WO2005054363A1 - 含フッ素ポリマー液状組成物及びフッ素系架橋体製造方法 - Google Patents
含フッ素ポリマー液状組成物及びフッ素系架橋体製造方法 Download PDFInfo
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- WO2005054363A1 WO2005054363A1 PCT/JP2004/017889 JP2004017889W WO2005054363A1 WO 2005054363 A1 WO2005054363 A1 WO 2005054363A1 JP 2004017889 W JP2004017889 W JP 2004017889W WO 2005054363 A1 WO2005054363 A1 WO 2005054363A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or 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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or 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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or 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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
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- 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 fluoropolymer liquid composition and a method for producing a fluorinated crosslinked product.
- a polymer electrolyte fuel cell which has been receiving attention in recent years, has a problem that is lower than the power of which a fluorine-containing electrolyte membrane is mainly used.
- a fluorine-containing electrolyte membrane is mainly used.
- Patent Document 1 JP-A-60-133031
- Patent Document 2 JP-A-54-107889
- Patent Document 3 JP-A-54-52690
- Patent Document 4 JP-A-61-276828
- Patent Document 5 JP-A-2000-188013
- Patent Document 6 JP-A-2002-53619
- Patent Document 7 JP-A-2003-128833
- an object of the present invention is to provide a polymer having an acid-acid salt type group, which is excellent in mechanical properties by being crosslinked after being applied to a substrate or impregnated in a porous material, and having a high water content.
- Means for Solving the Problems The object of the present invention is to provide a liquid composition capable of producing a crosslinked product having a small dimensional change.
- the present invention is a fluoropolymer liquid composition comprising a liquid medium and a crosslinkable fluoropolymer having a crosslinkable functional group (A).
- the fluorine-containing polymer liquid (A) contains particles of a cross-linkable fluorine-containing polymer (PD) having an acid salt type group or an organic group which is converted into a carboxyl group by hydrolysis in a liquid dispersion medium.
- Liquid fluoropolymer dispersion (AD) or a crosslinkable fluoropolymer (PS) having an acid salt type group or a precursor of an acid salt group (PS) Is a fluorine-containing polymer solution (AS) dissolved in an alcohol / water mixed solvent, and the above-mentioned acid salt group is a sulfonic acid group, a carboxyl group, -SO NR 2 R 3 , -SO NR 4 R 5 R 6
- R 7 -SO M 1 , one COONR RRR 11 or — COOM 2 (R 2 is a hydrogen atom or M
- R 3 represents an alkyl group or a sulfol-containing group.
- R 4 represents an alkyl group or a sulfol-containing group.
- R 9 , R 1C> and R 11 are the same or different and are each a hydrogen atom or an alkyl group
- M 2 And M 5 represents an L-valent metal.
- the L-valent metal is a metal belonging to Group 1, 2, 4, 8, 11, 12, 12, or 13 of the periodic table.
- the precursor of the acid salt type group is -SO F, -SO NR 22 R 23 (R 22 and R 23 are the same or different and represent an alkyl group.)
- a fluorine-containing polymer liquid composition which is an organic group that is converted to a carboxyl group by hydrolysis.
- the present invention is characterized in that a fluorine-containing crosslinked product is produced by applying the above-mentioned fluoropolymer liquid composition to a substrate or impregnating a porous material, followed by removing the liquid medium and performing a crosslinking treatment.
- This is a method for producing a fluorine-based crosslinked product.
- the above-mentioned fluoropolymer liquid composition is applied to a substrate or impregnated in a porous material, then the liquid medium is removed, and a crosslinking treatment is performed using a peroxide conjugate as a crosslinking reaction initiator.
- a method for producing a fluorinated crosslinked body which comprises producing a fluorinated crosslinked body.
- the fluorine-containing polymer liquid composition should have a crosslinkable functional group of I or -Br and have a polyfunctional unsaturated compound as a crosslinking agent (B). Can be.
- the fluoropolymer liquid composition of the present invention also provides a fluoropolymer liquid (A) comprising a liquid medium and a crosslinkable fluoropolymer having a crosslinkable functional group.
- the liquid medium is a liquid dispersion medium described below, or a fluorinated solvent or an alcohol Z water mixed solvent.
- the above-mentioned fluoropolymer liquid (A) is a liquid dispersion of particles comprising a crosslinkable fluoropolymer (PD) having an acid salt type group or an organic group which is converted into a carboxyl group by hydrolysis.
- a fluoropolymer liquid dispersion (AD) dispersed in a solvent or a crosslinkable fluoropolymer (PS) having an acid salt type group or a precursor of an acid salt group (PS) is a fluorine-based solvent. It is a fluoropolymer solution (AS) dissolved in an alcohol / water mixed solvent.
- the acid salt type group is a sulfonic acid group, a carboxyl group or SO NHR 3 (R 3 is
- R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 1G and R 11 are the same or different and are each a hydrogen atom Or an alkyl group, M ⁇ M 2 and M 5 represents a metal whose valence is L.
- the L-valent metal is a metal belonging to Group 1, Group 2, Group 4, Group 8, Group 11, Group 12, or Group 13 of the periodic table.
