WO2017006831A1 - 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 - Google Patents

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 Download PDF

Info

Publication number
WO2017006831A1
WO2017006831A1 PCT/JP2016/069364 JP2016069364W WO2017006831A1 WO 2017006831 A1 WO2017006831 A1 WO 2017006831A1 JP 2016069364 W JP2016069364 W JP 2016069364W WO 2017006831 A1 WO2017006831 A1 WO 2017006831A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
cation exchange
divalent
containing group
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/069364
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
宮武　健治
内田　誠
純平 三宅
崇史 望月
小野　英明
愛生 島田
尚樹 横田
菜摘 吉村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Takahata Precision Japan Co Ltd
University of Yamanashi NUC
Original Assignee
Takahata Precision Japan Co Ltd
University of Yamanashi NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Takahata Precision Japan Co Ltd, University of Yamanashi NUC filed Critical Takahata Precision Japan Co Ltd
Priority to US15/738,270 priority Critical patent/US10471420B2/en
Publication of WO2017006831A1 publication Critical patent/WO2017006831A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • 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
    • 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
    • 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
    • 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
    • C08G2261/122—Copolymers statistical
    • 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
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/19—Definition of the polymer structure partially conjugated
    • 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
    • C08G2261/30—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
    • 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
    • C08G2261/30—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
    • C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3424—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms non-conjugated, e.g. paracyclophanes or xylenes
    • 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
    • C08G2261/412—Yamamoto reactions
    • 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
    • C08G2261/50—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
    • 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
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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
    • H01M8/1037—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes
    • 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 using the same, and an electrolyte membrane for a fuel cell.
  • Nafion registered trademark
  • a cation exchange resin Since Nafion (registered trademark), which is a cation exchange resin, has high conductivity, it is used as a standard electrolyte membrane for fuel cells (Patent Documents 1 to 3, Non-Patent Documents 1 to 3).
  • Patent Document 1 has a problem that the chemical stability (durability, particularly radical resistance) is not sufficient. Moreover, the subject that the gas permeation
  • the present invention provides a cation exchange resin excellent in chemical characteristics (durability, solubility, gas permeation suppression effect) and mechanical characteristics (flexibility), and a cation exchange membrane and a fuel cell electrolyte using the same.
  • the object is to provide a membrane.
  • the cation exchange resin of the present invention is: A divalent hydrophobic unit represented by the following formula (1): 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, a divalent sulfur-containing group Or a divalent hydrophilic group consisting of a plurality of aromatic rings bonded to each other via a carbon-carbon bond, and at least one of the aromatic rings having a cation exchange group is repeated via a carbon-carbon bond. Having a divalent hydrophilic unit, The hydrophobic unit and the hydrophilic unit are bonded via a carbon-carbon bond.
  • Z 1 to Z 9 are the same or different from each other and represent a carbon atom or a silicon atom
  • R 1 to R 8 are the same or different from each other to represent a silicon-containing group, a nitrogen-containing group, or a phosphorus-containing group.
  • X 1 to X 18 are the same or different from each other, and represent a halogen atom, a pseudohalide, or a hydrogen atom
  • a is an integer of 1 or more
  • b, c, d, e, f, g, h, and i are the same or different from each other and represent an integer of 0 or more.
  • the hydrophilic group is a bisphenol residue substituted with a substituent having the cation exchange group represented by the following formula (2), or the following formula (2 ′).
  • the o-, m-, or p-phenylene group is preferably substituted with a substituent having the cation exchange group shown.
  • R is a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, or an aromatic group, which may be substituted with a substituent having the cation exchange group.
  • Alk is the same or different from each other and represents an alkyl group
  • Ion is the same or different from each other, and represents a substituent having a cation exchange group
  • a ′ and b ′ are Are the same or different from each other and represent an integer of 0 to 4
  • s, t and u are the same or different from each other and represent an integer of 0 to 4, and at least one of s, t and u is 1 The above is shown.
  • Alk represents an alkyl group
  • Ion represents a substituent having a cation exchange group
  • a ′ represents an integer of 0 to 4
  • s represents an integer of 1 to 4.
