JP4929575B2 - Polyarylene ether compounds having sulfonic acid group-containing naphthylene structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a novel polymeric material which provides an ion-conducting film which is excellent in heat resistance, processability and ion-conducting property and especially shows a good dimensional stability. <P>SOLUTION: A polyarylene ether compound into which a sulfonic acid group is introduced is useful as a polyelectrolyte film and can be obtained by synthesizing a polymer using naphthalene diol containing a sulfonic acid group as at least one of the monomer components. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a sulfonic acid group-containing aromatic polyarylene ether compound useful as a polymer electrolyte membrane.

  As an example of an electrochemical device using a polymer solid electrolyte as an ionic conductor instead of a liquid electrolyte, a water electrolyzer and a fuel cell can be raised. The polymer membrane used for these must be sufficiently stable chemically, thermally, electrochemically and mechanically with proton conductivity as a cation exchange membrane. For this reason, perfluorocarbon sulfonic acid membranes, typically “Nafion (registered trademark)” manufactured by DuPont, have been used as long-term usable products. However, if the Nafion membrane is to be operated at a temperature of 100 ° C. or higher, the moisture content of the membrane drops rapidly and the membrane softens significantly. In addition, in a fuel cell using methanol as a fuel, the performance is deteriorated due to methanol permeation in the membrane, and sufficient performance cannot be exhibited. Further, even in fuel cells that are currently being studied mainly using hydrogen as a fuel and operating at around 80 ° C., it is pointed out that the cost of the membrane is too high as an obstacle to the establishment of fuel cell technology.

In order to overcome such drawbacks, various polymer electrolyte membranes in which a sulfonic acid group is introduced into a non-fluorinated aromatic ring-containing polymer have been studied. As a polymer skeleton, considering heat resistance and chemical stability, aromatic polyarylene ether compounds such as aromatic polyarylene ether ketones and aromatic polyarylene ether sulfones can be regarded as promising structures, A sulfonated polyarylene ether sulfone (for example, see Non-patent Document 1), a sulfonated polyether ether ketone (for example, see Patent Document 1), and the like have been reported. In these methods, a sulfonic acid group is introduced by reacting a polymer with a sulfonating agent. However, a method for directly obtaining a sulfonated polymer by polymerization using a sulfonated monomer has also been reported (for example, Patent Documents). 2-4). However, these aromatic hydrocarbon-based membranes are also required to exhibit even better characteristics in terms of dimensional stability.
JP-A-6-93114 US Patent Application Publication No. 2002/0091225 International Publication No. 2003/095509 International Publication No. 2004/033534 Journal of Membrane Science (Netherlands) 1993, 83, p. 211-220

  An object of the present invention is to obtain a polymer material useful as an ion conductive membrane having outstanding dimensional stability by using a sulfonic acid group-containing polyarylene ether compound having a specific structure excellent in dimensional stability.

As a result of intensive studies, the present inventors have found that the above object can be achieved by the following sulfonic acid group-containing polyarylene ether compounds.

  That is, the present invention is achieved by the following (1) to (11).

(1) A polyarylene ether compound having a constituent represented by the general formula (1) in a molecular chain.
X represents hydrogen or a monovalent cation species, m and n are 0 or 1, and m + n is not 0.

(2) The polyarylene ether compound according to the first invention, further comprising a component represented by the general formula (2) and / or the general formula (3).
Y represents a sulfone group or a ketone group, and X represents H or a monovalent cation species. Ar ′, Ar ″ represents a divalent aromatic group which may contain a substituent, and includes a sulfonic acid group-containing naphthylene structure which gives the structure of the general formula (1).

(3) The polyarylene ether compound according to either the first invention or the second invention, wherein the sulfonic acid group content is in the range of 0.3 to 3.5 meq / g.

(4) A composition comprising 50 to 100% by mass of the polyarylene ether compound according to any one of the first to third inventions.

(5) An ion conductive membrane comprising the compound according to any one of the first to third inventions and / or the composition according to the fourth invention.

(6) A composite comprising the ion conductive membrane according to the fifth invention and an electrode.

(7) A fuel cell comprising the composite according to the sixth invention.

(8) The fuel cell according to the seventh invention, wherein methanol is used as a fuel.

(9) An adhesive comprising the compound according to any one of the first to third inventions.

(10) When polymerizing a sulfonic acid group-containing polyarylene ether compound by an aromatic nucleophilic substitution reaction, the sulfonic acid group-containing naphthalenediol represented by the general formula (4) is used as at least one monomer. A method for producing a polyarylene ether compound according to any one of the first to third inventions.
However, X is hydrogen or a monovalent cation species, m and n are 0 or 1, and m + n is not 0.

(11) A step of casting the solution containing the compound according to any one of the first to third inventions and a solvent so that the cast thickness is in the range of 10 to 1500 μm, and drying the cast solution. A process for producing an ion conductive membrane according to the fourth invention.

  The sulfonic acid group-containing aromatic polyarylene ether compound of the present invention exhibits excellent dimensional stability even under high-temperature and high-humidity conditions, and is excellent in ion conductivity, heat resistance and processability, and is a polymer such as a fuel cell. A material that exhibits outstanding performance as an electrolyte can be provided. The sulfonic acid group-containing polyarylene ether compound of the present invention is also characterized by low methanol permeability, and is useful as a polymer electrolyte membrane for direct methanol fuel cells.

Hereinafter, the present invention will be described in detail.
The present invention improves the dimensional stability by a specific polyarylene ether compound having excellent dimensional stability in which a sulfonic acid group is introduced on an aromatic ring, and has excellent heat resistance, workability, and ion conductivity. A polymer material useful as a conductive film is provided. That is, when synthesizing a sulfonic acid group-containing polyarylene ether compound by an aromatic nucleophilic substitution reaction, by using naphthalenediol containing a sulfonic acid group as at least one component of an aromatic diol monomer, the present invention is used. It has been reached. The method of directly synthesizing sulfonic acid group-containing polyarylene ethers by aromatic nucleophilic substitution has been performed mainly by introducing sulfonic acid groups into electron-withdrawing monomers such as dichlorodiphenylsulfone and difluorobenzophenone. . This is because the sulfonic acid group is electron-withdrawing, so the impact on the reactivity of these monomers is small. However, when the sulfonic acid group is introduced onto the aromatic ring of the diol monomer, the nucleophilicity of the diol monomer decreases. Therefore, it is considered that the fact that a good polymer could not be obtained had an influence. This time, by examining the synthesis of polyarylene ethers by aromatic nucleophilic substitution reaction using naphthalenediol containing sulfonic acid groups, good polymers can be obtained using these monomers, and the polymer characteristics are also improved. The inventors have found that the polymer electrolyte membrane is excellent.