- R 23 is the same or different and represents an alkyl group.
- R 23 is the following, such as -R 28 SO F
- z 2 represents an organic group.
- the organic group for example, -SO F, -SO H, -SO M 1 can be mentioned, -SO (NR 27 SO R 6
- R 27 represents an alkyl group, hydrogen or an L-valent metal. ) Can also be connected indefinitely. Also, —SO (NR 27 SO R 6 SO) NR 27 SO F, —SO (NR 27 SO R 6 SO) NR 27
- the organic group which is converted into a carboxyl group by hydrolysis is COOR 12 (R 12 represents an alkyl group) or CONR 24 R 25 (R 24 and R 25 are the same or different and each is an alkyl group). Represents a group or a hydrogen atom).
- R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 22 , R 23 , R 24 , R 25 and R 27 are as described above.
- a C1-C4 alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group. Among them, a methyl group or an ethyl group is preferable.
- R 23 for example, R 28 SO F, —SO (NR 29 SO R 6 SO) NR 29 SO— (k is 1 or more
- R 6 represents a fluorinated alkylene group.
- R 28 represents an alkylene group.
- NR 27 SO R 6 SO NR 27 SO F (k is 1 or more, 100 represent the following integer R 27 ⁇
- R 6 are the same as above. ).
- the fluoropolymer liquid (A) is composed of a crosslinkable fluoropolymer (PD) having a carboxyl group, an acid salt group, or an organic group that is hydrolyzed to convert to a carboxyl group. It is a fluoropolymer liquid dispersion (AD) or a fluoropolymer solution (AS) composed of a crosslinkable fluoropolymer (PS) having a precursor of a carboxyl group, an acid salt group or an acid-acid salt group. More preferably, it is a fluoropolymer liquid dispersion (AD) comprising a crosslinkable fluoropolymer (PD) having an acid salt type group—SO M 1 (M 1
- 3 1 / L is the same as above. More preferably, it is a fluoropolymer aqueous dispersion (ADA) which also has a cross-linkable fluoropolymer (PD) strength.
- ADA fluoropolymer aqueous dispersion
- PD cross-linkable fluoropolymer
- Y 1 represents a fluorine atom, a chlorine atom or a perfluoroalkyl group.
- N represents an integer of 0 to 3.
- the n number of Y 1 may be the same or different.
- Y 2 represents a fluorine atom or a chlorine atom, m represents an integer of 115.
- m Y 2 may be the same or different! ),
- the perfluoroalkyl group is preferably a group having 13 to 13 carbon atoms.
- the crosslinkable fluorine-containing polymer has the following general formula (II)
- Y 1 represents a fluorine atom, a chlorine atom or a perfluoroalkyl group.
- ⁇ represents an integer of 0 to 3.
- ⁇ ⁇ 1 may be the same or different.
- ⁇ 2 represents a fluorine atom or a chlorine atom,
- m represents an integer of 1 to 5.
- m Y 2 may be the same or different!
- X is a halogen atom, -OM 4
- R 16 R 17 R 18 (R 13 and R 14 are the same or different, a hydrogen atom, an alkali metal, an alkyl group or sulfo -. Represents a Le-containing group M 3 and M 4 represents an L-valent metal.
- R 1 5, R 16, R 17 and R 18 are the same or different, represented by a representative.) a hydrogen atom or an alkyl Le group having a carbon number of 1 one 4 Or a fluorine-containing polymer precursor obtained by polymerizing a fluorofluoroether derivative or a fluorine-containing polymer precursor derived from the above fluorine-containing polymer precursor. preferable.
- crosslinkable fluorine-containing polymer is a fluorine-containing polymer precursor, in the above general formula ( ⁇ ), —SO X (X is -OM 4 NR 13 R 14 or ONR 15 R 16 R 17 R 18 ; 4 is
- R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are the same as above (provided that -SO X is an acid-
- o) and COOM 3 are the crosslinkable fluorine-containing
- the above “derived from the fluoropolymer precursor” is obtained by hydrolyzing the fluoropolymer precursor in the presence of water as described below, or the above-mentioned general formula of the fluoropolymer precursor.
- the alkali metal as M 3 or M 4 in ( ⁇ ), or the alkali metal as R 13 and Z or R 14 or the L-valent metal in the sulfol-containing group may be exchanged for another metal or other cation. It was done.
- n in the above general formula ( ⁇ ) represents an integer of 0 to 3.
- N is preferably 0 or 1.
- M in the above general formula ( ⁇ ) represents an integer of 115.
- the above m is preferably 2.
- Y 1 represents a fluorine atom, a chlorine atom or a perfluoroalkyl group, and the n Y 1 s may be the same or different.
- the above perfluoroalkyl group is not particularly limited, and examples thereof include a perfluoroalkyl group having 13 to 13 carbon atoms such as a trifluoromethyl group and a pentafluoroethyl group.
- Y 2 in the above general formula ( ⁇ ) preferably represents a fluorine atom or a chlorine atom, and the m Y 2 s may be the same or different.
