrophobic group (b) consisting of an oxygen-containing group, a divalent sulfur-containing group, or a plurality of aromatic rings bonded to each other via a carbon-carbon bond is bonded to each other via a carbon-carbon bond. Examples include units formed.
  • the above-mentioned hydrophobic group (b) may be a unit formed by bonding a plurality of types to each other in a random shape, a regular shape such as alternating, or a block shape.
  • such a hydrophobic unit (b) is a unit formed by bisphenol residues represented by the above formula (2) bonded to each other via a carbon-carbon bond, and a unit formed by the above formula (3). Examples include units formed by bonding bisphenol residues represented by the following to each other via carbon-carbon bonds.
  • Such a hydrophobic unit (b) is represented by, for example, the following formula (12) or the following formula (13).
  • Alk', a', b', c', d', and l' are the same as Alk', a', b', c', d', and l' in formula (2) above. Indicates the significance, and r indicates 1 to 200.
  • Alk'', a'', b'', c'', d'', and l'' are Alk'', a'', b'', c' of the above formula (3) ', d'', and l'', and r represents 1 to 200.
  • r represents, for example, 1 to 200, preferably 1 to 50.
  • such a hydrophobic unit (b) is a unit formed by bonding bisphenol residues represented by the above formula (2') to each other via a carbon-carbon bond, and a unit formed by combining bisphenol residues represented by the above formula (2') with each other via a carbon-carbon bond, Examples include units formed by binding bisphenol residues represented by ') to each other via carbon-carbon bonds.
  • Such a hydrophobic unit (b) is represented by, for example, the following formula (12') or the following formula (13').
  • r represents, for example, 1 to 200, preferably 1 to 50.
  • the hydrophilic unit consists of a single aromatic ring, or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent a linking group that is a valent sulfur-containing group and/or a plurality of aromatic rings bonded to each other via carbon-carbon bonds, and at least one of the linking group or the aromatic ring is a cation exchange group-containing group.
  • Examples include units formed by bonding divalent hydrophilic groups bonding to each other via carbon-carbon bonds.
  • the divalent hydrophilic group may be a unit in which a plurality of divalent hydrophilic groups are bonded to each other in a random pattern, a regular pattern such as alternating, or a block pattern.
  • the hydrophilic unit is a unit formed by bisphenol residues represented by the above formula (4) bonded to each other via a carbon-carbon bond.
  • Such a hydrophilic unit is represented by the following formula (14), for example.
  • Alk''', Ion, R', a''', b''', c''', d''', and e''' are Alk'' in the above formula (4) ', Ion, R', a''', b''', c''', d''', and e''', and m represents 1 to 200.
  • m represents, for example, 1 to 200, preferably 1 to 50.
  • the hydrophilic unit is a unit formed by o-, m-, or p-phenylene residues represented by the above formula (5) bonded to each other via a carbon-carbon bond.
  • Such a hydrophilic unit is represented by the following formula (15), for example.
  • Alk''', Ion, a''', and c''' are Alk'', Ion, a''', and c''' of the above formula (5) (m indicates the same meaning as 1 to 200.)
  • m represents, for example, 1 to 200, preferably 1 to 50.
  • hydrophilic unit particularly preferably a unit formed by p-phenylene groups represented by the above formula (5a) bonding to each other via a carbon-carbon bond, and a unit formed by combining p-phenylene groups represented by the above formula (5b) Examples include units formed by bonding -phenylene groups to each other via carbon-carbon bonds.
  • Such a hydrophilic unit is represented by the following formula (15a) or the following formula (15b), for example.
  • m represents, for example, 1 to 200, preferably 1 to 50.
  • the above hydrophobic unit (a), the above hydrophobic unit (b), and the above hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond.
  • it is preferable that the above hydrophobic unit (a), the above hydrophobic unit (b), and the above hydrophilic unit are bonded via a carbon-carbon bond.
  • Such a cation exchange resin preferably includes a hydrophobic unit (a) represented by the above formula (11), a hydrophobic unit (b) represented by the above formula (12) or the above formula (13), and a hydrophobic unit (b) represented by the above formula (12) or the above formula (13). (14) or a cation exchange resin in which a hydrophilic unit represented by the above formula (15) is bonded via a carbon-carbon bond.
  • Such a cation exchange resin is represented by, for example, the following formula (17), the following formula (17'), the following formula (18), or the following formula (18').