  That is, the sulfonic acid group-containing polyarylene ether compound of the present invention is a polyarylene ether compound having a component represented by the following general formula (1) in the molecular chain. A polyarylene ether compound is a general term for compounds containing an ether bond in the manner of bonding an aromatic ring constituting a polymer chain in an aromatic polymer, and a bond other than an ether bond may be included. . In the present invention, it is preferable that an ether bond, a sulfone bond, a sulfide bond, a ketone bond, and a direct bond occupy a majority of the entire bonding mode among the bonding modes for connecting the aromatic rings.

  The naphthylene structure in the general formula (1) is different benzene such as 1,5-naphthylene, 1,6-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,6-naphthylene, 2,7-naphthylene. Those having a bond position on the ring are preferred, but those having a bond position on the same benzene ring such as 1,4-naphthylene and 2,3-naphthylene may also be used. The position where the sulfonic acid group is substituted is not particularly limited, but it can exist up to two on the naphthalene ring. When two sulfonic acid groups are present, one exists on a different benzene ring. It is preferable. The sulfonic acid group may be in the form of a salt with a monovalent metal salt such as sodium or potassium, or a monovalent cation species such as an ammonium salt, in addition to the acid type with a proton.

  The sulfonic acid group-containing polyarylene ether compound of the present invention includes a component containing a sulfonic acid group-containing dioxynaphthylene structure together with a component represented by the following general formula (2) or the following general formula (3). It is preferable. It is further preferable that both constituents of the general formula (2) and the general formula (3) are included.

Y represents a sulfone group or a ketone group, and X represents H or a monovalent cation species. Ar ′ and Ar ″ represent a divalent aromatic group which may contain a substituent, and may have a sulfonic acid group-containing naphthylene structure represented by the following general formula (5).

  The component represented by the general formula (3) is preferably a component represented by the following general formula (6). Ar ′ ′ ′ in the formula represents a divalent aromatic group which may contain a substituent, and may be a sulfonic acid group-containing naphthylene structure represented by the general formula (5).

  In the sulfonic acid group-containing polyarylene ether compound of the present invention, the introduction amount of the sulfonic acid group-containing dioxynaphthylene structure is introduced according to the amount of sulfonic acid group required for the whole polyarylene ether compound. In particular, the amount is not limited. Further, for example, it can be used in combination with other sulfonic acid group-containing monomers as shown in the general formula (2), but in that case, 20% or more of the amount of sulfonic acid groups introduced into the polyarylene ether compound. By introducing a sulfonic acid group corresponding to the above in a dioxynaphthylene structure containing a sulfonic acid group, the characteristics as a polymer electrolyte membrane can be made particularly excellent. It can be said that it is more preferable to introduce a sulfonic acid group corresponding to 30% or more of the amount of the sulfonic acid group introduced into the polyarylene ether compound by a sulfonic acid group-containing dioxynaphthylene structure, and more preferably 40% or more. Can be said

  In addition, the sulfonic acid group-containing polyarylene ether compound of the present invention contains a component that crosslinks by heat and / or light in its molecular chain, that is, as the main chain, side chain, or terminal group of the polymer. Also good. Examples of thermally crosslinkable groups include reactive unsaturated bond-containing components such as ethylene group, ethynyl group, and ethynylene group, but are not limited to these, and a new reaction between polymer chains is caused by reaction by heat. Any material that can form a bond may be used. Examples of photocrosslinkable groups include benzophenone groups, α-diketone groups, acyloin groups, acyloin ether groups, benzyl alkyl ketal groups, acetophenone groups, polynuclear quinones, thioxanthone groups, acylphosphine groups, and ethylenically unsaturated groups. Can be mentioned. Among them, a combination of a group capable of generating a radical by light such as a benzophenone group and a group capable of reacting with a radical such as an aromatic group having a hydrocarbon group such as a methyl group or an ethyl group is preferable. When using an ethylenically unsaturated group, photopolymerization of benzophenones, α-diketones, acyloins, acyloin ethers, benzyl alkyl ketals, acetophenones, polynuclear quinones, thioxanthones, acylphosphines, etc. It is preferable to add an initiator.

  The sulfonic acid group-containing polyarylene ether compound of the present invention preferably has a sulfonic acid group content in the range of 0.3 to 3.5 meq / g. When it is less than 0.3 meq / g, there is a tendency that sufficient ion conductivity is not exhibited when it is used as an ion conductive membrane, and even when it exceeds 3.5 meq / g, the ion conductivity reaches a peak. Tend. The sulfonic acid group content can be determined by a titration method described later after the sulfonic acid group is converted to an acid type structure by an acidic aqueous solution treatment. It can be calculated from the polymer composition. In addition, Preferably it is 1.0-3.0 meq / g.

  In order to give the Ar structure in the above general formula (1), which is a sulfonic acid group-containing polyarylene ether compound of the present invention, a dihalogenated compound represented by the following general formula (7) or general formula (8) is included as a monomer. Aromatic nucleophilic substitution reactions can be used. In the formula, Y represents a sulfone group or a ketone group, X represents a monovalent cation species, and Z represents chlorine or fluorine. Specific examples of the compound represented by the general formula (7) include 3,3′-disulfo-4,4′-dichlorodiphenyl sulfone, 3,3′-disulfo-4,4′-difluorodiphenyl sulfone, 3, 3′-disulfo-4,4′-dichlorodiphenyl ketone, 3,3′-disulfo-4,4′-difluorodiphenyl ketone, and those whose sulfonic acid group is converted to a salt with a monovalent cationic species Can be mentioned. The monovalent cation species may be sodium, potassium, other metal species, various amines, or the like, but is not limited thereto. Examples of the compound represented by the general formula (8) include 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2,4-dichlorobenzonitrile, 2,4-difluorobenzonitrile, and the like. it can.

  In the aromatic nucleophilic substitution reaction described above, 4,4′-dichlorodiphenylsulfone, 4,4′-dichlorodiphenylsulfone, which is an activated difluoroaromatic compound or dichloroaromatic compound that can be used in addition to the above general formulas (7) and (8), Examples include, but are not limited to, 4′-difluorodiphenyl sulfone, 4,4′-difluorobenzophenone, 4,4′-dichlorobenzophenone, decafluorobiphenyl, decafluorodiphenyl ether, decafluorobenzophenone, and aromatics. Other aromatic dihalogen compounds, aromatic dinitro compounds, aromatic dicyano compounds and the like that are active in nucleophilic substitution reactions can also be used. These compounds may be used alone or as a mixture of two or more. Among these, it can be said that it is preferable to use a dihalogenated compound represented by the general formula (7) and / or the general formula (8).

