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WO2013031634A1 - Copolymère séquencé, membrane électrolytique de type polymère, ensemble membrane-électrode, et pile à combustible à polymère solide - Google Patents

Copolymère séquencé, membrane électrolytique de type polymère, ensemble membrane-électrode, et pile à combustible à polymère solide Download PDF

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Publication number
WO2013031634A1
WO2013031634A1 PCT/JP2012/071307 JP2012071307W WO2013031634A1 WO 2013031634 A1 WO2013031634 A1 WO 2013031634A1 JP 2012071307 W JP2012071307 W JP 2012071307W WO 2013031634 A1 WO2013031634 A1 WO 2013031634A1
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Prior art keywords
polymer
block
polymer block
block copolymer
polymer electrolyte
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English (en)
Japanese (ja)
Inventor
謙太 俊成
竹友 山下
小野　友裕
須郷　望
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Kuraray Co Ltd
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Kuraray Co Ltd
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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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • 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
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C08F8/36—Sulfonation; Sulfation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H01M8/0293—Matrices for immobilising electrolyte solutions
    • 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
    • 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 block copolymer, a polymer electrolyte membrane, a membrane-electrode assembly, and a solid polymer fuel cell useful as a polymer electrolyte membrane of a solid polymer fuel cell.
  • Fuel cells have attracted attention as a clean power generation system that is friendly to the global environment. Fuel cells are classified into molten carbonate type, solid oxide type, phosphoric acid type, solid polymer type, etc., depending on the type of electrolyte.
  • Polymer electrolyte membranes used in polymer electrolyte fuel cells are required to have both high power generation characteristics under low humidity and mechanical strength when wet. Such a demand is particularly strong in a polymer electrolyte fuel cell using hydrogen as a fuel.
  • polymer electrolyte fuel cells have a tendency to be used at high temperatures, for example, around 100 ° C.
  • the polymer electrolyte membranes disclosed in Patent Documents 2 and 3 do not have sufficient heat resistance when used at high temperatures, and tend to have a low molecular weight associated with the decomposition of the polymer electrolyte membrane.
  • the present invention [1] A polymer block (A) having an ion conductive group, an amorphous olefin polymer block (B), and an aromatic vinyl compound polymer block (C) having no ion conductive group, and A block copolymer comprising 6 to 10 polymer blocks, wherein the polymer block (A) or the polymer block (C) is a terminal polymer block, and at least one of the terminal polymer blocks is a polymer.
  • a block copolymer which is the block (A) and the polymer block bonded to both ends of the polymer block (B) is only the polymer block (C); [2] The block copolymer according to the above [1], wherein the polymer block (A) is an aromatic vinyl compound polymer block having an ion conductive group; [3] The above [1] or [2], wherein the ion conductive group is a group represented by —SO 3 M or —PO 3 HM (wherein M represents a hydrogen atom, an ammonium ion or an alkali metal ion).
  • a block copolymer of [4] The block copolymer according to any one of the above [1] to [3], wherein the polymer block (B) is an amorphous olefin polymer block having a softening temperature of 30 ° C. or lower; [5]
  • the polymer block (C) is represented by the following general formula (a)
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 2 to R 4 each independently represents a hydrogen atom or an alkyl group having 3 to 8 carbon atoms
  • R 2 to R 4 At least one of these represents an alkyl group having 3 to 8 carbon atoms
  • a block copolymer that is compatible as a polymer electrolyte membrane of a polymer electrolyte fuel cell having both power generation characteristics and wet mechanical characteristics and improved heat resistance;
  • the polymer electrolyte membrane having excellent heat resistance, wet mechanical properties, and electrode bonding properties;
  • a membrane-electrode assembly including the polymer electrolyte membrane; and the membrane-electrode assembly described above,
  • a polymer electrolyte fuel cell having properties can be provided.
  • the block copolymer of the present invention comprises a polymer block (A) having an ion conductive group (hereinafter sometimes simply referred to as “polymer block (A)”), an amorphous olefin polymer block (B).
  • polymer block (B) and aromatic vinyl compound polymer block (C) having no ion conductive group
  • polymer block (C) A block copolymer comprising 6 to 10 polymer blocks, wherein the polymer block (A) or the polymer block (C) is a terminal polymer block, At least one of the terminal polymer blocks is a polymer block (A), and the polymer block bonded to both ends of the polymer block (B) is only the polymer block (C).
  • the block copolymer of the present invention is useful as a constituent component of the polymer electrolyte membrane. In this case, the block copolymer may be used alone or in combination of two or more.
  • other polymers, low molecular weight organic compounds, inorganic compounds, and the like may be included as long as the object of the present invention is not impaired.
  • the polymer block (A) which is one of the constituent components of the block copolymer of the present invention has a structure in which an ion conductive group is introduced into a polymer block (A 0 ) having no ion conductive group.
  • the block copolymer of the present invention is converted into a polymer block (A) in the block copolymer after producing a specific block copolymer having no ion conductive group, for example. It can be produced by selectively introducing an ion conductive group into the polymer block (A 0 ) at the power position.
  • polymer block (A 0 ) a polymer block having an aromatic vinyl compound unit as a repeating unit, a polyether ketone block, a polysulfide block, a polyphosphazene block, a polyphenylene block, a polybenzimidazole block, a polyether sulfone block, Polyphenylene oxide block, polycarbonate block, polyamide block, polyimide block, polyurea block, polysulfone block, polysulfonate block, polybenzoxazole block, polybenzothiazole block, polyphenylquinoxaline block, polyquinoline block, polytriazine block, polyacrylate block And polymer blocks such as polymethacrylate blocks.
  • a polymer block selected from an aromatic vinyl compound unit as a repeating unit, a polyether ketone block, a polysulfide block, a polyphosphazene block, a polyphenylene block, a polybenzimidazole block, a polyether sulfone block, and a polyphenylene oxide block. From the viewpoint of easy synthesis, a polymer block having an aromatic vinyl compound unit as a repeating unit is more preferable.
  • the aromatic ring of the aromatic vinyl compound unit is preferably a carbocyclic aromatic ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a pyrene ring.
  • aromatic vinyl compound capable of forming the above aromatic vinyl compound unit examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 2,4- Dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, vinylbiphenyl, vinylterphenyl, vinylnaphthalene, vinylanthracene, 4-phenoxystyrene, etc. Is mentioned.
  • the aromatic ring of the aromatic vinyl compound does not have a functional group that inhibits a reaction for introducing an ion conductive group.
  • the aromatic ring is a benzene ring
  • the hydrogen on the benzene ring especially hydrogen at the 4-position
  • an alkyl group especially an alkyl group having 3 or more carbon atoms
  • introduction may be difficult
  • the aromatic ring is not substituted with another functional group, or is substituted with a substituent such as an aryl group that can introduce an ion conductive group. .
