JP2006335815A - Proton conductor composition and proton-conductive composite membrane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a proton conductor composition and a proton-conductive composite membrane which each has sufficiently high proton conductivity even in high temperature regions above 100°C. <P>SOLUTION: This proton conductive membrane is obtained by adding an ozone-treated carbon material to a sulfonic group-having polyarylene, and can improve durability at high temperature. The carbon material is preferably contained in an amount of 0.01 to 4 pts.mass per 100 pts.mass of the sulfonic group-having polyarylene. The carbon material is preferably one or more selected from the group consisting of carbon black, activated carbon, carbon nanotubes and carbon nanohorns. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a proton conductor composition and a proton-conductive composite membrane that are suitably used for, for example, a polymer electrolyte fuel cell.

  A polymer electrolyte fuel cell includes a solid electrolyte membrane and a pair of catalyst electrodes that sandwich the solid electrolyte membrane. Hydrogen, which is a fuel, is ionized at one electrode, and this hydrogen ion diffuses in the solid polymer electrolyte membrane and then bonds with oxygen at the other electrode. At this time, if the two electrodes are connected by an external circuit, a current flows and power is supplied to the external circuit. Here, the solid polymer electrolyte membrane has functions of diffusing hydrogen ions, physically separating hydrogen and oxygen of the fuel gas, and blocking the flow of electrons.

  As such a solid polymer electrolyte membrane, a fluorine-based electrolyte membrane represented by a perfluorocarbon sulfonic acid membrane is known. Since this fluorine-based electrolyte membrane is excellent in chemical stability, it is used as a fuel cell used under severe conditions or as an electrolyte membrane for water decomposition.

Since the oxygen reduction reaction at the cathode of the polymer electrolyte fuel cell proceeds via hydrogen peroxide (H ₂ O ₂ ), it is caused by hydrogen peroxide or peroxide radicals generated in the catalyst layer. It is believed that the electrolyte membrane deteriorates. In addition, it is considered that radicals are generated when hydrogen molecules or oxygen molecules permeating through the electrolyte membrane react directly with oxygen molecules or oxygen molecules in the vicinity of the electrode, and in this case, the electrolyte membrane is also deteriorated. Yes.

  The fluorine-based electrolyte membrane has a relatively low glass transition point and cannot maintain mechanical strength at temperatures exceeding 100 ° C. Therefore, there is a problem that the operating temperature of such an electrolyte membrane must be limited to 100 ° C. or less, preferably 80 ° C. or less. Conventional fluorine-based electrolyte membranes are solid polymer fuels for space or military use. It was limited to special applications such as batteries.

  In addition, in order to apply conventional fluorine-based electrolyte membranes to low-pollution power sources for automobiles, consumer-use compact distributed power supplies, portable power supplies, etc., low-molecular hydrocarbons are reformed into hydrogen gas as raw fuel. When used, the reformed gas has to be cooled or carbon monoxide in the reformed gas needs to be removed, which makes the system complicated.

  The fuel cell is preferably operated at a high temperature because the electrode catalyst becomes highly active, the electrode overvoltage is reduced, and the poisoning of the electrode by carbon monoxide is reduced. Therefore, development of a solid polymer electrolyte membrane exhibiting sufficient proton conductivity even at high temperatures (100 ° C. or higher) is desired.

  As a fluorine-based electrolyte membrane having improved membrane mechanical strength, for example, Patent Document 1 discloses a membrane of a mixture comprising a fluorinated polymer having a sulfonic acid group and other fluorinated polymers. Yes.

  In addition, as a material other than the fluorine-based electrolyte membrane, the following Patent Document 2 discloses a solid polymer electrolyte made of sulfonated rigid polyphenylene. This polymer is mainly composed of a polymer obtained by polymerizing an aromatic compound composed of a phenylene chain, and this is reacted with a sulfonating agent to introduce a sulfonic acid group.

Patent Document 3 below discloses a solid polymer electrolyte membrane in which a carbon material subjected to ozone treatment is dispersed and blended.
JP 2000-243135 A US Pat. No. 5,403,675 JP 2004-152615 A

  In the fluorine-based electrolyte membrane of Patent Document 1, although mechanical strength is improved, chemical stability against radicals and durability in a high temperature region exceeding 100 ° C. are insufficient.

  In addition, the solid polymer electrolyte membrane of Patent Document 2 improves proton conductivity by increasing the amount of sulfonic acid groups introduced, but at the same time mechanical properties of the sulfonated polymer obtained, for example, elongation at break, bending resistance Such toughness and hot water resistance are significantly impaired.

  Further, in the solid polymer electrolyte membrane of Patent Document 3, since the base polymer is perfluorocarbon sulfonic acid, the mechanical strength cannot be maintained at a temperature exceeding 100 ° C. Moreover, since there is much content of a carbon material, proton conductivity is impaired and it has the problem that carbon materials contact and short-circuit.

  An object of the present invention is to provide a proton conductor composition capable of improving the chemical stability of an electrolyte membrane to radicals and obtaining a proton conductive membrane excellent in durability even in a high temperature region exceeding 100 ° C. is there.

  As a result of intensive studies in view of the problems in the prior art, the present inventors have used a polyarylene having a sulfonic acid group and a carbon material subjected to ozone treatment at a high temperature (100 ° C. or higher). In addition, the present inventors have found that a sufficient strength is maintained, chemical stability against radicals and excellent proton conductivity are exhibited, and the present invention has been completed. Specifically, the present invention provides the following.

  (1) A proton conductor composition comprising a polyarylene having a sulfonic acid group and a carbon material subjected to ozone treatment.

  (2) The proton conductor composition according to (1), containing 0.01 to 4 parts by mass of the carbon material with respect to 100 parts by mass of the polyarylene having the sulfonic acid group.

  (3) The proton conductor composition according to (1) or (2), wherein the carbon material is at least one selected from the group consisting of carbon black, activated carbon, carbon nanotubes, and carbon nanohorns.

（式（１）中、Ｙは２価の電子吸引性基を表し、Ｚは２価の電子供与性基又は直接結合を表し、Ａｒは−ＳＯ_３Ｈで表される置換基を有する芳香族基を表し、ｋは０〜１０の整数を表し、１は０〜１０の整数を表し、ｊは１〜４の整数を表す。） (4) The proton conductor composition according to any one of (1) to (3), wherein the polyarylene having the sulfonic acid group includes at least a repeating unit represented by the following general formula (1).

(In formula (1), Y represents a divalent electron-withdrawing group, Z represents a divalent electron-donating group or a direct bond, and Ar represents an aromatic having a substituent represented by —SO ₃ H. Represents a group, k represents an integer of 0 to 10, 1 represents an integer of 0 to 10, and j represents an integer of 1 to 4.)

（式（１）中、Ｙは２価の電子吸引性基を表し、Ｚは２価の電子供与性基又は直接結合を表し、Ａｒは−ＳＯ_３Ｈで表される置換基を有する芳香族基を表し、ｋは０〜１０の整数を表し、１は０〜１０の整数を表し、ｊは１〜４の整数を表す。）

（式（２）中、Ｒ^１〜Ｒ^８は互いに同一でも異なっていてもよく、水素原子、フッ素原子、アルキル基、フッ素置換アルキル基、アリル基、アリール基及びニトリル基からなる群より選ばれる原子又は基を表し、Ｗは２価の電子吸引性基又は単結合を表し、Ｔは単結合又は２価の有機基を表し、ｐは０又は正の整数を表す。）

（式（３）中、Ｂは独立に酸素原子又は硫黄原子であり、Ｒ^９〜Ｒ^１１は互いに同一でも異なっていてもよく、水素原子、フッ素原子、ニトリル基及びアルキル基からなる群より選ばれる原子又は基を表し、ｎは２以上の整数を表し、Ｑは下記一般式（ｑ）で表される構造を表す。）

（式（ｑ）中、Ａは独立に、２価の原子、２価の有機基、直接結合のいずれかであり、Ｒ^１２〜Ｒ^１９は互いに同一でも異なっていてもよく、水素原子、フッ素原子、ニトリル基、アルキル基及び芳香族基からなる群より選ばれる原子又は基を表す。） (5) The polyarylene having the sulfonic acid group includes a repeating unit represented by the following general formula (1) and at least one of the repeating units represented by the following general formulas (2) and (3). The proton conductor composition according to any one of (1) to (3).