  • R, Alk, a, b, c, and d have the same meanings as R, Alk, a, b, c, and d in the formula (11), and Alk', a', b' , c', d', and l' have the same meanings as Alk', a', b', c', d', and l' in the formula (12), and Alk''', Ion, R ', a''', b''', c'', d''', and e''' are Alk''', Ion, R', a''' in the formula (14), It has the same meaning as b''', c'', d''', and e''', q, r, and m represent the blending ratio or the number of repetitions, and represent 1 to 200, and o is , represents the number of repetitions and indicates 1 to 100
  • R, Alk, a, b, c, and d have the same meanings as R, Alk, a, b, c, and d in the formula (11), and Alk'', a'', b'', c'', d'', and l'' are the same as Alk'', a'', b'', c'', d'', and l'' in the above formula (13).
  • Alk''', Ion, R', a''', b''', c''', d''', and e''' are Alk'' in the above formula (14) ', Ion, R', a''', b''', c''', d''', and e''', and q, r, and m are the blending ratio or repetition. represents a number and represents 1 to 200; o represents the number of repetitions and represents 1 to 100.)
  • R, Alk, a, b, c, and d have the same meanings as R, Alk, a, b, c, and d in the formula (11), and Alk', a', b' , c', d', and l' have the same meanings as Alk', a', b', c', d', and l' in the formula (12), and Alk'''', Ion, a'''' and c''' have the same meanings as Alk'''', Ion, a'''' and c'''' in formula (15), and q, r, and m represents the blending ratio or the number of repetitions and represents 1 to 200, and o represents the number of repetitions and represents 1 to 100.)
  • R, Alk, a, b, c, and d have the same meanings as R, Alk, a, b, c, and d in the formula (11), and Alk'', a'', b'', c'', d'', and l'' are the same as Alk'', a'', b'', c'', d'', and l'' in the above formula (13).
  • Indicates the meaning, and Alk'''', Ion, a''', and c'''' are Alk'''', Ion, a'''', and c''' in the above formula (15).
  • '', q, r, and m represent the blending ratio or number of repetitions and represent 1 to 200; o represents the number of repetitions and represent 1 to 100.
  • a hydrophobic unit (a) represented by the above formula (11') and a hydrophobic unit (b) represented by the above formula (12') or the above formula (13') are used. and a hydrophilic unit represented by the above formula (15a) or the above formula (15b) are bonded via a carbon-carbon bond.
  • Such a cation exchange resin is represented by, for example, the following formula (18a), the following formula (18a'), the following formula (18b), or the following formula (18b').
  • l has the same meaning as l in the formula (11')
  • l' has the same meaning as l' in the formula (12')
  • Ion has the same meaning as l in the formula (15a)
  • q, r, and m represent the blending ratio or the number of repetitions and represent 1 to 200
  • o represents the number of repetitions and represent 1 to 100.
  • l has the same meaning as l in the formula (11')
  • l'' has the same meaning as l'' in the formula (13')
  • Ion has the same meaning as l in the formula (15a).
  • q, r, and m represent the blending ratio or number of repetitions and represent 1 to 200, and o represents the number of repetitions and represent 1 to 100.
  • l has the same meaning as l in the formula (11')
  • l' has the same meaning as l' in the formula (12')
  • Ion has the same meaning as l in the formula (15b)
  • q, r, and m represent the blending ratio or the number of repetitions and represent 1 to 200
  • o represents the number of repetitions and represent 1 to 100.
  • l has the same meaning as l in the formula (11')
  • l'' has the same meaning as l'' in the formula (13')
  • Ion has the same meaning as l in the formula (15b).
  • q, r, and m represent the blending ratio or number of repetitions and represent 1 to 200
  • o represents the number of repetitions and represent 1 to 100.
  • q, r, and m represent the blending ratio or the number of repetitions, and o represents the number of repetitions, and are appropriately set depending on the purpose and use.
  • the number of hydrophobic groups contained in the hydrophobic units (hydrophobic unit (a) and hydrophobic unit (b)) contained in the cation exchange resin of the present invention (the number of hydrophobic groups (a) and the hydrophobic group (b) )
  • the percentage of the number of hydrophobic groups (a) (q/(q+r) ⁇ 100) is preferably 5 to 65, more preferably 10 to 60, and 15 to 55 It is more preferable that Within this range, the cation exchange resin will have excellent gas permeability (particularly oxygen gas permeability).
