WO2005037879A1 - Procede de production d'un polymere de perfluorocarbone - Google Patents

Procede de production d'un polymere de perfluorocarbone Download PDF

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Publication number
WO2005037879A1
WO2005037879A1 PCT/JP2004/015243 JP2004015243W WO2005037879A1 WO 2005037879 A1 WO2005037879 A1 WO 2005037879A1 JP 2004015243 W JP2004015243 W JP 2004015243W WO 2005037879 A1 WO2005037879 A1 WO 2005037879A1
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Prior art keywords
perfluorocarbon
monomer
group
polymer
producing
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PCT/JP2004/015243
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English (en)
Japanese (ja)
Inventor
Katsuya Ueno
Nobuyuki Kasahara
Shin Tatematsu
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Asahi Glass Company, Limited
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Publication date
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Priority to JP2005514792A priority Critical patent/JPWO2005037879A1/ja
Publication of WO2005037879A1 publication Critical patent/WO2005037879A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1466—Monomers containing sulfur
    • C08F216/1475—Monomers containing sulfur and oxygen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • 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
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for producing a sulfonic acid type perfluorocarbon polymer having excellent stability.
  • a perfluorocarbon polymer having a sulfonic acid group (hereinafter, referred to as a sulfonic acid type perfluorocarbon polymer) is widely used as a base material for a cation exchange membrane for salt electrolysis or a diaphragm for a fuel cell.
  • a sulfonic acid type perfluorocarbon polymer is widely used as a base material for a cation exchange membrane for salt electrolysis or a diaphragm for a fuel cell.
  • fuel cells have attracted attention as a power generation system whose reaction product is water in principle and has almost no adverse effect on the global environment.
  • polymer electrolyte fuel cells have attracted attention. The reasons are as follows. (1) A highly conductive membrane was developed as a solid polymer electrolyte.
  • the sulfonic acid type perfluorocarbon polymer deteriorates when exposed to a long-term electrode reaction, and thus it is difficult to maintain the output as a fuel cell.
  • the cause of the deterioration of the polymer is that at least a part of the terminal group of the polymer main chain is an unstable COOH group or COF group, and the main chain is decomposed from the unstable terminal group in a chain.
  • Can be As a method for stabilizing the terminal group of the polymer there is a method of fluorinating the polymer (for example, see Patent Document 1). It is difficult to completely stabilize this.
  • Patent Document 1 Japanese Patent Publication No. 46-23245 (Claims)
  • the present invention selects a radical initiator and a chain transfer agent, conducts polymerization, and then conducts polymerization so that unstable terminals which are hardly fluorinated are formed in the polymer. It is an object of the present invention to efficiently obtain a sulfonic acid-type perfluorocarbon polymer having a stable terminal group by carrying out the conversion.
  • the present invention provides a radical polymerization initiator comprising a fluorine-containing compound, a saturated hydrocarbon having 1 to 12 carbon atoms, which may be partially substituted with a fluorine atom or a chain transfer agent comprising a hydrogen atom.
  • SO X (X
  • 2 groups are a fluorine atom or a chlorine atom) and a perfluorocarbon monomer having an ethylenic double bond (which may contain an oxygen atom having an ether bond);
  • a method for producing a perfluorocarbon polymer comprising co-polymerizing at least one perhalogenocarbon monomer containing no atom other than atoms, halogen atoms and oxygen atoms, followed by fluorination treatment. I will provide a.
  • a polymer having a terminal group which is easily fluorinated is polymerized and further subjected to fluorination treatment, so that the obtained polymer is highly perfluorinated.
  • a perfluorocarbon polymer having a sulfonic acid group obtained by hydrolysis and acidification using this polymer has excellent stability and is suitable for an electrolyte of a polymer electrolyte fuel cell.
  • the perfluorocarbon monomer may contain an oxygen atom having an ether bond.
  • Examples of the perhalogenocarbon monomer having a double bond and containing no atoms other than a carbon atom, a halogen atom and an oxygen atom include the following.
  • Perfluoro compounds such as tetrafluoroethylene, hexahenoleopropylene, and perphnolerobutynoleethylene Oloflefin.