(In formula (1), Y represents a divalent electron-withdrawing group, Z represents a divalent electron-donating group or a direct bond, and Ar represents an aromatic having a substituent represented by —SO ₃ H. Represents a group, k represents an integer of 0 to 10, 1 represents an integer of 0 to 10, and j represents an integer of 1 to 4.)

(In Formula (2), R ^{1 to} R ⁸ may be the same as or different from each other, and are selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, a fluorine-substituted alkyl group, an allyl group, an aryl group, and a nitrile group. Represents an atom or group, W represents a divalent electron-withdrawing group or a single bond, T represents a single bond or a divalent organic group, and p represents 0 or a positive integer.)

(In the formula (3), B is an oxygen atom or a sulfur atom independently, R ⁹ to R ¹¹ may be the same or different, selected from the group consisting of a hydrogen atom, a fluorine atom, a nitrile group and an alkyl group And n represents an integer of 2 or more, and Q represents a structure represented by the following general formula (q).)

(In the formula (q), A is independently a divalent atom, a divalent organic group or a direct bond, and R ^{12 to} R ¹⁹ may be the same as or different from each other, a hydrogen atom, fluorine Represents an atom or group selected from the group consisting of an atom, a nitrile group, an alkyl group and an aromatic group.)

  (6) A proton conducting membrane comprising the proton conductor composition according to any one of (1) to (5).

  According to the proton conductor composition of the present invention, it is possible to obtain a proton conducting membrane having sufficiently high proton conductivity even in a high temperature region of 100 ° C. or higher.

  Hereinafter, the proton conductor composition and the proton conductive composite membrane according to the present invention will be described in detail. The proton conductor composition according to the present invention includes polyarylene having a sulfonic acid group and a carbon material subjected to ozone treatment. First, polyarylene having a sulfonic acid group will be described.

<Polyarylene including general formula (1)>
The polyarylene having a sulfonic acid group used in the present invention is not particularly limited, but a polymer containing at least a structural unit represented by the following general formula (1) is preferable.

The general formula (1) will be described. In the formula (1), Y represents a divalent electron-withdrawing group, specifically, —CO—, —SO ₂ —, —SO—, —CONH—, _{-COO -, - (CF 2)} 1- ( wherein 1 is an integer of 1 to 10), - C (CF3) 2- and the like. Z represents a divalent electron-donating group or a direct bond. Specific examples of the electron-donating group include — (CH ₂ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, — CH = CH-, -C≡C-, and the following groups are exemplified.

  The electron-withdrawing group means a group having a Hammett substituent constant of 0.06 or more when the phenyl group is in the m-position and 0.01 or more when the p-position is p-position. Ar represents an aromatic group having a substituent represented by —SO 3 H, and examples of the aromatic group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthyl group. Of these groups, a phenyl group and a naphthyl group are preferable.

  K represents an integer of 0 to 10, preferably 0 to 2, l represents an integer of 0 to 10, preferably 0 to 2, and j represents an integer of 1 to 4.

<Method for Producing Polyarylene Containing General Formula (1)>
The polyarylene having a sulfonic acid group is prepared by producing a polyarylene having a sulfonic acid ester group from a monomer having a sulfonic acid ester group that can be a structural unit represented by the general formula (1). It can be synthesized by hydrolyzing a polyarylene having a sulfonic acid ester group to convert it into a sulfonic acid group.

  The polyarylene having a sulfonic acid group is synthesized by previously synthesizing a polyarylene composed of structural units having no sulfonic acid group and sulfonic acid ester group in the general formula (1), and sulphonating the polymer. You can also

Examples of the monomer that can be a structural unit of the general formula (1) include, for example, the following general formula (4):
And a sulfonic acid ester represented by (hereinafter also referred to as monomer (4)).

In formula (4), X is an atom selected from halogen atoms other than fluorine (chlorine, bromine, iodine), —OSO ₂ Z (wherein Z represents an alkyl group, a fluorine-substituted alkyl group, or an aryl group) or Y, Z, Ar, k, l and j are the same as Y, Z, Ar, k, l and j in the general formula (1).

R ^a represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, tert-butyl group, iso- Butyl group, n-butyl group, sec-butyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group, adamantyl group, adamantanemethyl group, 2-ethylhexyl group, bicyclo [2.2 .1] heptyl group, bicyclo [2.2.1] heptylmethyl group, tetrahydrofurfuryl group, 2-methylbutyl group, 3,3-dimethyl-2,4-dioxolanemethyl group, cyclohexylmethyl group, adamantylmethyl group A linear hydrocarbon group such as a bicyclo [2.2.1] heptylmethyl group, a branched hydrocarbon group, Cyclic hydrocarbon group, such as a hydrocarbon group having 5-membered heterocycles. Among these, n-butyl group, neopentyl group, tetrahydrofurfuryl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, adamantylmethyl group, and bicyclo [2.2.1] heptylmethyl group are preferable, and neopentyl group is particularly preferable. preferable.

Ar represents an aromatic group having a substituent represented by —SO ₃ R ^b , and examples of the aromatic group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthyl group. Of these groups, a phenyl group and a naphthyl group are preferable.

Substituents -SO ₃ R ^b is substituted one or two or more aromatic groups, when the substituent -SO ₃ R ^b is substituted two or more, these substituents is each independently But it can be different.

Here, R ^b represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, and specific examples thereof include the above hydrocarbon groups having 1 to 20 carbon atoms. Among these, n-butyl group, neopentyl group, tetrahydrofurfuryl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, adamantylmethyl group, and bicyclo [2.2.1] heptylmethyl group are preferable, and neopentyl group is particularly preferable. preferable.

  k represents an integer of 0 to 10, preferably 0 to 2, l represents an integer of 0 to 10, preferably 0 to 2, and j represents an integer of 1 to 4. Specific examples of the monomer (4) include the following compounds.

In the above compound, a compound in which a chlorine atom is replaced with a bromine atom, a compound in which —CO— is replaced with —SO ₂ —, a chlorine atom is replaced with a bromine atom, and
CO- is -SO ₂ - can also be mentioned such compounds replaced.

The R ^b group in the general formula (4) is derived from a primary alcohol, and the β carbon is a tertiary or quaternary carbon, which is excellent in stability during the polymerization process, and can generate sulfonic acid by deesterification. It is preferable in that it does not cause polymerization inhibition and cross-linking, and it is preferable that these ester groups are derived from primary alcohols and the β-position is a quaternary carbon.

  In the above general formula (4), specific examples of the compound having no sulfonic acid group or sulfonic acid ester group include the following compounds.

In the above compound, a compound in which a chlorine atom is replaced with a bromine atom, a compound in which —CO— is replaced with —SO ₂ —, and a chlorine atom in the above compound are replaced with a bromine atom, and —CO— is —SO ₂ —. And compounds that have been replaced with.

<Polyarylene containing general formulas (1) and (2)>
The polyarylene having a sulfonic acid group used in the present invention is not particularly limited, but a polymer containing a structural unit represented by the general formula (1) and a structural unit represented by the following general formula (2) It is also preferable. About the structural unit represented by General formula (1), since it is the same as that of the above, the description is abbreviate | omitted.

  Next, the following general formula (2) will be described.