  • the above aromatic vinyl compounds are aromatics having 8 to 15 carbon atoms such as styrene, ⁇ -methylstyrene, vinylbiphenyl and the like.
  • a vinyl compound is more preferable.
  • the hydrogen atom bonded to the ⁇ -position carbon atom ( ⁇ -carbon atom) of the aromatic ring is substituted with another substituent, and ⁇ -It may have a structure in which the carbon atom is a quaternary carbon atom.
  • substituent in which the hydrogen atom bonded to the ⁇ -carbon atom may be substituted include, for example, an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group).
  • Specific examples include ⁇ -methylstyrene, ⁇ -methyl-4-methylstyrene, ⁇ -methyl-4-ethylstyrene, ⁇ -methyl-2-methylstyrene, and 1,1-diphenylethylene.
  • the aromatic vinyl compound forming the polymer block (A 0 ) described above may be used alone or in combination of two or more.
  • one kind of aromatic vinyl compound is used alone, it is preferable to use any one of styrene, ⁇ -methylstyrene, and vinyl biphenyl.
  • copolymerizing a plurality of aromatic vinyl compounds in combination Are selected from the group consisting of styrene, ⁇ -methylstyrene, 4-methylstyrene, 4-ethylstyrene, ⁇ -methyl-4-methylstyrene, ⁇ -methyl-2-methylstyrene, and 1,1-diphenylethylene. More preferably, it is selected. Random copolymerization is preferable as a copolymerization method in the case where the polymer block (A 0 ) is formed by copolymerizing these plural types of aromatic vinyl compounds.
  • the polymer block (A 0 ) is a polymer block having an aromatic vinyl compound unit as a repeating unit, it contains one or more other monomer units as a repeating unit as long as the effects of the present invention are not impaired. You may go out.
  • monomers that can form such other monomer units include conjugated dienes having 4 to 8 carbon atoms (1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4- Hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-heptadiene, etc.), alkenes having 2 to 8 carbon atoms (ethylene, propylene, 1-butene, 2- Butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 1-heptene, 2-heptene, 1-octene, 2-octene, etc.),
  • the polymer block (A 0 ) is a polymer block having an aromatic vinyl compound unit as a repeating unit
  • the molecular weight per polymer block (A 0 ) is usually preferably in the range of 1,000 to 100,000, and in the range of 2,000 to 70,000, as the number average molecular weight in terms of standard polystyrene. More preferably, it is in the range of 3,000 to 50,000, more preferably in the range of 4,000 to 30,000, and in the range of 10,000 to 30,000. Is most preferred.
  • the molecular weight is large, the mechanical properties of the polymer electrolyte membrane tend to be excellent.
  • the molecular weight is 100,000 or less, the polymer electrolyte membrane can be easily formed and formed.
  • the molecular weight is 1,000 or more, microphase separation is likely to occur, and ion channels are easily formed. Therefore, ion conductivity tends to be high, and mechanical properties tend to be improved.
  • the polymer block (A) constituting the block copolymer of the present invention has an ion conductive group.
  • a proton etc. are mentioned as an ion in the case of mentioning ion conductivity by this invention.
  • the ion conductive group is not particularly limited as long as the polymer electrolyte membrane and the membrane-electrode assembly produced using the block copolymer can express sufficient ionic conductivity.
  • Examples of the ion conductive group that conducts a cation include a sulfonic acid group represented by —SO 3 M, —PO 3 HM, —CO 2 M (wherein M represents a hydrogen atom, an ammonium ion, or an alkali metal ion), A phosphonic acid group, a carboxyl group or a salt thereof can be used, and is represented by —SO 3 M or —PO 3 HM (wherein M is as defined above) from the viewpoint of exhibiting particularly high cation conductivity.
  • All the repeating units in the polymer block (A) do not need to have an ion conductive group, and the amount of the ion conductive group can be appropriately controlled according to the required performance.
  • a polymer block (A) Usually, it introduce
  • the ion conductive group is preferably on the aromatic ring from the viewpoint of facilitating ion channel formation.
  • the aromatic vinyl compound unit is a repeating unit, if there is an ion conductive group on the aromatic ring of the aromatic vinyl compound unit, the radical resistance of the block copolymer is improved.
  • the amount of ion-conducting group introduced is usually such that the ion exchange capacity of the block copolymer is 0 in order to exhibit sufficient ion conductivity for use as a polymer electrolyte membrane for a polymer electrolyte fuel cell.
  • An amount of .80 meq / g or more is preferred, an amount of 1.30 meq / g or more is more preferred, an amount of 1.40 meq / g or more is more preferred, and an amount of 1.80 meq / g or more is particularly preferred.
  • the amount is preferably 4.00 meq / g or less, and 3.60 meq / g or less. More preferable is an amount that is 3.20 meq / g or less.
  • the polymer block (A) may be cross-linked by a known method as long as the effects of the present invention are not impaired.
  • the polymer block (A) is cross-linked, the ion channel phase to be formed does not easily swell, the structure in the polymer electrolyte membrane is easily maintained, and the performance tends to be stable.
  • the polymer block (B) which is one of the components of the block copolymer of the present invention is an amorphous olefin polymer block.
  • the amorphous olefin polymer block refers to a polymer block having an olefin unit as a repeating unit and is amorphous.
  • the amorphous property can be confirmed by the measurement of dynamic viscoelasticity that there is no change in the storage elastic modulus derived from the crystalline olefin.
  • the polymer electrolyte membrane of the present invention using the block copolymer is elastic and flexible in the operating temperature range due to the presence of the polymer block (B), and the membrane-electrode assembly or solid In the production of a molecular fuel cell, it is excellent in moldability (assembling property, bonding property, tightening property, etc.).
  • the softening temperature of the polymer block (B) is preferably 50 ° C. or less, more preferably 40 ° C. or less, and more preferably 30 ° C. or less in view of a suitable use temperature range and molding temperature. Further preferred.
  • the repeating unit constituting such a polymer block (B) include alkene units having 2 to 8 carbon atoms, cycloalkene units having 5 to 8 carbon atoms, vinylcycloalkane units having 7 to 10 carbon atoms, and carbon numbers. Examples thereof include 7 to 10 vinylcycloalkene units, conjugated diene units having 4 to 8 carbon atoms, and conjugated cycloalkadiene units having 5 to 8 carbon atoms. These repeating units may be used individually by 1 type, or may use multiple types together.
  • alkene having 2 to 8 carbon atoms capable of forming the above repeating unit examples include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and 1-heptene.