  • the hydrophobic unit is a divalent fluorinated saturated hydrocarbon group or a divalent saturated hydrocarbon group.
  • the cation exchange membrane of the present invention is characterized by containing the above-mentioned cation exchange resin.
  • an electrolyte membrane for a fuel cell according to the present invention includes the cation exchange resin described above.
  • a cation exchange resin excellent in chemical characteristics and mechanical characteristics a cation exchange membrane using the cation exchange resin, and an electrolyte membrane for fuel cells.
  • the cation exchange resin of the present invention has a divalent hydrophobic unit and a divalent hydrophilic unit.
  • the divalent hydrophobic unit is represented by the following formula (1).
  • Z 1 to Z 9 are the same or different from each other and represent a carbon atom or a silicon atom
  • R 1 to R 8 are the same or different from each other to represent a silicon-containing group, a nitrogen-containing group, or a phosphorus-containing group.
  • X 1 to X 18 are the same or different from each other, and represent a halogen atom, a pseudohalide, or a hydrogen atom
  • a is an integer of 1 or more
  • b, c, d, e, f, g, h, and i are the same or different from each other and represent an integer of 0 or more.
  • Z 1 to Z 9 are the same or different from each other and represent a carbon atom or a silicon atom, preferably a carbon atom.
  • R 1 to R 8 are the same or different from each other and each represents a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, or a direct bond, preferably directly Indicates binding.
  • X 1 to X 18 are the same as or different from each other, and represent the above-described halogen atom or pseudohalide, or a hydrogen atom, preferably a halogen atom or a hydrogen atom.
  • examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
  • Pseudohalides include trifluoromethyl groups, —CN, —NC, —OCN, —NCO, —ONC, —SCN, —NCS, —SeCN, —NCSe, —TeCN, —NCTe, —N 3. .
  • a represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 4 to 8.
  • b, c, d, e, f, g, h and i are the same or different from each other, and represent an integer of 0 or more, preferably an integer of 0 to 10, more preferably Represents an integer of 0 to 3, more preferably 0 or 1.
  • the divalent hydrophobic unit is bonded to each other via a divalent hydrocarbon group and a carbon-carbon bond or a carbon-silicon bond, as represented by the following formula (1 ′). It may be. In this case, a hydrophobic unit including a divalent hydrocarbon group is used.
  • Z 1 to Z 9 , R 1 to R 8 , X 1 to X 18 , a, b, c, d, e, f, g, h, and i are the same as Z 1 to Z 9 , R 1 to R 8 , X 1 to X 18 , a, b, c, d, e, f, g, h and i have the same meanings, and R ′ is the same or different from each other and is divalent. Represents a hydrocarbon group or a direct bond.
  • divalent hydrocarbon group examples include methylene (—CH 2 —), ethylene, propylene, isopropylene (—C (CH 3 ) 2 —), butylene, isobutylene, sec-butylene, pentylene (pentene), and isopentylene.
  • a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane (above, a divalent aliphatic cyclic hydrocarbon group), o-, m -Or carbon atoms such as p-phenylene group 6 ⁇ Divalent aromatic hydrocarbon group 0 and the like.
  • the divalent hydrocarbon group is preferably a divalent saturated hydrocarbon group having 1 to 3 carbon atoms, specifically methylene (—CH 2 —), ethylene, propylene, isopropylene (—C (CH 3 ) 2- ), more preferably methylene (—CH 2 —), isopropylene (—C (CH 3 ) 2 —), particularly preferably isopropylene (—C (CH 3 ) 2 -).
  • the divalent hydrocarbon group is preferably an o-, m- or p-phenylene group.
  • the divalent hydrocarbon group may be optionally substituted with a substituent such as a halogen atom, an alkyl group, or a pseudohalide.
  • a substituent such as a halogen atom, an alkyl group, or a pseudohalide
  • the number of substitutions and the substitution position of the substituent such as a halogen atom, an alkyl group, or a pseudohalide are as follows: It is set as appropriate according to the purpose and application.
  • alkyl group examples 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, octyl group, etc.
  • alkyl groups having 1 to 20 carbon atoms examples include alkyl groups having 1 to 20 carbon atoms; cycloalkyl groups having 1 to 20 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.
  • Such a divalent hydrophobic unit is preferably a divalent fluorinated saturated hydrocarbon group or a divalent saturated hydrocarbon group, and more preferably one having the following structure.
  • R ′ has the same meaning as R ′ in formula (1 ′).
  • a represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably An integer of 2 to 6 is shown.
  • a divalent hydrophilic group is repeated via a carbon-carbon bond.
  • the divalent hydrophilic 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, and a divalent oxygen-containing group.
  • aromatic ring examples include monocyclic or polycyclic aromatic hydrocarbons having 6 to 20 carbon atoms such as benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, phenanthrene ring, and azole, Examples include heterocyclic compounds such as oxole, thiophene, oxazole, thiazole, pyridine and the like.
  • 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, or a pseudohalide if necessary.
  • a substituent such as a halogen atom, an alkyl group, or a pseudohalide
  • the number and position of substitution of the substituent such as a halogen atom, an alkyl group, or a pseudohalide depends on the purpose and application. It is set accordingly.
