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WO2011065460A1 - Electrolyte polymère, film d'électrolyte polymère, ensemble film-électrode et pile à combustible polymère solide - Google Patents

Electrolyte polymère, film d'électrolyte polymère, ensemble film-électrode et pile à combustible polymère solide Download PDF

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Publication number
WO2011065460A1
WO2011065460A1 PCT/JP2010/071088 JP2010071088W WO2011065460A1 WO 2011065460 A1 WO2011065460 A1 WO 2011065460A1 JP 2010071088 W JP2010071088 W JP 2010071088W WO 2011065460 A1 WO2011065460 A1 WO 2011065460A1
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Prior art keywords
polymer electrolyte
aromatic vinyl
polymer
block
polymer block
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PCT/JP2010/071088
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English (en)
Japanese (ja)
Inventor
竹友 山下
友裕 小野
和哉 清水
敬次 久保
望 須郷
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to JP2011543309A priority Critical patent/JP5629692B2/ja
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    • 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
    • H01M8/10—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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 polymer electrolyte excellent in ion conductivity under low humidity and less swollen by water, a polymer electrolyte membrane composed of the polymer electrolyte, and a membrane-electrode junction using the polymer electrolyte membrane And a polymer electrolyte fuel cell.
  • PEFCs polymer electrolyte fuel cells
  • a polymer electrolyte fuel cell is generally configured as follows. On both sides of the polymer electrolyte membrane having proton conductivity, a catalyst layer containing carbon powder carrying a white metal catalyst and an ion conductive binder made of a polymer electrolyte is disposed. A gas diffusion layer, which is a porous material through which fuel gas and oxidant gas are passed, is disposed outside each catalyst layer. Carbon paper, carbon cloth, or the like is used as the gas diffusion layer.
  • a structure in which a catalyst layer and a gas diffusion layer are integrated is called a gas diffusion electrode, and a structure in which a pair of gas diffusion electrodes is bonded to a polymer electrolyte membrane so that the catalyst layer faces the polymer electrolyte membrane is a membrane- It is called an electrode assembly (MEA; Mebrane Electrode Assembly).
  • MEA Mebrane Electrode Assembly
  • separators On both sides of the membrane-electrode assembly, separators having conductivity and airtightness are disposed.
  • a gas flow path for supplying fuel gas or oxidant gas (for example, air) to the electrode surface is formed in the contact portion of the membrane-electrode assembly and the separator or in the separator.
  • Electric power is generated by supplying a fuel gas to one electrode (fuel electrode) and an oxidant gas (such as air) containing oxygen to the other electrode (oxygen electrode). That is, at the fuel electrode, the fuel is ionized to generate protons and electrons, the protons pass through the polymer electrolyte membrane, and the electrons move through an external electric circuit formed by connecting the two electrodes, and are respectively transferred to the oxygen electrode. Reach and react with the oxidant gas to produce water. In this way, the chemical energy of the fuel can be directly converted into electric energy and taken out.
  • oxidant gas such as air
  • polymer electrolyte fuel cells usually perform intermittent operation that repeats start-up, operation, and stop, instead of continuous operation, in general applications as described above.
  • the polymer electrolyte membrane is wet during operation, but the humidity of the membrane decreases when stopped. For this reason, a polymer electrolyte membrane having high proton conductivity even under low humidity is desired in order to quickly exhibit performance at start-up.
  • Nafion a registered trademark of Nafion, DuPont
  • Nafion is a perfluorocarbon sulfonic acid polymer, because it is chemically stable.
  • Nafion is excellent in ionic conductivity under low humidity, but there is a possibility that a fluorine-based compound that adversely affects the environment may be generated as a decomposition product during long-term use or disposal. Further, since it has drawbacks such as high fuel permeability and high cost, an alternative material has been demanded.
  • hydrocarbon-based materials have been proposed as alternatives to perfluorocarbon sulfonic acid-based polymers such as Nafion.
  • PES polyethersulfone
  • PEEK polyetheretherketone
  • Patent Document 1 proposes a sulfonated product of PES. Since such a material does not contain fluorine, no fluorine compound is generated even if the material is deteriorated.
  • the raw material polymer itself is advantageous in terms of price compared to the perfluorocarbon sulfonic acid polymer.
  • the ion conductive groups are uniformly dispersed in the molecule, so the density of the ion conductive groups is low and it is difficult to achieve high ion conductivity. is there.
  • a sulfonated product of a modified PES having a polymer block having an ion conductive group introduced therein and a polymer block having no ion conductive group introduced therein has also been proposed.
  • it is a condensation polymer, an exchange reaction of repeating units occurs at the time of synthesis and the block structure is destroyed, so that a phase separation structure cannot be obtained and sufficient ion channels cannot be formed.
  • the polymer electrolyte membrane described in Patent Document 3 is composed of a block polymer having an aromatic vinyl polymer block and an aliphatic vinyl polymer block, which does not cause the above-described repeating unit exchange reaction.
  • the structure is retained. Therefore, ion channels can be formed by the phase separation structure unique to the block polymer.
  • the polymer electrolyte membrane composed of a block polymer having an aromatic vinyl polymer block and an aliphatic vinyl polymer block has insufficient performance in a low humidity state. There was a limit. Therefore, the actual situation is that sufficient ion conductivity cannot be secured in a low humidity state.
  • the polymer electrolyte membrane is used in a solid polymer fuel cell, it is desired that the polymer electrolyte membrane is less swelled by water in contact with the polymer electrolyte membrane during power generation of the polymer electrolyte fuel cell.
  • the polymer electrolyte membrane is deformed by swelling, peeling of the polymer electrolyte membrane from the electrode tends to occur in the membrane-electrode assembly.
  • a significant change in the shape of the polymer electrolyte membrane, and hence breakdown may occur, which may adversely affect long-term durability.
  • a block copolymer comprising at least an aromatic vinyl polymer block (A) and an aliphatic vinyl polymer block (B) as constituent components.
  • the aromatic vinyl polymer block (A) has an ion conductive group content per repeating unit of 1.5 to 3.0, and the aliphatic vinyl polymer block (B) has found that the above-mentioned problems can be solved by providing a polymer electrolyte characterized by not having an ion conductive group.
  • a polymer electrolyte comprising a block copolymer having at least an aromatic vinyl polymer block (A) and an aliphatic vinyl polymer block (B) as constituent components, wherein the aromatic vinyl polymer block ( The ion conductive group content per repeating unit in A) is 1.5 to 3.0, and the aliphatic vinyl polymer block (B) does not have an ion conductive group.
  • the present invention relates to a polymer electrolyte.
  • the invention according to claim 2 2.
  • the invention according to claim 3 2.
  • the aliphatic vinyl polymer block (B) is an alkene unit having 2 to 8 carbon atoms, a cycloalkene unit having 5 to 8 carbon atoms, a vinyl cycloalkane unit having 7 to 10 carbon atoms, or a vinyl having 7 to 10 carbon atoms. It is a rubbery polymer block containing as a main component at least one repeating unit selected from the group consisting of a cycloalkene unit, a conjugated diene unit having 4 to 8 carbon atoms, and a conjugated cycloalkadiene unit having 5 to 8 carbon atoms.
  • the invention according to claim 5 The polymer electrolyte according to claim 1, wherein the ion conductive group is a proton conductive group.
  • the invention according to claim 6 The aromatic vinyl polymer block (C) mainly comprising an aromatic vinyl compound unit having no ion conductive group as a repeating unit is contained as a constituent component in an amount of 20 to 60% by weight.
  • the present invention relates to a polymer electrolyte.
  • the invention according to claim 7 provides The aromatic vinyl compound unit, which is the main repeating unit of the aromatic vinyl polymer block (C), is a substituted aromatic vinyl compound having 1 to 3 C 1-8 hydrocarbon groups on the aromatic ring. It is a compound unit, It is related with the polymer electrolyte of Claim 6.
  • the invention according to claim 8 provides The present invention relates to a polymer electrolyte membrane comprising the polymer electrolyte according to claim 1.
  • the invention described in claim 9 The present invention relates to a membrane-electrode assembly having a multilayer structure of at least the polymer electrolyte membrane according to claim 8 and an electrode layer.
  • the invention according to claim 10 provides A solid polymer fuel cell comprising the membrane-electrode assembly according to claim 9.
  • the aromatic vinyl polymer block (A) and the aliphatic vinyl polymer block (B) undergo microphase separation, and the aromatic vinyl polymer block (A) and the aliphatic vinyl polymer block (B) have the property of gathering together, and since the aromatic vinyl polymer block (A) has an ion conductive group, the aromatic vinyl polymer block (A) An ion channel is formed by the aggregation of each other, and becomes a path for ions such as protons.
  • microphase separation means phase separation in a microscopic sense, and more specifically, means phase separation in which the formed domain size is less than or equal to the wavelength of visible light (3800 to 7800 mm). Shall.