  • Perfluoronorethone ethers such as perfluoroethyl vinyl ether, perfluoropropylvinyl ether, and perphnolerobutene-norevi-noreeteneole.
  • Cyclic perfluoro compounds such as nofluoro (1,3 diquinol), perfluoro (2,2 dimethyl-1,3 diquinol), perfluoro (2-methylene 4-methyl-1,3-dioxolan).
  • Non-perfluoroolefin monomers such as trifluoroethylene.
  • Fluoroacrylic monomers such as 1,1-dihydroperfluorophenol phthalate acrylate and 1,1-dihydroperfluorophenol methacrylate.
  • perhalogenoolefins such as tetrafluoroethylene, chloro opening trifluoroethylene, hexafluoropropylene, etc., and having an SO X group and having an ethylenic double bond
  • the production method of the present invention in the production of a copolymer with a perfluorocarbon monomer, or a multi-component copolymer of these monomers and at least one perhalogeno monomer having a double bond other than the above-mentioned perhydrogenoolefins
  • the adoption of, has a remarkable effect and is preferred.
  • the perhalogeno olefins tetrafluoroethylene is particularly preferred! /.
  • known polymerization methods such as suspension polymerization, solution polymerization, emulsion polymerization, and bulk polymerization can be used as the polymerization method for copolymerizing the above-mentioned monomers without limitation. Is preferred. Since water is used as a polymerization medium in suspension polymerization and emulsion polymerization, it is difficult to stably perform polymerization in which the perfluorocarbon monomer is hardly dissolved in the polymerization medium. In addition, in bulk polymerization, it is difficult to stably perform polymerization in which it is difficult to efficiently remove heat generated by polymerization.
  • a fluorine-containing organic solvent is preferable.
  • perfluorocarbons having 3 to 10 carbon atoms hydrofluorocarbons having 3 to 10 carbon atoms, hide-opening fluorocarbons having 3 to 10 carbon atoms, and 3 to 10 carbon atoms A group consisting of black and white fluorocarbons.
  • halogenocarbons may preferably have any of a linear, branched or cyclic structure and may contain an etheric oxygen atom in the molecule, but are preferably saturated compounds.
  • Specific polymerization media include the following.
  • the perfluorocarbon include perfluorocyclobutane, perfluorohexane, perfluoro (dipropyl ether), perfluorocyclohexane, perfluoro (2-butyltetrahydrofuran) and the like. It is preferable that the number of fluorine atoms in the molecule is larger than the number of hydrogen atoms in the fluoridated carbon. CH OC F OC F F
  • Hydrochloride Fluorocarbon has less than 3 hydrogen atoms
  • Examples thereof include 1,1,2-trifluorotrifluoroethane.
  • the amount of the polymerization medium used is preferably 10 to 90% by volume relative to the volume of the polymerization reactor, and more preferably 30 to 70%.
  • the amount of the polymerization medium is small, the amount of the perfluorocarbon monomer that can be dissolved in the polymerization medium is also small, and the amount of the obtained polymer is small, so that the production efficiency is low and industrially disadvantageous.
  • the amount of the polymerization medium is too large, it is difficult to uniformly stir the whole.
  • a substantial polymerization medium includes water.
  • the chain transfer agent in the present invention hydrogen, a saturated hydrocarbon having 112 carbon atoms, a fluorocarbon having a saturated hydride having 112 carbon atoms and the like are used. Specifically preferred are methane, ethane and CH F
  • the terminal group has an SO X group that can be easily fluorinated.
  • a perfluorocarbon polymer is formed.
  • the molecular weight of the polymer obtained by using the chain transfer agent can be controlled.
  • the chain transfer agents methane is particularly useful because it has a high chain transfer property, it is easy to control the molecular weight of the polymer, and the terminal group of the polymer is CH.
  • the amount of the chain transfer agent used is such that the perfluorocarbon monomer having a SO X group is
  • the mass ratio is preferably 0.1 to 50% based on the total amount of the mixture with the halogenocarbon monomer. If the amount of the chain transfer agent is too small, it is difficult to control the molecular weight of the polymer by the chain transfer. It is difficult. If the amount of the chain transfer agent is too large, the production amount of the perfluorocarbon monomer and the perhalogenocarbon monomer is reduced, so that the production efficiency is lowered and this is industrially disadvantageous.