  • the monomer for forming the polymer block (B) has a plurality of carbon-carbon double bonds
  • any of them may be used for polymerization, and in the case of a conjugated diene, a 1,2-bond Or a 1,4-bond.
  • a polymer block formed by polymerizing a conjugated diene usually retains a carbon-carbon double bond, but from the viewpoint of improving heat-resistant deterioration, a hydrogenation reaction is performed after the polymerization, and the carbon-carbon double bond is obtained. Is preferably hydrogenated.
  • the hydrogenation rate of such a carbon-carbon double bond is preferably 30 mol% or more, more preferably 50 mol% or more, and further preferably 95 mol% or more.
  • the polymer block (B) can eliminate or reduce the carbon-carbon double bond, thereby suppressing the deterioration of the polymer electrolyte membrane.
  • the hydrogenation rate of the carbon-carbon double bond can be calculated by a commonly used method such as an iodine number measurement method or 1 H-NMR measurement.
  • the polymer block (B) is flexible and flexible in the operating temperature range when the block copolymer is used for a polymer electrolyte membrane, and is a membrane-electrode assembly or a solid polymer fuel. From the viewpoint of excellent formability (assembly, bonding, fastening, etc.) in the production of batteries, alkene units having 2 to 8 carbon atoms, cycloalkene units having 5 to 8 carbon atoms, and vinylcyclohexane having 7 to 10 carbon atoms.
  • the polymer block is preferably a polymer block comprising at least one repeating unit selected from the group consisting of alkene units, conjugated diene units having 4 to 8 carbon atoms and conjugated cycloalkadiene units having 5 to 8 carbon atoms. More preferred is a polymer block comprising at least one repeating unit selected from alkene units having 8 to 8 carbon atoms and conjugated diene units having 4 to 8 carbon atoms. More preferably a polymer block comprising at least one repeating unit selected from the emission unit and a conjugated diene unit having 4 to 6 carbon atoms.
  • alkene unit is an isobutene unit, two structural units based on 1,3-butadiene units (1-butene unit, 2-butene unit), and three structural units based on isoprene units. (2-methyl-1-butene unit, 3-methyl-1-butene unit, 2-methyl-2-butene unit), and two types of structures based on 1,3-butadiene units due to their high flexibility
  • Three structural units based on units (1-butene units, 2-butene units) or isoprene units (2-methyl-1-butene units, 3-methyl-1-butene units, 2-methyl-2-butene units) ) Is most preferred.
  • conjugated diene units are 1,3-butadiene units and isoprene units.
  • the polymer block (B) has a saturated hydrocarbon structure. If so, an ion conductive group is hardly introduced into the polymer block (B), which is preferable. Therefore, when a hydrogenation reaction of a carbon-carbon double bond remaining in the polymer block (B) after polymerizing a block copolymer having no ion conductive group is performed, before introducing the ion conductive group. It is desirable to do this.
  • the polymer block (B) may contain other monomer units as long as the purpose of the polymer block (B) to impart elasticity to the block copolymer in the operating temperature range is not impaired.
  • aromatic vinyl compounds such as styrene and vinyl naphthalene
  • halogen-containing vinyl compounds such as vinyl chloride, vinyl esters (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, etc.), vinyl ethers (methyl vinyl ether, isobutyl vinyl ether, etc.)
  • Other monomer units formed from the above may be included.
  • the copolymerization method with other monomers is preferably random copolymerization. It is preferable that the usage-amount of these other monomers is 5 mol% or less of the monomer which forms a polymer block (B).
  • the molecular weight per polymer block (B) is preferably in the range of 5,000 to 250,000, and in the range of 7,000 to 150,000, as the number average molecular weight in terms of standard polystyrene. More preferably, it is in the range of 8,000 to 100,000, more preferably in the range of 10,000 to 70,000.
  • the polymer block (C) which is one of the components of the block copolymer of the present invention, is an aromatic vinyl compound polymer having no ion conductive group, and has a polarity different from that of the polymer block (A). Microphase separation is likely to occur due to the difference and the chemical structure of the polymer block (B).
  • the polymer block (C) When the polymer block (C) is in a microphase-separated state with the polymer block (A) and the polymer block (B), and the softening temperature (that is, when the polymer block (C) becomes a polymer independently) (Softening temperature) of the block copolymer, it functions as a constraining phase in the block copolymer.
  • the softening temperature of the polymer block (C) is 20 in comparison with the softening temperature of the polymer block (B) (that is, the softening temperature of the polymer when the polymer block (B) independently becomes a polymer). It is preferable that the polymer block is higher than °C. From the viewpoint of functioning as a constraining phase in a wide use temperature range, it is more preferably higher than the softening temperature of the polymer block (B), more preferably higher than 70 °C. More preferably. From the same viewpoint, the softening temperature of the polymer block (C) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 100 ° C. or higher.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 2 to R 4 each independently represents a hydrogen atom or an alkyl group having 3 to 8 carbon atoms
  • R 2 to R 4 Is preferable from the viewpoint of easy synthesis and functioning as a constrained phase, wherein at least one represents an alkyl group having 3 to 8 carbon atoms).
  • the presence of R 2 to R 4 allows the polymer block Introduction of an ion conductive group into (C) is hindered.
  • the softening temperature of the polymer block is relatively high, the operating temperature range can be widened.
  • Examples of the aromatic vinyl compound represented by the general formula (a) for forming an aromatic vinyl compound unit include 4-n-propylstyrene, 4-isopropylstyrene, 4-n-butylstyrene, and 4-isobutyl. Examples thereof include styrene, 4-tert-butylstyrene, 4-n-octylstyrene, ⁇ -methyl-4-tert-butylstyrene, ⁇ -methyl-4-isopropylstyrene, and the like.
  • the copolymerization method is preferably random copolymerization.
  • the polymer block (C) may contain one or more other monomer units as long as the effects of the present invention are not impaired.
  • monomers that can form such other monomer units include conjugated dienes having 4 to 8 carbon atoms (1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4 -Hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-heptadiene, etc.), alkenes having 2 to 8 carbon atoms (ethylene, propylene, 1-butene, 2 -Butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 1-heptene, 2-heptene, 1-octene, 2-octene, etc.), (meth) acrylic acid esters ((meth) acrylic) Methyl ester, ethyl (meth
  • the molecular weight per polymer block (C) is preferably in the range of 1,000 to 50,000 as the number average molecular weight in terms of standard polystyrene, and preferably in the range of 1,500 to 30,000. More preferably, it is in the range of 2,000 to 20,000.
  • the molecular weight of the polymer block (C) is large, the mechanical properties of the polymer electrolyte membrane tend to be excellent, but when it is 50,000 or less, the moldability and film formability of the polymer electrolyte are good. Moreover, if it is 1,500 or more, it will become the tendency for a mechanical characteristic to improve.