  • examples of the aromatic ring substituted with a halogen atom include a benzene ring substituted with 1 to 4 halogen atoms (for example, a benzene ring substituted with 1 to 4 fluorine atoms, and 1 to 4 chlorine atoms).
  • 1 to 4 halogen atoms are the same or different from each other, such as a benzene ring substituted with 1, a benzene ring substituted with 1 to 4 bromine, a benzene ring substituted with 1 to 4 iodine, etc. May be included).
  • divalent hydrocarbon group examples include the divalent hydrocarbon groups described above.
  • the number of aromatic rings bonded to the divalent hydrocarbon group is one or two, and preferably two.
  • the hydrocarbon group when one aromatic ring is further bonded to a divalent hydrocarbon group, the hydrocarbon group is trivalent, and when two more aromatic rings are bonded, The hydrocarbon group is tetravalent (in the case of 1 carbon atom, 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 through, for example, a carbon-carbon bond.
  • the cation exchange group is introduced into the main chain or the side chain in the hydrophilic group, and specifically, is not particularly limited, and is a sulfonic acid group (—SO 3 H), a phosphoric acid group (—PO 3 H), a carboxylic acid Any known cation exchange group such as an acid (—COOH) can be employed. From the viewpoint of cation conductivity, a sulfonic acid group is preferable.
  • the substituent having a cation exchange group may be substituted with at least one of the aromatic rings, and may be substituted with a plurality of aromatic rings. , All aromatic rings may be substituted. Further, when two aromatic rings are bonded to a divalent hydrocarbon group, the substituent having a cation exchange group may be substituted with at least one of the aromatic rings, for example, the side One of the aromatic rings in the chain may be substituted, or both may be substituted. A plurality of substituents having a cation exchange group may be substituted on one aromatic ring.
  • Such a hydrophilic group is preferably a bisphenol residue substituted with a substituent having the cation exchange group represented by the following formula (2), or the cation represented by the following formula (2 ′).
  • An o-, m- or p-phenylene group substituted with a substituent having an ion exchange group can be mentioned.
  • R is a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, or an aromatic group, which may be substituted with a substituent having the cation exchange group.
  • Alk is the same or different from each other and represents an alkyl group
  • Ion is the same or different from each other, and represents a substituent having a cation exchange group
  • a ′ and b ′ are Are the same or different from each other and represent an integer of 0 to 4
  • s, t and u are the same or different from each other and represent an integer of 0 to 4, and at least one of s, t and u is 1 The above is shown.
  • Alk represents an alkyl group
  • Ion represents a substituent having a cation exchange group
  • a ′ represents an integer of 0 to 4
  • s represents an integer of 1 to 4.
  • 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 direct bond, preferably isopropylene (—C (CH 3 ) 2- ). R may be substituted with a substituent having a cation exchange group.
  • Alk is the same as or different from each other and represents an alkyl group.
  • alkyl group examples 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, octyl group, etc.
  • alkyl groups having 1 to 20 carbon atoms examples include alkyl groups having 1 to 20 carbon atoms; cycloalkyl groups having 1 to 20 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.
  • Ion is the same or different from each other, and represents a substituent having the above-described cation exchange group, and preferably represents the above-described sulfonic acid group.
  • 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 0 is shown.
  • s, t, and u are the same or different from each other and represent an integer of 0 to 4, and at least one of s, t, and u represents 1 or more.
  • Alk is the same as or different from each other and represents the above-described alkyl group.
  • Ion represents a substituent having the above-described cation exchange group, and preferably represents the above-described sulfonic acid group.
  • a ′ represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
  • s represents an integer of 1 to 4.
  • substitution position of the substituent having a cation exchange group is appropriately set according to the purpose and application.
  • hydrophilic groups include those having the following structure.
  • Ion represents a substituent having a cation exchange group or a hydrogen atom, and at least one is a substituent having a cation exchange group.
  • a plurality of Ions are bonded to one benzene ring structure. May be.
  • hydrophilic group examples include a p-phenylene group represented by the following formula (3 ′) and an m-phenylene group represented by the following formula (3 ′′).
  • Ion ′ represents a substituent having a cation exchange group.
  • the divalent hydrophilic unit is formed by repeating a divalent hydrophilic group via a carbon-carbon bond, but the divalent hydrophilic group is a carbon-carbon. It is preferably formed repeatedly through bonding.
  • the unit corresponds to a block of a generally used block copolymer.
  • the hydrophilic unit is preferably a bisphenol A residue (hydrophilic group) substituted with a substituent having a cation exchange group represented by the above formula (2) and / or represented by the above formula (2 ′). And a unit formed by bonding o-, m- or p-phenylene groups (hydrophilic groups) substituted with a substituent having a cation exchange group to each other via a carbon-carbon bond. It may be a unit formed by bonding a plurality of types of hydrophilic groups to each other via a carbon-carbon bond.