  Examples of aromatic diol component monomers that can be used as Ar ′ in the constituent represented by the general formula (2) and Ar ″ in the constituent represented by the general formula (3) include: 4,4′-biphenol, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane 2,2-bis (4-hydroxyphenyl) butane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4- Hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-2,5-dimethylphenyl) methane, bis (4-hydroxyphenyl) phenyl Tan, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-phenyl) -4-hydroxyphenyl) fluorene, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, hydroquinone, resorcin, 1,4-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ) Thioether In addition to these, various aromatic diols that can be used for the polymerization of polyarylene ether compounds by aromatic nucleophilic substitution reaction can also be used. Substituents such as a group, a halogen, a cyano group, a sulfonic acid group and a salt compound thereof may be bonded, and the kind of the substituent is not particularly limited, and may be 0 to 2 per aromatic ring. These aromatic diols can be used alone or in combination with a plurality of aromatic diols.

  In the polymerization of the polyarylene ether compound of the present invention, a halogenated aromatic hydroxy compound can be added as a reactive monomer component for polymerization. The halogenated aromatic hydroxy compound used in this case is not particularly limited, but 4-hydroxy-4′-chlorobenzophenone, 4-hydroxy-4′-fluorobenzophenone, 4-hydroxy-4′-chlorodiphenylsulfone. 4-hydroxy-4′-fluorodiphenylsulfone, 4-chloro-4 ′-(p-hydroxyphenyl) diphenylsulfone, 4-fluoro-4 ′-(p-hydroxyphenyl) benzophenone, and the like. it can. These can be used alone or can be used as a mixture of two or more.

  In addition, when the above-mentioned crosslinkable terminal structure is introduced, it can be obtained by adding a monofunctional end-blocking agent that gives a crosslinkable group-containing terminal structure during the polymerization of the polyarylene ether compound of the present invention. . Examples of monofunctional end-capping agents are specifically 3-fluoropropene, 3-fluoro-1-propyne, 4-fluoro-1-butene, 4-fluoro-1-butyne, 3-fluorocyclohexene, 4 -Fluorostyrene, 3-fluorostyrene, 2-fluorostyrene, 4-fluoroethynylbenzene, 3-fluoroethynylbenzene, α-fluoro-4-ethynyltoluene, 4-fluorostilbene, 4- (phenylethynyl) fluorobenzene, 3 -(Phenylethynyl) fluorobenzene, 3-chloropropene, 3-chloro-1-propyne, 4-chloro-1-butene, 4-chloro-1-butyne, 3-chlorocyclohexene, 4-chlorostyrene, 3-chloro Styrene, 2-chlorostyrene, 4-chloroethynylbenzene, 3-chloroethini Benzene, α-chloro-4-ethynyltoluene, 4-chlorostilbene, 4- (phenylethynyl) chlorobenzene, 3- (phenylethynyl) chlorobenzene, 3-hydroxypropene, 3-hydroxy-1-propyne, 4-hydroxy-1 -Butene, 4-hydroxy-1-butyne, 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, 4-hydroxyethynylbenzene, 3-ethynylphenol, 4-ethynylbenzyl alcohol, 4-hydroxystilbene, 4- (Phenylethynyl) phenol, 3- (phenylethynyl) phenol, 4-chlorobenzophenone, 4-fluorobenzophenone, 4-hydroxybenzophenone, 4-methylphenol, 3-methylphenol, 2-methylphenol, 4 Ethylphenol, 3-ethylphenol, 4-propyl phenol, 4-butylphenol, 4-pentylphenol, 4-benzyl-phenol, and the like. These crosslinking group-containing end-capping agents may be used alone or in combination of two or more.

  Specific examples of the monomer having a crosslinkable group include 1-butene-3,4-diol, 3,5-dihydroxystyrene, 3,5-dihydroxystilbene, 1-butyne-3,4-diol, -Butene-3,4-diol, 2,4-hexadiyne-1,6-diol, 2-ethynylhydroquinone, 2- (phenylethynyl) hydroquinone, 5-ethynylresorcin, 2-butene-1,4-diol, 4 , 4′-dihydroxystilbene, 1,4-butynediol, 1,2-bis (4-hydroxyphenyl) acetylene, 1,2-bis (3-hydroxyphenyl) acetylene, 3,3-difluoropropene, 3,3 -Difluoropropyne, 3,3,3-trifluoropropyne, 3,4-difluoro-1-butene, 1,4-difluoro-2- Butene, 3,4-difluoro-1-butyne, 1,4-difluoro-2-butyne, 1,6-difluoro-2,4-hexadiyne, 3,4-difluorostyrene, 2,6-difluorostyrene, 2, 5-difluoroethynylbenzene, 3,5-difluoroethynylbenzene, α, α-difluoro-4-ethynyltoluene, α, α, α-trifluoro-4-ethynyltoluene, 2,4-difluorostilbene, 4,4 ′ -Difluorostilbene, 1,2-bis (4-fluorophenyl) acetylene, 3,4-difluoro (phenylethynyl) benzene, 3,3-dichloropropene, 3,3-dichloropropyne, 3,3,3-trichloro Propyne, 3,4-dichloro-1-butene, 1,4-dichloro-2-butene, 3,4-dichloro-1-butyne, 1,4 Dichloro-2-butyne, 3,4-dichlorostyrene, 2,6-dichlorostyrene, 2,4-difluorocinamic acid, 2,5-dichloroethynylbenzene, 3,5-dichloroethynylbenzene, α, α-dichloro -4-ethynyltoluene, α, α, α-trichloro-4-ethynyltoluene, 2,4-dichlorostilbene, 4,4′-dichlorostilbene, 1,2-bis (4-chlorophenyl) acetylene, 3,4- Dichloro (phenylethynyl) benzene, 4,4′-dihydroxybenzophenone, 4,4′-dichlorobenzophenone, 4,4′-difluorobenzophenone, 4-chlorobenzophenone, 4-fluorobenzophenone, 4-hydroxybenzophenone 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydro) Cyphenyl) propane, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy-3) , 5-dimethylphenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-2,5-dimethylphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, 4- Benzylresorcin, 2,5-dimethylresorcin, 4-ethylresorcin, etc. are mentioned. By adding these crosslinking group monomers in the polymerization of the polyarylene ether compound of the present invention, a crosslinking group can be introduced into the molecular chain.