  • the block copolymer of the present invention is a block copolymer comprising the aforementioned polymer block (A), polymer block (B) and polymer block (C), and comprising 6 to 10 polymer blocks.
  • the polymer block (A) or the polymer block (C) is a terminal polymer block, at least one of the terminal polymer blocks is a polymer block (A), and the polymer block (B)
  • the polymer block bonded to both ends is only the polymer block (C).
  • the bond mode of the polymer block in the block copolymer is represented by the following formula (b), formula (c), or formula (d).
  • a -... [CBC] ...- C (b) A -...
  • both ends are a polymer block (A) and a polymer block (C), and the polymer block (C) is bonded to both ends of the polymer block (B) between them [C— BC] unit is present.
  • both ends are polymer blocks (A), and there are [CBC] units in which the polymer block (C) is bonded to both ends of the polymer block (B). ing.
  • both ends are a polymer block (A) and a polymer block (C), the polymer block (B) is bonded to the terminal polymer block (C), and the polymer block ( [CBC] unit having another polymer block (C) bonded to the other end of B) is present.
  • At least one of the terminal polymer blocks is the polymer block (A), which is advantageous from the viewpoint of improving the ionic conductivity of the polymer electrolyte membrane.
  • the stability of the emulsion when the polymer electrolyte membrane is produced from the emulsion of the block copolymer of the present invention described later is increased.
  • the heat resistance is improved by the presence of the [CBC] unit in the block copolymer of the present invention.
  • bonding mode of the polymer block in the block copolymer of the present invention include: ABCBCCA, ACCBBCBC, ACAA 6-component block copolymers such as C—B—C; 7-component block copolymers such as A—C—B—C—A—C—A, A—C—B—C—B—C—A; A-C-B-C-A-C-A-C, A-C-A-C-A-A-C-B-C, A-C-A--C--B--C--A--C, A-- CBCBCBCAC, ACBCBCACBCBC, ACCABCBCBC, AC- 8-component block copolymers such as BCBCBCBC; ABCBCCACACA, ACACABCBC A-C-A, A-C-A-C-C-C-B-C-A, A-C-B--C--A, A-C-B--C-BC 9-
  • the number average molecular weight of the block copolymer of the present invention is not particularly limited, but is in the range of 11,000 to 500,000 as the number average molecular weight in terms of standard polystyrene when no ion conductive group is introduced. More preferably, it is in the range of 14,000 to 450,000, more preferably in the range of 17,000 to 350,000, and particularly preferably in the range of 20,000 to 300,000. .
  • the mass ratio of the total amount of the polymer block (A 0 ) and the total amount of the polymer block (C) is preferably 80:20 to 10:90, more preferably 75:25 to 15:85. 65:35 to 20:80 is more preferable.
  • the mass ratio of the polymer block (C) is within the above range, it becomes easy to maintain the strength when dried and wet.
  • the mass ratio of the polymer block (A 0 ) is within the above range, the amount of ion conductive groups introduced into the polymer block increases, and the ion conductivity when the polymer electrolyte membrane is formed is increased. It can be secured sufficiently.
  • the mass ratio of the total amount of the polymer block (B) and the total amount of the polymer block (C) is preferably 85:15 to 5:95, more preferably 75:25 to 10:90, More preferably, it is 70:30 to 12:88.
  • the mass ratio of the polymer block (C) is in the above range, the strength as the polymer electrolyte membrane is easily maintained.
  • the mass ratio of the said polymer block (B) is the said range, it will become easy to hold
  • the production method of the block copolymer of the present invention is not particularly limited, and a known method can be used. After producing a block copolymer having no ion conductive group, the ion conductive group is introduced. The method is preferred.
  • the method for producing a block copolymer of the present invention comprises a polymer block (A 0 ), a polymer block (B), the type of monomer units constituting the polymer block (C), and the molecular weight of each polymer block.
  • the radical polymerization method, the anionic polymerization method, the cationic polymerization method, the coordination polymerization method, and the like can be appropriately selected depending on the above, but the radical polymerization method, the anionic polymerization method, and the cationic polymerization method are preferable industrially.
  • the so-called living polymerization method is preferred from the viewpoint of molecular weight control, molecular weight distribution control, polymer structure control, polymer block (A 0 ), polymer block (B), and ease of bonding of polymer block (C).
  • the living radical polymerization method, the living anion polymerization method, and the living cation polymerization method are preferable.
  • a polymer block (C) having an aromatic vinyl compound such as 4-tert-butylstyrene as a main repeating unit, a polymer block (A 0 ) having an aromatic vinyl compound as a main repeating unit such as styrene, and a conjugated diene A method for producing a block copolymer having no ion conductive group composed of a polymer block (B) composed of, etc. will be described.
  • the living anion polymerization method is preferred from the viewpoint of the molecular weight distribution, the ease of bonding of the polymer block (C), the polymer block (B) and the polymer block (A 0 ).
  • styrene is polymerized using an anionic polymerization initiator in a cyclohexane solvent at a temperature of 10 to 100 ° C., and then an aromatic vinyl compound such as 4-tert-butylstyrene, a conjugated diene, 4 Examples thereof include a method in which -tert-butylstyrene, styrene, and 4-tert-butylstyrene are sequentially polymerized to obtain an A 0 -C—B—C—A 0 —C type 6-block copolymer.
  • the block copolymer having no ion-conductive group produced in this way has a conjugated diene unit having 4 to 8 carbon atoms constituting the polymer block (B) before introducing the ion-conductive group. It is preferable to hydrogenate the carbon-carbon double bond that it has.
  • the polymer block after the hydrogenation reaction becomes the amorphous olefin polymer block (B) of the block copolymer of the present invention.
  • a method of the hydrogenation reaction a solution of a copolymer obtained by anionic polymerization or the like is charged into a pressure vessel, a Ziegler catalyst such as Ni / Al is added, and the hydrogenation reaction is performed in a hydrogen atmosphere. A method can be illustrated.
  • a method for obtaining the block copolymer of the present invention by introducing an ion conductive group into the polymer block (A 0 ) of the block copolymer having no ion conductive group will be described.
  • a method for introducing a sulfonic acid group into a block copolymer having no ion conductive group (sulfonation) will be described.
  • sulfonation a known sulfonation method can be applied. For example, a solution or suspension is prepared from the block copolymer and an organic solvent, and a sulfonating agent is added, or a gas is directly applied to the block copolymer. And the like, and the like.