- Y 1 is preferably a trifluoromethyl group, and ⁇ 2 is more preferably a fluorine atom
- the fluorofluoroether derivative is a Y 1 force trifluoromethyl group in the above general formula ( ⁇ ), Y 2 is a fluorine atom, n force is 0 or 1, and m force is 2. Is even more preferred.
- the fluoropolymer precursor is preferably a binary or higher copolymer obtained by polymerizing the above-mentioned fluorobutyl ether derivative and a fluoroethylenic monomer.
- the composition ratio of the fluoroether derivative to the fluorine-containing ethylenic monomer is preferably from 1:99 to 50:50, more preferably from 5:95 to 30: 70! /.
- the fluorine-containing ethylenic monomer is not particularly limited as long as it has a vinyl group, and is different from the above fluorovinyl ether derivative.
- fluorine-containing ethylenic monomer examples include, for example, the following general formula
- Rf 1 represents a fluorine atom, a chlorine atom, Rf 2 or ORf 2
- Rf 2 has an ether oxygen having 19 to 19 carbon atoms, and may have a straight-chain or branched chain.
- Y 3 represents a hydrogen atom or a fluorine atom
- Y 4 represents a hydrogen atom, a fluorine atom, a chlorine atom, Rf 3 or ORf 3.
- Rf 3 represents an ether oxygen having 19 to 19 carbon atoms. And represents a linear or branched fluoroalkyl group.
- a hydrogen-containing fluoroethylenic monomer represented by the following formula:
- the above-mentioned fluorobutyl ether is preferably a perfluoroalkyl group having Rf 4 of 13 to 13 carbon atoms! /.
- fluorinated ethylenic monomer one or more kinds can be used.
- the crosslinkable fluoropolymer can be polymerized by a conventionally known polymerization method such as solution polymerization, emulsion polymerization and suspension polymerization.
- the crosslinkable fluoropolymer may be a seed polymer.
- the fluorine-containing polymer is So x 1 ⁇ 1 of the limmer precursor represents a halogen atom.
- coz ⁇ z 1 is
- Examples of the alkoxyl group in COZ 1 include an alkoxyl group having 114 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Among them, a methoxy group or an ethoxy group is preferable.
- the hydrolysis is performed by adding an alkali, preferably an aqueous alkali solution.
- alkali include alkalis that may be used for hydrolysis.
- examples include alkali metal or alkaline earth metal hydroxides and carbonates.
- hydroxide examples include: Examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like.
- carbonate include sodium carbonate, sodium hydrogen carbonate, and the like.
- the hydrolysis is usually carried out at a normal temperature of 130 ° C. for 1 minute to 10 hours.
- the precursor of the acid-acid salt type group of the fluoropolymer precursor is SOF
- the crosslinkable fluoropolymer has a crosslinkable functional group.
- the crosslinkable functional group is a group consumed in a crosslinking reaction.
- the above “crosslinking” is to form a crosslinking bond.
- Examples of the above-mentioned crosslinkable functional group include, in addition to the above-mentioned acid-acid salt type group and precursor of the acid-acid salt type group, an odo group [-1], a bromo group [-Br], a cyano group, and a cross-linkable carboxy group.
- examples include a sil group, a cyanato group, a hydroxyl group, a perfluorovinyl group, a carbonyl group and a carbonyl group.
- the above-mentioned acid salt-type groups, organic groups that are converted to carboxyl groups by hydrolysis, and precursors of acid salt-type groups include functional groups of a type that can be consumed in the crosslinking reaction.
- a functional group of a kind that can be consumed in a crosslinking reaction, and a group consumed in the crosslinking reaction is the above-mentioned crosslinkable functional group! /, And a functional group is not consumed in the crosslinking reaction!
- an acid-acid salt type group an organic group capable of being converted to a carboxyl group by hydrolysis, and a precursor of an acid salt-type group (hereinafter sometimes referred to as a "non-crosslinkable functional group").
- the type of functional group that can be consumed in the crosslinking reaction include a carboxyl group and the like.
- the “crosslinkable carboxyl group” refers to a carbohydrate consumed in a crosslinking reaction. Since it is a xyl group, it should be conceptually distinguished from the carboxyl group which is not consumed in the crosslinking reaction and remains as the above-mentioned acid group even after the crosslinking treatment described later.
- the crosslinkable fluoropolymer in the present invention has both a carboxyl group as an acid group and the above-mentioned crosslinkable carboxyl group, usually both carboxyl groups are present in total in excess with respect to the crosslinking agent (B).
- Carboxyl groups not consumed in the crosslinking reaction remain even by the crosslinking treatment, and the remaining carboxyl groups can function as the above-mentioned acid groups.
- the carboxyl group consumed in the crosslinking reaction is the above-mentioned crosslinkable carboxyl group, and the carboxyl group remaining without being consumed in the crosslinking reaction is a carboxyl group as an acid group.
- the crosslinkable fluoropolymer depends on the crosslinking reaction conditions and the like, but preferably has an equivalent weight [EW] of 300 to 5000 after the crosslinking reaction.
- a more preferred lower limit of EW after the crosslinking reaction is 500, and a more preferred upper limit is 1500.
- the equivalent weight [EW] after the above-mentioned crosslinking reaction represents the amount of the above-mentioned non-crosslinkable functional group, and does not represent the amount of the crosslinkable functional group.