  • Such a hydrophilic unit is represented by, for example, the following formula (4) or the following formula (4 ′).
  • R, Alk, Ion, a ′, b ′, s, t and u have the same meaning as R, Alk, Ion, a ′, b ′, s, t and u in the above formula (2).
  • M represents an integer of 1 to 200.
  • Alk, Ion, a ′ and s are the same as Alk, Ion, a ′ and s in the above formula (2 ′), and m is a numerical value of 1 to 200.
  • Such a hydrophilic unit is particularly preferably a unit formed by bonding p-phenylenes represented by the above formula (3 ′) to each other via a carbon-carbon bond, represented by the above formula (3 ′′).
  • Such a hydrophilic unit is represented by, for example, the following formula (5 ′), the following formula (5 ′′), or the following formula (5 ′ ′′).
  • the hydrophobic unit and the hydrophilic unit described above are bonded via a carbon-carbon bond.
  • a hydrophobic unit represented by the above formula (1 ′) and a hydrophilic unit represented by the above formula (4) are each a carbon-carbon bond. And a cation exchange resin bonded via the. Further, as represented by the following formula (6 ′), the hydrophobic unit represented by the above formula (1 ′) and the hydrophilic unit represented by the above formula (4 ′) are bonded via a carbon-carbon bond. And cation exchange resins.
  • Z 1 to Z 9 , R 1 to R 8 , R ′, X 1 to X 18 , a, b, c, d, e, f, g, h, and i are represented by the above formula (1 ′)
  • Z 1 to Z 9 , R 1 to R 8 , R ′, X 1 to X 18 , a, b, c, d, e, f, g, h and i have the same meanings as R, Alk, Ion , A ′, b ′, s, t and u have the same significance as R, Alk, Ion, a ′, b ′, s, t and u in the above formula (2), and l and m are blending ratios And o represents an integer of 1 to 100.)
  • Z 1 to Z 9 , R 1 to R 8 , R ′, X 1 to X 18 , a, b, c, d, e, f, g, h, and i are represented by the above formula (1 ′)
  • Z 1 to Z 9 , R 1 to R 8 , R ′, X 1 to X 18 , a, b, c, d, e, f, g, h and i have the same meanings as Alk, Ion, a 'And s have the same meaning as Alk, Ion, a' and s in the above formula (2)
  • l and m represent the compounding ratio
  • o represents an integer of 1 to 100.
  • the number average molecular weight of the cation exchange resin is adjusted to 10 to 1000 kDa, preferably 30 to 500 kDa.
  • a cation exchange resin more preferably, as shown by the following formula (7), a hydrophobic unit represented by the above formula (1a ′) and a hydrophilic unit represented by the above formula (5 ′ ′′) And a cation exchange resin bonded through a carbon-carbon bond.
  • the hydrophobic unit represented by the above formula (1c ′) and the hydrophilic unit represented by the above formula (5 ′ ′′) are bonded via a carbon-carbon bond.
  • Examples include bound cation exchange resins. Particularly preferred is a cation exchange resin represented by the following formula (7 ") or (7" ').
  • R ′ and a are the same as R ′ and a in the above formula (1 ′), and Ion ′ and Ion ′′ are Ion ′ in the above formula (3 ′) and the above formula (3 ′ ') Is the same as Ion'', l, m and n are compounding ratios, and o is an integer of 1 to 100.
  • R ′ and a are the same as R ′ and a in the above formula (1 ′), and Ion ′ and Ion ′′ are Ion ′ in the above formula (3 ′) and the above formula (3 ′ ') Is the same as Ion'', l, m and n are compounding ratios, and o is an integer of 1 to 100.
  • Ion ′ and Ion ′′ have the same meanings as Ion ′ in the above formula (3 ′) and Ion ′′ in the above formula (3 ′′), and l, m, and n represent the compounding ratio. , O represents an integer of 1-100.
  • Ion ′ and Ion ′′ have the same meanings as Ion ′ in the above formula (3 ′) and Ion ′′ in the above formula (3 ′′), and l, m, and n represent the compounding ratio. , O represents an integer of 1-100.
  • 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 a known method can be adopted. Preferably, a method using a polycondensation reaction is employed.
  • first monomer a monomer for forming a divalent hydrophobic unit
  • second monomer a monomer for forming a hydrophilic unit
  • a conventionally known general method can be employed.
  • cross coupling in which dihalides react with each other to form a carbon-carbon direct bond is employed.
  • Examples of the first monomer for forming the divalent hydrophobic unit include compounds represented by the following formula (11).
  • Z 1 to Z 9 , R 1 to R 8 , X 1 to X 18 , b, c, d, e, f, g, h and i are Z 1 to Z in the above formula (1 ′)).
  • 9 , R 1 to R 8 , X 1 to X 18 , b, c, d, e, f, g, h, and i, and X ′ are the same or different from each other, Indicates a halide.
  • the first monomer for forming the divalent hydrophobic unit is bonded to each other via a divalent hydrocarbon group and a carbon-carbon bond or a carbon-silicon bond, as shown by the following formula (11 ′). May be.
  • the first monomer including a divalent hydrocarbon group is used.
  • Z 1 to Z 9 , R 1 to R 8 , R ′, X 1 to X 18 , a, b, c, d, e, f, g, h, and i are represented by the above formula (1 ′)
  • Z 1 to Z 9 , R 1 to R 8 , R ′, X 1 to X 18 , a, b, c, d, e, f, g, h and i have the same meanings
  • X ′ is the above (It has the same meaning as X ′ in formula (11).)
  • R ′ and a are the same as those in the above formula (1a ′), formula (1b ′), formula (1c ′).
  • X ′ has the same meaning as X ′ in formula (11 ′).