  • the number average molecular weight of such a cation exchange resin is, for example, 10 to 1000 kDa, preferably 30 to 500 kDa.
  • the method for producing the cation exchange resin is not particularly limited, and any known method can be employed. Preferably, a method using a polycondensation reaction is employed.
  • a monomer for forming a hydrophobic group (a) is prepared, a monomer for forming a hydrophobic group (b) is prepared, and a monomer having a cation exchange group-containing group is prepared.
  • a monomer for forming a hydrophilic group is prepared, and a monomer for forming a hydrophobic group (a), a monomer for forming a hydrophobic group (b), and a monomer for forming a hydrophilic group having a cation exchange group-containing group are copolymerized.
  • a cation exchange resin can be produced by synthesizing a polymer.
  • a monomer for forming a hydrophobic group (a) is prepared, a monomer for forming a hydrophobic group (b) is prepared, a monomer for forming a hydrophilic group having a cation exchange group-containing group precursor functional group is prepared, and a monomer for forming a hydrophobic group (b) is prepared.
  • a polymer is synthesized by copolymerizing a monomer for forming a functional group (a), a monomer for forming a hydrophobic group (b), and a monomer for forming a hydrophilic group having a cation exchange group-containing group precursor functional group.
  • a cation exchange resin can be produced by ionizing the cation exchange group-containing group precursor functional group therein.
  • a monomer for forming a hydrophobic group (a) is prepared, a monomer for forming a hydrophobic group (b) is prepared, a monomer for forming a hydrophilic group is prepared, and a monomer for forming a hydrophobic group (a) and a hydrophobic group are prepared.
  • the hydrophobic group-forming monomer (a) is a compound represented by the following formula (21), which corresponds to the above formula (1).
  • R, Alk, a, b, c, and d have the same meanings as R, Alk, a, b, c, and d in the above formula (1), and T and T' are the same as each other. or, differently, a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom).
  • hydrophobic group-forming monomer (a) include compounds represented by the following formula (21'), which corresponds to the above formula (1').
  • T and T' are the same or different and are a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or (Indicates a hydrogen atom.)
  • the hydrophobic group-forming monomer (b) is preferably a compound represented by the following formula (22), which corresponds to the above formula (2), and a compound represented by the following formula (23), which corresponds to the above formula (3).
  • Alk', a', b', c', d', and l' are the same as Alk', a', b', c', d', and l' in formula (2) above.
  • T and T' are the same or different and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom.
  • Alk'', a'', b'', c'', d'', and l'' are Alk'', a'', b'', c' of the above formula (3) ', d'', and l'', and T and T' are the same or different and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom.
  • hydrophobic group-forming monomer (b) particularly preferably a compound represented by the following formula (22') corresponding to the above formula (2'), and a compound represented by the following formula (22') corresponding to the above formula (3'), Examples include compounds represented by 23').
  • l' has the same meaning as l' in formula (2'), and T and T' are the same or different and each represents a halogen atom, a pseudohalide, a boronic acid group, or a boronic acid derivative. , or indicates a hydrogen atom
  • T and T' are the same or different and each represents a halogen atom, a pseudohalide, a boronic acid group, a boron (Indicates an acid derivative or a hydrogen atom.)
  • the monomer for forming a hydrophilic group having a cation exchange group-containing group is preferably a compound represented by the following formula (24), which corresponds to the above formula (4), and a compound represented by the following formula (24), which corresponds to the above formula (5).
  • Examples include the compound represented by (25).
  • Alk''', Ion, R', a''', b''', c''', d''', and e''' are Alk'' in the above formula (4) ', Ion, R', a''', b''', c''', d''', and e''', and T and T' are the same or different from each other. , a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom).
  • Alk''', Ion, a''', and c''' are Alk''', Ion, a''', and c''' of the above formula (5)
  • T and T' are the same or different and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or a hydrogen atom.
  • the monomer for forming a hydrophilic group having a cation exchange group-containing group particularly preferably a compound represented by the following formula (25a) corresponding to the above formula (5a), and a compound represented by the following formula (25a) corresponding to the above formula (5b) Examples include the compound represented by (25b).