  • the optimum amount of the chain transfer agent varies depending on the type of the chain transfer agent used, and 0.1 to 10% is preferable for methane, and 10 to 50% is preferable for CHF.
  • the polymerization initiator in the present invention a radical polymerization initiator which also has a fluorine-containing compound power is employed, but this polymerization initiator is preferable because it forms a copolymer having a stable terminal group.
  • a compound represented by any of the following formulas 17 is preferable.
  • R n is a perfluoroalkyl group having 11 to 10 carbon atoms
  • R i2 and R i3 are polyfluoroalkyl groups having 3 or more carbon atoms
  • X is a halogen atom
  • R M Is a fluorine atom or a perfluoroalkyl group having 12 to 12 carbon atoms
  • nl, n2 and n3 are each independently an integer of 1 or more.
  • bis (fluoroacyl) peroxides represented by the formula 1 are preferred! / ⁇ . Specifically, (CF COO), (CF CF COO), (CF CF CF COO), (HCF CF COO
  • the amount of the polymerization initiator to be used is preferably 0.01-1% by mass with respect to the mass of the perhalogenocarbon monomer, and more preferably 0.01-0.5%. If the amount of the polymerization initiator is too small, the molecular weight of the produced polymer becomes too large, resulting in poor processability and the possibility of using as an electrolyte material. If the amount of the polymerization initiator is too large, the molecular weight of the generated polymer will be reduced, for example, the electrolyte material of a polymer electrolyte fuel cell When used as a material, there is a possibility that strength sufficient for use may not be obtained.
  • the polymerization temperature in the present invention is selected based on the 10-hour half-life temperature of the polymerization initiator in the solvent used (the temperature at which the amount of the initiator becomes half after 10 hours from the start of polymerization). 75 ° C or lower is preferable. If the temperature is higher than 75 ° C., not only does the economy become poor, but also the number of generated COF terminal groups tends to increase.
  • the polymerization pressure in the present invention is preferably 0.1-lOMPa. If the polymerization pressure is too low, the content of COF terminal groups in the obtained polymer tends to increase, and if the polymerization pressure is too high, it is not preferable in terms of production equipment. More preferably, 0.3 to 5 MPa is employed.
  • a specific polymerization initiator and a specific chain transfer agent are selected respectively, so that the polymer obtained by polymerization has a terminal group which is easily fluorinated and a terminal group which is perfluorinated, Few unstable terminal groups.
  • the terminal group which is easily fluorinated include -CFH, -CFH, -CH and the like.
  • Unstable end groups include COF, -COOH
  • the obtained polymer is subjected to a fluorination treatment.
  • the method of the fluorination treatment is not particularly limited, and a known method of replacing a hydrogen atom with a fluorine atom is employed. From the viewpoint of reaction efficiency, a fluorination treatment using a fluorine gas is preferably employed.
  • the method of fluorination treatment with fluorine gas involves suspending or dissolving the fluorinated copolymer in a solvent such as carbon tetrachloride, black fluorocarbon, and perfluorocarbon having low reactivity with fluorine.
  • a gas-Z method in which the polymer is directly fluorinated with fluorine gas diluted with an inert gas, if necessary, or a gas-Z solid method in which the polymer is directly exposed to fluorine gas and fluorinated.
  • a reactor made of a material having corrosion resistance to fluorine gas to improve the contact between the polymer to be fluorinated and the fluorine gas.
  • the reaction is preferably performed with stirring or vibration.
  • a predetermined concentration of fluorine is placed in a reactor in which the polymer to be fluorinated is present.
  • a circulating method in which a raw gas is circulated to perform a fluorination treatment, a Notch method in which a predetermined concentration of a fluorinated gas is sealed and fluorinated, and the like are exemplified.
  • the polymer obtained by the method of the present invention is highly fluorinated.
  • the SO X group becomes a sulfonic acid group.
  • a polymer electrolyte fuel cell using this sulfonic acid type perfluorocarbon polymer as an electrolyte material has excellent durability because the electrolyte material has excellent stability.