  • Particularly preferable examples of the first monomer include compounds represented by the following formula (11a ′′) and the following formula (11c ′′).
  • the second monomer for forming 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, Examples thereof include dihalogenated compounds composed of a divalent oxygen-containing group, a divalent sulfur-containing group, or a plurality of aromatic rings bonded to each other via a carbon-carbon bond.
  • the dihalogenated compound for forming such a hydrophilic unit is preferably a compound represented by the following formula (12) corresponding to the above formula (2), and a formula represented by the following formula (3 ′). And a compound represented by (12 ′).
  • X ′ is the same or different from each other and represents a halogen atom or a pseudohalide.
  • X ′ is the same or different from each other and represents a halogen atom or a pseudohalide.
  • a compound represented by the following formula (13 ′) is particularly preferable.
  • the blending amounts of the first monomer and the second monomer are respectively the desired hydrophobic unit and hydrophilic unit in the obtained cation exchange resin precursor polymer.
  • the blending ratio is adjusted.
  • the first monomer and the second monomer are dissolved in a solvent such as N, N-dimethylacetamide or dimethyl sulfoxide, and bis (cycloocta-1,5-diene) nickel (0) or the like is used as a catalyst.
  • a solvent such as N, N-dimethylacetamide or dimethyl sulfoxide
  • bis (cycloocta-1,5-diene) nickel (0) or the like is used as a catalyst.
  • a known method such as a polymerization method can be employed.
  • 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 precursor polymer preferably a cation exchange resin precursor polymer represented by the following formula (16) or a cation exchange resin precursor polymer represented by the following formula (16 ′) is obtained. It is done.
  • Z 1 to Z 9 , R 1 to R 8 , R ′, X 1 to X 18 , a, b, c, d, e, f, g, h, i, R, Alk, a ′, b ′, l, m, and o are Z 1 to Z 9 , R 1 to R 8 , R ′, X 1 to X 18 , a, b, c, d, e, f, g in the above formula (6).
  • H, i, R, Alk, a ′, b ′, l, m, and o are the same.
  • Z 1 to Z 9 , R 1 to R 8 , R ′, X 1 to X 18 , a, b, c, d, e, f, g, h, i, Alk, a ′, l, m and o are Z 1 to Z 9 , R 1 to R 8 , R ′, X 1 to X 18 , a, b, c, d, e, f, g, h, i in the above formula (6 ′).
  • Alk, a ′, l, m and o are the same.
  • the cation exchange resin precursor polymer is more preferably a cation exchange resin precursor polymer represented by the following formula (17) or the following formula (17 ′), and particularly preferably the following formula (17 ′). ') Or a cation exchange resin precursor polymer represented by the following formula (17' '').
  • R ′, a, R ′′, l, m and n have the same meaning as R ′, a, R ′′, l, m and n in the above formula (7).
  • R ′, a, R ′′, l, m and n have the same meaning as R ′, a, R ′′, l, m and n in the above formula (7 ′).
  • the method for introducing a substituent having a cation exchange group is not particularly limited, and a known method can be employed.
  • a substituent having a cation exchange group is introduced by an aromatic electrophilic substitution reaction.
  • the substituent which has a cation exchange group is introduce
  • it is a cation exchange resin shown by said Formula (6), or said Formula (6)
  • the cation 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.
  • capacitance can be calculated
  • Capacity of cation exchange group (meq./g)] Introduction amount of cation exchange group per hydrophilic unit ⁇ repeating unit of hydrophilic unit ⁇ 1000 / (molecular weight of hydrophobic unit ⁇ number of repeating units of hydrophobic unit + molecular weight of hydrophilic unit) X number of repeating units of hydrophilic unit + molecular weight of cation exchange group x amount of cation exchange group introduced per hydrophilic unit x number of repeating units of hydrophilic unit) (20)
  • the amount of cation exchange groups introduced is defined as the number of cation 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 in the hydrophilic unit.
  • Such a cation exchange resin comprises a divalent hydrophobic unit represented by the above formula (1) and 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, a divalent sulfur-containing group, or a plurality of aromatic rings bonded to each other via a carbon-carbon bond, A divalent hydrophilic group, at least one of which has a cation exchange group, has a divalent hydrophilic unit repeated through a carbon-carbon bond, and the hydrophobic unit and the hydrophilic unit are carbon-carbon. Are connected through bonds.
  • this cation exchange resin has a hydrophobic unit having excellent chemical and mechanical properties and a hydrophilic unit in which a cation exchange group is introduced into a structure containing an aromatic ring excellent in gas permeation suppression effect. Excellent mechanical properties (durability, solubility, gas permeation suppressing effect) and mechanical properties (flexibility).
  • this cation exchange resin has high flexibility, it is possible to improve the handling property when a membrane-electrode assembly (MEA) using the cation exchange resin is produced.
  • this cation exchange resin has high solubility in an organic solvent (for example, it dissolves in a low boiling point organic solvent such as methanol or ethanol), when used as a binder for forming an electrode catalyst layer, an electrode catalyst It is expected that the durability can be improved without requiring a high boiling point solvent such as dimethyl sulfoxide, which may cause deterioration of the above.