- the crosslinkable fluoropolymer is preferably used as a resin instead of a rubber after the crosslinking reaction.
- the fluoropolymer liquid composition of the present invention is composed of the fluoropolymer liquid (A) and the crosslinking agent (B), depending on the type of the crosslinkable functional group and the crosslinking system used. Is preferred.
- the cross-linking agent (B) can be cross-linked without using the cross-linking agent (B), for example, when the cross-linkable functional group is a cross-linkable carboxyl group, a cyano group, 1 I, 1 Br, or the like. is there.
- the crosslinkable functional group is I or Br
- crosslinking can be performed without using the crosslinking agent (B), but crosslinking may be performed using the crosslinking agent (B).
- crosslinking agent (B) examples include those capable of reacting with a carboxyl group, an alkoxycarbol group or a cyano group, particularly those used in oxazole crosslinking systems, imidazole crosslinking systems, and thiazole crosslinking systems.
- the crosslinking agent (B) used in the oxazole cross-linking system, imidazole cross-linking system, and thiazole cross-linking system is, for example, the following general formula (IV) [0028] [Formula 1]
- one of R 1 and R 2 represents -NH, and the other represents -NH
- R represents a perfluoroalkylene group having 11 to 10 carbon atoms.
- bisaminophenol-based crosslinking agents bisaminothiophenol-based crosslinking agents, bisdiaminophenyl-based crosslinking agents, etc. are conventionally used in crosslinking systems having a tolyl group as a crosslinking point. Reacts with a carboxyl group and an alkoxycarbol group of the compound to form an oxazole ring, a thiazole ring, and an imidazole ring to give a crosslinked product.
- crosslinking agent (B) a compound having a plurality of 3-amino-4-hydroxyphenyl groups and Z or 3-amino-4 mercaptophenyl groups, or the following general formula ( ⁇ ): [Formula 7]
- R, R u and R 1 are as defined above.
- the crosslinking agent (B1) for example, 2, 2-bis (3-amino-4-hydroxy Hue - Le) to Xafluoropropane (generic name: bis (aminophenol) AF), 2,2 bis (3 amino-4 mercaptophenol) hexafluoropropane, tetraaminobenzene, bis 3,4-diaminopheninolemethane, bis 3, 4-diaminophenol and 2,2 bis (3,4-diaminophenol) hexafluoropropane.
- Examples of the crosslinking agent (B) include a polyamine compound, a polyisocyanate, and a polyepoxy compound.
- Examples of the polyamined conjugate include polyamines such as hemisamethylenediamine, triethylenetetramine, and triethylenediamine; and combinations of polyamine salts and guandinine derivatives.
- Examples of the above polyisocyanate-to-animate conjugate include tolylene diisocyanate, diphenolemethanediisocyanate, hexamethylene diisocyanate and the like.
- the polyisocyanate-to-animal conjugate may be of a block type in which a prepolymer or a curing temperature can be selected.
- Examples of the cross-linking agent (B) include a combination of an epoxy conjugate and a quaternary ammonium salt, a quaternary phosphonium salt or a basic conjugate.
- the crosslinker (B) may be the crosslinker (B1) represented by the general formula ( ⁇ ). Like,.
- R 19 and R 2 are a force that is both NH, or one is N
- H and the other is preferably NH—Ph.
- the crosslinking agent (B) is preferably a polyfunctional unsaturated compound.
- the polyfunctional unsaturated compound may be any compound having a reaction activity with respect to a polymer radical originating from iodine atom and Z or bromine atom generated by heating or decomposition of a peroxide compound described later.
- the type is not particularly limited.
- Preferred polyfunctional unsaturated compounds include, for example, various diatalates, trimethylolpropane triatalylate HTMTPA), trimethylolpropane trimethatalylate, triallyl isocyanurate (TAIC), triaryl cyanurate, triallyl trimellitate , Pentaerythritol triatalylate, pentaerythritol tetraatalylate, dipentaerythritol hexaatalate, N, N'-m phenylene bismaleimide, dipropargyl terephthalate, diaryl phthalate, tetraaryl terephthalamide, triallyl phosphate, etc. Is mentioned. Among them, those having three or more crosslinkable functional groups per molecule are more preferably triallyl isocyanurate, which is preferable from the viewpoint of easy crosslinking of the crosslinkable fluorine-containing polymer.
- the amount of the polyfunctional unsaturated compound to be used is about 0.05 to 10 parts by mass with respect to 100 parts by mass of the crosslinkable fluoropolymer, and a preferable lower limit is 0.5 part by mass, and a preferable upper limit is 0.5 parts by mass. The limit is 5 parts by weight.
- the cross-linking agent (B) may be used in any of the fluoropolymer liquid composition (AS) and the fluoropolymer liquid dispersion (AD) described below for the fluoropolymer liquid composition of the present invention.
- the content is preferably 0.05 to 20% by mass of the solid content of the fluoropolymer liquid composition of the present invention, and more preferably 0.1% by mass or more.
- the solid content of the fluoropolymer liquid composition is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the fluoropolymer liquid composition.