  • the sulfonating agent examples include sulfuric acid, a mixture of sulfuric acid and aliphatic acid anhydride, chlorosulfonic acid, a mixture of chlorosulfonic acid and trimethylsilyl chloride, sulfur trioxide, a mixture of sulfur trioxide and triethyl phosphate, Aromatic organic sulfonic acids represented by 2,4,6-trimethylbenzenesulfonic acid and the like can be mentioned.
  • the organic solvent include halogenated hydrocarbons such as methylene chloride, linear aliphatic hydrocarbons such as hexane, and cyclic aliphatic hydrocarbons such as cyclohexane. These may be used individually by 1 type, or may be used in mixture of multiple types.
  • the reaction solution is poured into water to precipitate the block copolymer, and then the organic solvent and water are used. And a method in which water as a terminator is gradually added to the reaction solution to precipitate the block copolymer, and then the solvent and water are distilled off.
  • a method of gradually adding water to the reaction solution to precipitate the block copolymer is preferable.
  • a method (phosphonation) for introducing a phosphonic acid group into a block copolymer having no ion conductive group will be described.
  • a known method can be applied to the phosphonation. For example, a solution or suspension is prepared from the block copolymer and an organic solvent, and anhydrous aluminum chloride and chloromethyl ether are added to introduce a halomethyl group into the aromatic ring. Then, a method of introducing phosphonic acid groups by adding phosphorus trichloride and anhydrous aluminum chloride and further carrying out a hydrolysis reaction can be mentioned.
  • a solution or suspension is prepared from the block copolymer and an organic solvent, phosphorus trichloride and anhydrous aluminum chloride are added, phosphinic acid groups are introduced into the aromatic ring, and nitric acid is added to oxidize the phosphinic acid groups. And a method for forming a phosphonic acid group.
  • the ion exchange capacity of the block copolymer is preferably 0.80 meq / g or more, more preferably 1.30 meq / g or more, still more preferably 1.40 meq / g or more, particularly Preferably, it is 1.80 meq / g or more, while it is preferably 4.00 meq / g or less, more preferably 3.80 meq / g or less, and even more preferably 3.60 meq / g or less. It is desirable that When the ion exchange capacity is in the above range, practical ion conduction performance can be obtained.
  • the ion exchange capacity of the block copolymer of the present invention, or the sulfonation rate or phosphonation rate of the aromatic vinyl compound unit in the polymer block (A) is determined by acid value titration method, infrared spectroscopic measurement, nuclear magnetic resonance spectrum. It can be calculated using analytical means such as ( 1 H-NMR spectrum) measurement.
  • the ion conductive group such as a sulfonic acid group or a phosphonic acid group may be a salt neutralized with a metal ion such as an alkali metal ion or a counter ion such as an ammonium ion.
  • the polymer electrolyte membrane of the present invention comprises the block copolymer of the present invention as a constituent component.
  • the polymer electrolyte membrane of the present invention can be added to various additives such as a softening agent, a stabilizer, a light stabilizer, an antistatic agent, a release agent, a flame retardant, a pigment, a dye, and a whitening agent unless the effects of the present invention are impaired.
  • a softening agent such as a stabilizer, a light stabilizer, an antistatic agent, a release agent, a flame retardant, a pigment, a dye, and a whitening agent unless the effects of the present invention are impaired.
  • An agent or the like may be contained. These may contain only 1 type, respectively, and may contain multiple types in combination.
  • softener examples include petroleum softeners such as paraffinic, naphthenic or aromatic process oils, paraffin, vegetable oil softeners, or plasticizers.
  • Stabilizers include phenol-based stabilizers, sulfur-based stabilizers, phosphorus-based stabilizers, and the like.
  • phenol-based stabilizers include 2,6-di-t-butyl-p-cresol, pentaerythryl- Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 -Hydroxybenzyl) benzene, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxy) Phenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazin
  • Examples of the light stabilizer include compounds having a 2,2,6,6-tetraalkylpiperidine skeleton or hindered amines.
  • Examples of hindered amines include dimethyl succinate / 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly ((6- (1,1,3 , 3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-pipedyl) imino) hexamethylene ((2,2, 6,6-tetramethyl-4-pipedyl) imino)), 2- (2,3-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2, 6,6-pentamethyl-4-piperidyl), 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl
  • antistatic agent examples include stearoamidopropyldimethyl- ⁇ -hydroxyethylammonium nitrate.
  • Examples of the mold release agent include higher alcohol and / or glycerin monoester.
  • Examples of the higher alcohol include cetyl alcohol and stearyl alcohol.
  • Examples of the glycerin monoester include monoglycerides of higher fatty acids such as stearic acid monoglyceride and stearic acid diglyceride.
  • the flame retardant examples include organic halogen flame retardants such as tetrabromobisphenol A, decabromodiphenyl oxide, and brominated polycarbonate; non-halogen flame retardants such as antimony oxide, aluminum hydroxide, zinc borate, and tricresyl phosphate. Is mentioned.
  • pigments, dyes, and brighteners examples include terphenyl; fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent brighteners, and fluorescent bleaching agents.
  • the content of the block copolymer in the polymer electrolyte constituting the polymer electrolyte membrane of the present invention is preferably 90% by mass or more, and 93% by mass or more. More preferably, it is more preferably 95% by mass or more.
  • the polymer electrolyte membrane of the present invention preferably has a thickness in the range of 5 to 200 ⁇ m from the viewpoint of performance, membrane strength, handling properties, etc. required as a polymer electrolyte membrane for a solid polymer fuel cell, A range of 7 to 100 ⁇ m is more preferable, and a range of 8 to 70 ⁇ m is more preferable. If the film thickness is 5 ⁇ m or more, the mechanical properties and gas barrier properties of the film tend to be sufficient. On the other hand, if the film thickness is 200 ⁇ m or less, the film resistance becomes small and sufficient ion conductivity is exhibited, so that power generation characteristics tend to be good.
  • the block copolymer of the present invention and, if necessary, the above-mentioned additives are mixed with an appropriate solvent, and the block copolymer of 5% by mass or more is mixed.
  • a polymer electrolyte having a desired thickness is prepared by preparing a uniform solution or emulsified solution of the coalescence, applying it to a release-treated PET film using a coater or applicator, and removing the solvent under appropriate conditions. Examples thereof include a method for obtaining a film.
  • the solvent used for the preparation of the homogeneous solution of the block copolymer is not particularly limited as long as a solution having a viscosity capable of solution coating can be prepared.
  • halogenated hydrocarbons such as methylene chloride; toluene, xylene, benzene Aromatic hydrocarbons such as hexane, heptane, etc .; linear aliphatic hydrocarbons such as hexane and heptane; cycloaliphatic hydrocarbons such as cyclohexane; ethers such as tetrahydrofuran; methanol, ethanol, propanol, 2-propanol, butanol, isobutyl alcohol, etc. Alcohol.