  • Ion has the same meaning as Ion in the formula (5a) above, and T and T' are the same or different and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or hydrogen (indicates an atom)
  • T and T' are the same or different and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative, or hydrogen (indicates an atom)
  • a hydrophobic group-forming monomer (a), a hydrophobic group-forming monomer (b), and a hydrophilic group-forming monomer having a cation exchange group-containing group are mixed, for example, with N,N-dimethyl
  • Known methods can be employed, such as dissolving the compound in a solvent such as acetamide or dimethyl sulfoxide and copolymerizing it using bis(cycloocta-1,5-diene)nickel (0) as a catalyst.
  • the reaction temperature in the cross-coupling reaction is, for example, -100 to 300°C, preferably -50 to 200°C, and the reaction time is, for example, 1 to 48 hours, preferably 2 to 5 hours.
  • a cation exchange resin can be obtained by ionizing the cation exchange group-containing group precursor functional group of the obtained polymer.
  • the ionization method is not particularly limited, and any known method can be used. For example, a method can be adopted in which the precursor functional group is ionized by dissolving the polymer in an appropriate solvent.
  • the reaction temperature in the ionization reaction depends on the amount of ionic groups introduced, but is generally -20 to 100°C, preferably 20 to 80°C, and the reaction time is, for example, 2 to 120 hours, preferably It is 5 to 72 hours.
  • a cation-exchange resin can be obtained by introducing the cation-exchange group-containing group into the obtained polymer.
  • the method for introducing the cation exchange group-containing group is not particularly limited, and any known method can be employed.
  • a cation exchange group-containing group is introduced by an aromatic electrophilic substitution reaction using sulfuric acid, chlorosulfuric acid, sulfur trioxide, or the like.
  • the ion exchange group capacity of the cation exchange resin is, for example, 0.1 to 5.0 meq. /g, preferably 0.5 to 4.0 meq. /g.
  • ion exchange group capacity can be determined by the following formula (30).
  • [Ion exchange group capacity (meq./g)] Amount of cation exchange group introduced per hydrophilic unit x Repeating unit of hydrophilic unit x 1000/(Molecular weight of hydrophobic unit x Number of repeating units of hydrophobic unit + Molecular weight of hydrophilic unit x Number of repeating units of hydrophilic unit + molecular weight of ion exchange group x number of repeating units of hydrophilic unit) (30)
  • the amount of ion exchange groups introduced is defined as the number of ion exchange groups per unit hydrophilic group.
  • the amount of cation exchange group introduced is the number of moles (mol) of the cation exchange group introduced into the main chain or side chain of the hydrophilic group.
  • Such a cation exchange resin consists of a divalent hydrophobic group (a) containing a bisphenol residue represented by the above formula (1) and a single aromatic ring, or a divalent hydrocarbon group, divalent silicon-containing group, divalent nitrogen-containing group, divalent phosphorus-containing group, divalent oxygen-containing group, divalent sulfur-containing group, or multiple groups bonded to each other via carbon-carbon bonds.
  • a divalent hydrophobic group (b) consisting of an aromatic ring and a divalent hydrocarbon group consisting of a single aromatic ring, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group group, a divalent oxygen-containing group, or a divalent sulfur-containing group, and/or a plurality of aromatic rings bonded to each other via carbon-carbon bonds; At least one is composed of a divalent hydrophilic group bonded to a cation exchange group-containing group, and the hydrophobic group (a) is composed of a simple substance, or the hydrophobic group (a) is an ether bond, a thioether bond, , or consisting of a hydrophobic unit (a) repeated via a carbon-carbon bond and the hydrophobic group (b) alone, or the hydrophobic group (b) is an ether bond, a thioether bond, or a carbon-carbon bond.
  • the hydrophobic unit (a) has a hydrophobic unit (b) that is repeated via a bond, and a hydrophilic unit that is composed of the hydrophilic group alone or in which the hydrophilic group is repeated via a carbon-carbon bond. ), the hydrophobic unit (b), and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond.
  • this cation exchange resin has a divalent hydrophobic group (a) and a divalent hydrophilic group introduced, so it has electrical properties (cation conductivity) and chemical properties (gas permeability). and water content).
  • the hydrophilic group since the hydrophilic group has hydrophilic units repeated via carbon-carbon bonds (that is, it does not contain an ether bond), it has excellent durability such as radical resistance. More specifically, if the hydrophilic unit contains an ether bond, decomposition by hydroxyl radicals (.OH) may occur, for example, as described below, and radical resistance may not be sufficient.