- the fluoropolymer liquid composition of the present invention comprises a fluoropolymer liquid (A) and at least one alcohol selected from the group consisting of methanol, ethanol, propanol and tetrafluoropropanol (A). It is preferable that it comprises C).
- the alcohol (C) is more preferably 2,2,3,3-tetrafluoropropanol, which is more preferably tetrafluoropropanol.
- the alcohol content of the alcohol (C) is preferably 10 to 80% by volume of the fluoropolymer solution (A).
- the fluoropolymer liquid composition may be composed of the fluoropolymer liquid (A), the alcohol (C), and the above-mentioned crosslinking agent (B).
- the fluoropolymer liquid composition of the present invention is preferably composed of a fluoropolymer liquid (A) and further a film-forming aid (D).
- a fluoropolymer liquid (A) is preferably composed of a fluoropolymer liquid (A) and further a film-forming aid (D).
- the film-forming auxiliary (D) By adding the film-forming auxiliary (D), the film-forming property is remarkably improved, and the production of a thin film by the casting method becomes easy.
- the film-forming auxiliary (D) is preferably an organic liquid that is compatible with water and has a boiling point of more than 100 ° C and not more than 300 ° C. If the temperature is below 100 ° C, the boiling point is usually the same as or lower than that of water, so that particles having a crosslinkable fluoropolymer (PD) force are dispersed in an aqueous dispersion medium!
- a fluoropolymer liquid dispersion (AD) is obtained by mixing water (ADA) with a film-forming auxiliary (D) and then evaporating water (organosol), the film-forming auxiliary (D) remains. It is not possible to remove the aqueous dispersion medium while performing the process.
- a preferred lower limit of the boiling point of the film-forming auxiliary (D) is 150 ° C, and a preferred upper limit is 250 ° C.
- the film-forming auxiliary (D) includes the fluoropolymer liquid (A) of the present invention, the fluoropolymer aqueous dispersion (ADA), or the crosslinkable fluoropolymer dissolved in an alcohol Z water mixed solvent.
- ADA fluoropolymer aqueous dispersion
- AS crosslinkable fluoropolymer dissolved in an alcohol Z water mixed solvent.
- AS fluoropolymer solution
- the above film-forming auxiliary (D), the precursor of the acid 'salt groups is SO NR 22 R 23 (R 22 and R 23
- the film-forming auxiliary (D) is preferably one in which 0.1 to 100 parts by mass is blended with respect to 1 part by mass of the crosslinkable fluoropolymer.
- the fluoropolymer liquid composition comprises the fluoropolymer liquid (A) and the film-forming auxiliary (D). And the cross-linking agent (B) described above, or the fluorine-containing polymer liquid (A), the cross-linking agent (B), and a film-forming auxiliary (D) and an alcohol ( C).
- the above-mentioned fluoropolymer liquid composition may be a composition that can act as the fluoropolymer liquid (A) and further with the active substance (E)! /.
- Examples of the active substance (E) include a catalyst and the like which will be described later for the method for producing a fluorine-containing crosslinked product of the present invention.
- the fluoropolymer liquid composition comprises a fluoropolymer liquid (A), an active substance (E), It may be at least one selected from the group consisting of a bridging agent (B), an alcohol (C) and a film-forming auxiliary (D)! /.
- the fluoropolymer liquid (A) is preferably a fluoropolymer liquid dispersion (AD).
- the solid content of the fluoropolymer liquid dispersion (AD) is preferably 2 to 80% by mass. It is preferred that As described above, when the fluoropolymer liquid composition of the present invention is composed of the fluoropolymer liquid dispersion (AD) and the crosslinker (B), the crosslinker (B) is used. It is preferably 0.1 to 20% by mass of the solid content of the composition.
- the fluoropolymer liquid dispersion (AD) is preferably an aqueous fluoropolymer dispersion (ADA) in which the liquid dispersion medium is an aqueous dispersion medium. Is preferably 10 to 100% by mass. If the water content of the aqueous dispersion medium is less than 10% by mass, dispersibility tends to deteriorate, which is not preferable. A more preferred lower limit is 40% by mass.
- the "aqueous dispersion medium” is a dispersion medium of a crosslinkable fluoropolymer (PD) and contains water.
- PD crosslinkable fluoropolymer
- any water-soluble organic solvent may be used as long as it is water-based.
- the aqueous dispersion medium may have additives such as a surfactant and a stabilizer usually used for an aqueous dispersion.
- the aqueous dispersion of the fluoropolymer has sufficient dispersion stability even if it does not substantially contain a surfactant. It has the property.
- the fluoropolymer aqueous dispersion may be the dispersion itself after polymerization, or may be included in the dispersion after polymerization.
- the crosslinkable fluorine-containing polymer is a fluorine-containing polymer precursor having an acid-acid salt type group precursor, it may be one obtained through the above-mentioned hydrolysis.
- the aqueous fluoropolymer dispersion (ADA) is preferably purified for the purpose of removing inorganic salts, low molecular weight impurities, ultra-low molecular weight polymers, and the like.
- the purification method include ultrafiltration.
- the fluoropolymer liquid dispersion (AD) is an aqueous dispersion of the fluoropolymer aqueous dispersion (AD).