  • the aromatic vinyl polymer block (A) has an ion conductive group content of 1.5 to 3.0 per repeating unit, and the aliphatic vinyl polymer block (B) has an ion conductivity.
  • the ion channel is dense and ion-conducting groups are present.
  • the polymer electrolyte membrane comprising the polymer electrolyte of the present invention
  • phase separation occurs remarkably and ion conductivity becomes high, and particularly has high ion conductivity under low humidity.
  • the membrane-electrode assembly comprising the polymer electrolyte fuel cell, it is possible to obtain high output characteristics even under a low humidity, and there is little swelling due to water, and the bonding property to the electrode is also improved. Excellent.
  • the block copolymer constituting the polymer electrolyte of the present invention contains an aromatic vinyl polymer block (A) as a constituent component.
  • the aromatic vinyl polymer block (A) has an aromatic vinyl compound unit as a main repeating unit and an ion conductive group content per repeating unit of 1.5 to 3.0. It is appropriately selected depending on the required performance of the molecular electrolyte. From the viewpoint of ion conductivity, it is preferably 1.7 or more, and from the viewpoint of ease of introduction of the sulfonic acid group, it is preferably 1.5 to 2.0.
  • the aromatic vinyl compound unit that is a repeating unit of the aromatic vinyl polymer block (A) is a structure that can be formed by polymerization of an aromatic vinyl compound.
  • the aromatic vinyl compound refers to a compound having at least one functional group containing at least one aromatic ring and an addition polymerizable carbon double bond directly bonded to a carbon atom on at least one aromatic ring.
  • Examples thereof include compounds in which hydrogen on an aromatic ring such as a benzene ring is substituted with a substituent such as a vinyl group, a 1-alkylethenyl group (eg, an isopropenyl group), or a 1-arylethenyl group.
  • a substituent such as a vinyl group, a 1-alkylethenyl group (eg, an isopropenyl group), or a 1-arylethenyl group.
  • Specific examples include styrene, ⁇ -methylstyrene, and diphenylethylene.
  • the aromatic vinyl compound that can form an aromatic vinyl compound unit that is a repeating unit of the aromatic vinyl polymer block (A) preferably has 10 or more carbon atoms that form an aromatic ring.
  • a compound having a plurality of aromatic rings having 10 or less carbon atoms such as a benzene ring and a compound having a condensed ring obtained by condensing the aromatic rings having 10 or less carbon atoms can be given.
  • aromatic vinyl compound having a plurality of benzene rings examples include vinyl biphenyl, vinyl terphenyl, phenoxystyrene, and diphenylethylene.
  • examples of the condensed ring include a naphthalene ring, a phenanthrene ring, an anthracene ring, a pyrene ring, a chrysene ring, and a fluorene ring.
  • aromatic vinyl compounds include vinyl naphthalene, vinyl phenanthrene, vinyl anthracene, vinyl pyrene, and vinyl chrysene vinyl fluorene.
  • vinyl naphthalene, vinyl biphenyl, and vinyl terphenyl are preferred because the molecular weight of the repeating unit is small and the structure is compact, which is advantageous for increasing the density of the ion channel.
  • Vinyl biphenyl is even more preferred.
  • the average molecular weight of the aromatic vinyl compound unit is preferably 400 or less, preferably 300 or less, and more preferably 200 or less.
  • the average molecular weight is a polymer block obtained by substituting all ion conductive groups of the aromatic vinyl polymer block with hydrogen (that is, the corresponding ion conductivity). It is calculated assuming a polymer block having no group. If the average molecular weight of the repeating unit is too large, the density of the ion channel may decrease, which is not preferable.
  • aromatic vinyl compound When the aromatic vinyl compound is polymerized into the aromatic vinyl polymer block (A), two or more aromatic vinyl compounds may be used in combination.
  • the form in the case of copolymerizing two or more of these may be random copolymerization, block copolymerization, graft copolymerization or tapered copolymerization.
  • the aromatic vinyl polymer block (A) may contain one or more other monomer units as long as the effects of the invention are not impaired.
  • monomers that can constitute 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, 1,4-heptadiene, 3,5-heptadiene, etc.), carbon number 2-8 Alkenes (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) acrylate esters (methyl (methylene
  • the aromatic vinyl polymer block (A) occupies 5 to 50% by weight of the polymer electrolyte in order for the polymer electrolyte membrane to satisfy both ion conductivity and water resistance. From the viewpoint of ionic conductivity, it is more preferable to occupy 35 to 50% by weight, and from the viewpoint of water resistance, it is more preferable to occupy 5 to 25% by weight. To achieve both ionic conductivity and water resistance, 20% is preferable. More preferably, it accounts for ⁇ 40% by weight.
  • the aromatic vinyl polymer block (A) is advantageous in causing microphase separation from the aliphatic vinyl polymer block (B) by using the aromatic vinyl compound block as a main repeating unit.
  • That the aromatic vinyl compound unit is the main repeating unit means that the aromatic vinyl polymer block (A) accounts for more than 80% by weight, and in order to impart sufficient ion conductivity, 90% It is more preferable to occupy 95% by weight or more, and even more preferably 95% by weight or more. If it is less than 80% by weight, the ion conductive group content per repeating unit in the aromatic vinyl polymer block (A) decreases, and the density of the ion conductive group also decreases, so that the effect of the present invention is obtained. It may disappear.
  • the weight ratio is calculated assuming a polymer block in which all ion conductive groups of the aromatic vinyl polymer block are substituted with hydrogen (that is, a polymer block having no corresponding ion conductive group).
  • the aromatic vinyl polymer block (A) referred to in the present invention is not limited to those in which the same type of monomer continuously constitutes the main chain, but the aromatic vinyl compound unit is a main repeating unit, and is uniform. Any material capable of forming a phase is included.
  • the phase can be observed with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the molecular weight per aromatic vinyl polymer block (A) is appropriately selected depending on the properties of the polymer electrolyte, required performance, other polymer components, and the like.
  • the mechanical properties of the resulting polymer electrolyte membrane tend to be high, but when it is too large, it becomes difficult to form and form a block copolymer, and when the molecular weight is small, the microphase separation structure, and thus Since it is difficult to form an ion channel, ion conductivity and mechanical properties tend to be lowered. Therefore, it is important to appropriately select a molecular weight according to required performance.
  • the molecular weight per aromatic vinyl polymer block (A) is calculated as a structure in which an ion conductive group is substituted with hydrogen (that is, a block copolymer having no corresponding ion conductive group), it is calculated in terms of standard polystyrene.
  • the number average molecular weight is usually selected from 1,000 to 1,000,000, preferably selected from the range of 2,000 to 250,000, and selected from 3,000 to 100,000. More preferably, it is selected from 4,000 to 50,000, more preferably from 5,000 to 25,000. Further, from the viewpoint of ease of solution preparation during film formation and film forming properties, it is preferably selected from 5,000 to 10,000.
  • the aromatic vinyl polymer block (A) may be crosslinked by a known method within a range not impairing the effects of the present invention. By introducing cross-linking, the ion channel phase formed by the aromatic vinyl polymer block (A) is less likely to swell, and changes in mechanical properties (such as tensile properties) between drying and wetting tend to be further reduced. It is in.
  • the number of moles of ion conductive groups per 1 g of aromatic vinyl polymer block (A) is preferably 4.8 meq / g or more in order to exhibit the effects of the present invention. .1 meq / g or more is more preferable, and 5.6 meq / g or more is even more preferable.
  • the ion conductive group possessed by the aromatic vinyl polymer block (A) is not particularly limited, and a functional group having ion conductivity can be used, particularly those having high affinity with anions and / or cations, Those in which some of the functional groups are easily dissociated as ions are suitable, and examples thereof include sulfonic acid groups, phosphonic acid groups, carboxylic acid groups, quaternary ammonium salts, and quaternary salts of pyridine.
  • a proton conductive group or a salt obtained by exchanging protons of the proton conductive group with other ions is excellent in proton conductivity, and examples thereof include sulfonic acid groups, phosphonic acid groups, carboxylic acid groups, and salts thereof.
  • sulfonic acid groups and phosphonic acid groups and their salts are preferably used.
  • the ion exchange capacity can be adjusted by appropriately selecting the type and concentration of the ion conductive group.
  • the position of the ion conductive group in the aromatic vinyl polymer block (A) is not particularly limited, but it is introduced onto the aromatic ring of the aromatic vinyl compound unit for ease of introduction of the ion conductive group. Is preferred.
  • the block copolymer constituting the polymer electrolyte of the present invention comprises an aliphatic vinyl polymer block (B) as a constituent component.
  • the aliphatic vinyl polymer block (B) has an aliphatic vinyl compound unit as a main repeating unit and does not have an ion conductive group.
  • the aliphatic vinyl compound unit which is the main repeating unit of the aliphatic vinyl polymer block (B), is a structure that can be formed by polymerization of an aliphatic vinyl compound.