  • hydrophilic units of cation exchange resins which have hydrophilic units in which hydrophilic groups are repeated via carbon-carbon bonds, do not contain ether bonds, so decomposition by the above mechanism does not occur, and as a result, As a result, it has excellent durability such as radical resistance.
  • the present invention includes a cation exchange membrane containing the above cation exchange resin.
  • the cation exchange membrane can be reinforced with a known reinforcing material such as a porous base material, and can also be reinforced with biaxial stretching treatment to control molecular orientation, crystallinity, residual Various treatments such as heat treatment can be performed to control stress. Further, a known filler can be added to the cation exchange membrane in order to increase its mechanical strength, and the cation exchange membrane and a reinforcing agent such as a glass nonwoven fabric can be combined by pressing.
  • a known reinforcing material such as a porous base material
  • biaxial stretching treatment to control molecular orientation, crystallinity, residual Various treatments such as heat treatment can be performed to control stress.
  • a known filler can be added to the cation exchange membrane in order to increase its mechanical strength, and the cation exchange membrane and a reinforcing agent such as a glass nonwoven fabric can be combined by pressing.
  • ком ⁇ онентs commonly used in cation exchange membranes such as compatibilizers to improve compatibility, antioxidants to prevent resin deterioration, and handling during molding into films, etc.
  • Antistatic agents, lubricants, and the like for improving properties can be included as appropriate within a range that does not affect processing or performance as a cation exchange membrane.
  • the thickness of the cation exchange membrane is not particularly limited, and is appropriately set depending on the purpose and use.
  • the thickness of the cation exchange membrane is, for example, 1 to 350 ⁇ m, preferably 5 to 200 ⁇ m.
  • the present invention includes an electrolyte membrane containing the above cation exchange resin.
  • the electrolyte membrane of the present invention can be applied to various electrochemical applications such as fuel cells, water electrolysis hydrogen generators, and electrochemical hydrogen pumps, but is particularly suitable for use in water electrolysis hydrogen generators.
  • an electrolyte membrane is used in a structure in which a catalyst layer, an electrode base material, and a separator are sequentially laminated on both sides.
  • electrolyte membrane of the present invention is called a composite (MEA) and is suitably used as an electrolyte membrane constituting such an MEA.
  • the above-described cation exchange resin can be used (that is, the electrolyte membrane contains the above-described cation exchange resin).
  • the electrolyte membrane can be reinforced with a known reinforcing material such as a porous base material, and may also be reinforced with biaxial stretching treatment to control molecular orientation, crystallinity, residual Various treatments such as heat treatment can be performed to control stress. Further, a known filler can be added to the electrolyte membrane in order to increase its mechanical strength, and the electrolyte membrane and a reinforcing agent such as a glass nonwoven fabric can be combined by pressing.
  • a known reinforcing material such as a porous base material
  • biaxial stretching treatment to control molecular orientation, crystallinity, residual Various treatments such as heat treatment can be performed to control stress.
  • a known filler can be added to the electrolyte membrane in order to increase its mechanical strength, and the electrolyte membrane and a reinforcing agent such as a glass nonwoven fabric can be combined by pressing.
  • various additives commonly used in electrolyte membranes such as compatibilizers to improve compatibility, antioxidants to prevent resin deterioration, and ease of handling during molding into films, are also added.
  • An antistatic agent, a lubricant, etc. for improving the electrolyte membrane can be appropriately contained within a range that does not affect the processing and performance as an electrolyte membrane.
  • the thickness of the electrolyte membrane is not particularly limited, and is appropriately set depending on the purpose and use.
  • the thickness of the electrolyte membrane is, for example, 1.2 to 350 ⁇ m, preferably 5 to 200 ⁇ m.
  • the present invention also includes a binder for forming an electrode catalyst layer containing the above-described cation exchange resin, and a battery electrode catalyst layer containing the binder for forming an electrode catalyst layer. Since the above-mentioned cation exchange resin has excellent cation conductivity and gas permeability, gas diffusivity can be easily adjusted and controlled by using it as a binder for forming an electrode catalyst layer.
  • a binder for forming an electrode catalyst layer is prepared.
  • the content of the cation exchange resin is, for example, 2 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the binder for forming an electrode catalyst layer.
  • the binder for forming an electrode catalyst layer in forming the catalyst layer of the electrode (battery electrode catalyst layer), the cation exchange resin can be contained in the catalyst layer (battery electrode catalyst layer).