R ^{1 to} R ⁸ may be the same as or different from each other, and each represents an atom or group selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, a fluorine-substituted alkyl group, an allyl group, an aryl group, and a nitrile group.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, and a hexyl group, and a methyl group and an ethyl group are preferable. Examples of the fluorine-substituted alkyl group include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, trifluoromethyl group, pentafluoroethyl group, and the like. Etc. are preferable. Examples of the allyl group include a propenyl group. Examples of the aryl group include a phenyl group and a pentafluorophenyl group.

W represents a single bond or a divalent electron-withdrawing group, and T represents a single bond or a divalent organic group.
p is 0 or a positive integer, and the upper limit is usually 100, preferably 10-80.

  The polyarylene having a sulfonic acid group used in the present invention includes the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). The polymer represented by is preferable.

In formula (a), W, T, Y, Z, Ar, k, l, j, p, and R ^{1 to} R ⁸ are as defined above. x and y represent molar ratios when x + y = 100 mol%.

  The polyarylene having a sulfonic acid group used in the present invention contains 0.5 to 100 mol%, preferably 10 to 99.999 mol% of the structural unit represented by the formula (1) in the formula (2). It is preferable to contain the structural unit represented by 99.5 to 0 mol%, preferably 90 to 0.001 mol%.

<Method for Producing Polyarylene Containing General Formulas (1) and (2)>
The polyarylene having a sulfonic acid group includes a monomer having a sulfonic acid ester group that can be a structural unit represented by the general formula (1) and an oligomer that can be a structural unit represented by the general formula (2). It can be synthesized by copolymerizing to produce a polyarylene having a sulfonic acid ester group, hydrolyzing the polyarylene having the sulfonic acid ester group, and converting the sulfonic acid ester group to a sulfonic acid group.

  The polyarylene having a sulfonic acid group is a polyarylene composed of a structural unit having no sulfonic acid group or sulfonic acid ester group in the general formula (1) and a structural unit represented by the general formula (2). It is also possible to synthesize in advance and sulphonate this polymer.

Examples of the oligomer that can be the structural unit of the general formula (2) include an oligomer represented by the following general formula (5) (hereinafter also referred to as oligomer (5)). Here, R < ¹ > -R < ⁸ >, W, T, p are synonymous with R < ¹ > -R < ⁸ > in the said General formula (2), respectively.

In the formula (5), R ′ and R ″ may be the same as or different from each other, and a halogen atom or —OSO ₂ Z excluding a fluorine atom (where Z is an alkyl group, a fluorine-substituted alkyl group or an aryl group) The group represented by this is shown. Examples of the alkyl group represented by Z include a methyl group and an ethyl group, examples of the fluorine-substituted alkyl group include a trifluoromethyl group, and examples of the aryl group include a phenyl group and a p-tolyl group.

  As the compound represented by the general formula (5), when p = 0, for example, 4,4′-dichlorobenzozophenone, 4,4′-dichlorobenzanilide, bis (chlorophenyl) difluoromethane, 2, 2-bis (4-chlorophenyl) hexafluoropropane, 4-chlorobenzoic acid-4-chlorophenyl, bis (4-chlorophenyl) sulfoxide, bis (4-chlorophenyl) sulfone, 2,6-dichlorobenzonitrile, 9,9- Bis (4-hydroxyphenyl) fluorene is mentioned. Among these compounds, compounds in which a chlorine atom is replaced with a bromine atom or an iodine atom, and compounds in which at least one of halogen atoms substituted in the 4-position in these compounds are substituted in the 3-position are also included.

  When p = 1, examples of the compound represented by the general formula (5) include 4,4′-bis (4-chlorobenzoyl) diphenyl ether and 4,4′-bis (4-chlorobenzoylamino). ) Diphenyl ether, 4,4′-bis (4-chlorophenylenosulfonyl) diphenyl ether, 4,4′-bis (4-chlorophenyl) diphenyl ether dicarboxylate, 4,4′-bis [(4-chlorophenyl) -1, 1,1,3,3,3-hexafluorobropinole] diphenyl ether, 4,4′-bis [(4-chlorophenyl) tetrafluoroethyl] diphenyl ether, and in these compounds, the chlorine atom is replaced by a bromine atom or an iodine atom. Replaced compounds, and in these compounds, the halogen atom substituted at the 4-position is the 3-position. Substituted compounds, can also be mentioned, such as addition at least one compound substituted in the 3-position of the group obtained by substituting at the 4-position of diphenyl ether in these compounds.

  Furthermore, the compound represented by the general formula (5) includes 2,2-bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] -1,1,1,3,3,3-hexa. Examples include fluoropropane, bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] sulfone, and a compound represented by the following formula.

The compound represented by the general formula (5) can be synthesized, for example, by the method shown below. First, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, dimethylsulfoxide, etc., in order to convert the bisphenol linked with an electron-withdrawing group into the corresponding alkali metal salt of bisphenol In a polar solvent having a high dielectric constant, an alkali metal such as lithium, sodium or potassium, an alkali metal hydride, an alkali metal hydroxide, an alkali metal carbonate or the like is added.

  The alkali metal is reacted in excess with respect to the hydroxyl group of phenol, and is usually used in an amount of 1.1 to 2 times equivalent, preferably 1.2 to 1.5 times equivalent. In this case, fluorine, chlorine, etc. activated with an electron-withdrawing group in the presence of water and an azeotropic solvent such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, and phenetole Aromatic halogen-substituted aromatic dihalide compounds such as 4,4′-difluorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-chlorofluorobenzozophenone, bis (4-chlorophenyl) sulfone, bis (4-fluorophenyl) sulfone, 4-fluorophenyl-4′-chlorophenylsulfone, bis (3-nitro-4-chlorophenyl) sulfone, 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, hexafluorobenzene , Decafluoro Phenyl, 2,5-difluoro pen zone phenone, 1,3-bis (4-chlorobenzoyl) reacting benzene. In terms of reactivity, a fluorine compound is preferable, but in consideration of the following aromatic coupling reaction, it is necessary to assemble an aromatic nucleophilic substitution reaction so that the terminal is a chlorine atom.

  The active aromatic dihalide is used in an amount of 2 to 4 times mol, preferably 2.2 to 2.8 times mol, of bisphenol. Prior to the aromatic nucleophilic substitution reaction, an alkali metal salt of bisphenol may be used. The reaction temperature is 60 ° C to 300 ° C, preferably 80 ° C to 250 ° C. The reaction time ranges from 15 minutes to 100 hours, preferably from 1 hour to 24 hours. The most preferable method is to use a chlorofluoro compound having one halogen atom having a different reactivity as the active aromatic dihalide represented by the following formula, and a nucleophilic substitution reaction with phenoxide occurs preferentially by the fluorine atom. It is convenient to obtain the desired activated terminal chloro form.

  In the formula, W is as defined for the general formula (5). Further, as described in JP-A-2-159, a flexible compound comprising a target electron-withdrawing group and electron-donating group may be synthesized by combining a nucleophilic substitution reaction and an electrophilic substitution reaction. . Specifically, an aromatic bishalide activated with an electron-withdrawing group, such as bis (4-chlorophenyl) sulfone, is subjected to a nucleophilic substitution reaction with phenol to form a bisphenoxy compound, and then this bisphenoxy compound and 4-chloro The desired compound can be obtained from Friedel-Craft reaction with benzoic acid chloride.

  Examples of the aromatic bishalide activated with the electron-withdrawing group used here include the compounds exemplified above. The phenol compound may be substituted, but an unsubstituted compound is preferable from the viewpoint of heat resistance and flexibility. In addition, it is preferable to set it as an alkali metal salt for the substitution reaction of a phenol, and the compound illustrated above is mentioned as an alkali metal compound which can be used. The amount used is 1.2 to 2 moles per mole of phenol. In the reaction, the polar solvent described above or an azeotropic solvent with water can be used.