  • the aliphatic vinyl compound refers to a compound having at least one functional group containing an addition polymerizable carbon double bond directly bonded to a carbon atom that does not constitute at least one aromatic ring.
  • Examples of the aliphatic vinyl compound unit 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 vinylcycloalkene units having 7 to 10 carbon atoms. And conjugated diene units having 4 to 8 carbon atoms and conjugated cycloalkadiene units having 5 to 8 carbon atoms. You may use the repeating unit chosen from these groups individually or in combination of 2 or more types.
  • the form in the case of polymerizing (copolymerizing) two or more kinds may be random copolymerization, block copolymerization, graft copolymerization or tapered copolymerization.
  • the monomer to be polymerized has a plurality of carbon-carbon double bonds
  • any of them may be used for the polymerization.
  • a conjugated diene a plurality of kinds of polymerizable positions (for example, 1, 3 -Diene 1,2-bond, 3,4-bond, 1,4-bond polymerization), but there is no particular limitation, and the ratio (for example, ratio of 1,2-bond to 1,4-bond) ) Is not particularly limited.
  • the alkene having 2 to 8 carbon atoms includes ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1- Cycloalkene having 5 to 8 carbon atoms such as hexene, 2-hexene, 1-heptene, 2-heptene, 1-octene, 2-octene, etc., and vinyl having 7 to 10 carbon atoms such as cyclopentene, cyclohexene, cycloheptene and cyclooctene
  • cycloalkanes include vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, and vinylcyclooctane.
  • Examples of vinylcycloalkene having 7 to 10 carbon atoms include vinylcyclopentene, vinylcyclohexene, vinylcycloheptene, and vinylcyclooctene.
  • Examples of the conjugated cycloalkadiene having 5 to 8 carbon atoms such as heptadiene and 2,4-heptadiene include cyclopentadiene and 1,3-cyclohexadiene. These monomers may be used independently and may use 2 or more types together.
  • the monomer for forming the aliphatic vinyl polymer block (B) has a plurality of carbon-carbon double bonds as in the case of vinylcycloalkene, conjugated diene or conjugated cycloalkadiene
  • the repeating unit after polymerization has a carbon-carbon double bond
  • a structure in which this is further saturated can be used as the repeating unit. This can be obtained by hydrogenating the remaining carbon-carbon double bond when the monomer is polymerized.
  • a carbon-carbon double bond has a structure in which 30 mol% or more thereof is hydrogenated.
  • the abundance (or hydrogenation rate) of the carbon-carbon double bond can be calculated by a commonly used method, for example, iodine value measurement method, 1 H-NMR measurement or the like.
  • the aliphatic vinyl polymer block (B) has a carbon number of 2 from the viewpoint of giving the resulting block copolymer elasticity and, in turn, good moldability in the production of a membrane-electrode assembly and a polymer electrolyte fuel cell. It consists of alkene units of ⁇ 8, cycloalkene units of 5 to 8 carbon atoms, vinylcycloalkene units of 7 to 10 carbon atoms, conjugated diene units of 4 to 8 carbon atoms and conjugated cycloalkadiene units of 5 to 8 carbon atoms.
  • preferred as the alkene unit are structural units saturated with double bonds of isobutene units, 1,3-butadiene units (1-butene units, 2-butene units), and structural units saturated with double bonds of isoprene units.
  • the aliphatic vinyl compound unit is the main repeating unit, that is, the aliphatic vinyl compound unit exceeds 50% by weight and exceeds 70% by weight. Preferably, it exceeds 90% by weight.
  • the aliphatic vinyl polymer block (B) has other repeating units as long as the purpose of the aliphatic vinyl polymer block (B) to give elasticity to the block copolymer is not impaired.
  • aromatic vinyl compound units such as styrene units and vinylnaphthalene units, halogen-containing vinyl compound units such as vinyl chloride units, acrylate ester units having 1 to 12 carbon side chains, and sides having 1 to 12 carbon atoms It may contain a methacrylic ester unit having a chain.
  • the copolymerization form of the monomer and the other monomer is random copolymerization.
  • the amount of such other monomer used is less than 50% by weight of the aliphatic vinyl polymer block (B), more preferably less than 30% by weight, and even more preferably less than 10% by weight. preferable.
  • the aliphatic vinyl polymer block (B) is a rubber-like polymer block
  • the block copolymer becomes elastic and flexible as a whole, and a membrane-electrode assembly and a polymer electrolyte fuel cell are produced.
  • formability assembling property, joining property, tightening property, etc.
  • the rubber-like polymer block here means a polymer block having a glass transition point or softening point of 30 ° C. or lower, preferably 20 ° C. or lower, more preferably 10 ° C. or lower.
  • the main component is at least one repeating unit selected from the group consisting of a vinylcycloalkene unit having 10 to 10, a conjugated diene unit having 4 to 8 carbon atoms, and a conjugated cycloalkadiene unit having 5 to 8 carbon atoms, More preferably, the main component is at least one repeating unit selected from the group consisting of alkene units having 2 to 5 carbon atoms and conjugated diene units having 4 to 5 carbon atoms.
  • the molecular weight per aliphatic vinyl polymer block (B) is appropriately selected depending on the properties of the polymer electrolyte, required performance, other polymer components, and the like.
  • the number average molecular weight in terms of standard polystyrene is usually selected from 1,000 to 1,000,000, preferably from 5,000 to 500,000, and preferably 10,000 to 200,000. It is more preferable to select between.
  • the aliphatic vinyl polymer block (B) is a rubbery polymer block, it is particularly selected from 15,000 to 120,000 from the viewpoint of achieving both moldability and flexibility. preferable.
  • the aliphatic vinyl polymer block (B) does not have an ion conductive group.
  • having no ion-conducting group means that the ion-conducting group is not substantially ion-conducting, and enhances microphase separation from the aromatic vinyl polymer block (A).
  • the ion conductive group content per repeating unit is preferably 0.1 or less, more preferably 0.01 or less, and most preferably not at all. However, in production, it may be advantageous to contain about 0.001 to 0.05 ion conductive groups per repeating unit.
  • the aliphatic vinyl polymer block (B) is hydrophobic, phase separation with the aromatic vinyl polymer block (A) occurs favorably.
  • it is preferably substantially free of hydrophilic groups such as hydroxyl groups and amino groups, and it is also preferred that substantially no polar groups such as ester groups are present.
  • the block structure of the block copolymer comprising the aromatic vinyl polymer block (A) and the aliphatic vinyl polymer block (B) as constituent components is not particularly limited, the aromatic vinyl polymer block (A) It is desirable that there is a plurality, and that both ends of at least one aliphatic vinyl polymer block (B) are not terminals of the block copolymer.
  • Examples include an ABA type triblock copolymer, an ABBA type triblock copolymer and an AB type diblock copolymer, an ABBA type AB block copolymer.
  • Block copolymers may be used alone or in combination of two or more.
  • the block copolymer has a plurality of aromatic vinyl polymer blocks (A) and / or aliphatic vinyl polymer blocks (B), these blocks may be the same or different. .
  • the weight ratio of the aromatic vinyl polymer block (A) and the aliphatic vinyl polymer block (B) constituting the block copolymer is obtained.
  • it is appropriately selected depending on the required performance of the block copolymer to be obtained, it is preferably 95: 5 to 55:45 from the viewpoint of ionic conductivity, and 45:55 to 5:95 is preferable from the viewpoint of water resistance. In order to achieve both ionic conductivity and water resistance, 60:40 to 40:60 is preferable.
  • this weight ratio is 95: 5 to 5:95, it is advantageous for the ion channel formed by the aromatic vinyl polymer block (A) to be a cylindrical or continuous phase by microphase separation.
  • the hydrophobic vinyl polymer block (B) which is hydrophobic, has an appropriate ratio and exhibits excellent water resistance.
  • the weight ratio is calculated assuming a polymer block in which all ion conductive groups of the block copolymer are replaced with hydrogen.
  • the block copolymer used in the present invention includes those partially containing graft bonds.
  • Examples of the block copolymer partially containing a graft bond include those in which a part of the constituting polymer block is grafted to the main structure (for example, main chain) of the block copolymer.
  • the number average molecular weight of the block copolymer used in the present invention is not particularly limited, but the number average molecular weight not considering the ion conductive group is usually 10,000 to 1,000,000 as the number average molecular weight in terms of standard polystyrene. Preferably, 15,000 to 700,000 is more preferable, and 20,000 to 500,000 is even more preferable.
  • the block copolymer constituting the polymer electrolyte of the present invention needs to have an ion conductive group in the aromatic vinyl polymer block (A).
  • ions in the present invention when referring to ionic conductivity include protons.
  • the ion conductive group is not particularly limited as long as the membrane-electrode assembly produced using the polymer electrolyte can exhibit sufficient ionic conductivity, and in particular, —SO 3 M or —PO
  • a sulfonic acid group, a phosphonic acid group or a salt thereof represented by 3 HM (wherein M represents a hydrogen atom, an ammonium ion or an alkali metal ion) is preferably used.