  • the hydrophilic group has a hydrophilic unit that is repeated via a carbon-carbon bond (that is, it does not contain an ether bond), it is excellent in durability such as radical resistance. More specifically, when an ether bond is contained in the hydrophilic unit, for example, as described below, decomposition by hydroxyl radical (.OH) may occur, and radical resistance may not be sufficient.
  • the hydrophilic unit of the cation exchange resin having a hydrophilic unit in which the hydrophilic group is repeated via a carbon-carbon bond does not contain an ether bond, decomposition by the above mechanism does not occur. As a result, it has excellent durability such as radical resistance.
  • the present invention includes a cation exchange membrane obtained using such a cation exchange resin. More specifically, it includes a cation exchange membrane containing a cation exchange resin into which a cation exchange group has been introduced. The present invention also includes a fuel cell electrolyte membrane containing such a cation exchange resin.
  • the cation exchange membrane for example, it can be reinforced by a known reinforcing material such as a porous substrate, and further, for example, biaxial stretching treatment for controlling molecular orientation, crystallinity, residual Various treatments such as heat treatment for controlling the stress can be performed.
  • 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.
  • compatibilizers for improving compatibility for example, antioxidants for preventing resin deterioration, for example, handling in molding as a film
  • An antistatic agent, a lubricant, and the like for improving the properties can be appropriately contained as long as the processing and performance as a cation exchange membrane are not affected.
  • the thickness of the cation exchange membrane is not particularly limited, and is appropriately set according to the purpose and application.
  • the thickness of the cation exchange membrane is, for example, 1 to 350 ⁇ m, preferably 5 to 200 ⁇ m.
  • Applications of the fuel cell of the present invention include, for example, power sources for driving motors in automobiles, ships, airplanes, etc., and power sources in communication terminals such as mobile phones.
  • the reaction was stopped by dropping the reaction mixture into a 0.1 M aqueous nitric acid solution, and the precipitated reddish brown solid was collected by filtration.
  • the obtained reddish brown solid was washed with methanol, and the filtrate was recovered. Furthermore, it wash
  • reaction was stopped by dropping the reaction mixture into methanol, and the precipitated white solid was collected by filtration.
  • the resulting black solid was washed several times with concentrated hydrochloric acid, pure water and methanol, and then vacuum dried at 60 ° C. overnight.
  • cation exchange resin precursor polymer (0.50 g) and a 30% aqueous fuming sulfuric acid solution (9 mL) were added to a 50 mL round bottom flask and allowed to react at room temperature for 3 days.
  • the reaction was stopped by dropping the reaction mixture into ice water, and the precipitated brown solid was collected by filtration. The obtained brown solid was washed several times with pure water and then vacuum dried at 80 ° C. overnight.
  • a cation exchange resin SPAF was formed by a solution casting method.
  • CCM catalyst coated film
  • FIG. 1 shows the results of linear sweep voltammetry when a SPAF film or Nafion (registered trademark) NRE211 is used in the cell.
  • gas humidification 100% RH, 80% RH, 53% RH, and 30% RH potential sweep range 0.15-0.60 V, potential sweep speed 0.5 mV / s, Measurement was performed by controlling the potential.
  • 100 ml / min of hydrogen was supplied to the anode side and 100 ml / min of nitrogen was supplied to the cathode side.
  • the current value detected at this time indicates the oxidation current at the cathode of hydrogen gas that has permeated through the electrolyte membrane from the anode to the cathode, and serves as an index of the amount of hydrogen permeated through the membrane.
  • the hydrogen permeation amount of the SPAF cell is about 25% of the Nafion (registered trademark) NRE211 cell having the same perfluoro main chain, and SPAF shows a high gas barrier property. all right.
  • FIG. 2 shows current density-voltage characteristics when a SPAF film or Nafion (registered trademark) NRE211 is used in a cell. This power generation characteristic was evaluated under the conditions of a cell temperature of 80 ° C. and 100% RH. Hydrogen (utilization rate 70%) was used as the anode gas, and air (utilization rate 40%) was used as the cathode gas. The cell resistance was measured with a resistance measuring instrument with a fixed frequency of 1 kHz.
  • the SPAF cell showed a performance higher than that of the Nafion (registered trademark) NRE211 cell.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Sustainable Development (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Fuel Cell (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Conductive Materials (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
PCT/JP2016/069364 2015-07-03 2016-06-29 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 Ceased WO2017006831A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/738,270 US10471420B2 (en) 2015-07-03 2016-06-29 Cation exchange resin, and cation exchange membrane and fuel cell electrolyte membrane using same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-134000 2015-07-03
JP2015134000A JP6162179B2 (ja) 2015-07-03 2015-07-03 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