  • the sulfonic acid-type perfluorocarbon polymer electrolyte material according to the present invention has a number of COF end groups of preferably 20 or less per 10 6 carbon atoms, more preferably 16 or less. .
  • quantification of unstable terminal groups was performed as follows. That is, the polymer having a SO F group obtained in this example and the number of unstable terminal groups for comparison were
  • N f X A / t
  • N the number of unstable terminal groups (number Z carbon atoms 10 6), A: absorbance, f: factor, t: thickness of the film (mm).
  • CF H (hereinafter referred to as a chain transfer agent)
  • TFE tetrafluoroethylene
  • the white powder was a film with 240 ° C was measured IR and, as the unstable terminal groups, COF groups included 10 13 6 per carbon atom, COOH group, CH OH group
  • CF CF groups was 1 or less per 10 6 carbon atoms, respectively.
  • TFE-PSVE copolymer was fluorinated in the same manner as in Example 1 to obtain 77.4 g of a white TFE-PSVE copolymer.
  • TFE-PSVE copolymer Polymerization was carried out in the same manner as in Example 1 except that the charged amount of R-32 was 25.Og and the pressure in the reaction tank was 1.1 lOMPaG, to obtain 112.lg of a TFE-PSVE copolymer.
  • the obtained TFE-PSVE copolymer was subjected to a fluorination treatment in the same manner as in Example 1 to obtain 11.3 g of a white TFE-PSVE copolymer.
  • Example 2 Polymerization was carried out in the same manner as in Example 1 to obtain 79.6 g of a TFE-PSVE copolymer.
  • the obtained TFE-PSVE copolymer was fluorinated in the same manner as in Example 1 to obtain 76.9 g of a white TFE-PSVE copolymer.
  • Example 2 Polymerization was carried out in the same manner as in Example 1 except for the above, to obtain 66.3 g of a TFE-PSVE copolymer.
  • the obtained TFE-PSVE copolymer was fluorinated in the same manner as in Example 1 to obtain 66.3 g of a white TFE-PSVE copolymer.
  • the copolymer COF groups as unstable terminal to have been included 10 16 6 per carbon atom, COOH group, -CH OH group, CF CF2 group is carbon atom 10
  • Example 2 Polymerization was carried out in the same manner as in Example 1 except that the charged amount of SVE was set to 512.3 g and the pressure of the reaction vessel was set to 0.80 MPa, to obtain 120.8 g of a TFE-PSVE copolymer.
  • the obtained TFE-PSVE copolymer was fluorinated in the same manner as in Example 1 to obtain 115.8 g of a white TFE-PSVE copolymer.
  • the copolymer COF groups as unstable terminal to have been included 10 11 6 per carbon atom, COOH group, -CH OH group, -CF CF group carbon atom 10 6 cells per
  • Example 2 In the same manner as in Example 1, a white TFE-PSVE copolymer 105. Og was obtained. The obtained TFE-PSVE copolymer was fluorinated in the same manner as in Example 1 to obtain 101.2 g of a white TFE-PSVE copolymer.
  • the copolymer COF groups as unstable terminal to have been included 48 10 6 per carbon atom, COOH group, CH OH group, -CF CF group carbon atom 10 6 Core
  • the perfluorocarbon polymer obtained by the present invention is highly fluorinated and has a small amount of unstable terminal groups.
  • the sulfonic acid-type perfluorocarbon polymer obtained by hydrolyzing and acidifying this polymer is stable, and when used as an electrolyte for a polymer electrolyte fuel cell, for example, a solid polymer-type fuel having excellent durability can be obtained. A battery is obtained.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

La présente invention se rapporte à un procédé de production d'un polymère de perfluorocarbone selon lequel un monomère perfluorocarbone (qui peut contenir un atome d'oxygène de liaison éther) ayant un groupe -SO2X (où X représente un atome de fluor ou un atome de chlore) et une double liaison éthylène, et un monomère perhalogéno ayant une double liaison et ne contenant pas d'autres atomes que des atomes de carbone, des atomes d'halogène et des atomes d'oxygène sont copolymérisés dans un milieu de polymérisation au moyen d'un initiateur de polymérisation radicalaire comprenant un composé contenant du fluor et un agent de transfert de chaîne composé d'hydrogène ou d'un hydrocarbure saturé ayant 1 à 2 atomes de carbone, où une partie des atomes d'hydrogène peuvent être substitués par des atomes de fluor, puis le produit obtenu est soumis à une fluoration. Un polymère de perfluorocarbone ayant un groupe -SO2X qui est obtenu conformément à un tel procédé possède quelques groupes d'extrémité labiles dans une molécule et présente par conséquent une excellente stabilité.