  When the sulfonic acid group-containing polyarylene ether compound of the present invention is polymerized by an aromatic nucleophilic substitution reaction, an activated difluoroaromatic compound as exemplified by the above general formula (7) and general formula (8) and / or Alternatively, a polymer can be obtained by reacting a dichloroaromatic compound and an aromatic diol in the presence of a basic compound. The polymerization can be carried out in the temperature range of 0 to 350 ° C., but is preferably 50 to 250 ° C. When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and when the temperature is higher than 350 ° C., the polymer tends to be decomposed. The reaction can be carried out in the absence of a solvent, but is preferably carried out in a solvent. Examples of the solvent that can be used include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenyl sulfone, sulfolane, and the like. And any solvent that can be used as a stable solvent in the aromatic nucleophilic substitution reaction. These organic solvents may be used alone or as a mixture of two or more. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, and those that can convert an aromatic diol into an active phenoxide structure may be used. It can use without being limited to. In the aromatic nucleophilic substitution reaction, water may be generated as a by-product. In this case, regardless of the polymerization solvent, water can be removed from the system as an azeotrope by coexisting toluene or the like in the reaction system. As a method for removing water out of the system, a water absorbing material such as molecular sieve can also be used. When the aromatic nucleophilic substitution reaction is carried out in a solvent, it is preferable to charge the monomer so that the resulting polymer concentration is 5 to 50% by mass. When the amount is less than 5% by mass, the degree of polymerization tends to be difficult to increase. On the other hand, when the amount is more than 50% by mass, the viscosity of the reaction system becomes too high, and the post-treatment of the reaction product tends to be difficult. For the polymerization, it is preferable to add monomers at the beginning of the reaction to form a polymer having a highly random chain distribution. After completion of the polymerization reaction, the solvent is removed from the reaction solution by evaporation, and the residue is washed as necessary to obtain the desired polymer. In addition, the polymer can be obtained by precipitating the polymer as a solid by adding the reaction solution in a solvent having low polymer solubility, and collecting the precipitate by filtration. If necessary, a filtration treatment may be performed before the precipitation.

  The sulfonic acid group-containing polyarylene ether compound of the present invention preferably has a polymer log viscosity measured by a method described later of 0.1 or more. When the logarithmic viscosity is less than 0.1, the membrane is likely to be brittle when formed as an ion conductive membrane. The reduced specific viscosity is more preferably 0.3 or more. On the other hand, if the reduced specific viscosity exceeds 5, problems in processability such as difficulty in dissolving the polymer occur, which is not preferable. As the solvent for measuring the logarithmic viscosity, polar organic solvents such as N-methyl-2-pyrrolidone and N, N-dimethylacetamide can be generally used. Can also be measured.

  The sulfonic acid group-containing polyarylene ether compound of the present invention can be used as a simple substance, but can also be used as a resin composition in combination with other polymers. Examples of these polymers include polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyamides such as nylon 6, nylon 6,6, nylon 6,10 and nylon 12, polymethyl methacrylate and polymethacrylate. Acrylate resins such as polymethyl acrylate, polyacrylic acid esters, polyacrylic acid resins, polymethacrylic acid resins, polyethylene, polypropylene, various polyolefins including polystyrene and diene polymers, polyurethane resins, cellulose acetate, Cellulosic resins such as ethyl cellulose, polyarylate, aramid, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polysulfone, polyether Heat curing of aromatic polymers such as sulfone, polyether ether ketone, polyether imide, polyimide, polyamide imide, polybenzimidazole, polybenzoxazole, polybenzthiazole, epoxy resin, phenol resin, novolac resin, benzoxazine resin There are no particular restrictions on the conductive resin. Resin compositions with basic polymers such as polybenzimidazole and polyvinylpyridine can be said to be a preferred combination for improving polymer dimensionality. In addition to these basic polymers, acidic compositions such as sulfonic acid groups and phosphonic acid groups are also included. When a group is introduced, the processability of the composition becomes more preferable. When used as these resin compositions, the sulfonic acid group-containing polyarylene ether compound of the present invention is preferably contained in an amount of 50% by mass or more and less than 100% by mass of the entire resin composition. More preferably, it is 70 mass% or more and less than 100 mass%. When the content of the sulfonic acid group-containing polyarylene ether compound of the present invention is less than 50% by mass of the entire resin composition, the sulfonic acid group concentration of the ion conductive membrane containing this resin composition is lowered and good ions are obtained. There is a tendency that the conductivity cannot be obtained, and the unit containing the sulfonic acid group becomes a discontinuous phase and the mobility of ions to be conducted tends to be lowered. In addition, the compound and composition of the present invention may contain, for example, an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a cross-linking agent, a viscosity modifier, an antistatic agent, an antibacterial agent, an antifoaming agent. Various additives such as an agent, a dispersant, and a polymerization inhibitor may be included.

  As a thing used for a composition with the above-mentioned acidic group containing basic polymer, the acidic group containing polybenzimidazole containing the structural component represented by following formula (9) is preferable.

In Formula (9), m ¹ represents an integer of 1 to 4, R ¹ represents a tetravalent aromatic binding unit capable of forming an imidazole ring, R ² represents a divalent aromatic unit, and R ¹ Each of R ² and R ² may be a single aromatic ring, a conjugate of a plurality of aromatic rings or a condensed ring, and may have a stable substituent. Z ³ represents a sulfonic acid group and / or a phosphonic acid group, and a part thereof may have a salt structure.

  The route for synthesizing the acidic group-containing polybenzimidazole compound containing the structure represented by the above formula (9) is not particularly limited, but usually aromatic tetramines capable of forming an imidazole ring in the compound and those And one or more compounds selected from the group consisting of these derivatives and one or more compounds selected from the group consisting of aromatic dicarboxylic acids and derivatives thereof. At that time, by using a dicarboxylic acid containing a sulfonic acid group or a phosphonic acid group or a salt thereof as at least a part of the dicarboxylic acid to be used, a sulfonic acid group or a phosphonic acid group is added to the obtained polybenzimidazole. Can be introduced. One or more dicarboxylic acids containing a sulfonic acid group or a phosphonic acid group can be used in combination, but a sulfonic acid group-containing dicarboxylic acid and a phosphonic acid group-containing dicarboxylic acid can be used simultaneously.

  Here, a benzimidazole-based binding unit that is a constituent element of a polybenzimidazole-based compound, an aromatic dicarboxylic acid-bonding unit having a sulfonic acid group and / or a phosphonic acid group, neither a sulfonic acid group nor a phosphonic acid group The aromatic dicarboxylic acid bonding unit and other bonding units are preferably bonded by random polymerization and / or alternating polymerization. Moreover, these polymerization formats are not limited to one type, and two or more polymerization types may coexist in the same compound.