  Chlorobenzoic acid chloride is used in an amount of 2 to 4 times mol, preferably 2.2 to 3 times mol of the bisphenoxy compound. Further, the Friedel-Crafts reaction between the bisphenoxy compound and the acylating agent chlorobenzoic acid chloride is preferably performed in the presence of a Friedel-Craft activator such as aluminum chloride, boron trifluoride, or zinc chloride. . The Friedel-Craft activator is used in an amount of 1.1 to 2 times equivalent to 1 mol of an active halide compound such as chlorobenzoic acid as an acylating agent. The reaction time ranges from 15 minutes to 10 hours, and the reaction temperature ranges from -20 ° C to 80 ° C. As the solvent used, chlorobenzene, nitrobenzene and the like which are inert to Friedel-Craft reaction can be used.

Further, in the general formula (5), the compound in which p is 2 or more includes, for example, a bisphenol serving as a source of etheric oxygen that is the electron donating group T in the general formula (5) and an electron withdrawing group W. A compound in combination with at least one group selected from> C═O, —SO ₂ — and> C (CF ₃ ) 2, specifically 2,2-bis (4-hydroxyphenyl) -1 , 1,1,3,3,3-hexafluoropropane, 2,2-bis (4-hydroxyphenyl) ketone, 2,2-bis (4-hydroxyphenyl) sulfone and other alkali metal salts of bisphenol and excess Substitution reaction with an active aromatic halogen compound such as 4,4-dichlorobenzophenone or bis (4-chlorophenyl) sulfone is carried out using N-methyl-2-pyrrolidone, N, N-dimethylacetate. It is obtained by sequentially polymerizing the monomer in the presence of a polar solvent such as amide or sulfolane.

  Examples of such compounds include compounds represented by the following formulas.

  In the above chemical formula, p is 0 or a positive integer, and the upper limit is usually 100, preferably 10-80.

  The polyarylene having a sulfonate group is synthesized by reacting the above-described monomer (4) and oligomer (5) in the presence of a catalyst. The catalyst used in this case contains a transition metal compound. The catalyst system includes i) a transition metal salt and a compound that becomes a ligand (hereinafter referred to as “ligand component”), or a transition metal complex in which a ligand is coordinated (copper salt). And (ii) a reducing agent as an essential component, and a salt may be added to increase the polymerization rate.

  Here, as the transition metal salt, nickel compounds such as nickel chloride, nickel bromide, nickel iodide, nickel acetylacetonate; palladium compounds such as palladium chloride, palladium bromide and palladium iodide; iron chloride and iron bromide And iron compounds such as iron iodide; cobalt compounds such as cobalt chloride, cobalt bromide, and cobalt iodide. Of these, nickel chloride, nickel bromide and the like are particularly preferable.

  Examples of the ligand component include triphenylphosphine, 2,2′-bipyridine, 1,5-cyclooctadiene, 1,3-bis (diphenylphosphino) propane, and the like. Of these, triphenylphosphine and 2,2'-bipyridine are preferred. The compound which is the said ligand component may be used individually by 1 type, and may use 2 or more types together.

  Furthermore, as the transition metal complex in which the ligand is coordinated, for example, nickel kenolebis chloride (triphenylphosphine), nickel bis (triphenylphosphine), nickel iodide bis (triphenylenophosphine), nickel nitrate Bis (triphenylphosphine), nickel chloride (2,2′-bipyridine), nickel bromide (2,2 ′-)-bipyridine), nickel iodide (2,2 ′-)-bipyridine), nickel nitrate (2 , 2′-bipyridine), bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like. Of these, nickel chloride bis (triphenylphosphine) and nickel chloride (2,2'-bipyridine) are preferred.

  Examples of the reducing agent that can be used in the catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, calcium, and the like. Of these, zinc, magnesium and manganese are preferred. These reducing agents can be used after being more activated by contacting with an acid such as an organic acid.

  Examples of the “salt” that can be used in the above catalyst system include sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, potassium fluoride, potassium chloride, potassium bromide, Examples include potassium compounds such as potassium iodide and potassium sulfate, and ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate. Of these, sodium bromide, sodium iodide, potassium bromide, tetraethylammonium bromide, and tetraethylammonium iodide are preferred.

  The proportion of each component used is usually 0.0001 to 10 mol, preferably 0.01, based on 1 mol of the total amount of the above monomers ((4) + (5), the same shall apply hereinafter) for the transition metal salt or transition metal complex. -0.5 mol. When the amount is less than 0.0001 mol, the polymerization reaction may not proceed sufficiently. On the other hand, when the amount exceeds 10 mol, the molecular weight may decrease.

  In the catalyst system, when a transition metal salt and a ligand component are used, the proportion of the ligand component used is usually 0.1 to 100 mol, preferably 1 to 10 mol, relative to 1 mol of the transition metal salt. . When the amount is less than 0.1 mol, the catalytic activity may be insufficient. On the other hand, when the amount exceeds 100 mol, the molecular weight may decrease.

  Moreover, the usage-amount of a reducing agent is 0.1-100 mol normally with respect to the total of 1 mol of the said monomer, Preferably it is 1-10 mol. If the amount is less than 0.1 mol, polymerization may not proceed sufficiently. If the amount exceeds 100 mol, purification of the resulting polymer may be difficult.

  Furthermore, when using "salt", the usage-ratio is 0.001-100 mol normally with respect to the total of 1 mol of the said monomer, Preferably it is 0.01-1 mol. If it is less than 0.001 mol, the effect of increasing the polymerization rate may be insufficient, and if it exceeds 100 mol, purification of the resulting polymer may be difficult.

Examples of the polymerization solvent that can be used when the monomer (4) and the oligomer (5) are reacted include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl. -2-pyrrolidone, γ-butyrolactone, N, N′-dimethylimidazolidinone and the like. Of these, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N, N′-dimethylimidazolidinone are preferable. The total concentration of the monomers in the polymerization solvent is usually 1 to 90% by mass, preferably 5 to 40% by mass. The polymerization temperature for the polymerization is usually 0 to 200 ° C, preferably 50 to 120 ° C. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.

  The polyarylene having a sulfonic acid ester group obtained by using the monomer (4) can be converted into a polyarylene having a sulfonic acid group by hydrolyzing the sulfonic acid ester group and converting it to a sulfonic acid group. .

As a hydrolysis method, (1) a method in which polyarylene having a sulfonate group is added to an excess amount of water or alcohol containing a small amount of hydrochloric acid, and the mixture is stirred for 5 minutes or more (2) in trifluoroacetic acid And a method of reacting the polyarylene having the sulfonic acid ester group for about 5 to 10 hours at a temperature of about 80 to 120 ° C. (3) The sulfonic acid ester group (—SO ₃ R) in the polyarylene having the sulfonic acid ester group After the polyarylene is reacted at a temperature of about 80 to 150 ° C. for about 3 to 10 hours in a solution containing 1 to 3 times moles of lithium bromide with respect to 1 mole, for example, a solution such as N-methylpyrrolidone, Examples include a method of adding hydrochloric acid.

  The polyarylene having the sulfonic acid group includes a monomer having no sulfonic acid group and a sulfonic acid ester group in the monomer (4) represented by the general formula (4), and an oligomer represented by the general formula (5). It is also possible to synthesize a polyarylene copolymer in advance by copolymerizing with (5) and sulphonate the polyarylene copolymer. In this case, after producing a polyarylene having no sulfonic acid group by a method according to the above synthesis method, a sulfonic acid group is introduced into the polyarylene having no sulfonic acid group using a sulfonating agent. A polyarylene having a group can be obtained.