Publications (1)

Publication Number Publication Date
WO2017006831A1 true WO2017006831A1 (ja) 2017-01-12

Family

ID=57685201

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/069364 Ceased WO2017006831A1 (ja) 2015-07-03 2016-06-29 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

Country Status (3)

Country Link
US (1) US10471420B2 (OSRAM)
JP (1) JP6162179B2 (OSRAM)
WO (1) WO2017006831A1 (OSRAM)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023135358A (ja) * 2022-03-15 2023-09-28 株式会社小松製作所 オイルフィルタ装置
WO2024014269A1 (ja) * 2022-07-15 2024-01-18 国立大学法人山梨大学 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

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6888778B2 (ja) * 2017-02-22 2021-06-16 国立大学法人山梨大学 陰イオン交換樹脂、電解質膜、電極触媒層形成用バインダー、電池電極触媒層および燃料電池
CN112154162B (zh) * 2018-05-18 2022-07-26 Ａｇｃ株式会社 含氟聚合物的制造方法及含氟离子交换聚合物的制造方法
JP7513971B2 (ja) * 2020-07-16 2024-07-10 国立大学法人山梨大学 陰イオン交換樹脂の製造方法および電解質膜の製造方法
JP7513970B2 (ja) * 2020-07-16 2024-07-10 国立大学法人山梨大学 陰イオン交換樹脂の製造方法および電解質膜の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006045512A (ja) * 2004-06-29 2006-02-16 Sumitomo Chemical Co Ltd 高分子電解質膜及びそれを用いた燃料電池
JP2013047309A (ja) * 2011-08-29 2013-03-07 Daihatsu Motor Co Ltd 陰イオン交換樹脂、燃料電池用電解質層、電極触媒層形成用バインダー、電池電極触媒層および燃料電池
US20130108944A1 (en) * 2011-10-28 2013-05-02 Ford Motor Company Sulfonated poly(phenylene) copolymer electrolyte for fuel cells
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
JP2013538797A (ja) * 2010-08-04 2013-10-17 コンパニー ゼネラール デ エタブリッスマン ミシュラン 芳香族パーフルオロアルカンモノマー

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4029783A (en) 1973-08-03 1977-06-14 Boehringer Mannheim G.M.B.H. N-substituted 1-amino-3-phenoxy-propan-2-ol compounds and therapeutic compositions containing them
US4030988A (en) 1973-12-17 1977-06-21 E. I. Du Pont De Nemours And Company Process for producing halogen and metal hydroxides with cation exchange membranes of improved permselectivity
US3969285A (en) 1973-12-17 1976-07-13 E. I. Du Pont De Nemours And Company Heat-treated fluorocarbon sulfonylamine cation permselectivity
US4026785A (en) 1975-12-22 1977-05-31 Olin Corporation Adjustable electrode
CN102276844A (zh) * 2005-09-16 2011-12-14 住友化学株式会社 高分子电解质、以及使用该高分子电解质的高分子电解质膜、膜-电极接合体和燃料电池
US8492460B2 (en) * 2006-07-28 2013-07-23 GM Global Technology Operations LLC Fluorinated polymer blocks for PEM applications
US7973088B2 (en) * 2006-08-25 2011-07-05 Sumitomo Chemical Company, Limited Polymer electrolyte membrane, method for producing the same, and proton conductivity evaluation method for polymer electrolyte membrane
KR20120082007A (ko) * 2009-09-24 2012-07-20 조지아 테크 리서치 코포레이션 음이온 교환 고분자전해질