- the fluoropolymer liquid (A) may be a fluoropolymer solution (AS).
- the crosslinkable fluoropolymer (PS) may be 0.1 to 10 of a fluoropolymer liquid composition. It is preferable that the content be in mass%.
- the crosslinking agent (B) is It is preferably 0.1 to 20% by mass of the solid content of the polymer liquid composition.
- the liquid medium obtained by dissolving the crosslinkable polymer (PS) in the fluoropolymer solution (AS) is a crosslinkable fluoropolymer (PS) having a precursor of an acid salt type group.
- PS crosslinkable fluoropolymer
- the fluorine-based solvent has a fluorine atom in the molecule and has a boiling point of 30 to 150 ° C.
- the above-mentioned fluorine-based solvent may be any of aromatic and aliphatic as long as it has a fluorine atom in the molecule and has a boiling point of 30 to 150 ° C.
- the fluorine-based solvent is not particularly limited, and includes, for example, chlorofluorocarbon, perfluorobenzene, and the like. Among them, the following general formula (VIII)
- the above-mentioned fluorinated fluorocarbon is preferably those in which the b force O or 1, c in the above general formulas (VIII) and (IX) is 1 or 2, CF
- Perfluorocyclobutane can also be used as the above-mentioned fluorofluorocarbon.
- Examples of the alcohol used in the alcohol Z water mixed solvent include methanol, ethanol, and isopropyl alcohol.
- the mixing ratio of alcohol in the alcohol Z water mixed solvent, 10: 90- 9 0: 10 (alcohol: water, volume 0/0) it is preferably a! /.
- the alcohol used in the alcohol / water mixed solvent can be the same as the alcohol (C) for improving the film-forming property described above. It is essential because it is essential for dissolving the crosslinkable fluoropolymer (PS). This is a concept that should be distinguished from non-alcohol (C).
- the dissolving treatment of the crosslinkable fluoropolymer (PS) in the fluoropolymer solution (AS) is performed at a boiling point of the fluorine-based solvent or the alcohol-Z water mixed solvent or higher, preferably 120 ° C or higher, more preferably It is performed at 150 ° C or higher. Therefore, the dissolution treatment is preferably performed in a pressure vessel.
- the time of the dissolution treatment depends on the temperature of the dissolution treatment, but is usually 10 minutes to 300 hours.
- the above boiling point and the temperature of the dissolution treatment are values at normal temperature and normal pressure.
- the above “normal temperature” is a normal temperature in a normal sense, and is usually 20 to 30 ° C.
- the liquid temperature was returned to-and normal temperature when heated to produce the fluoropolymer liquid dispersion (AD) or the fluoropolymer solution (AS). It can be prepared by adding a crosslinking agent (B) later.
- a crosslinking agent (B) By preparing the fluoropolymer liquid composition of the present invention by such a procedure, if the crosslinking agent (B) is added during the heating, the crosslinking reaction proceeds, and the desired fluoropolymer liquid composition is obtained. The problem of not being able to obtain is not caused.
- the fluoropolymer liquid composition of the present invention can be suitably used as a proton conductive material, particularly, a material for a proton conductive membrane.
- the process for producing a fluorine-containing crosslinked product of the present invention comprises applying the fluoropolymer liquid composition of the present invention to a substrate or impregnating a porous material, followed by removing the liquid medium and performing a crosslinking treatment.
- This is for producing a system crosslinked product.
- the fluorinated crosslinked product has a higher mechanical property than a film obtained without applying the fluorinated polymer liquid composition to a substrate or impregnating a porous material with a liquid medium and then performing a crosslinking treatment.
- the dimensional change due to the amount of moisture can be reduced, and as a result, the durability can be improved.
- the method for producing a fluorinated crosslinked product of the present invention is generally capable of industrially efficiently and stably producing a fluorinated crosslinked product by using the fluoropolymer liquid composition of the present invention. .
- the substrate is not particularly limited, and includes, for example, the above-described porous support, resin molded body, metal plate, and the like, and an electrolyte membrane, a porous carbon electrode, and the like used for a fuel cell or the like are preferable. .
- the porous material may be any of organic and inorganic materials as long as it has a porous structure.
- organic and inorganic materials for example, glass wool, ceramic, alumina, polytetrafluoroethylene resin, polytetrafluoroethylene molding Body stretched porous film, carbon, and various types of polymers.
- the liquid solvent can be usually removed by drying at normal temperature and under Z or heating.
- a film obtained by applying the above-mentioned fluoropolymer liquid composition to a substrate or impregnating a porous material into a film can be easily dissolved in water or the like if the above-mentioned drying is performed only at room temperature. It is preferable to perform drying under.
- the “under heating” in the removal of the liquid medium is usually 80 to 400 ° C., preferably 200 ° C. or more.
- the above-mentioned fluorine-containing crosslinked product may contain a substrate or a porous material. However, when it is applied to a substrate, it is peeled off from the surface of the substrate by immersion in water or the like. Alternatively, it can be obtained as a thin film containing no base material.
- the crosslinking treatment is preferably a crosslinking treatment using high energy.