  As a method for introducing a sulfonic acid group, for example, a polyarylene having no sulfonic acid group is known in the absence of a solvent or in the presence of a solvent, such as sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, sulfuric acid, or sodium bisulfite. And a sulfonating agent using a sulfonating agent of [Polymer Preprints, Japan, Vo1.42, No. 1]. 3, p. 730 (1993); Po1mer Preprints, Japan, Vol. 43, no. 3, p. 736 (1994); Po1mer Preprints, Japan, Vo1, 42, N0, 7, p. 2490-2492 (1993)].

  Examples of the solvent used for sulfonation include hydrocarbon solvents such as n-hexane, ether solvents such as tetrahydrofuran and dioxane, aprotic polar solvents such as dimethylacetamide, dimethylformamide and dimethylsulfoxide, and tetrachloroethane. , Halogenated hydrocarbons such as dichloroethane, chloroform and methylene chloride. Although reaction temperature does not have a restriction | limiting in particular, Usually, -50-200 degreeC, Preferably it is -10-100 degreeC. Moreover, reaction time is 0.5 to 1,000 hours normally, Preferably it is 1 to 200 hours.

  The amount of sulfonic acid group in the polyarylene (b) having a sulfonic acid group produced by the method as described above is usually 0.3 to 5 meq / g, preferably 0.5 to 3 meq / g, more preferably 0. .8 to 2.8 meq / g. If it is less than 0.3 meq / g, the proton conductivity is low and not practical. On the other hand, if it exceeds 5 meq / g, the water resistance may be significantly lowered, which is not preferable.

  The amount of the sulfonic acid group can be adjusted, for example, by changing the type, usage ratio, and combination of the monomer (4) and the oligomer (5). The molecular weight of the polyarylene having a sulfonic acid group thus obtained is 10,000 to 1,000,000, preferably 20,000 to 800,000 in terms of polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC). If it is less than 10,000, there are insufficient coating properties such as cracks in the molded film, and there are also problems in strength properties. On the other hand, when it exceeds 1,000,000, there is a problem that the solubility becomes insufficient and the workability is deteriorated because the solution viscosity becomes high.

  The proton conductor composition of the present invention may contain an antioxidant, preferably a hindered phenol compound having a molecular weight of 500 or more. Examples of hindered phenol compounds include triethylene glycol-bis [3- (3-tert-butyl 5-methyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 245), 1,6-hexanediol-bis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX259), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5- Di-t-butylanilino) -3,5-triazine (trade name: IRGANOX565), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010 ), 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyl) Enyl) propionate] (trade name: IRGANOX1035), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) (trade name: IRGANOX1076), N, N-hexamethylenebis (3 5-di-t-butyl-4-hydroxy-hydrocinnamamide) (IRGAONOX 1098), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxy Benzyl) benzene (trade name: IRGANOX 1330), tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate (trade name: IRGANOX 3114), 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl ] -2,4,8,10-spiro [5.5] undecane (trade name: SumilizerGA-80), and the like.

  The hindered phenol compound is preferably used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyarylene having a sulfonic acid group.

<Polyarylene containing general formulas (1) and (3)>
The polyarylene having a sulfonic acid group used in the present invention is not particularly limited. However, the polyarylene includes a structural unit represented by the general formula (1) and a structural unit represented by the following general formula (3). It is also preferable that it is a coalescence. About the structural unit represented by General formula (1), since it is the same as that of the above, the description is abbreviate | omitted.

  Next, the following general formula (3) will be described.

(In the formula (3), B is an oxygen atom or a sulfur atom independently, R ⁹ to R ¹¹ may be the same or different, selected from the group consisting of a hydrogen atom, a fluorine atom, a nitrile group and an alkyl group And n represents an integer of 2 or more, and Q represents a structure represented by the following general formula (q).)

(In the formula (q), A is independently a divalent atom, a divalent organic group or a direct bond, and R ^{12 to} R ¹⁹ may be the same as or different from each other, a hydrogen atom, fluorine An atom or group selected from the group consisting of an atom, a nitrile group, an alkyl group, and an aromatic group, which includes derivatives thereof.

  The polymer containing at least the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) is preferably a block copolymer. In this block copolymer, a sulfonic acid group is introduced into the aromatic group represented by Ar in the general formula (1) to form a sulfonated product. As a result, the sulfonated first repeating unit forms a hydrophilic part, and the non-sulfonated second repeating unit becomes a hydrophobic part, so that a block copolymer having a hydrophilic part and a hydrophobic part is obtained. Can do.

  Moreover, since the repeating unit represented by the general formula (3) includes a nitrile group (—CN) in the structure, the heat resistance and acid resistance of the polyarylene polymer can be increased, and the repetition unit The unit hydrophobicity can be further increased, and phase separation between the hydrophilic part and the hydrophobic part can be promoted, so that ionic conductivity can be efficiently imparted even with a small amount of water, and the dimensional change rate of the polyarylene polymer. Can be kept low. Therefore, excellent heat resistance, acid resistance, and ion conductivity can be obtained. Moreover, since the sulfonated dimensional change rate of the polyarylene polymer is lowered, excellent adhesion between the polymer electrolyte membrane and the electrode catalyst layer can be obtained when a membrane-electrode structure is formed.

In the general formula (3), examples of the alkyl group represented by R ^{1 to} R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, and a hexyl group. Etc. are preferred. Moreover, in General formula (3), n is an integer greater than or equal to 2, and an upper limit is 100 normally, Preferably it is 80.

In the general formula (q), examples of the alkyl group represented by R ^{4 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, and a hexyl group. Etc. are preferred. In the general formula (q), examples of the aromatic group represented by R ^{4 to} R ¹¹ include a phenyl group, a naphthyl group, a pyridyl group, a phenoxydiphenyl group, a phenylphenyl group, and naphthoxyphenyl. it can.

In the general formula (q), examples of the divalent organic group represented by A include —CO—, —CONH—, — (CF ₂ ) _p — (wherein p is an integer of 1 to 10). , —C (CF 3) 2 —, —COO—, —SO—, —SO ₂ — and the like, —O—, —S—, —CH═CH—, —C≡C—, and the following An electron donating group such as a group represented by the formula can be exemplified. The electron-withdrawing group refers to a group having a Hammett substituent constant of 0.06 or more when the phenyl group is in the m-position and 0.01 or more when the p-position is p-position.

  In the general formula (q), the electron donating group may be a group represented by the following general formula (6).

(In formula, R < ¹² > -R < ¹⁹ > is a hydrogen atom, a fluorine atom, an alkyl group, or an aromatic group, Comprising: You may mutually be same or different, and an aromatic group contains the derivative.)

In the general formula (6), examples of the alkyl group represented by R ^{12 to} R ¹⁹ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, and a hexyl group. Etc. are preferred. In the general formula (6), examples of the aromatic group represented by R ^{12 to} R ¹⁹ include a phenyl group, a naphthyl group, a pyridyl group, a phenoxydiphenyl group, a phenylphenyl group, and a naphthoxyphenyl. it can.

In the structure represented by the general formula (q), the A is —CONH—, — (CF ₂ ) _P — (wherein p is an integer of 1 to 10), —C (CF ₃ ). 2 -, - COO -, - SO-, and -S0 ₂ - first and structure is one organic group selected from the group consisting of an organic group represented by a direct bond or the formula (4) A certain second structure may be included.

  In this case, the structure represented by the general formula (q) includes 70 to 99 mol% of the first structure and 1 to 30 mol% of the second structure (provided that the first structure and the first structure The total of the two structures is preferably 100 mol%). Further, the content of the first structure is more preferably 20 to 99 mol%, further preferably 30 to 95 mol%, particularly preferably 35 to 90 mol%. Moreover, 1-80 mol% is more preferable, as for content of a 2nd structure, 5-70 mol% is still more preferable, and 10-65 mol% is especially preferable. When the content of the first structure and the content of the second structure are in this range, the first repeating unit represented by the general formula (1) and the first structure represented by the general formula (3) It becomes possible to suppress the dimensional change rate of the polyarylene polymer containing 2 repeating units.