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006045512A (ja) * 2004-06-29 2006-02-16 Sumitomo Chemical Co Ltd 高分子電解質膜及びそれを用いた燃料電池
JP2013538797A (ja) * 2010-08-04 2013-10-17 コンパニー ゼネラール デ エタブリッスマン ミシュラン 芳香族パーフルオロアルカンモノマー
JP2013047309A (ja) * 2011-08-29 2013-03-07 Daihatsu Motor Co Ltd 陰イオン交換樹脂、燃料電池用電解質層、電極触媒層形成用バインダー、電池電極触媒層および燃料電池
US20130108944A1 (en) * 2011-10-28 2013-05-02 Ford Motor Company Sulfonated poly(phenylene) copolymer electrolyte for fuel cells
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023135358A (ja) * 2022-03-15 2023-09-28 株式会社小松製作所 オイルフィルタ装置
WO2024014269A1 (ja) * 2022-07-15 2024-01-18 国立大学法人山梨大学 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

Also Published As

Publication number Publication date
US20180178210A1 (en) 2018-06-28
JP2017014423A (ja) 2017-01-19
JP6162179B2 (ja) 2017-07-12
US10471420B2 (en) 2019-11-12

Similar Documents

Publication Publication Date Title
CN107112563B (zh) 新型聚合物及其制备方法
JP6162179B2 (ja) 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
JP6156358B2 (ja) 高分子電解質組成物、およびそれを用いた高分子電解質膜、膜電極複合体および固体高分子型燃料電池
JP4424129B2 (ja) ブロック共重合体及びその用途
JP5960763B2 (ja) 陰イオン交換樹脂、燃料電池用電解質膜、電極触媒層形成用バインダー、電池電極触媒層および燃料電池
JP5338990B2 (ja) 高分子電解質膜、それを用いた膜電極複合体および固体高分子型燃料電池
JP6653434B2 (ja) 陰イオン交換樹脂の製造方法、燃料電池用電解質膜の製造方法、電極触媒層形成用バインダーの製造方法、電池電極触媒層の製造方法および燃料電池の製造方法
WO2013042746A1 (ja) 高分子電解質組成物成形体、およびそれを用いた固体高分子型燃料電池
JP7087315B2 (ja) 高分子電解質組成物ならびにそれを用いた高分子電解質膜、触媒層付き電解質膜、膜電極複合体、固体高分子形燃料電池、電気化学式水素ポンプおよび水電解式水素発生装置
JP5827077B2 (ja) 陰イオン交換樹脂、燃料電池用電解質層、電極触媒層形成用バインダー、電池電極触媒層および燃料電池
JP2016033199A (ja) 陰イオン交換樹脂、燃料電池用電解質層、燃料電池および陰イオン交換樹脂の製造方法
WO2015141450A1 (ja) 陰イオン交換樹脂、燃料電池用電解質膜、電極触媒層形成用バインダー、電池電極触媒層および燃料電池
WO2014050928A1 (ja) 陰イオン交換樹脂、燃料電池用電解質層、電極触媒層形成用バインダー、電池電極触媒層および燃料電池
JP2009087763A (ja) 高分子電解質及びこれを用いた燃料電池用電解質膜
WO2014157389A1 (ja) 電解質膜用組成物、固体高分子電解質膜、該電解質膜の製造方法、膜－電極接合体、固体高分子型燃料電池、水電解セルおよび水電解装置
JP2015122308A (ja) 高分子電解質、膜電極接合体、および固体高分子形燃料電池
JP2010031231A (ja) 新規な芳香族化合物および含窒素芳香環を有するポリアリーレン系共重合体
JP6166438B2 (ja) 陰イオン交換樹脂、燃料電池用電解質膜、電極触媒層形成用バインダー、電池電極触媒層および燃料電池
JP2010015980A (ja) 高分子電解質、架橋高分子電解質、高分子電解質膜およびその用途
JP5549970B2 (ja) 超強酸基を有する芳香族高分子電解質及びその利用
KR20140142036A (ko) 아민기-함유 실세스퀴옥산을 이용한 폴리벤즈이미다졸 나노복합막, 이의 제조 방법, 및 이를 포함하는 연료전지
KR101304240B1 (ko) 솔젤 반응을 이용한 기능성 물질 포함 하이브리드 막의 제조방법
JP5512488B2 (ja) 固体高分子型燃料電池用膜−電極構造体
CN100506892C (zh) 具有氧碳基的聚合物及其用途
JP6819047B2 (ja) 高分子電解質用のジフェニルスルホン化合物、高分子電解質、高分子電解質の製造方法、膜電極接合体、及び、固体高分子形燃料電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16821300

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15738270

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16821300

Country of ref document: EP

Kind code of ref document: A1