- the cross-linking treatment using high energy is performed by heating, although it is preferable to perform heating, radiation irradiation, electron beam irradiation, or light irradiation, in terms of the availability of equipment and ease of handling. Is more preferable.
- the heating in the above crosslinking treatment is usually performed in an oven or a pressurizer at 100 to 400 ° C. for 1 minute to 10 hours.
- the crosslinking treatment is more preferably performed in a nitrogen atmosphere, which is preferably performed substantially in the absence of oxygen. In the presence of oxygen, radicals generated by cleavage of the peroxide compound are likely to be trapped by oxygen and hinder the progress of crosslinking.
- the method for producing a fluorinated crosslinked product of the present invention also comprises a step of applying the above-mentioned fluorinated polymer liquid composition of the present invention to a substrate or impregnating a porous material, and then removing the liquid medium to start a crosslinking reaction.
- a fluorine-containing crosslinked product may be produced by performing a crosslinking treatment using a peroxide compound as an agent.
- the fluorine-containing polymer liquid composition has a crosslinking functional group of -1 or -Br, and a polyfunctional crosslinking agent (B). Those using unsaturated compounds are preferred.
- the polyfunctional unsaturated compound triallyl isocyanate is preferred!
- the peroxide compound may have an appropriate decomposition rate at a temperature higher than the boiling point of the liquid medium and lower than the decomposition temperature of the crosslinkable fluoropolymer, and may have an evaporation temperature that does not readily evaporate.
- Preferred such compounds include, for example, di-t-butyl peroxyalkanes such as 2,5 dimethyl-2,5-di (t-butylperoxy) hexane.
- the mixing amount of the peroxide compound is preferably 0.001 to 15 parts by mass with respect to 100 parts by mass of the fluoropolymer. If the amount is less than 0.001 part by mass relative to 100 parts by mass of the fluoropolymer, the crosslinking reaction may be insufficient. If the amount exceeds 5 parts by mass with respect to 100 parts by mass of the fluoropolymer, the amount of peroxide residue increases and the strength may decrease.
- the more preferable lower limit of the amount of the peroxide compound is 0.01 part by mass and the more preferable upper limit is 1 part by mass with respect to 100 parts by mass of the fluoropolymer.
- the coating or impregnation is performed at a relatively low temperature and then the temperature is raised to perform a crosslinking treatment.
- the application or impregnation may be repeated alternately with the crosslinking treatment.
- the above-mentioned fluorine-based crosslinked product is not particularly limited, but can be used, for example, as proton conductivity, particularly as an electrolyte membrane, an ion exchange membrane, or the like.
- the film thickness can be 5 to 200 m.
- a preferable lower limit of the film thickness is 10 / zm, and a preferable upper limit of the film thickness is 50 ⁇ m.
- the membrane expansion rate is low even after being impregnated for a long time.
- a crosslinkable polymer having 18 mol% of perfluoro (ethylvinyl ether) sulfol chloride unit is provided.
- the film expansion coefficient is usually 10% by volume or less before the impregnation.
- the above-mentioned fluorine-containing crosslinked body is not particularly limited, and examples thereof include an electrolyte membrane of a polymer electrolyte fuel cell, a membrane for a lithium battery, a membrane for salt electrolysis, a membrane for water electrolysis, a membrane for hydrohalic acid electrolysis, and an oxygen concentrator. It can be used for membranes for instruments, membranes for humidity sensors, membranes for gas sensors, etc.
- the fluorine-containing crosslinked product obtained by the method for producing a fluorine-containing crosslinked product of the present invention may include an active substance-fixed crosslinked substance containing the active substance (E).
- the active substance (E) is not particularly limited as long as it has an activity in the active substance-fixed crosslinked body, and may be selected according to the purpose of the active substance-fixed crosslinked body of the present invention. Force appropriately selected For example, a catalyst can be suitably used.
- the catalyst is not particularly limited as long as it is a catalyst usually used as an electrode catalyst.
- a metal containing platinum, ruthenium, or the like examples include an organometallic complex in which at least one of its central metals is platinum or ruthenium.
- the metal containing platinum, ruthenium, etc. may be a ruthenium-containing metal, for example, ruthenium alone, but the platinum-containing metal, which is preferably a platinum-containing metal, is not particularly limited.
- the above catalyst is usually used by being supported on a carrier such as silica, alumina and carbon.
- the active substance-fixed crosslinked body usually contains a component such as an electrode constituting a solid polymer electrolyte fuel cell, and may be an electrode body for a solid polymer electrolyte fuel cell. preferable.
- the electrode assembly for a solid polymer electrolyte fuel cell is in contact with the electrolyte membrane. It can be used as a combined membrane-electrode assembly (MEA).
- the fluoropolymer liquid composition of the present invention has the above-described constitution, it is possible to industrially efficiently and stably produce a crosslinked body having excellent mechanical properties and durability and having a small dimensional change due to water content. it can.
- the resulting solution is impregnated with a polytetrafluoroethylene [PTFE] porous membrane (manufactured by Daikin Industries, Ltd.), air-dried for 30 minutes, and then dried in an oven set at 80-100 ° C for 30 minutes to obtain a coating film. Formed. After that, baking was performed at 200 ° C for 10 minutes, and the film was immersed in pure water to peel off the glass sheet thin film.