  The proton conductor composition may contain an anti-aging agent, preferably a hindered phenol compound having a molecular weight of 500 or more, similar to the polyarylene containing the general formulas (1) and (2).

<Method for Producing Polyarylene Containing General Formulas (1) and (3)>
For example, the polyarylene having a sulfonic acid group is obtained by co-existing a compound represented by the general formula (4) and a compound represented by the following general formula (7) in the presence of a catalyst containing a transition metal compound. It can be synthesized by a polymerization reaction.

In the general formula (7), B, R ^{1 to} R ³ , n, and Q have the same meaning as in the general formula (3), and X ′ is a halogen atom (chlorine, bromine, iodine) excluding fluorine, —OSO _2. An atom or group selected from the group consisting of CH _{3 and} —OSO ₂ CF ₃ is shown.

  The compound represented by the general formula (7) can be synthesized, for example, by the following reaction.

  First, a divalent atom or organic group or a bisphenol linked by a direct bond, such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, and dimethylsulfoxide, has a high polarity. Add an alkali metal such as lithium, sodium or potassium, an alkali metal hydride, an alkali metal hydroxide, an alkali metal carbonate or the like in the polar solvent to dissolve in a solvent and form the corresponding alkali metal salt of bisphenol. . The alkali metal is reacted in excess with respect to the hydroxyl group of phenol, and is usually used in an amount of 1.1 to 2 times equivalent, preferably 1.2 to 1.5 times equivalent. At this time, it is preferable to promote the progress of the reaction by coexisting a solvent azeotropic with water such as benzene, toluene, xylene, chlorobenzene, and anisole.

  Subsequently, the alkali metal salt of the bisphenol is reacted with a benzonitrile compound substituted with a halogen atom such as chlorine and a nitrile group. Examples of the benzonitrile-based compound include 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2,5-dichlorobenzonitrile, 2,5-difluorobenzonitrile, 2,4-dichlorobenzonitrile, Examples include 2,4-difluorobenzonitrile, 2,6-dinitrobenzonitrile, 2,5-dinitrobenzonitrile, 2,4-dinitrobenzonitrile and the like. Of the above compounds, dichlorobenzonitrile compounds are preferable, and 2,6-dichlorobenzonitrile is more preferable.

  The benzonitrile-based compound is used in an amount of 1.0001 to 1 mol, preferably 1.001 to 2 mol per mol of bisphenol. Further, after the completion of the reaction, for example, 2,6-dichlorobenzonitrile may be added in excess to allow both ends to be chlorine atoms, and further reacted. When difluorobenzonitrile compounds or dinitrobenzonitrile compounds are used, it is necessary to devise the reaction so that both ends become chlorine atoms, such as by adding dichlorobenzonitrile compounds in the second half of the reaction. It is. The reaction is performed at a reaction temperature of 60 ° C. to 300 ° C., preferably 80 ° C. to 250 ° C., and for a reaction time of 15 minutes to 100 hours, preferably 1 hour to 24 hours.

  The oligomer or polymer obtained by the reaction can be purified by a general purification method of the polymer, for example, a dissolution-precipitation operation. The molecular weight can be adjusted by the reaction molar ratio of excess aromatic dichloride and bisphenol. In the reaction system, since the aromatic dichloride substituted with a nitrile group is present in excess, the molecular terminals of the resulting oligomer or polymer are aromatic chlorides substituted with a nitrile group.

  Specific examples of the oligomer or polymer compound having an aromatic chloride substituted with a nitrile group at the molecular end include the following compounds.

  In the copolymerization reaction between the compound represented by the general formula (4) and the compound represented by the general formula (7), the amount of the compound represented by the general formula (4) is 99. The amount of the compound represented by the general formula (7) is 0.001 to 90 mol%, preferably 0 to 999 to 10 mol%, preferably 99.9 to 20 mol%. The range is from 1 to 80 mol%.

  The catalyst used in the copolymerization reaction is a catalyst system containing a transition metal compound, and this catalyst system is a compound that becomes a transition metal salt and a ligand (hereinafter referred to as a ligand component) or a ligand. Transition metal gold type (including a copper salt) coordinated with a reducing agent, and a salt may be added to increase the polymerization rate.

  Here, transition metal salts include nickel compounds such as nickel chloride, nickel bromide, nickel iodide, nickel acetylacetonate, palladium compounds such as palladium chloride, palladium bromide, palladium iodide, iron chloride, iron bromide And iron compounds such as iron iodide, and cobalt compounds such as cobalt chloride, cobalt bromide, and cobalt iodide. Of the transition metal salts, nickel chloride, nickel bromide and the like are particularly preferable.

  Examples of the ligand component include triphenylphosphine, 2,2′-bipyridine, 1,5-cyclooctadiene, 1,3-bis (diphenylphosphino) propane, and the like. Of these, triphenylphosphine and 2,2'-bipyridine are preferred. The compound which is the said ligand component can be used individually by 1 type or in combination of 2 or more types.

  Further, examples of the transition metal complex coordinated with the ligand include nickel chloride bis (triphenylphosphine), nickel bromide bis (triphenylphosphine), nickel iodide bis (triphenylphosphine), nickel nitrate. Bis (triphenylphosphine), nickel chloride (2,2'-bipyridine), nickel bromide (2,2'-bipyridine), nickel iodide (2,2'-bipyridine), nickel nitrate (2,2'- Bipyridine), bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like. Of the transition metal complexes coordinated with the ligand, nickel chloride bis (triphenylphosphine) and nickel chloride (2,2'-bipyridine) are preferred.

  Examples of the reducing agent that can be used in the catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, calcium, and the like. Of the reducing agents, zinc, magnesium and manganese are preferred. The reducing agent can be used after being more activated by contacting with an acid such as an organic acid.

  Examples of the salt that can be used in the catalyst system include sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, and sodium sulfate, potassium fluoride, potassium chloride, potassium bromide, and iodine. And potassium compounds such as potassium iodide and potassium sulfate, and ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate. Of the salts, sodium bromide, sodium iodide, potassium bromide, tetraethylammonium bromide, and tetraethylammonium iodide are preferred.

  In the catalyst system, the ratio of the transition metal salt or transition metal complex used is usually 0 with respect to 1 mol in total of the compound represented by the general formula (4) and the compound represented by the general formula (7). 0.0001 to 10 mol, preferably 0.01 to 0.5 mol. When the amount is less than 0.0001 mol, the polymerization reaction may not proceed sufficiently. On the other hand, when the amount exceeds 10 mol, the molecular weight may decrease.

  In the catalyst system, when a transition metal salt and a ligand component are used, the amount of the ligand component used is usually 0.1 to 100 mol, preferably 1 to 10 mol per mol of the transition metal salt. Is a mole. When the amount is less than 0.1 mol, the catalytic activity may be insufficient. On the other hand, when the amount exceeds 100 mol, the molecular weight may decrease.

  In the catalyst system, the reducing agent is used in a proportion of usually 0.1 to 1 mol in total of the compound represented by the general formula (4) and the compound represented by the general formula (7). 100 moles, preferably 1 to 10 moles. If the amount is less than 0.1 mol, polymerization may not proceed sufficiently. If the amount exceeds 100 mol, purification of the resulting polymer may be difficult.

  Further, when the salt is used in the catalyst system, the use ratio is usually based on 1 mol in total of the compound represented by the general formula (6) and the compound represented by the general formula (7). 0.001 to 100 mol, preferably 0.01 to 1 mol. If it is less than 0.001 mol, the effect of increasing the polymerization rate may be insufficient, and if it exceeds 100 mol, purification of the resulting polymer may be difficult.