  The sulfonic acid group-containing polyarylene ether compound and the resin composition thereof according to the present invention can be formed into a molded body such as a fiber or a film by an arbitrary method such as extrusion, spinning, rolling, or casting. Among these, it is preferable to mold from a solution dissolved in an appropriate solvent. Examples of the solvent include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and hexamethylphosphonamide, and alcohols such as methanol and ethanol. An appropriate one can be selected, but is not limited thereto. A plurality of these solvents may be used as a mixture within a possible range. The compound concentration in the solution is preferably in the range of 0.1 to 50% by mass. If the compound concentration in the solution is less than 0.1% by mass, it tends to be difficult to obtain a good molded product, and if it exceeds 50% by mass, the workability tends to deteriorate. A method of obtaining a molded body from a solution can be performed using a conventionally known method. For example, the molded product can be obtained by removing the solvent by heating, drying under reduced pressure, immersion in a compound non-solvent that can be mixed with a solvent that dissolves the compound, or the like. When the solvent is an organic solvent, the solvent is preferably distilled off by heating or drying under reduced pressure. At this time, it can be formed into various shapes such as a fiber shape, a film shape, a pellet shape, a plate shape, a rod shape, a pipe shape, a ball shape, and a block shape in a composite form with other compounds as necessary. . When combined with a compound having a similar dissolution behavior, it is preferable in that good molding can be achieved. The sulfonic acid group in the molded article thus obtained may contain a salt form with a cationic species, but it can be converted to a free sulfonic acid group by acid treatment as necessary. You can also.

An ion conductive membrane can also be produced from the sulfonic acid group-containing polyarylene ether compound of the present invention and the resin composition thereof. The most preferable method for forming the ion conductive membrane is casting from a solution, and the ion conductive membrane can be obtained by removing the solvent from the cast solution as described above. Examples of the solution include a solution using an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and an alcohol solvent in some cases. . The removal of the solvent is preferably by drying from the uniformity of the ion conductive membrane. Moreover, in order to avoid decomposition | disassembly and alteration of a compound or a solvent, it can also dry at the lowest temperature possible under reduced pressure. Further, when the viscosity of the solution is high, when the substrate or the solution is heated and cast at a high temperature, the viscosity of the solution is lowered and the casting can be easily performed. The thickness of the solution at the time of casting is not particularly limited, but is preferably 10 to 1500 μm. More preferably, it is 50-500 micrometers. If the thickness of the solution is thinner than 10 μm, the form as an ion conductive membrane tends to be not maintained, and if it is thicker than 1500 μm, a non-uniform polymer electrolyte membrane tends to be easily formed. As a method for controlling the cast thickness of the solution, a known method can be used. For example, the thickness can be controlled with the amount and concentration of the solution with a constant thickness using an applicator, a doctor blade, or the like, and with a cast area constant using a glass petri dish or the like. The cast solution can obtain a more uniform film by adjusting the solvent removal rate. For example, when removing the solvent by heating, the evaporation rate can be reduced by lowering the temperature in the first stage. Further, when immersed in a non-solvent such as water, the coagulation rate and solvent removal rate of the compound can be adjusted by leaving the solution in air or an inert gas for an appropriate time. The ion conductive film of the present invention can have any film thickness depending on the purpose, but it is preferably as thin as possible from the viewpoint of ion conductivity. Specifically, it is preferably 5 to 250 μm, more preferably 5 to 100 μm, and most preferably 5 to 50 μm. If the thickness of the ion conductive membrane is less than 5 μm, handling of the ion conductive membrane becomes difficult and a short circuit or the like tends to occur when a fuel cell is produced. If the thickness of the ion conductive membrane is greater than 250 μm, the electric resistance value of the ion conductive membrane increases. The power generation performance tends to decrease. When used as an ion conductive membrane, the sulfonic acid group in the membrane may contain a metal salt, but it can be converted to free sulfonic acid by an appropriate acid treatment. In this case, it is also effective to immerse the membrane in an aqueous solution of sulfuric acid, hydrochloric acid, etc. with or without heating. The ion conductivity of the ion conductive film is preferably 1.0 × 10 ⁻³ S / cm or more. When the ionic conductivity is 1.0 × 10 ⁻³ S / cm or more, a good output tends to be obtained in a fuel cell using the ion conductive membrane, and is less than 1.0 × 10 ⁻³ S / cm. In some cases, the output of the fuel cell tends to decrease.

The ion conductive membrane of the present invention is also useful for direct methanol fuel cells using methanol as fuel. An ion conductive membrane having a methanol permeation rate of 7 mmol / m ² · sec or less measured at 25 ° C. using a 5 M aqueous methanol solution and having an average thickness of 50 μm is preferable. The methanol permeation rate is more preferably 4 mmol / m ² · sec or less, and more preferably 1 mmol / m ² · sec or less. This is because power generation characteristics particularly excellent when such methanol permeability is exhibited. Since methanol permeation characteristics may depend on the film thickness, methanol permeability evaluation is performed by preparing a sample having an average thickness of 50 μm, but when actually used as an ion conductive membrane for a fuel cell, The film thickness is not limited. The film having an average thickness of 50 μm substantially indicates a film having an average thickness in the range of 48 μm to 52 μm.

When the sulfonic acid group-containing polyarylene ether compound of the present invention and the resin composition thereof contain a component that crosslinks by heat and / or light, the crosslinked structure is formed by heat treatment and / or light irradiation treatment. Introducing can further improve the dimensional stability. The heating temperature at the time of thermal crosslinking varies depending on the structure of the crosslinkable polyarylene ether, the type of crosslinking group, the amount of crosslinking group introduced, and the like, but is usually 150 to 450 ° C, preferably 200 to 400 ° C. The heating time varies depending on the heating temperature and the structure of the crosslinkable polyarylene ether, but is usually 0.5 to 50 hours, preferably 1 to 24 hours. The pressure may be normal pressure, reduced pressure, or increased pressure. The gas atmosphere may be an air atmosphere, a nitrogen atmosphere, or an argon atmosphere. When the heating temperature is high, the sulfonic acid group is preferably heat-treated in a salt state. The light source used for photocrosslinking is not particularly limited, and a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. The irradiation dose may vary depending on the polymer structure and its thickness, usually, 100~50000mJ / cm ^2, preferably 300~30000mJ / cm ^2.