  • a carboxyl group or a salt thereof can also be used.
  • the aromatic vinyl polymer block (A) having an ion conductive group is particularly effective for improving the radical resistance of the polymer electrolyte.
  • the amount of ion-conducting group introduced is appropriately selected depending on the required performance of the resulting block copolymer, etc., but exhibits sufficient ion conductivity for use as a polymer electrolyte membrane for a polymer electrolyte fuel cell.
  • the block copolymer has an ion exchange capacity (overall IEC) of 0.40 meq / g or more, and preferably 0.50 meq / g or more. It is more preferable that the amount is 0.60 meq / g or more.
  • the upper limit of the ion exchange capacity of the block copolymer is preferably 4.5 meq / g or less, because if the ion exchange capacity becomes too large, the hydrophilicity tends to increase and the water resistance tends to be insufficient. It is more preferably 0.0 meq / g or less, and further preferably 3.5 meq / g or less.
  • the block copolymer used in the present invention may contain an aromatic vinyl polymer block (C) mainly comprising an aromatic vinyl compound unit having no ion conductive group as a repeating unit.
  • the aromatic vinyl polymer block (C) accounts for 20 to 60% by weight of the polymer electrolyte, it is excellent in mechanical strength when used as a membrane, which is preferable. More preferably, it occupies 23 to 50% by weight, and further preferably occupies 25 to 40% by weight.
  • the aromatic vinyl polymer block (C) having an aromatic vinyl compound unit mainly having no ion conductive group as a repeating unit is a polymer block having an aromatic vinyl compound unit as a main repeating unit.
  • the polymer block is excellent in shape stability of a polymer electrolyte molded body (for example, a polymer electrolyte membrane). Therefore, it is particularly useful when the aliphatic vinyl polymer block (B) is a rubbery polymer block.
  • the aromatic vinyl polymer block (C) is preferably phase-separated from both the aromatic vinyl polymer block (A) and the aliphatic vinyl polymer block (B) to form a constrained phase. That is, since the aromatic vinyl polymer block (C) having no ionic conductivity forms an independent phase, the shape stability is further improved.
  • the aromatic vinyl polymer block (C) is mainly composed of an aromatic vinyl compound unit having no ion conductive group as a repeating unit.
  • the aromatic vinyl-based compound unit having mainly no ion-conducting group as a repeating unit means that the aromatic vinyl-based polymer block (C) has substantially no ion conductivity.
  • the ion conductive group content per repeating unit of the aromatic vinyl polymer block (C) is 0.1 or less, more preferably 0.01 or less, and most preferably not at all. It is. Alternatively, it is preferably 1/10 or less, more preferably 1/20, and even more preferably 1/100 or less with respect to the ion conductive group of the aromatic vinyl polymer block (A). .
  • the aromatic vinyl polymer block (C) does not substantially have ionic conductivity, and phase separation with the aromatic vinyl polymer block (A) forming the ion channel is favorably expressed. Efficient ion conduction can be performed.
  • aromatic vinyl polymer block (C) is hydrophobic, phase separation with the aromatic vinyl polymer block (A) occurs favorably.
  • it is preferably substantially free of hydrophilic groups such as hydroxyl groups and amino groups, and it is also preferred that substantially no polar groups such as ester groups are present.
  • the aromatic vinyl compound unit which is the main repeating unit of the aromatic vinyl polymer block (C) is a structure which can be formed by polymerization of an aromatic vinyl compound.
  • the aromatic vinyl compound refers to a compound having at least one functional group containing at least one aromatic ring and an addition polymerizable carbon double bond directly bonded to a carbon atom on at least one aromatic ring.
  • the aromatic ring of the aromatic vinyl compound is preferably a carbocyclic aromatic ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a pyrene ring.
  • the aromatic vinyl compound unit is preferably a substituted aromatic vinyl compound unit having 1 to 3 hydrocarbon groups having 1 to 8 carbon atoms on the aromatic ring. Examples thereof include compounds in which hydrogen on the aromatic ring is substituted with a substituent such as a vinyl group, 1-alkylethenyl group (eg, isopropenyl group), 1-arylethenyl group.
  • styrene 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-n-propylstyrene, 4-isopropylstyrene, 4-n-butylstyrene, 4-isobutylstyrene, 4- t-butylstyrene, 4-n-octylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2-methoxystyrene, 3-methoxy Styrene, 4-methoxystyrene, vinylnaphthalene, vinylanthracene, alkyl groups having 1 to 4 hydrogen atoms bonded to ⁇ -carbon atoms (methyl group, ethyl group, n-propyl group, isopropy
  • the aromatic vinyl polymer block (C) may contain one or more other monomer units within a range not impairing the effects of the present invention.
  • examples of such other monomers 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, 1,4-heptadiene, 3,5-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 ester (Methyl (meth)
  • the aromatic vinyl polymer block (C) is preferably used in the range of 60% by weight or less of the block copolymer, more preferably in the range of 50% by weight or less, and in the range of 40% by weight or less. Is more preferable.
  • the ratio of the aromatic vinyl polymer block (C) to the aromatic vinyl polymer block (A) is not particularly limited, but the ratio of the monomer units before introducing the ion conductive group is 85: It is preferably in the range of 15 to 0: 100, and in the range of 65:35 to 20:80 in order to achieve both the mechanical strength of the aromatic vinyl polymer block (C) and high ionic conductivity. Preferably, it is in the range of 55:45 to 35:65, more preferably in the range of 45:55 to 35:65.
  • the aromatic vinyl polymer block (C) may be composed of a polymer block having an aromatic vinyl compound unit represented by the following general formula (a) as a main repeating unit.
  • the alkyl group having 1 to 4 carbon atoms represented by R 1 in the general formula (a) may be linear or branched, and is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group. , Isobutyl group, tert-butyl group and the like.
  • the alkyl group having 1 to 8 carbon atoms represented by R 2 to R 4 in the general formula (a) may be linear or branched, and is methyl, ethyl, propyl, isopropyl, butyl, sec -Butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, 1-methylpentyl group, heptyl group, octyl group and the like.
  • aromatic vinyl compound unit represented by the general formula (a) include 4-methylstyrene unit, 4-tert-butylstyrene unit, ⁇ , 4-dimethylstyrene unit, ⁇ -methyl-4. -Tert-butylstyrene units and the like may be mentioned, and these may be used alone or in combination of two or more.
  • the form in the case of polymerizing (copolymerizing) two or more of these may be random copolymerization, block copolymerization, graft copolymerization, or tapered copolymerization.
  • R 1 is 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 1 to 8 carbon atoms, but at least one of them is carbon Represents an alkyl group of 1 to 8)
  • the polymer electrolyte of the present invention there is a method of introducing an ion conductive group after producing a block copolymer having no ion conductive group.
  • an ion conductive group for example, when a sulfonic acid group is introduced as an ion conductive group, the sulfonation reaction of polystyrene takes place preferentially at the para position of the aromatic ring, so that the main repeating unit of the aromatic vinyl polymer block is the 4-methylstyrene unit.
  • the aromatic vinyl polymer block (C) is obtained by polymerization of an aromatic vinyl compound (for example, a substituted aromatic vinyl compound) in which introduction of an ion conductive group is unlikely to occur. It is possible to use a monomer that is sufficiently less reactive in introducing an ion conductive group than an aromatic vinyl compound (for example, an unsubstituted aromatic vinyl compound) for constituting the combined block (A). It is advantageous in producing the polymer electrolyte of the present invention by a method of introducing an ion conductive group after producing a block copolymer not having it.
  • the polymer electrolyte of the present invention is produced by a method of introducing an ion conductive group into the block copolymer, it corresponds to the aromatic vinyl polymer block (C) in the block copolymer before the introduction of the ion conductive group.
  • the aromatic vinyl polymer block is very difficult to introduce an ion conductive group.
  • the ion conductive group introduction rate of the polymer block (A) is significantly higher than that of the aromatic vinyl polymer block (C) in all cases.
  • the ion conductive group of the aromatic vinyl polymer block (A) preferably occupies at least 85%, more preferably 90% or more of the total ion conductive group of the block copolymer, 95% It is more preferable to occupy the above.
  • the above-described aromatic vinyl compound unit is the main repeating unit of the aromatic vinyl polymer block (C) and exceeds 50% by weight. Further, it is more preferably 70% by weight or more, and still more preferably 90% by weight or more.
  • the molecular weight of the aromatic vinyl polymer block (C) is appropriately selected depending on the properties of the polymer electrolyte, required performance, other polymer components, and the like. When the molecular weight is large, the mechanical properties of the polymer electrolyte tend to be high, but when it is too large, it becomes difficult to mold and form a block copolymer, and when the molecular weight is small, the mechanical properties tend to be low, It is important to select the molecular weight appropriately according to the required performance.
  • the number average molecular weight in terms of standard polystyrene is usually preferably selected from 800 to 500,000, more preferably from 2,000 to 150,000, more preferably from 3,000 to 50,000. More preferably, it is selected from among 000.