  Examples of the polymerization solvent that can be used for the copolymerization reaction include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-ptyrolactone, Examples include sulfolane, γ-ptylolactam, dimethylimidazolidinone, and tetramethylurea. Of these, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable. The polymerization solvent is preferably used after sufficiently dried.

  The total concentration of the compound represented by the general formula (4) and the compound represented by the general formula (7) in the polymerization solvent is usually 1 to 90% by weight, preferably 5 to 40% by weight. is there. The polymerization temperature is usually 0 to 200 ° C., preferably 50 to 120 ° C., and the polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.

  The molecular weight of the polyarylene polymer obtained as described above is 10,000 to 1,000,000, preferably 20,000 to 800,000 in terms of polystyrene-converted weight average molecular weight by gel permeation chromatography (hereinafter abbreviated as GPC). It is. When the weight average molecular weight in terms of polystyrene is less than 10,000, the coating properties are insufficient, such as cracking in the molded hilm, and there are also problems with the strength properties. On the other hand, when the polystyrene equivalent weight average molecular weight exceeds 1,000,000, there are problems such as insufficient solubility, high solution viscosity, and poor processability.

  The sulfonated product of the polyarylene polymer may be a sulfonated product of the polyarylene polymer itself, and a polyarylene-based polymer using a compound having Ar substituted with a sulfonate group in the general formula (4). After the sulfonated product of the polymer is synthesized, the sulfonated product may be hydrolyzed to obtain a sulfonated product of the corresponding polyarylene polymer.

  In order to sulfonate the polyarylene polymer having no sulfonic acid group, a sulfonic acid group is introduced into the polyarylene polymer using a sulfonating agent. As a method for introducing the sulfonic acid group, for example, a polyarylene polymer having no sulfonic acid group may be prepared by using a known sulfonating agent such as sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, sulfuric acid, sodium hydrogen sulfite, or the like. And sulfonated under known conditions (for example, Polymer Preprints, Japan, Vol. 42, No. 3, p. 730 (1993), Polymer Preprints, Japan, Vol. 43, No. 43). 3, p.736 (1994), Polymer Preprints, Japan, Vol.42, No. 7, p.2490-2492 (1993)).

  That is, as the sulfonation reaction conditions, the polyarylene polymer having no sulfonic acid group is reacted with the sulfonating agent in the absence of a solvent or in the presence of a solvent. Examples of the solvent include hydrocarbon solvents such as n-hexane, ether solvents such as tetrahydrofuran and dioxane, aprotic polar solvents such as dimethylacetamide, dimethylformamide, and dimethylsulfoxide, tetrachloroethane, dichloroethane, and chloroform. And halogenated hydrocarbons such as methylene chloride. The reaction temperature is not particularly limited, but is usually −50 to 200 ° C., preferably −10 to 100 ° C. Moreover, reaction time is 0.5 to 1,000 hours normally, Preferably it is 1 to 200 hours.

  On the other hand, when the sulfonated product of the polyarylene polymer is hydrolyzed to the sulfonated product of the corresponding polyarylene polymer, first, it is substituted with a sulfonate group in the general formula (4). In the same manner as in the copolymerization reaction, the compound having Ar is reacted with the compound represented by the general formula (7) to synthesize a sulfonated product of a polyarylene polymer.

As a method for hydrolysis of the sulfonated product of the polyarylene polymer, the sulfonated product of the polyarylene polymer is added to an excess amount of water or alcohol containing a small amount of hydrochloric acid for 5 minutes or more. A method of mirroring, a method of reacting the sulfonated product of the polyarylene polymer in trifluoroacetic acid at a temperature of about 80 to 120 ° C. for about 5 to 10 hours, a sulfonate ester in the polyarylene polymer In a solution containing 1 to 3 moles of lithium bromide with respect to 1 mole of the group (—SO ₃ R), such as N-methylpyrrolidone, the polymer is heated at a temperature of about 80 to 150 ° C. An example is a method of adding hydrochloric acid after the reaction for about 10 hours.

According to the hydrolysis, by converting the sulfonate group (—SO ₃ R) of the sulfonate esterified product of the polyarylene polymer into a sulfonate group (—SO ₃ H), a corresponding polyarylene series is obtained. A sulfonated polymer can be obtained. In sulfonated said polyarylene polymer, more than 90% of the polyarylene polymer sulfonic acid ester group in the sulfonic acid ester of (-SO 3 _R) is a sulfonic acid group (-SO 3 _H) Preferably it has been converted.

  The amount of sulfonic acid group in the sulfonated polyarylene polymer thus obtained is 0.5 to 3 meq / g, preferably 0.8 to 2.8 meq / g. If it is less than 0.5 meq / g, sufficient proton conductivity may not be obtained. On the other hand, if it exceeds 3 meq / g, the hydrophilicity will be improved, resulting in a water-soluble polymer or not water-soluble. Even if it becomes soluble in hot water or does not reach water solubility, durability may be lowered.

  The amount of the sulfonic acid group is the ratio of the compound represented by the general formula (4) and the compound represented by the general formula (7), and the compound represented by the general formula (4), It can be easily adjusted by changing the type and combination with the compound represented by the general formula (7).

In addition, the structure of the sulfonated product of the polyarylene polymer has an S = O absorption of 1,030 to 1,045 cm ⁻¹ , 1,160 to 1,190 cm ⁻¹ and 1,130 to ¹ according to an infrared absorption spectrum. , 250 cm- ¹ C-O-C absorption, 1,640-1,660 cm- ¹ C = O absorption, etc., and these composition ratios can be determined by neutralization titration of sulfonic acid or elemental analysis. You can know more. Moreover, the structure of the sulfonated product of the polyarylene polymer can be confirmed from the peak of aromatic protons at 6.8 to 8.0 ppm by nuclear magnetic resonance spectrum ( ¹ H-NMR).

<Carbon material with ozone treatment>
In the present invention, a quinone carbonyl group (= 0) can be selectively formed on the surface of the carbon material by ozone treatment of the carbon material. “Ozone treatment” in the present invention means all treatments performed by contacting a carbon material with ozone. That is, it may be a gas phase process or a liquid phase process. As the gas phase treatment, a method of supplying and treating ozone generated using an ozone generator as a gas, a method of performing low temperature ozone treatment after oxidation treatment with high temperature air, and the like can be applied. Further, as the liquid phase treatment, there is a method in which a carbon material powder is dispersed in water and stirred, and ozone gas generated using an ozone generator is introduced into the carbon material powder and then treated. Further, molecular oxygen, atomic oxygen, oxygen treatment using dry or wet air and / or nitrogen oxide treatment may be used in combination. Further, oxidation with combustion gas, low-temperature plasma treatment with oxygen or air, and the like may be used in combination.

  A known ultraviolet (UV) ozone treatment apparatus may be used. This UV ozone treatment method is a sensitized oxidation process using short wavelength UV light. As this sensitized oxidation process, for example, photochemical oxidative decomposition combining the generation of ozone by the reaction of light having a short wavelength of 184.9 nm with oxygen and the chemical bond dissociation effect of light having a short wavelength of 253.7 nm, for example. Depending on the process, it is also possible to remove organic contaminants that cannot be removed by wet processing but remain.

<Proton conductor composition>
The proton conductor composition of the present invention includes a polyarylene having a sulfonic acid group and a carbon material subjected to ozone treatment. The content of the carbon material subjected to the ozone treatment in the proton conductor composition includes 0.01 to 4 parts by mass of the carbon material subjected to the ozone treatment with respect to 100 parts by mass of the polyarylene having a sulfonic acid group. Is preferable, and it is more preferable to contain 0.1-3 mass parts.

  When the content of the carbon material is less than 0.01 parts by mass, the absolute amount of quinone carbonyl groups that inactivate the peroxide and / or radical species to be generated is small, and sufficient durability can be imparted. Since it becomes impossible, it is not preferable. Moreover, when this content exceeds 4 mass%, the movement of the proton in a proton conductive membrane will be inhibited, and a voltage drop will be caused. Moreover, it is not preferable because the carbon materials are in contact with each other and easily short-circuited.