  Moreover, the joined body of the ion conductive film or film of the present invention and the electrode can be obtained by bonding the above-described ion conductive film or film of the present invention to the electrode. As a method for producing this joined body, a conventionally known method can be used. For example, an adhesive is applied to the electrode surface and the ion conductive film and the electrode are bonded, or the ion conductive film and the electrode are bonded. There is a method of heating and pressurizing. Among these, a method of applying and bonding an adhesive mainly composed of the sulfonic acid group-containing polyarylene ether compound and the resin composition of the present invention to the electrode surface is preferable. This is because it is considered that the adhesion between the ion conductive film and the electrode is improved, and that the ion conductivity of the ion conductive film is less impaired.

  A fuel cell can also be produced using the above-described joined body of an ion conductive membrane or film and an electrode. Since the ion conductive membrane or film of the present invention is excellent in heat resistance, processability, ion conductivity and dimensional stability, it can withstand operation at high temperatures, is easy to produce, and has good output. A fuel cell can be provided. It is also preferable to use it as a fuel cell using methanol as a direct fuel.

EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these Examples. Various measurements were performed as follows.
Solution viscosity: The polymer powder was dissolved in N-methylpyrrolidone at a concentration of 0.5 g / dl, the viscosity was measured using an Ubbelohde viscometer in a constant temperature bath at 30 ° C., and the logarithmic viscosity ln [ta / tb] / Evaluation was made in c) (ta is the number of seconds that the sample solution was dropped, tb was the number of seconds that the solvent was dropped, and c was the polymer concentration).
TGA: Using a thermogravimetry meter (TGA-50) manufactured by Shimadzu Corporation, measurement was performed in an argon atmosphere at a heating rate of 10 ° C./min (while maintaining at 150 ° C. for 30 minutes to sufficiently remove moisture) .
Ion conductivity measurement: A platinum wire (diameter: 0.2 mm) is pressed against the surface of a strip-shaped membrane sample on a self-made measurement probe (Teflon (registered trademark)), and a constant temperature and humidity oven at 80 ° C. and 95% RH. The sample was held in (Nagano Scientific Machinery Co., Ltd., LH-20-01), and the impedance between the platinum wires was measured by SOLARTRON 1250 FREQUENCY RESPONSE ANALYSER. The measurement was performed while changing the distance between the electrodes, and the conductivity obtained by canceling the contact resistance between the film and the platinum wire was calculated from the gradient obtained by plotting the distance measured between the electrodes and the resistance measurement value estimated from the CC plot. Moreover, the same measurement was performed by immersing the measurement probe in ultrapure water kept at 25 ° C., and proton conductivity in water was also calculated.
Conductivity [S / cm] = 1 / film width [cm] × film thickness [cm] × resistance interelectrode gradient [Ω / cm]
Sulfonic acid group content: A sample dried overnight under a nitrogen atmosphere was weighed, stirred with an aqueous sodium hydroxide solution, and then ion exchange capacity (IEC) was determined by back titration with an aqueous hydrochloric acid solution.
Methanol permeation rate: A membrane immersed in a 5M (mol / liter) methanol aqueous solution adjusted to 25 ° C. for 24 hours is sandwiched between H-type cells, 100 ml of 5M methanol aqueous solution is placed on one side of the cell, and 100 ml of ultrapure is placed on the other cell It was calculated by injecting water (18 MΩ · cm) and measuring the amount of methanol diffusing into the ultrapure water through the ion exchange membrane while stirring the cells on both sides at 25 ° C. (The area of the ion exchange membrane is 2.0 cm ² ).
Water absorption: The sample dried under reduced pressure was weighed and immersed in water at 80 ° C. for 1 hour. After wiping off the adhering water on the sample surface, the weight was measured. The weight increase rate relative to the dry weight was determined as the water absorption rate.
Tensile test: Tensilon UTMII manufactured by Toyo Baldwin is used for tensile tests at 20 ° C and 65% relative humidity, and Tensilon UTMIII manufactured by Toyo Baldwin is used for tensile tests in water at 20 ° C. It was measured.
Power generation evaluation: After adding a small amount of ultrapure water and isopropyl alcohol to a Pt / Ru catalyst-supported carbon (TEC 61E54, Tanaka Kikinzoku Kogyo Co., Ltd.) and moistening, a 20% Nafion (registered trademark) solution manufactured by DuPont (product number: SE-) Was added so that the weight ratio of Pt / Ru catalyst-supported carbon to Nafion was 2.5: 1. Next, stirring was performed to prepare an anode catalyst paste. The catalyst paste was applied and dried by screen printing on carbon paper TGPH-060 manufactured by Toray as a gas diffusion layer so that the amount of platinum deposited was 2 mg / cm ² , thereby producing a carbon paper with an electrode catalyst layer for anode. . Further, after adding a small amount of ultrapure water and isopropyl alcohol to a Pt catalyst-supporting carbon (Tanaka Kikinzoku Kogyo Co., Ltd. TEC10V40E) and moistening it, a DuPont 20% Nafion solution (product number: SE-20192) is added to the Pt catalyst-supporting carbon. A cathode catalyst paste was prepared by adding carbon and Nafion at a weight ratio of 2.5: 1 and stirring. This catalyst paste was applied and dried on a carbon paper TGPH-060 manufactured by Toray made with a water-repellent finish so that the amount of platinum deposited was 1 mg / cm ² , thereby producing a carbon paper with an electrode catalyst layer for cathode. By sandwiching the membrane sample between the two types of carbon paper with the electrode catalyst layer so that the electrode catalyst layer is in contact with the membrane sample, by pressurizing and heating at 130 ° C. and 8 MPa for 3 minutes by a hot press method, A membrane-electrode assembly was obtained. This joined body was incorporated into an evaluation fuel cell FC25-02SP manufactured by Electrochem, and a power generation test was performed using a fuel cell power generation tester (manufactured by Toyo Corporation). Power generation was performed at a cell temperature of 40 ° C. while supplying a 2 mol / l aqueous methanol solution (1.5 ml / min) and high-purity oxygen gas (80 ml / min) adjusted to 40 ° C. to the anode and cathode, respectively.