  • the block copolymer used in the present invention comprises an aromatic vinyl polymer block (C), an aromatic vinyl polymer block (A) and an aliphatic vinyl polymer block (B), the block copolymer
  • the structure of the polymer is not particularly limited, but examples include an ABCA tetrablock copolymer, an ABBC tetrablock copolymer, and an ABCB tetrablock copolymer.
  • Copolymer C—B—C—A tetrablock copolymer, A—B—A—C tetra block copolymer, A—C—B—C—A penta block copolymer, C—A—B—A -C pentablock copolymer, ABCCBCA pentablock copolymer, CBABBC pentablock copolymer, ABCBAB block Polymer, ABCA-A-C pentablock copolymer, AB C—B—C—Pentablock copolymer, A—A—A—B—C—Penta block copolymer, A—A—A—C—B—Penta block copolymer, B—A—B—A—C Pentablock copolymer, BACBCA pentablock copolymer, BABBCB pentablock copolymer, CACBBC pentablock copolymer Etc.
  • C blocks From the viewpoint of restraint, it is preferable to have a plurality of C blocks, and it is particularly preferable to have C blocks at both ends. Moreover, when emulsifying and using the polymer electrolyte of this invention, it is preferable to have A block at both ends from a viewpoint of the ease of preparation of an emulsion. Further, from the viewpoint of solubility and dispersibility in an organic solvent, a C—A—C—B—C pentablock copolymer is desirable.
  • the block copolymer used in the present invention includes those partially containing graft bonds.
  • Examples of the block copolymer partially containing a graft bond include those in which a part of the constituting polymer block is graft-bonded to a main part (for example, main chain) of the block copolymer.
  • the production method of the block copolymer in the polymer electrolyte used in the present invention is not particularly limited, and a known method can be used, but after producing the block copolymer having no ion conductive group.
  • a method of bonding an ion conductive group is preferable.
  • a polymer block having no ion conductive group corresponding to the aromatic vinyl polymer block (A) in the block copolymer having no ion conductive group is referred to as an aromatic vinyl polymer block (A ) '.
  • the production method of the polymer block (B) is appropriately selected from a radical polymerization method, an anionic polymerization method, a cationic polymerization method, a coordination polymerization method, and the like. From the industrial easiness, a radical polymerization method and an anionic polymerization method are used.
  • the cationic polymerization method is preferably selected.
  • the so-called living polymerization method is preferable from the viewpoints of molecular weight control, molecular weight distribution control, polymer structure control, ease of bonding between the aromatic vinyl polymer block (A) ′ and the aliphatic vinyl polymer block (B), and the like.
  • a living radical polymerization method, a living anion polymerization method, and a living cation polymerization method are preferable.
  • Specific examples of the production method include an aromatic vinyl polymer block (A) ′ having an aromatic vinyl compound such as 4-vinylbiphenyl as a main repeating unit and an aliphatic vinyl polymer block (B) comprising a conjugated diene.
  • a method for producing a block copolymer containing as a component will be described. In this case, it is produced by a living anionic polymerization method from the viewpoint of industrial ease, molecular weight, molecular weight distribution, ease of bonding between the aromatic vinyl polymer block (A) ′ and the aliphatic vinyl polymer block (B), and the like. And the following specific synthesis examples are shown.
  • An aromatic vinyl compound such as 4-vinylbiphenyl is polymerized at a temperature of 10 to 40 ° C. using an anionic polymerization initiator in a toluene solvent, and then conjugated diene, 4-vinylbiphenyl, etc.
  • a method of sequentially polymerizing aromatic vinyl compounds to obtain an A′-BA ′ type block copolymer is provided.
  • An aromatic vinyl compound such as 4-vinylbiphenyl is polymerized at a temperature of 10 to 40 ° C. using an anionic polymerization initiator in a toluene solvent, and then conjugated diene is polymerized.
  • aromatic vinyl polymer block (C) having an aromatic vinyl compound such as 4-tert-butylstyrene as the main repeating unit, and aromatic vinyl compounds such as 4-vinylbiphenyl.
  • a method for producing a block copolymer comprising as constituent components an aromatic vinyl polymer block (A) ′ as a repeating unit and a polymer block (B) comprising a conjugated diene will be described.
  • the living anionic polymerization method is preferred from the viewpoint of industrial ease, molecular weight, molecular weight distribution, ease of bonding of polymer blocks (C), (B) and (A) ′, and the following specific synthesis Examples are given and can be adopted / applied.
  • An aromatic vinyl compound such as 4-tert-butylstyrene is polymerized at a temperature of 10 to 40 ° C. using an anionic polymerization initiator in a toluene solvent, and then conjugated diene, 4-vinylbiphenyl
  • a method of obtaining a CBA ′ type block copolymer by sequentially polymerizing aromatic vinyl compounds such as
  • An aromatic vinyl compound such as 4-tert-butylstyrene is polymerized at a temperature of 10 to 40 ° C. using an anionic polymerization initiator in a toluene solvent, and then an aromatic such as 4-vinylbiphenyl is used.
  • An aromatic vinyl compound such as 4-tert-butylstyrene is polymerized at a temperature of 10 to 40 ° C. using an anionic polymerization initiator in a toluene solvent, and then an aromatic such as 4-vinylbiphenyl.
  • C—A′-BA—C type block by sequentially polymerizing aromatic vinyl compounds such as aromatic vinyl compounds, conjugated dienes, 4-vinylbiphenyl, and aromatic vinyl compounds such as 4-tert-butylstyrene A method for obtaining a copolymer.
  • the block copolymer thus produced is subjected to a hydrogenation reaction of double bonds of conjugated diene units having 4 to 8 carbon atoms constituting the aliphatic vinyl polymer block (B).
  • a hydrogenation reaction a solution of a block copolymer obtained by anionic polymerization or the like is charged into a pressure vessel, and a hydrogenation reaction is performed in a hydrogen atmosphere using a Ziegler type hydrogenation catalyst such as a Ni / Al type. The method of performing can be illustrated.
  • Sulfonation can be performed by a known sulfonation method.
  • a sulfonation method an organic solvent solution or suspension of a block copolymer is prepared, a sulfonating agent is added and mixed, a method of adding a gaseous sulfonating agent directly to the block copolymer, etc. Is exemplified.
  • Sulfonating agents used 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.
  • organic solvent to be used include halogenated hydrocarbons such as methylene chloride, linear aliphatic hydrocarbons such as hexane, cyclic aliphatic hydrocarbons such as cyclohexane, and the like. You may use it, selecting suitably from several combinations.
  • a method for removing the sulfonated product as a solid from the reaction solution containing the sulfonated product of the block copolymer a method of pouring the reaction solution into water and precipitating the sulfonated product, and then distilling off the solvent at atmospheric pressure, Stopper water is gradually added and suspended in the reaction solution, and the sulfonated product is precipitated, and then the solvent is distilled off at atmospheric pressure. From the viewpoint of increasing the washing efficiency, a method of gradually adding and suspending the stopper water in the reaction solution to precipitate the sulfonated product is suitably used.
  • Phosphonation can be performed by a known phosphonation method. Specifically, for example, an organic solvent solution or suspension of a block copolymer is prepared, and the copolymer is reacted with chloromethyl ether or the like in the presence of anhydrous aluminum chloride to introduce a halomethyl group into the aromatic ring. Thereafter, there may be mentioned a method in which phosphorus trichloride and anhydrous aluminum chloride are added and reacted, followed by a hydrolysis reaction to introduce a phosphonic acid group.
  • a method may be exemplified in which phosphorus trichloride and anhydrous aluminum chloride are added to the copolymer and reacted to introduce a phosphinic acid group into the aromatic ring, and then the phosphinic acid group is oxidized with nitric acid to form a phosphonic acid group.
  • the ion exchange capacity of the block copolymer is preferably 0.40 meq / g or more, more preferably 0.50 meq / g or more, and further preferably 0.60 meq / g.
  • the ion exchange capacity of the sulfonated or phosphonated block copolymer, or the sulfonation rate or phosphonation rate in the aromatic vinyl compound in the block copolymer is determined by acid value titration, infrared spectroscopic measurement, nuclear It can be calculated using analytical means such as magnetic resonance spectrum ( 1 H-NMR spectrum) measurement.
  • the ion conductive group may be introduced in the form of a salt neutralized with a suitable metal ion (for example, alkali metal ion) or counter ion (for example, ammonium ion).
  • a suitable metal ion for example, alkali metal ion
  • counter ion for example, ammonium ion
  • a block copolymer having a sulfonic acid group in a salt form can be obtained by ion exchange by an appropriate method.
  • the polymer electrolyte 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 foaming agent, a pigment, and a dye as long as the effects of the present invention are not impaired. Further, each of them may contain a brightener or the like alone or in combination of two or more.
  • softener examples include petroleum softeners such as paraffinic, naphthenic or aromatic process oils, paraffin, vegetable oil softeners, plasticizers, and the like.