  • a tetrahydrofuran solvent, a mixed solvent of tetrahydrofuran and methanol are preferable, and a mixed solvent of toluene and isobutyl alcohol and a mixed solvent of toluene and 2-propanol are particularly preferable.
  • the block copolymer of the present invention has a protective colloid forming ability because the polymer block (A) having an ion conductive group is hydrophilic and the polymer block (B) and the polymer block (C) are hydrophobic.
  • An emulsion can be obtained without using a surfactant. Further, by using a polar solvent such as water as the dispersion medium, particles having an ion conductive group having a high polarity in the outer shell can be easily produced.
  • a known method can be used as a method for preparing the emulsion.
  • the block copolymer of the present invention is phase-separated within the particles, so that all the ion conductive groups are not exposed in the outer shell, so that the ion conductivity is improved. May have undesirable effects. Therefore, although it depends on the molecular weight of the block copolymer and the ratio of each polymer block, it is desirable to finely disperse until the average particle size becomes 1 ⁇ m or less.
  • a known method can be used as a fine dispersion method. From the viewpoint of preventing impurities from mixing, a high-pressure collision method or the like is preferable, not a method that does not use media such as balls for grinding in a ball mill.
  • the solvent is removed under appropriate conditions, and the desired thickness is obtained.
  • a polymer electrolyte membrane is obtained.
  • the conditions for removing the solvent may be in a temperature range in which ion conductive groups such as sulfonic acid groups possessed by the block copolymer do not fall off. A plurality of temperatures may be combined, or drying under ventilation and drying under reduced pressure may be combined.
  • a method of removing the solvent in a short time by hot air drying in the range of 60 to 100 ° C. a method of removing the solvent in a short time by hot air drying of about 100 to 140 ° C., or about 1 to 3 hours at 25 ° C.
  • Examples include a method of drying and then drying with hot air at 100 ° C. for a short time, a method of drying at about 25 ° C. for about 1 to 3 hours, and then drying at about 25 to 40 ° C. under reduced pressure for about 1 to 12 hours. It is done. From the viewpoint of easy preparation of a polymer electrolyte membrane having good mechanical properties, a method of removing the solvent by hot air drying at about 60 to 100 ° C.
  • a method of drying for about an hour or the like is preferably used.
  • the membrane-electrode assembly of the present invention includes the above-described polymer electrolyte membrane of the present invention.
  • a catalyst paste containing an ion conductive binder, a conductive catalyst carrier, and a dispersion medium can be obtained by a printing method or a spray method.
  • a joined body of the catalyst layer and the gas diffusion layer is formed, and each of the catalyst layers is in contact with the polymer electrolyte membrane with the two joined bodies thus formed.
  • the ion conductive group may be converted to a proton type by acid treatment after joining, in a state where the ion conductive group is made into a salt with a metal such as sodium.
  • ion conductive binder used in the production of the membrane-electrode assembly
  • perfluorosulfonic acid such as “Nafion” (registered trademark, manufactured by DuPont) and “Gore-select” (registered trademark, manufactured by Gore).
  • Polymers, sulfonated polyethersulfone, sulfonated polyetherketone, polybenzimidazole impregnated with phosphoric acid or sulfuric acid, and the like can be used.
  • the same structure as the polymer electrolyte membrane (polymer repeating unit, copolymerization ratio, molecular weight, ion conductive group, ion exchange capacity) Etc. are common or similar; in particular, it is preferable to use an ion conductive binder having a repeating unit of a polymer and an ion conductive group common or similar).
  • Examples of the conductive catalyst carrier constituting the catalyst layer formed in the membrane-electrode assembly include carbon blacks such as furnace black, channel black and acetylene black, and carbon materials such as activated carbon and graphite. These may be used individually by 1 type, or may use multiple types together.
  • the catalyst metal only needs to have an action of promoting the oxidation reaction of fuel such as hydrogen or methanol and the reduction reaction of oxygen.
  • fuel such as hydrogen or methanol
  • the particle size of the catalytic metal is usually 10 to 300 angstroms. It is advantageous in terms of cost to use these on the conductive catalyst carrier described above.
  • the catalyst layer may contain a water repellent such as polytetrafluoroethylene, polyvinylidene fluoride, styrene butadiene copolymer, polyether ether ketone, etc., if necessary.
  • the gas diffusion layer of the membrane-electrode assembly is made of a material having conductivity and gas permeability, and examples of such a material include porous materials made of carbon fibers such as carbon paper and carbon cloth. Moreover, in order to improve the water repellency of the gas diffusion layer, a water repellency treatment may be performed.
  • the polymer electrolyte fuel cell of the present invention includes a pure hydrogen type using hydrogen, a methanol reforming type using hydrogen obtained by reforming methanol, and a hydrogen obtained by reforming natural gas, depending on the fuel used. Can be classified into a natural gas reforming type using hydrogen, a gasoline reforming type using hydrogen obtained by reforming gasoline, a direct methanol type using methanol directly.
  • the amorphous nature of the polymer block (B) was judged.
  • the polymer block (B) was amorphous for all the polymer electrolyte membranes obtained in the following Examples and Comparative Examples.
  • the softening temperature of the polymer block (B) and the polymer block (C) was measured from the peak temperature of the loss tangent.
  • the peak temperature of the loss tangent of a polymer block (C) and a polymer block (A) is near, it divided
  • Reference Examples 1 to 6 are production examples of block copolymers composed of polystyrene, hydrogenated polyisoprene and poly (4-tert-butylstyrene).
  • Reference Example 1 After drying, 664 ml of dehydrated cyclohexane and 1.65 ml of sec-butyllithium (1.0 mol / L cyclohexane solution) were added to an autoclave with an internal volume of 1400 ml purged with nitrogen, and then stirred at 60 ° C.
  • the number average molecular weight of the obtained STSTITST-1 was 196,000, the 1,4-bond content of the polyisoprene moiety determined from 1 H-NMR (400 MHz) was 93.8%, and the content of styrene units was 35 The content of .4 mass% and 4-tert-butylstyrene unit was 24.4 mass%.
  • a cyclohexane solution of STSTITST-1 obtained above was prepared and placed in a pressure vessel that was purged with nitrogen. Using a Ni / Al Ziegler catalyst, a hydrogen pressure of 0.5 to 1.0 MPa at 70 ° C. was applied. A timed hydrogenation reaction was carried out, from a polymer block (A 0 ) made of polystyrene, a polymer block (B) made of hydrogenated polyisoprene, and a polymer block (C) made of poly (4-tert-butylstyrene).
  • STSTITST-2 Poly (4-tert-butylstyrene)- - polystyrene -b- poly (4-tert-butylstyrene) (hereinafter, abbreviated as STSTITST-2) was synthesized.