- the obtained thin film has a thickness of 15 ⁇ m.
- a part of the obtained aqueous fluoropolymer dispersion (BDA-1) is coagulated with nitric acid, washed with water and dried, and the crosslinkable fluoropolymer obtained has an iodine content of 0.1% and 300 ° C. C melting NM R force
- the estimated PFSF content is 18.5 mol 0 /. Met.
- the coated glass plate is sealed with aluminum foil and baked at 170 ° C for 10 minutes.After cooling, the aluminum foil cover is also taken out and immersed in pure water to peel off the glass plate thin film. Immediately removed from the water, air-dried at room temperature. The obtained thin film had a thickness. When the obtained thin film was immersed in pure water at room temperature for 15 hours, the swelling ratio (volume ratio) of the film was 10% or less.
- the PFSF content, from which the NMR force was also estimated, was 23.4 mol%, and the swelling ratio of the film was 160%.
- Example 3 When the same operation as in Example 3 was performed except that Perhexa 25B and TAIC were not added, when the obtained thin film was immersed in pure water at room temperature for 15 hours, the film was dissolved in water.
- Example 3 50 ml of the fluoropolymer dispersion obtained in Example 3 from which low molecular substances were removed and purified and concentrated by centrifugal ultrafiltration, 100 ml of pure water, and 20 mg of ammonium persulfate were placed in the same autoclave, and After sufficiently replacing the reaction vessel with xafluoropropylene [HFP] gas, pressurize the HFP gas to 20 g at 4 ° C and IMPa to TFE, then raise the temperature to 60 ° C, and co-polymerize TFE and HFP. The coalescence was block polymerized.
- HFP xafluoropropylene
- the glass plate with the coating was sealed with aluminum foil, baked at 170 ° C for 10 minutes, heated at 295 ° C for 5 minutes, cooled, taken out of the aluminum foil, and treated with pure water.
- the thin film was peeled off by immersion in the glass plate, immediately removed from water and air-dried at room temperature.
- the obtained thin film had a thickness of 15 m.
- the swelling ratio of the film was 0.
- the ion exchange capacity of the obtained membrane was measured by a titration method, it was 870 gZ equivalent.
- the content of PFSF estimated 300 ° C melt NMR force, 23. 0 mol 0/0, the swelling rate of the film was 5%.
- the fluoropolymer liquid composition of the present invention can be suitably used for, for example, an electrolyte membrane.
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Description
Claims
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US10/580,964 US20070141425A1 (en) | 2003-12-01 | 2004-12-01 | Liquid fluoropolymer composition and process for producing crosslinked fluorochemical |
JP2005515951A JP4839837B2 (ja) | 2003-12-01 | 2004-12-01 | 含フッ素ポリマー液状組成物及びフッ素系架橋体製造方法 |
US12/629,817 US7847001B2 (en) | 2003-12-01 | 2009-12-02 | Liquid fluoropolymer composition and process for producing crosslinked fluorochemical |
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US10/580,964 A-371-Of-International US20070141425A1 (en) | 2003-12-01 | 2004-12-01 | Liquid fluoropolymer composition and process for producing crosslinked fluorochemical |
US12/629,817 Continuation US7847001B2 (en) | 2003-12-01 | 2009-12-02 | Liquid fluoropolymer composition and process for producing crosslinked fluorochemical |
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JP2008540738A (ja) * | 2005-05-03 | 2008-11-20 | スリーエム イノベイティブ プロパティズ カンパニー | カルボニル末端基の量を減らしたフッ素化イオノマー |
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JP2008031464A (ja) * | 2006-07-04 | 2008-02-14 | Sumitomo Chemical Co Ltd | 高分子電解質エマルションおよびその用途 |
JP2009102490A (ja) * | 2007-10-22 | 2009-05-14 | Daikin Ind Ltd | 含フッ素ポリマー分散体及び含フッ素ポリマー分散体製造方法 |
JP2009158372A (ja) * | 2007-12-27 | 2009-07-16 | Samsung Sdi Co Ltd | 燃料電池用バインダー組成物、膜電極接合体、及び燃料電池 |
JP2012522882A (ja) * | 2009-04-06 | 2012-09-27 | インテグリス・インコーポレーテッド | 非脱湿潤性多孔質膜 |
WO2018235911A1 (ja) * | 2017-06-21 | 2018-12-27 | Agc株式会社 | 含フッ素重合体、官能基含有含フッ素重合体および電解質膜の製造方法 |
WO2022163814A1 (ja) * | 2021-01-28 | 2022-08-04 | ダイキン工業株式会社 | フルオロポリマー組成物の製造方法 |
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US7847001B2 (en) | 2010-12-07 |
US20100080931A1 (en) | 2010-04-01 |
US20070141425A1 (en) | 2007-06-21 |
JP4839837B2 (ja) | 2011-12-21 |
JP2010180408A (ja) | 2010-08-19 |
JP5573246B2 (ja) | 2014-08-20 |
JPWO2005054363A1 (ja) | 2007-06-28 |
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