  • Stabilizers include phenol-based stabilizers, sulfur-based stabilizers, phosphorus-based stabilizers, and the like. Specific examples include 2,6-di-t-butyl-p-cresol, pentaerythryl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Benzene, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethyleneb
  • the content of the block copolymer in the polymer electrolyte of the present invention is preferably 50% by weight or more, more preferably 70% by weight or more, and 90% by weight or more. It is even more preferable.
  • the polymer electrolyte membrane of the present invention suitable for use in a polymer electrolyte fuel cell or the like preferably has a thickness of about 5 to 300 ⁇ m, preferably 6 to 200 ⁇ m, from the viewpoints of membrane resistance, membrane strength, handling properties, and the like. More preferably, it is about 7 to 100 ⁇ m. When it is desired to lower the membrane resistance, 7 to 30 ⁇ m is preferable. When the membrane resistance is kept low and the membrane strength is increased, 20 to 60 ⁇ m is preferable. When the membrane strength is important, 50 to 100 ⁇ m is preferable.
  • any method for preparing the polymer electrolyte membrane any method can be adopted as long as it is a normal method for such preparation.
  • a solution coating method for obtaining a polymer electrolyte membrane having a desired thickness, or a polytetrafluoroethylene sheet or the like of 5% by weight or less a solution coating method for obtaining a polymer electrolyte membrane having a desired thickness, or a polytetrafluoroethylene sheet or the like of 5% by weight or less.
  • the solvent is gradually removed over 1 to several days to obtain a polymer electrolyte membrane having a desired thickness.
  • a method of forming a film using a known method such as a cast method, hot press molding, roll molding, extrusion molding, etc. can be used, but it is easy to adjust a polymer electrolyte membrane having good strength and flexibility. Therefore, the solution coating method is preferably used.
  • the same or different block copolymer solution may be newly applied on the obtained polymer electrolyte membrane layer and dried to be laminated. Further, the same or different polymer electrolyte membranes obtained as described above may be laminated by being pressure-bonded by hot roll molding or the like.
  • the solvent used when preparing the polymer electrolyte membrane in a uniform solution system is capable of preparing a solution having a viscosity that allows solution coating without destroying the structure of the block copolymer. If there is no particular limitation. Specifically, halogenated hydrocarbons such as methylene chloride and chlorobenzene, aromatic hydrocarbons such as toluene, xylene, and benzene, linear aliphatic hydrocarbons such as hexane and heptane, and cyclic fats such as cyclohexane.
  • halogenated hydrocarbons such as methylene chloride and chlorobenzene
  • aromatic hydrocarbons such as toluene, xylene, and benzene
  • linear aliphatic hydrocarbons such as hexane and heptane
  • cyclic fats such as cyclohexane.
  • Examples include aromatic hydrocarbons, ethers such as tetrahydrofuran, alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol and isobutyl alcohol, or mixed solvents thereof.
  • ethers such as tetrahydrofuran
  • alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol and isobutyl alcohol, or mixed solvents thereof.
  • one or more combinations can be appropriately selected and used from the solvents exemplified above.
  • a mixed solvent of benzene and methanol, chlorobenzene is preferable, and a mixed solvent of toluene and isobutyl alcohol, a mixed solvent of toluene and isopropyl alcohol, and chlorobenzene are particularly preferable.
  • the aromatic vinyl polymer block (A) having an ion conductive group is hydrophilic and the aliphatic vinyl polymer block (B) is hydrophobic, it has a protective colloid forming ability, and a surfactant is used.
  • An emulsion can be obtained without any problems. Further, by using a polar solvent such as water, 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, it is preferable to apply the phase inversion emulsification method in that the distribution of the dispersed particle diameter can be narrowed. That is, a polar solvent such as water is added while stirring a solution obtained by dissolving the block polymer in a suitable organic solvent with an emulsifier. Initially, a polar solvent such as water is dispersed in the organic solvent system as particles, but when the polar solvent exceeds a certain amount, it becomes a co-continuous state, and the viscosity rapidly increases. Further, when a polar solvent is added, the polar solvent becomes a continuous phase and the organic solvent becomes fine particles, and the viscosity rapidly decreases. By using this method, an emulsion having a uniform dispersed particle size can be obtained.
  • the block polymer When the dispersion particle size of the emulsion is larger than 1 ⁇ m, the block polymer has a phase-separated structure within the particle, and not all ion conductive groups have come out in the outer shell. It cannot be used effectively. Therefore, when a block polymer is used, it is desirable to make fine particles until the average dispersed particle size is 1 ⁇ m or less, depending on the molecular weight of the polymer used and the block ratio. In many cases, since the average dispersed particle size in the pre-emulsification is 1 ⁇ m or more, further fine dispersion is required.
  • a known method can be used, but a method that does not use a medium such as a ball for grinding in a ball mill is preferable from the viewpoint of preventing impurities from being mixed.
  • Specific examples include a high-pressure collision method.
  • the solvent removal conditions in the solution coating method may be arbitrarily selected as long as the conditions are such that the solvent can be completely removed at a temperature equal to or lower than the temperature at which ion conductive groups such as sulfonic acid groups of the block copolymer are removed. Is possible.
  • a plurality of temperatures may be arbitrarily combined, or a combination of ventilation and vacuum may be arbitrarily combined. Specifically, a method of removing the solvent by hot air drying at about 60 to 100 ° C. over 4 minutes, a method of removing the solvent in 2 to 4 minutes by hot air drying at about 100 to 140 ° C., After preliminarily drying at about 25 ° C.
  • Examples include a method of drying for about 1 to 12 hours by vacuum drying under an atmosphere of about 40 ° C. From the viewpoint of easy preparation of a polymer electrolyte membrane having good strength and flexibility, a method of removing the solvent by hot air drying at about 60 to 100 ° C. over 4 minutes, or about 1 to 3 hours at about 25 ° C. Then, after pre-drying, dry with hot air drying at about 100 ° C. over several minutes, or after pre-drying at about 25 ° C. for about 1 to 3 hours and then in an atmosphere at about 25-40 ° C. under vacuum A method of drying for about 1 to 12 hours by drying is preferably used.
  • the membrane-electrode assembly of the present invention using a polymer electrolyte membrane produced from the polymer electrolyte of the present invention will be described.
  • a known method can be applied.
  • a catalyst paste containing an ion conductive binder is applied on the gas diffusion layer by a printing method or a spray method and dried.
  • a solution or suspension containing an ion conductive binder is applied to both surfaces of the polymer electrolyte membrane and / or the catalyst layer surface of a pair of gas diffusion electrodes, and the polymer electrolyte membrane and the catalyst layer surface There is a method of bonding them together by thermocompression bonding.
  • the solution or suspension may be applied to one or both of the polymer electrolyte membrane and the catalyst layer surface.
  • the catalyst paste is applied to a base film made of polytetrafluoroethylene (PTFE) and dried to form a catalyst layer, and then a pair of base films on the base film is formed.
  • PTFE polytetrafluoroethylene
  • the catalyst layer is transferred to both sides of the polymer electrolyte membrane by thermocompression bonding, and the base film is peeled off to obtain a joined body of the polymer electrolyte membrane and the catalyst layer.
  • a gas diffusion layer is formed on each catalyst layer by hot pressing.
  • Examples of the ion conductive binder constituting the membrane-electrode assembly include existing perfluorosulfones such as “Nafion” (registered trademark, manufactured by DuPont) and “Gore-select” (registered trademark, manufactured by Gore).
  • An ion conductive binder made of an acid polymer, an ion conductive binder made of a sulfonated polyethersulfone or a sulfonated polyetherketone, an ion conductive binder made of polybenzimidazole impregnated with phosphoric acid or sulfuric acid can be used. .
  • an ion conductive binder from the block copolymer which comprises the polymer electrolyte membrane of this invention.
  • the polymer electrolyte membrane is composed of a plurality of materials such as a multilayer structure
  • the polymer electrolyte constituting the surface in contact with the gas diffusion electrode of the polymer electrolyte membrane, or the same type of material as the polymer electrolyte that is the main component of the surface More preferably, an ion conductive binder formed from the same material is used.
  • the constituent material of the catalyst layer of the membrane-electrode assembly is not particularly limited as the conductive material / catalyst support, and examples thereof include carbon materials.
  • the carbon material include carbon black such as furnace black, channel black, and acetylene black, activated carbon, graphite, and the like. These may be used alone or in combination of two or more.
  • the catalyst metal may be any metal that promotes the oxidation reaction of fuel such as hydrogen or methanol and the reduction reaction of oxygen, such as platinum, gold, silver, palladium, iridium, rhodium, ruthenium, iron, Cobalt, nickel, chromium, tungsten, manganese, palladium, etc., or alloys thereof, for example, platinum-ruthenium alloy can be mentioned.
  • the particle size of the metal serving as a catalyst is usually 10 to 300 angstroms.