  • the number average molecular weight of STSTITST-2 obtained was 126,000
  • the 1,4-bond content of the polyisoprene moiety determined from 1 H-NMR (400 MHz) was 93.7%
  • the content of styrene units was 35
  • the content of 4% by mass and 4-tert-butylstyrene unit was 34.4% by mass.
  • a cyclohexane solution of STSTITST-2 obtained above was prepared, put into a pressure vessel with nitrogen substitution, and Ni / Al Ziegler catalyst was used at 0.5 to 1.0 MPa under hydrogen pressure at 70 ° C. for 18 hours.
  • a timed hydrogenation reaction was carried out, from a polymer block (A 0 ) made of polystyrene, a polymer block (B) made of hydrogenated polyisoprene, and a polymer block (C) made of poly (4-tert-butylstyrene).
  • Polystyrene-b-poly (4-tert-butylstyrene) -b-polyisoprene-b-poly (4-tert-butylstyrene) -b-polystyrene-b-poly (4-tert-butylstyrene) (hereinafter, (Abbreviated as STITST).
  • the number average molecular weight of the obtained STITST was 79,000, the 1,4-bond content of the polyisoprene moiety determined from 1 H-NMR (400 MHz) was 94.2%, and the content of styrene units was 35.5. The content of 4% by mass and 4-tert-butylstyrene unit was 39.6% by mass.
  • the copolymer polystyrene-b-poly (4-tert-butylstyrene) -b-hydrogenated polyisoprene-b-poly (4-tert-butylstyrene) -b-polystyrene-b-poly (4-tert- Butylstyrene) hereinafter abbreviated as STETST.
  • Tert-butylstyrene 21.6 ml, styrene 30.1 ml, isoprene 86.9 ml, styrene 30.1 ml and 4-tert-butylstyrene 21.6 ml were sequentially added and polymerized to obtain poly (4-tert-butylstyrene)- b-Polystyrene-b-polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene) (hereinafter abbreviated as TSIST) was synthesized.
  • TSIST poly (4-tert-butylstyrene)- b-Polystyrene-b-polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • the number average molecular weight of the obtained TSIST was 79,100
  • the 1,4-bond content of the polyisoprene moiety determined from 1 H-NMR (400 MHz) was 94.0%
  • the content of styrene units was 35.0.
  • the content of 4% by mass and 4-tert-butylstyrene unit was 24.0% by mass.
  • the cyclohexane solution of TSIST obtained above was prepared, put into a pressure vessel that was purged with nitrogen, and hydrogenated at a hydrogen pressure of 0.5 to 1.0 MPa and 70 ° C. for 18 hours using a Ni / Al Ziegler catalyst.
  • TSEST poly (4-tert-butylstyrene)
  • the number average molecular weight of STITS obtained was 90,000, the 1,4-bond content of the polyisoprene moiety determined from 1 H-NMR (400 MHz) was 94.0%, and the content of styrene units was 32.8. The content of mass% and 4-tert-butylstyrene unit was 26.5 mass%.
  • STETS polystyrene
  • the number average molecular weight of the obtained STIT was 53,700
  • the 1,4-bond content of the polyisoprene moiety determined from 1 H-NMR (400 MHz) was 94.0%
  • the content of styrene units was 24.0.
  • the content of 4% by mass and 4-tert-butylstyrene unit was 45.0% by mass.
  • a cyclohexane solution of STIT obtained above was prepared and added to a pressure vessel that was purged with nitrogen, and then a Ni / Al Ziegler catalyst was used at a hydrogen pressure of 0.5 to 1.0 MPa at 70 ° C. for 18 hours.
  • a hydrogenation reaction is performed, and a polymer block (A 0 ) made of polystyrene, a polymer block (B) made of hydrogenated polyisoprene, and a polymer block (C) made of poly (4-tert-butylstyrene)
  • a block copolymer polystyrene-b-poly (4-tert-butylstyrene) -b-hydrogenated polyisoprene-b-poly (4-tert-butylstyrene) (hereinafter abbreviated as STET) was obtained.
  • An attempt was made to calculate the amount of residual double bonds derived from the resulting STET polyisoprene by 1 H-NMR (400 MHz), which was below the detection limit.
  • the number average molecular weight of the obtained STIT was 79,000, the 1,4-bond content of the polyisoprene moiety determined from 1 H-NMR (400 MHz) was 94.0%, and the content of styrene units was 35.8. The content of 4% by mass and 4-tert-butylstyrene unit was 39.4% by mass.
  • a cyclohexane solution of STIT obtained above was prepared and added to a pressure vessel that was purged with nitrogen, and then a Ni / Al Ziegler catalyst was used at a hydrogen pressure of 0.5 to 1.0 MPa at 70 ° C. for 18 hours.
  • a hydrogenation reaction is performed, and a polymer block (A 0 ) made of polystyrene, a polymer block (B) made of hydrogenated polyisoprene, and a polymer block (C) made of poly (4-tert-butylstyrene)
  • a block copolymer polystyrene-b-poly (4-tert-butylstyrene) -b-hydrogenated polyisoprene-b-poly (4-tert-butylstyrene) (hereinafter abbreviated as STET) was obtained.
  • An attempt was made to calculate the amount of residual double bonds derived from the resulting STET polyisoprene by 1 H-NMR (400 MHz), which was below the detection limit.
  • Example 1 (Production of block copolymer (1)) After heating and drying, 72.7 ml of methylene chloride and 36.4 ml of acetic anhydride were added to a 200 ml three-necked flask purged with nitrogen, and 16.3 ml of concentrated sulfuric acid was added dropwise with stirring at 0 ° C., and further at 0 ° C. for 60 minutes. A sulfonating agent was prepared by stirring. On the other hand, 20 g of the block copolymer STSTETST-1 obtained in Reference Example 1 was placed in a 3 L glass reactor equipped with a stirrer, and the system was purged with nitrogen. And stirred for 4 hours to dissolve.
  • the washing and filtration operations are repeated until there is no change in the pH of the washing water, and the resulting block copolymer is dried under reduced pressure to obtain the sulfonated STSTSTST-1 (hereinafter referred to as the block copolymer) which is the block copolymer of the present invention.
  • Polymer (1) was obtained.
  • the sulfonation rate of the benzene ring of the styrene unit of the obtained block copolymer (1) was 100 mol% from 1 H-NMR (400 MHz) analysis, and the ion exchange capacity was 2.65 meq / g from the titration result. It was.