  • the target product was extracted from the reaction solution with ethyl acetate, and the resulting organic layer was washed with water and then dehydrated with sodium sulfate. This solution was concentrated, and aniline was distilled off from the solution under reduced pressure.
  • Precursor compound (1.00 g, 3.75 mmol) and 6M hydrochloric acid (10 mL) were added to a 100 mL eggplant flask, and H 2 O (10 mL) in which NaNO 2 (0.620 g, 8.99 mmol) was dissolved was added in a 0°C ice bath. ) was slowly added dropwise. Thereafter, the mixture was reacted at 0°C for 30 minutes. Then, concentrated hydrochloric acid (10 mL) in which CuCl(I) (1.50 g, 15.1 mmol) was dissolved was added and reacted for 8 hours. The mixture was allowed to cool to room temperature and filtered through Celite using hexane.
  • the cation exchange resin obtained in the example has improved gas permeability compared to the cation exchange resin obtained in the comparative example (particularly the oxygen gas permeability is higher than that of Nafion 212 (trade name) ) and has excellent electrical properties (cationic conductivity) and chemical properties (gas permeability and water content).
  • An electrolyte membrane comprising the cation exchange resin according to any one of [1] to [9].
  • a binder for forming an electrode catalyst layer comprising the cation exchange resin according to any one of [1] to [9].
  • a battery electrode catalyst layer comprising the binder for forming an electrode catalyst layer according to [12].

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PCT/JP2023/023602 2022-07-15 2023-06-26 陽イオン交換樹脂、陽イオン交換膜、電解質膜、電極触媒層形成用バインダーおよび電池電極触媒層 Ceased WO2024014269A1 (ja)

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US18/993,519 US20260001983A1 (en) 2022-07-15 2023-06-26 Cation exchange resin, cation exchange membrane, electrolyte membrane, binder for forming electrode catalyst layer, and battery electrode catalyst layer
EP23839443.1A EP4556509A1 (en) 2022-07-15 2023-06-26 Cation exchange resin, cation exchange membrane, electrolyte membrane, binder for forming electrode catalyst layer, and battery electrode catalyst layer
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10216532A (ja) * 1997-02-10 1998-08-18 Chisso Corp 強酸性陽イオン交換樹脂およびこれを用いるビスフェノ−ル誘導体の製造方法
JP2006206779A (ja) * 2005-01-28 2006-08-10 Toyobo Co Ltd スルホン酸基含有ポリマー、そのポリマーを含むポリマー組成物、そのポリマーを用いたイオン交換樹脂およびイオン交換膜、そのイオン交換膜を用いて得られる膜／電極接合体および燃料電池、並びにそのポリマーの製造方法
JP2009165937A (ja) * 2008-01-15 2009-07-30 Mitsubishi Chemicals Corp 陽イオン交換樹脂、及びその製造方法、並びにそれを用いたビスフェノール類の製造方法
WO2017006831A1 (ja) * 2015-07-03 2017-01-12 国立大学法人山梨大学 陽イオン交換樹脂、ならびにそれを用いた陽イオン交換膜および燃料電池用電解質膜

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10216532A (ja) * 1997-02-10 1998-08-18 Chisso Corp 強酸性陽イオン交換樹脂およびこれを用いるビスフェノ−ル誘導体の製造方法
JP2006206779A (ja) * 2005-01-28 2006-08-10 Toyobo Co Ltd スルホン酸基含有ポリマー、そのポリマーを含むポリマー組成物、そのポリマーを用いたイオン交換樹脂およびイオン交換膜、そのイオン交換膜を用いて得られる膜／電極接合体および燃料電池、並びにそのポリマーの製造方法
JP2009165937A (ja) * 2008-01-15 2009-07-30 Mitsubishi Chemicals Corp 陽イオン交換樹脂、及びその製造方法、並びにそれを用いたビスフェノール類の製造方法
WO2017006831A1 (ja) * 2015-07-03 2017-01-12 国立大学法人山梨大学 陽イオン交換樹脂、ならびにそれを用いた陽イオン交換膜および燃料電池用電解質膜
JP2017014423A (ja) 2015-07-03 2017-01-19 国立大学法人山梨大学 陽イオン交換樹脂、ならびにそれを用いた陽イオン交換膜および燃料電池用電解質膜

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