  • the catalyst layer may contain a water repellent as necessary.
  • the water repellent include various thermoplastic resins such as polytetrafluoroethylene, polyvinylidene fluoride, styrene butadiene copolymer, and polyether ether ketone.
  • 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 water repellency, this material may be subjected to water repellency treatment.
  • the membrane-electrode assembly of the present invention uses a pure hydrogen type using hydrogen as a fuel gas, a methanol reforming type using hydrogen obtained by reforming methanol, and hydrogen obtained by reforming natural gas. Natural gas reforming type, gasoline reforming type using hydrogen obtained by reforming gasoline, direct methanol type using methanol directly, etc. is there.
  • the polymer electrolyte membrane comprising the polymer electrolyte of the present invention has high proton conductivity at low humidity and low resistance, and the membrane-electrode assembly comprising the polymer electrolyte membrane uses hydrogen as a fuel.
  • the membrane-electrode assembly comprising the polymer electrolyte membrane uses hydrogen as a fuel.
  • the number average molecular weight was measured by the gel permeation chromatography (GPC) method under the following conditions.
  • Device manufactured by Tosoh Corporation, trade name: HLC-8220GPC Eluent: THF
  • Column manufactured by Tosoh Corporation, trade name: 1 TSK-GEL (TSKgel G3000HxL (inner diameter 7.6 mm, effective length 30 cm)), TSKgel Super Multipore HZ-M (inner diameter 4.6 mm, effective length 15 cm) 3 in total)
  • Detector RI Liquid feed amount: 0.35 ml / min
  • Number average molecular weight calculation Standard polystyrene conversion
  • the number average molecular weight (GPC measurement, standard polystyrene conversion) of the obtained tBSVBtBSItBS is 35,000, the 1,4-bond amount determined from 1 H-NMR measurement is 93.0%, and the content of 4-vinylbiphenyl units is included. The amount was 36.6% by weight, and the content of 4-tert-butylstyrene units was 30.4% by weight.
  • tBSVBtBSEPtBS poly(2-tert-butylstyrene) -b-poly (4-vinylbiphenyl) -b-poly (4-tert-butylstyrene) -b-hydrogenated polyisoprene-b-poly (4-tert- Butylstyrene)
  • tBSVBIVBtBS poly (4-tert-butylstyrene) -b-poly (4-vinylbiphenyl) -b-polyisoprene-b -Poly (4-vinylbiphenyl) -b-poly (4-tert-butylstyrene)
  • the number average molecular weight (GPC measurement, standard polystyrene conversion) of the obtained tBSVBIVBtBS is 158,000, the 1,4-bond amount determined from 1 H-NMR measurement is 94.0%, and the content of 4-vinylbiphenyl units The amount was 33.9% by weight, and the content of 4-tert-butylstyrene units was 22.0% by weight.
  • tBSVBEPVBtBS Poly (4-tert-butylstyrene) -b-poly (4-vinylbiphenyl) -b-hydrogenated polyisoprene-b-poly (4-vinylbiphenyl) -b-poly (4-tert-butylstyrene)
  • ⁇ Reference Example 3> (Production of block copolymer consisting of polystyrene, hydrogenated polyisoprene and poly (4-tert-butylstyrene))
  • Into a 1400 mL autoclave 820 ml of dehydrated cyclohexane and 1.7 ml of sec-butyllithium (1.25 M-cyclohexane solution) were charged, and then 19.8 ml of 4-tert-butylstyrene and 27.7 ml of styrene were successively added at 50 ° C.
  • tBSSIStBS Polystyrene-b-polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • the number average molecular weight (GPC measurement, standard polystyrene conversion) of the obtained tBSSIStBS was 86,000, the 1,4-bond content determined from 1 H-NMR measurement was 94.0%, and the styrene unit content was 32. The content of 9.9% by weight and 4-tert-butylstyrene unit was 29.8% by weight.
  • tBSSEPStBS poly (4-tert-butylstyrene) -b-polystyrene-b-hydrogenated polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • tBSSIStBS polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • the number average molecular weight (GPC measurement, standard polystyrene conversion) of the obtained tBSSIStBS was 72,000, the 1,4-bond amount determined from 1 H-NMR measurement was 94.0%, and the styrene unit content was 29. The content of 4% by weight and 4-tert-butylstyrene unit was 30.0% by weight.
  • tBSSEPStBS poly (4-tert-butylstyrene) -b-polystyrene-b-hydrogenated polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • tBSSIStBS Polystyrene-b-polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • the number average molecular weight (GPC measurement, standard polystyrene conversion) of the obtained tBSSIStBS was 64,000, the 1,4-bond content determined from 1 H-NMR measurement was 94.2%, and the styrene unit content was 41.
  • the content of 2-wt% and 4-tert-butylstyrene units was 29.4 wt%.
  • tBSSEPStBS poly (4-tert-butylstyrene) -b-polystyrene-b-hydrogenated polyisoprene-b-polystyrene-b-poly (4-tert-butylstyrene)
  • ⁇ Production Example 1> (Aromatic vinyl polymer block (A) mainly composed of sulfonated 4-vinylbiphenyl units, aliphatic vinyl polymer block (B) mainly composed of hydrogenated isoprene units, and aroma mainly composed of 4-tert-butylstyrene)
  • a sulfonated tBSVBtBSEPtBS which is a polymer electrolyte of the present invention.
  • the sulfonic acid group content per repeating unit of the polymer block containing 4-vinylbiphenyl unit modified with sulfonic acid group which is the aromatic vinyl polymer block (A) having sulfonic acid group of the obtained sulfonated tBSVBtBSEPtBS is The titration was 1.96, and the ion exchange capacity of the polymer electrolyte was 3.0 meq / g.
  • ⁇ Production Example 2> (Aromatic vinyl polymer block (A) mainly composed of sulfonated 4-vinylbiphenyl units, aliphatic vinyl polymer block (B) mainly composed of hydrogenated isoprene units, and mainly composed of 4-tert-butylstyrene units)
  • Block copolymer composed of aromatic vinyl polymer block (C) (synthesis of sulfonated tBSVBtBSEPtBS) 5 g of the block copolymer (tBSVBtBSEPtBS) obtained in Reference Example 1 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour and then purged with nitrogen, followed by addition of 200 ml of methylene chloride and stirring at room temperature.
  • a sulfonated tBSVBtBSEPtBS which is a polymer electrolyte of the present invention.
  • the ion exchange capacity of the polymer electrolyte was 2.77 meq / g.
  • Block copolymer composed of aromatic vinyl polymer block (C) (synthesis of sulfonated tBSVBEPVBtBS) 5 g of the block copolymer (tBSVBEPVBtBS) obtained in Reference Example 2 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour and then purged with nitrogen, and then 180 ml of methylene chloride was added and stirred at room temperature.
  • a sulfonated tBSVBEPVBtBS which is a polymer electrolyte of the present invention.
  • the content of sulfonic acid group per repeating unit of the polymer block containing 4-vinylbiphenyl unit modified with sulfonic acid group, which is the aromatic vinyl polymer block (A) of the obtained sulfonated tBSVBEPVBtBS is 1.54 from titration.
  • the ion exchange capacity of the polymer electrolyte was 2.33 meq / g.
  • Block copolymer consisting of a polymer block (C) (synthesis of sulfonated tBSSEPStBS) 40 g of the block copolymer (tBSSEPStBS) obtained in Reference Example 3 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour and then purged with nitrogen, and then 500 ml of methylene chloride was added and stirred at room temperature. And dissolved.
  • a sulfonation reagent obtained by reacting 61.4 ml of acetic anhydride and 27.5 ml of sulfuric acid at 0 ° C. in 123 ml of methylene chloride was gradually added dropwise over 5 minutes.
  • 20 ml of distilled water as a stopper was added.
  • 0.7 L of distilled water was slowly poured into the polymer solution to coagulate and precipitate the polymer.
  • the methylene chloride was removed by distillation at atmospheric pressure, followed by filtration.
  • the solid content obtained by filtration was transferred to a beaker, 1.3 L of distilled water was added, and washing was performed with stirring, followed by filtration and recovery.
  • a sulfonated tBSSEPStBS which is a polymer electrolyte not belonging to the present invention.
  • the content of sulfonic acid group per repeating unit of the polymer block containing styrene group modified with sulfonic acid group of the obtained sulfonated tBSSEPStBS is 1.00 from 1 H-NMR analysis, and the ion exchange of the polymer electrolyte The capacity was 2.52 meq / g.
  • Block copolymer consisting of a polymer block (C) (synthesis of sulfonated tBSSEPStBS) 40 g of the block copolymer (tBSSEPStBS) obtained in Reference Example 3 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour and then purged with nitrogen, and then added with 452 ml of methylene chloride and stirred at room temperature. And dissolved.
  • a sulfonation reagent obtained by reacting 55.5 ml of acetic anhydride and 24.8 ml of sulfuric acid at 0 ° C. in 111 ml of methylene chloride was gradually added dropwise over 5 minutes.