PCT/JP2004/015243 2003-10-15 2004-10-15 Procede de production d'un polymere de perfluorocarbone WO2005037879A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1914251A1 (fr) * 2006-10-17 2008-04-23 Solvay Solexis S.p.A. procédé de stabilisation d'un fluoropolymère portant des groupes échangeurs d'ions
JPWO2006019097A1 (ja) * 2004-08-18 2008-05-08 旭硝子株式会社 燃料電池用電解質ポリマー、その製造方法、電解質膜、及び膜・電極接合体
JP2008308681A (ja) * 2007-05-16 2008-12-25 Asahi Glass Co Ltd パーフルオロポリマーの製造方法、製造装置、および固体高分子形燃料電池用電解質膜の製造方法
JP2015520283A (ja) * 2012-06-20 2015-07-16 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． テトラフルオロエチレンコポリマー
JPWO2015002008A1 (ja) * 2013-07-03 2017-02-23 旭硝子株式会社 含フッ素ポリマーの製造方法

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JPH06271607A (ja) * 1993-03-17 1994-09-27 Asahi Glass Co Ltd 弗素系重合体の製造法
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JPH11152310A (ja) * 1997-11-20 1999-06-08 Asahi Glass Co Ltd 含フッ素脂肪族環構造含有重合体の製造方法
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JPH06234816A (ja) * 1992-12-18 1994-08-23 Asahi Glass Co Ltd スルホン酸型官能基を有するパーフルオロカーボン重合体の製造方法
JPH06271607A (ja) * 1993-03-17 1994-09-27 Asahi Glass Co Ltd 弗素系重合体の製造法
JPH07179508A (ja) * 1993-10-15 1995-07-18 Ausimont Spa テトラフルオロエチレンと他のパーフルオロ化モノマーとの共重合体の製造法
JPH11152310A (ja) * 1997-11-20 1999-06-08 Asahi Glass Co Ltd 含フッ素脂肪族環構造含有重合体の製造方法
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2006019097A1 (ja) * 2004-08-18 2008-05-08 旭硝子株式会社 燃料電池用電解質ポリマー、その製造方法、電解質膜、及び膜・電極接合体
JP5168903B2 (ja) * 2004-08-18 2013-03-27 旭硝子株式会社 燃料電池用電解質ポリマー、その製造方法、電解質膜、及び膜・電極接合体
EP1914251A1 (fr) * 2006-10-17 2008-04-23 Solvay Solexis S.p.A. procédé de stabilisation d'un fluoropolymère portant des groupes échangeurs d'ions
WO2008046816A1 (fr) * 2006-10-17 2008-04-24 Solvay Solexis S.P.A. Procédé destiné à stabiliser un polymère fluoré possédant des groupes échangeurs d'ions
JP2010506986A (ja) * 2006-10-17 2010-03-04 ソルヴェイ・ソレクシス・エッセ・ピ・ア イオン交換基を有するフルオロポリマーを安定化する方法
US8207235B2 (en) 2006-10-17 2012-06-26 Solvay Solexis S.P.A. Process for stabilizing fluoropolymer having ion exchange groups
JP2008308681A (ja) * 2007-05-16 2008-12-25 Asahi Glass Co Ltd パーフルオロポリマーの製造方法、製造装置、および固体高分子形燃料電池用電解質膜の製造方法
JP2015520283A (ja) * 2012-06-20 2015-07-16 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． テトラフルオロエチレンコポリマー
JPWO2015002008A1 (ja) * 2013-07-03 2017-02-23 旭硝子株式会社 含フッ素ポリマーの製造方法

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