  • Example 2 (Production of block copolymer (2)) After drying, 262 ml of methylene chloride and 131 ml of acetic anhydride were added to a three-necked flask with an internal volume of 1000 ml purged with nitrogen, and 58.7 ml of concentrated sulfuric acid was added dropwise with stirring at 0 ° C., followed by stirring at 0 ° C. for 60 minutes. To prepare a sulfonating agent.
  • the sulfonation rate of the benzene ring of the styrene unit of the obtained block copolymer (2) was 100 mol% from 1 H-NMR (400 MHz) analysis, and the ion exchange capacity was 2.65 meq / g from the titration result.
  • Example 3 (Production of block copolymer (3)) After drying, 14.3 ml of methylene chloride and 28.5 ml of acetic anhydride were added to a 100 ml three-necked flask purged with nitrogen, and 16.6 ml of concentrated sulfuric acid was added dropwise with stirring at 0 ° C. A sulfonating agent was prepared by stirring for a minute. On the other hand, 20 g of the block copolymer STETST obtained in Reference Example 3 was placed in a 3 L glass reaction vessel equipped with a stirrer and purged with nitrogen, and then 250 ml of methylene chloride was added and stirred at room temperature for 4 hours. Dissolved.
  • block copolymer sulfonated STETST (hereinafter referred to as block copolymer) of the block copolymer of the present invention.
  • block copolymer (3) The sulfonation rate of the benzene ring of the styrene unit of the obtained block copolymer (3) was 100 mol% from 1 H-NMR (400 MHz) analysis, and the ion exchange capacity was 2.64 meq / g from the titration result.
  • a block copolymer that does not belong to the present invention.
  • the sulfonation rate of the benzene ring of the styrene unit in the obtained block copolymer (4) was 100 mol% from 1 H-NMR (400 MHz) analysis, and the ion exchange capacity was 2.65 meq / g from the titration result.
  • the washing and filtration operations are repeated until there is no change in the pH of the washing water, and the resulting block copolymer is dried under reduced pressure to obtain a sulfonated STETS (hereinafter referred to as block copolymer) which does not belong to the present invention.
  • block copolymer a sulfonated STETS (hereinafter referred to as block copolymer) which does not belong to the present invention.
  • Combined (5)) was obtained.
  • the sulfonation rate of the benzene ring of the styrene unit of the obtained block copolymer (5) was 100 mol% from 1 H-NMR (400 MHz) analysis, and the ion exchange capacity was 2.52 meq / g from the titration result.
  • the reaction was stopped by adding 22 ml of distilled water, and another 500 ml of distilled water was added dropwise with stirring.
  • the block copolymer did not precipitate, and the solid content could not be recovered by filtration.
  • Table 1 shows the ion exchange capacities of the unions (1) to (5).
  • Proton conductivity A test piece of 1 cm ⁇ 4 cm was cut out from the obtained polymer electrolyte membrane, sandwiched between a pair of gold electrodes, and attached to an open measurement cell. The measurement cell was placed in an atmosphere at a temperature of 80 ° C. and a relative humidity of 30%, and the proton conductivity was measured by the AC impedance method.
  • the polymer electrolyte membrane obtained in the example or the comparative example was sandwiched between the two electrodes prepared as described above so that the polymer electrolyte membrane and the catalyst surface face each other, and the outer side thereof was composed of two heat resistant films and
  • the membrane-electrode assembly was produced by sandwiching two stainless plates in order and hot pressing (115 ° C., 2 MPa, 8 min).
  • the obtained membrane-electrode assembly is sandwiched between two conductive separators that also serve as gas supply channels, and the outside is sandwiched between two current collector plates and two clamping plates.
  • An evaluation cell for a molecular fuel cell (electrode area: 25 cm 2 ) was obtained.
  • the main peak and the low molecular weight peak are divided perpendicularly to the baseline of the GPC chart at the valley between these peaks, and the area (Sa) of the region including the main peak and the region including the low molecular weight peak
  • the area (Sb) was determined, and the value of Sb / (Sa + Sb) was expressed as a percentage and used as the low molecular weight reduction rate.
  • Table 2 shows the test results of the above 1) to 4) for the polymer electrolyte membranes obtained in Examples 1 to 3 and Comparative Example 1.
  • the polymer electrolyte membrane of the present invention is suppressed from lowering the molecular weight of the polymer electrolyte membrane in a 90 ° C. heat resistance test without impairing high ion conductivity, power generation properties, and wet mechanical properties. . That is, the membrane-electrode assembly and the polymer electrolyte fuel cell using the polymer electrolyte membrane of the present invention have both output characteristics and mechanical characteristics when wet, and are excellent in heat resistance.
  • the block copolymer of the present invention is useful as a polymer electrolyte membrane of a polymer electrolyte fuel cell having both heat generation characteristics and wet mechanical characteristics and improved heat resistance.

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Abstract

Cette invention concerne : un copolymère séquencé offrant un bon équilibre entre les caractéristiques de sortie et les caractéristiques mécaniques à l'état humide, tout en présentant une résistance à la chaleur améliorée ; une membrane électrolytique de type polymère ; un ensemble membrane- électrode ; et une pile à combustible à polymère solide. Plus particulièrement, cette invention concerne un copolymère séquencé qui est constitué de (A) une séquence de polymère ayant un groupe conducteur d'ions, de (B) une séquence de polymère d'oléfine amorphe et de (C) une séquence de polymère à base d'un composé de vinyle aromatique ne contenant pas de groupe conducteur d'ions, ledit copolymère séquencé étant constitué de 6 à 10 séquences de polymères. Chaque séquence de polymère terminale est constituée de la séquence de polymère (A) ou de la séquence de polymère (C), et au moins une des séquences de polymères terminales est constituée de la séquence de polymère (A). Seule la séquence de polymère (C) est liée à chaque extrémité de la séquence de polymère (B). Cette invention concerne également une membrane électrolytique de type polymère qui utilise ledit copolymère séquencé ; un ensemble membrane-électrode ; et une pile à combustible à polymère solide.
PCT/JP2012/071307 2011-08-31 2012-08-23 Copolymère séquencé, membrane électrolytique de type polymère, ensemble membrane-électrode, et pile à combustible à polymère solide Ceased WO2013031634A1 (fr)

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JP2016125050A (ja) * 2014-12-31 2016-07-11 奇美實業股▲ふん▼有限公司 共役ジエン−ビニル芳香族炭化水素共重合体
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EP3076470B1 (fr) 2015-04-03 2019-10-16 Samsung Electronics Co., Ltd. Batterie secondaire au lithium

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JPWO2015156087A1 (ja) * 2014-04-11 2017-04-13 日本メクトロン株式会社 組成物
JP2016125050A (ja) * 2014-12-31 2016-07-11 奇美實業股▲ふん▼有限公司 共役ジエン−ビニル芳香族炭化水素共重合体

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