  • 20 ml of distilled water as a stopper was added.
  • 0.7 L of distilled water was slowly poured into the polymer solution to coagulate and precipitate the polymer.
  • the methylene chloride was removed by distillation at atmospheric pressure, followed by filtration.
  • the solid content obtained by filtration was transferred to a beaker, 1.3 L of distilled water was added, and washing was performed with stirring, followed by filtration and recovery.
  • a sulfonated tBSSEPStBS which is a polymer electrolyte not belonging to the present invention.
  • the content of sulfonic acid group per repeating unit of the polymer block containing styrene group modified with sulfonic acid group of the obtained sulfonated tBSSEPStBS is 1.00 from 1 H-NMR analysis, and the ion exchange of the polymer electrolyte The capacity was 2.30 meq / g.
  • Block copolymer composed of aromatic vinyl polymer block (C) (synthesis of sulfonated tBSVBtBSEPtBS) 5 g of the block copolymer (tBSVBtBSEPtBS) obtained in Reference Example 1 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour and then purged with nitrogen, followed by addition of 200 ml of methylene chloride and stirring at room temperature.
  • a sulfonated tBSVBtBSEPtBS which is a polymer electrolyte not belonging to the present invention.
  • the content of sulfonic acid groups per repeating unit of the polymer block containing a benzene ring of 4-vinylbiphenyl units modified with sulfonic acid groups of the obtained sulfonated tBSVBtBSEPtBS is 1.30 from titration.
  • the ion exchange capacity was 2.17 meq / g.
  • Block copolymer consisting of a polymer block (C) (synthesis of sulfonated tBSSEPStBS) 40 g of the block copolymer (tBSSEPStBS) obtained in Reference Example 5 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour and then purged with nitrogen, and then added with 540 ml of methylene chloride and stirred at room temperature. And dissolved.
  • a sulfonation reagent obtained by reacting 89.0 ml of acetic anhydride and 51.8 ml of sulfuric acid at 0 ° C. in 44.5 ml of methylene chloride was gradually added dropwise over 5 minutes.
  • 20 ml of distilled water as a stopper was added.
  • 0.6 L of distilled water was slowly poured into the polymer solution to solidify and precipitate the polymer.
  • the methylene chloride was removed by distillation at atmospheric pressure, followed by filtration.
  • the solid content obtained by filtration was transferred to a beaker, 1.3 L of distilled water was added, and washing was performed with stirring, followed by filtration and recovery.
  • a sulfonated tBSSEPStBS which is a polymer electrolyte not belonging to the present invention.
  • the content of sulfonic acid group per repeating unit of the polymer block containing styrene group modified with sulfonic acid group of the obtained sulfonated tBSSEPStBS is 1.00 from 1 H-NMR analysis, and the ion exchange of the polymer electrolyte The capacity was 2.99 meq / g.
  • Example 1 (Production of polymer electrolyte membrane) A 25 wt% toluene / isobutyl alcohol (weight ratio 6/4) solution of the sulfonated tBSVBtBSEPtBS (ion exchange capacity 3.0 meq / g) obtained in Production Example 1 was prepared, and a release-treated PET film [(stock ) “Toyobo Ester Film K1504” manufactured by Toyobo Co., Ltd.] was coated at a thickness of about 250 ⁇ m and dried in a hot air dryer at 100 ° C. for 4 minutes to obtain a film having a thickness of 35 ⁇ m.
  • a release-treated PET film [(stock ) “Toyobo Ester Film K1504” manufactured by Toyobo Co., Ltd.] was coated at a thickness of about 250 ⁇ m and dried in a hot air dryer at 100 ° C. for 4 minutes to obtain a film having a thickness of 35 ⁇ m.
  • Example 2 (Production of polymer electrolyte membrane) A 30% by weight toluene / isobutyl alcohol (weight ratio 6/4) solution of the sulfonated tBSVBtBSEPtBS (ion exchange capacity 2.77 meq / g) obtained in Production Example 2 was prepared, and a release-treated PET film [(Strain ) "Toyobo Ester Film K1504" manufactured by Toyobo Co., Ltd.] with a thickness of about 150 ⁇ m, and dried in a hot air dryer at 100 ° C. for 4 minutes to obtain a 20 ⁇ m thick film.
  • a release-treated PET film [(Strain ) "Toyobo Ester Film K1504" manufactured by Toyobo Co., Ltd.] with a thickness of about 150 ⁇ m, and dried in a hot air dryer at 100 ° C. for 4 minutes to obtain a 20 ⁇ m thick film.
  • Example 3 (Production of polymer electrolyte membrane) A 1% by weight chlorobenzene solution of the sulfonated tBSVBEPVBtBS (ion exchange capacity 2.33 meq / g) obtained in Production Example 3 was prepared and cast into a container made of a polytetrafluoroethylene sheet. By gradually removing the solvent, a 29 ⁇ m thick film was obtained.
  • ⁇ Comparative Example 1> (Production of polymer electrolyte membrane) A 18% by weight toluene / isopropyl alcohol (5/5 by weight) solution of the sulfonated tBSSEPStBS obtained in Production Example 4 was prepared, and a release-treated PET film [“Toyobo Ester Film K1504” manufactured by Toyobo Co., Ltd.] A film having a thickness of about 350 ⁇ m was coated thereon, dried at 100 ° C. for 4 minutes, and then peeled off from the PET film to obtain a film having a thickness of 30 ⁇ m.
  • ⁇ Comparative Example 2> (Production of polymer electrolyte membrane) A 19% by weight toluene / isopropyl alcohol (weight ratio 5/5) solution of the sulfonated tBSSEPStBS obtained in Production Example 5 was prepared, and a release-treated PET film ["Toyobo Ester Film K1504" manufactured by Toyobo Co., Ltd.] A film with a thickness of about 350 ⁇ m was coated thereon, dried at 100 ° C. for 4 minutes, and then peeled off from the PET film to obtain a film with a thickness of 31 ⁇ m.
  • a polymer electrolyte membrane of 1 cm ⁇ 4 cm was sandwiched between a pair of platinum electrodes and attached to an open cell.
  • the measurement cell was installed in a constant temperature and humidity chamber adjusted to a temperature of 80 ° C. and a relative humidity of 30%, and the ionic conductivity of the membrane was measured by an AC impedance method.
  • Table 1 shows the measurement results of ionic conductivity and linear expansion coefficient of the polymer electrolytes used in Examples 1 to 3 and Comparative Examples 1 to 4 and the produced polymer electrolyte membranes.
  • Example 1 has a higher ion conductivity and a lower linear expansion coefficient even if the ion exchange capacity is substantially the same. That is, the polymer electrolyte membrane of the present invention has high ion conductivity and high shape stability in water. The same can be said for the comparison between Example 3 and Comparative Example 2. Moreover, when Example 2 and Comparative Example 4 which show comparable ionic conductivity are compared, Example 2 has a much lower linear expansion coefficient and is excellent in shape stability in water.
  • the polymer electrolyte membrane comprising the polymer electrolyte of the present invention is excellent in ionic conductivity under low humidity. Therefore, the low humidity of the membrane-electrode assembly and the solid polymer fuel cell using the same The output characteristics below are also excellent. Further, the polymer electrolyte membrane is less swollen by water and has good shape stability in water.
  • a membrane-electrode assembly excellent in output characteristics under low humidity and a solid polymer fuel cell can be provided.

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Abstract

L'invention concerne : un électrolyte polymère qui a une haute conductivité ionique même lorsqu'il est placé dans des conditions de basse humidité, qui est gonflé avec de l'eau dans une moindre mesure, et qui peut servir d'alternative aux électrolytes polymères contenant du fluor tels que Nafion ; et un film d'électrolyte polymère, un ensemble film-électrode et une pile à combustible à polymère solide chacun produits à l'aide de l'électrolyte polymère. L'invention concerne en particulier : un électrolyte polymère comprenant un copolymère séquencé composé d'au moins une séquence polymère de vinyle aromatique (A) et une séquence polymère de vinyle aromatique (B) comme constituants, et caractérisé en ce que la teneur d'un groupe conducteur ionique dans la séquence polymère de vinyle aromatique (A) est de 1,5 à 3,0 groupes par motif répété et la séquence polymère de caoutchouc (B) ne comporte aucun groupe conducteur ionique ; et un film d'électrolyte polymère, un ensemble film-électrode et une pile à combustible polymère solide, chacun d'entre eux étant produit à l'aide de l'électrolyte polymère.
PCT/JP2010/071088 2009-11-30 2010-11-26 Electrolyte polymère, film d'électrolyte polymère, ensemble film-électrode et pile à combustible polymère solide Ceased WO2011065460A1 (fr)

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US8377514B2 (en) 2008-05-09 2013-02-19 Kraton Polymers Us Llc Sulfonated block copolymer fluid composition for preparing membranes and membrane structures
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