Example 1
3,3′-disulfo-4,4′-dichlorodiphenylsulfone disodium salt (abbreviation: S-DCDPS) 10.7322 g (0.021246 mole), 2,6-dichlorobenzonitrile (abbreviation: DCBN) 13.7481 g ( 0.079926 mole), 4,4′-biphenol 15.0714 g (0.080938 mole), 1,7-dihydroxynaphthalene-3-sulfonic acid sodium 5.3059 g (0.0202345 mole), potassium carbonate 16.0804 g (0.080938 mole) ) Was weighed into a 200 ml four-necked flask and flushed with nitrogen. 124 ml of N-methyl-2-pyrrolidone was added and the mixture was stirred with heating, the reaction temperature was raised to 195-200 ° C., and the reaction was carried out for 12 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.67.
9 g of the polymer was dissolved in 21 ml of NMP, cast to a thickness of about 450 μm on a glass plate on a hot plate, NMP was distilled off until it became a film, and then immersed in water overnight. The obtained film was immersed in dilute sulfuric acid (6 ml of concentrated sulfuric acid, 300 ml of water) for 1 day to remove the salt, and then immersed in pure water twice for 1 hour to remove the acid component and dried. did. When the ion conductivity of this film was measured, it showed a value of 0.16 S / cm at 80 ° C. and 95% RH and 0.06 S / cm in 25 ° C. water. The weight loss starting temperature (measured based on the sample weight at 200 ° C.) by thermogravimetry of this film was 297 ° C., and the 3% weight reduction temperature was 379 ° C. The IEC determined by titration was 1.48. When this film was immersed in hot water at 80 ° C. for 1 hour, the water absorption was 38%. The methanol permeation rate was 3.7 mmol / m ² · sec. Further, when a tensile test of this film was performed, the elastic modulus was 1.47 GPa and the strength was 52 MPa at 20 ° C. and 65% RH, and the elastic modulus was 0.26 GPa, the strength was 32 MPa, and the elongation was 97% under 20 ° C. water immersion conditions. there were. FIG. 1 shows the IR spectrum of this film.

Example 2
S-DCDPS 7.9965 g (0.016278 mole), DCBN 15.58665 g (0.09224 mole), 4,4′-biphenol 14.1452 g (0.075965 mole), 1,7-dihydroxynaphthalene-3-sulfonic acid sodium 8.5368 g (0.032556 mole) and 17.2483 g (0.12480 mole) of potassium carbonate were weighed into a 200 ml four-necked flask and flushed with nitrogen. 130 ml of N-methyl-2-pyrrolidone was added, and the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. and reacted for 15 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.47.
The obtained polymer was formed in the same manner as in Example 1 to obtain a film. When the ion conductivity of this film was measured, it showed a value of 0.11 S / cm at 80 ° C. and 95% RH and 0.05 S / cm in water at 25 ° C. The weight loss starting temperature (measured based on the sample weight at 200 ° C.) by thermogravimetry of this film was 317 ° C., and the 3% weight reduction temperature was 383 ° C. The IEC determined by titration was 1.37. When this film was immersed in hot water at 80 ° C. for 1 hour, the water absorption was 34%. The methanol permeation rate was 2.8 mmol / m ² · sec.

Example 3
S-DCDPS 3.2888 g (0.0066948 mole), DCBN 10.3640 g (0.060252 mole), 4,4′-biphenol 7.6792 g (0.041239 mole), sodium 1,7-dihydroxynaphthalene-3-sulfonate 6.7411 g (0.025708 mole) and 10.6407 g (0.076989 mole) of potassium carbonate were weighed into a 200 ml four-necked flask and flushed with nitrogen. 77 ml of N-methyl-2-pyrrolidone was added, and the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. to react for 15 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.37.
The obtained polymer was formed in the same manner as in Example 1 to obtain a film. When the ionic conductivity of this film was measured, it showed a value of 0.11 S / cm at 80 ° C. and 95% RH and 0.04 S / cm in 25 ° C. water. The weight loss starting temperature (measured based on the sample weight at 200 ° C.) by thermogravimetry of this film was 309 ° C., and the 3% weight reduction temperature was 371 ° C. The IEC determined by titration was 1.41. When this film was immersed in hot water at 80 ° C. for 1 hour, the water absorption was 30%. The methanol permeation rate was 2.8 mmol / m ² · sec.

Example 4
DCBN 9.2391 g (0.05371 mole, 4,4′-biphenol 4.5008 g (0.02417 mole), 1,7-dihydroxynaphthalene-3-sulfonic acid sodium 7.7465 g (0.02754 mole), potassium carbonate 8.5371 g ( 0.06177 mole) was weighed into a 200 ml four-necked flask and flushed with nitrogen, charged with 60 ml of N-methyl-2-pyrrolidone, heated and stirred, and the reaction temperature was raised to 195-200 ° C. for 16 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands, and the resulting polymer was dipped in fresh water for one day and dried.The logarithmic viscosity of the polymer was 0.24. showed that.

Example 5
S-DCDPS 9.4855 g (0.019309 mole), DCBN 13.2853 g (0.077236 mole), 4,4′-biphenol 16.0000 g (0.085924 mole), disodium 1,7-dihydroxynaphthalene-3,6-disulfonate 3.8684 g (0.010620 mole) and 15.3449 g (0.11103 mole) of potassium carbonate were weighed into a 200 ml four-necked flask and flushed with nitrogen. 120 ml of N-methyl-2-pyrrolidone was added, and the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. to react for 20 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands. The obtained polymer was dipped in fresh water for one day and then dried. A polymer having a logarithmic viscosity of 0.51 was obtained.

Comparative Example 1
Four 1 liters of S-DCDPS 66.9937 g (0.13631 mole), DCBN 47.6049 g (0.27676 mole), 4,4′-biphenol 76.5331 g (0.4110 mole), potassium carbonate 65.3256 g (0.47265 mole) Weighed into a neck flask and flushed with nitrogen. 535 ml of N-methyl-2-pyrrolidone was added, and the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. to react for 5 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands. The obtained polymer was dipped in fresh water for one day and then dried. A polymer having a logarithmic viscosity of 1.63 was obtained.
The obtained polymer was formed in the same manner as in Example 1 to obtain a film. When the ion conductivity of this film was measured, it showed a value of 0.14 S / cm at 80 ° C. and 95% RH and 0.06 S / cm in water at 25 ° C. The IEC determined by titration was 1.61. When this film was immersed in hot water at 80 ° C. for 1 hour, the water absorption was 46%. The methanol permeation rate was 4.4 mmol / m ² · sec.

Example 6
3,3 ', 4,4'-tetra-diaminodiphenyl sulfone ^{1.500g (5.389 × 10 -3 mole)} , 2,5- dicarboxylate benzenesulfonic acid 1.445g (5.389 × 10 ^-3 mole) 20.5 g of polyphosphoric acid (phosphorus pentoxide content: 75%) and 16.5 g of phosphorus pentoxide are weighed into a polymerization vessel. Flow nitrogen and raise the temperature to 100 ° C while stirring gently on an oil bath. After maintaining at 100 ° C. for 1 hour, the temperature was raised to 150 ° C. for 1 hour, and the temperature was raised to 200 ° C. and polymerized for 4 hours. After completion of the polymerization, the mixture was allowed to cool, water was added, the polymer was taken out, and washing with water was repeated until the pH test paper became neutral using a home mixer. The obtained polymer was dried under reduced pressure at 80 ° C. overnight. The logarithmic viscosity of the polymer was 1.33. 1 g of this polymer was dissolved in 10 ml of N-methyl-2-pyrrolidone by heating and mixed with the film-forming solution prepared in Example 1, the cast thickness was adjusted, and the outside was 50 μm thick as in Example 1. A film was prepared. When the ion conductivity of this film was measured, it showed a value of 0.04 S / cm in 25 ° C. water. The methanol permeation rate was 2.9 mmol / m ² · sec.

Example 7
3,3 ', 4,4'-tetra-diaminodiphenyl sulfone ^{1.830g (6.575 × 10 -3 mole)} , 3,5- dicarboxyphenyl phosphonic acid 1.084g (4.405 × 10 ^-3 mole) , 0.360 g (2.170 × 10 ⁻³ mole) of terephthalic acid, 20.5 g of polyphosphoric acid (phosphorus pentoxide content: 75%) and 16.5 g of phosphorus pentoxide are weighed in a polymerization vessel. Flow nitrogen and raise the temperature to 100 ° C while stirring gently on an oil bath. After maintaining at 100 ° C. for 1 hour, the temperature was raised to 150 ° C. for 1 hour, and the temperature was raised to 200 ° C. and polymerized for 7 hours. After completion of the polymerization, the mixture was allowed to cool, and water was added to take out the polymerized product, followed by repeated washing with a home mixer until the pH test paper was neutral. The obtained polymer was dried under reduced pressure at 80 ° C. overnight. The logarithmic viscosity of the polymer measured using sulfuric acid was 1.07.
A blend film was produced in the same manner as in Example 6 using 1 g of this polymer. When the ion conductivity of this film was measured, it showed a value of 0.04 S / cm in 25 ° C. water. The methanol permeation rate was 2.6 mmol / m ² · sec.

Example 8
88.485 gg (0.30814 mole) of 4,4′-dichlorodiphenylsulfone, 13.197 g (0.07087 mole) of 4,4′-biphenol, 62.216 g of sodium 1,7-dihydroxynaphthalene-3-sulfonate (0. 23727 mole) and 48.976 g (0.35436 mole) of potassium carbonate were weighed into a 2000 ml four-necked flask and flushed with nitrogen. 500 ml of N-methyl-2-pyrrolidone was added, and the mixture was heated and stirred, and the reaction temperature was raised to 195 to 200 ° C. and reacted for 19 hours. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands. The obtained polymer was dipped in fresh water for one day and then dried. The logarithmic viscosity of the polymer was 0.51.
4.5 g of this polymer and 4.5 g of the polymer obtained in Comparative Example 1 were mixed, and a film was obtained in the same manner as in Example 1. When the ionic conductivity of this film was measured, it showed a value of 0.12 S / cm at 80 ° C. and 95% RH and 0.06 S / cm in 25 ° C. water. The IEC determined by titration was 1.59. The methanol permeation rate was 3.2 mmol / m ² · sec.

Example 9
When power generation evaluation was performed using the film produced in Example 1, good power generation characteristics of 0.34 V at a current density of 100 mA were obtained.

Example 10
In the production of the membrane-electrode assembly described above, a membrane-electrode assembly was produced using the 10% N-methyl-2-pyrrolidone solution of the polymer synthesized in Example 1 instead of the Nafion solution. What was obtained was a good bonded body without electrode peeling.

  The sulfonic acid group-containing aromatic polyarylene ether compound of the present invention can provide a polymer electrolyte material that is excellent not only in ion conductivity but also in heat resistance, workability, and dimensional stability. These can be used for fuel cells and water electrolyzers that use hydrogen or methanol as raw materials as ion-conducting membranes, but can also be used as various battery electrolytes, display elements, sensors, binders, additives, etc. There is expected.

IR spectrum of the film described in Example 1.

Claims (10)

A polyarylene ether compound having a constituent represented by the general formula (1) in the molecular chain and a constituent represented by the general formula (2) and the general formula (3).
X represents hydrogen or a monovalent cation species, m and n are 0 or 1, and m + n is not 0. Ar represents a divalent aromatic group which may contain a substituent.
Y represents a sulfone group or a ketone group, and X represents H or a monovalent cation species. Ar ′ and Ar ″ each represent a divalent aromatic group that may contain a substituent, and may contain a sulfonic acid group-containing naphthylene structure that gives the structure of the general formula (1).   The polyarylene ether compound according to claim 1, wherein the sulfonic acid group content is in the range of 0.3 to 3.5 meq / g. 3. Polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate containing 50% by mass or more and less than 100% by mass of the polyarylene ether compound according to claim 1 Polyesters, nylon 6, nylon 6,6, nylon 6,10, nylon 12 Polyamides, polymethyl methacrylate, polymethacrylates, polymethylacrylates, polyacrylates Acrylate resins, polyacrylic acid resins, polymethacrylic acid resins, polyethylene, polypropylene, various polyolefins including polystyrene and diene polymers, polyurethane resins, cellulose acetate, ethyl cellulose Cellulosic resin, polyarylate, aramid, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polysulfone, polyethersulfone, polyetheretherketone, polyetherimide, polyimide, polyamideimide, polybenzimidazole, polybenzoxazole, polybenzthiazole A composition comprising at least one resin selected from the group consisting of an aromatic polymer, an epoxy resin, a phenol resin, a novolac resin, and a benzoxazine resin. The compound according to claim 1. Alternatively, an ion conductive membrane comprising the composition according to claim 3.   A composite comprising the ion conductive membrane according to claim 4 and an electrode.   A fuel cell comprising the composite according to claim 5.   The fuel cell according to claim 6, wherein methanol is used as a fuel.   An adhesive comprising the compound according to claim 1. When polymerizing a sulfonic acid group-containing polyarylene ether compound by an aromatic nucleophilic substitution reaction, the sulfonic acid group-containing naphthalenediol represented by the general formula (4) is used as at least one monomer. The manufacturing method of the polyarylene ether type compound in any one of Claims 1-2.
However, X is hydrogen or a monovalent cation species, m and n are 0 or 1, and m + n is not 0.   A step comprising casting the solution containing the compound according to any one of claims 1 to 3 and a solvent so as to have a cast thickness in a range of 10 to 1500 μm, and a step of drying the cast solution. The manufacturing method of the ion conductive film of Claim 4.