<Proton conducting membrane>
The proton conducting membrane according to the present invention is produced by forming into a film using the proton conductor composition.

  The method for producing the proton conductive membrane is not particularly limited, and for example, a composition containing the polymer component and the ozone-treated carbon material is dissolved in an organic solvent to obtain a homogeneous solution-like composition. Then, a casting method in which this solution is cast on a substrate to form a film, or a method in which a polymer component is mixed and melted and then extruded to form a film can be used.

  The organic solvent used in the casting method is not particularly limited, and examples thereof include aprotic polar solvents such as γ-butyrolactone, dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, and dimethylurea. These solvents may be further mixed with alcohol solvents such as methanol, ethanol, N-propyl alcohol, iso-propyl alcohol, 1-methoxy-2-propanol.

  Moreover, when performing casting, solid content concentration of the solution which melt | dissolved the polymer component in the organic solvent, ie, the ratio of a polymer component, is 3-40 mass%, Preferably it is 5-35 mass%. If it is lower than the above range, a coating film having a sufficient thickness may not be obtained, and pinholes tend to be easily generated. On the other hand, if it exceeds the above range, it cannot be cast sufficiently and is uniform. A smooth coating film may not be obtained, and surface smoothness may be lacking.

As a substrate used in the casting method, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a nylon 6 film, a nylon 6,6 film, a polypropylene film, a plastic film such as a polycarbonate film, and a glass plate are used. Preferably, a PET film or a glass plate is used.

  The thickness of the plastic film (plate) used as the substrate is usually 50 to 250 μm, preferably 75 to 200 μm, and the thickness of the glass plate is usually 1 to 5 mm.

  After film formation by the casting method, a proton conducting membrane is obtained by heating and drying at room temperature to 200 ° C., preferably 50 to 150 ° C., for 5 to 180 minutes, preferably 5 to 120 minutes. Drying can be performed under conditions of normal pressure to vacuum. Further, the heating may be performed by sequentially raising the temperature.

  The dry film thickness of the proton conducting membrane produced as described above is usually 10 to 150 μm, preferably 20 to 80 μm.

  The proton conducting membrane of the present invention is a conducting membrane comprising a polyarylene having a sulfonic acid group and a carbon material that has been subjected to ozone treatment (including lamination) and comprising only the polyarylene having a sulfonic acid group. Compared to the above, it maintains strength properties, toughness, hot water resistance, and the like, and exhibits excellent proton conductivity even at high temperatures.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. Various measurement items in the examples were determined as follows.

(Equivalent sulfonic acid group (ion exchange capacity))
The obtained polyarylene having a sulfonic acid group was washed with distilled water until the washing water became neutral, sufficiently washed with water except for the remaining free acid, and then dried. Thereafter, a predetermined amount is weighed and dissolved in a THF / water mixed solvent, titrated with a standard solution of NaOH using phenolphthalein as an indicator, and an equivalent amount of sulfonic acid groups (ion exchange capacity) from the neutralization point. (Meq / g) was determined.

(Molecular weight measurement)
The weight average molecular weight and number average molecular weight of the polyarylene having a sulfonic acid group in this example are molecular weights in terms of polystyrene measured by GPC using tetrahydrofuran (THF) as a solvent.

(Proton conductivity)
For AC resistance, the membrane sample is formed into a strip shape having a width of 5 mm, a platinum wire (φ = 0.5 mm) is pressed against the surface of the membrane sample, the membrane sample is held in a constant temperature and humidity apparatus, and a platinum wire It was calculated from the AC impedance measurement. The impedance at an AC of 10 kHz was measured in an environment of 85 ° C. and a relative humidity of 90%. As a resistance measuring device, a Solartron SI1260 impedance analyzer was used, and as a constant temperature and humidity device, a small environmental tester SH-241 manufactured by Espec was used. Five platinum wires were pressed at intervals of 5 mm, the distance between the wires was changed to 5 to 20 mm, and the AC resistance was measured. The specific resistance of the membrane was calculated from the line-to-line distance and the resistance gradient, the AC impedance was calculated from the reciprocal of the specific resistance, and the proton conductivity was determined from this impedance.
Specific resistance R [Ω-cm] = 0.5 [cm] × film thickness [cm] × resistance line gradient [Ω / cm]

(Fenton reagent resistance)
Hydrogen peroxide water was pure and diluted to a concentration of 3%, and iron sulfate was dissolved therein so that the iron ion (Fe ²⁺ ) concentration was 40 ppm. A fixed-size membrane trial (sulfonated polymer film) was immersed in this solution and allowed to stand at 40 ° C. for 15 hours. The ratio of the weight of the film after immersion to the weight of the film before immersion was defined as the weight retention rate (%).

(Creep resistance evaluation)
Creep resistance was measured as the rate of film thickness reduction after applying a load of 15 kgf / cm 2 to the film trial for 1000 hours under a temperature of 120 ° C. and a DRY environment.

[Synthesis Example 1]
(Oligomer adjustment)
To a three-necked flask of IL equipped with a stirrer, thermometer, Dean-Stark tube, and three-way cock for introducing nitrogen, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3 -67.3 g (0.20 mol) of hexafluoropropane (bisphenol AF), 60.3 g (0.24 mol) of 4,4'-dichlorobenzophenone (4,4'-DCBP), 71.9 g of potassium carbonate (0 .52 mol), 300 mL of N, N-dimethylacetamide (DMAc), and 150 mL of toluene were heated in an oil bath in a nitrogen atmosphere and reacted at 130 ° C. with stirring. When water produced by the reaction was azeotroped with toluene and reacted while being removed from the system with a Dean-Stark tube, almost no water was observed in about 3 hours. The reaction temperature was gradually increased from 130 ° C to 150 ° C. Thereafter, most of the toluene was removed while gradually raising the reaction temperature to 150 ° C., and the reaction was continued at 150 ° C. for 10 hours. Then, 10.0 g (0.040 mol) of 4,4′-DCBP was added, and Reacted for 5 hours. The resulting reaction solution was allowed to cool, and the precipitate of the inorganic compound produced as a by-product was removed by filtration, and the filtrate was poured into 4 L of methanol. The precipitated product was separated by filtration, collected, dried, and dissolved in 300 mL of tetrahydrofuran. This was reprecipitated in 4 L of methanol to obtain 95 g (yield 85%) of the target compound. The number average molecular weight in terms of polystyrene determined by GPC (THF solvent) of the obtained polymer was 11,200. Further, the obtained compound was an oligomer represented by the following formula (hereinafter referred to as “BCPAF oligomer”).

[Synthesis Example 2]
(Synthesis of sulfonated polymer)
To a 1 L three-necked flask equipped with a stirrer, thermometer, cooling tube, Dean-stark tube, and nitrogen-introduced three-way cock, neopentyl 3- (2,5-dichlorobenzoyl) benzenesulfonate (A-SO ₃ neo-Pe) 39.58 g (98.64 mmol), BCPAF oligomer obtained in (1) (Mn = 11,200) 15.23 g (1.36 mmol), Ni (PPh ₃ ) ₂ C1 ₂ 1.67 g ( 2.55 mmol), 10.49 g (40 mmol) of PPh ₃ , 10.45 g (3 mmol) of Na, 15.69 g (240 mmol) of zinc dust and 390 ml of dry NMP were added under nitrogen. The reaction system was heated with stirring (finally heated to 75 ° C.) and allowed to react for 3 hours. The polymerization reaction solution was diluted with 250 ml of THF, stirred for 30 minutes, filtered using Celite as a filter aid, and the filtrate was poured into 1500 ml of a large excess of methanol to coagulate. The coagulated product was collected by filtration, air-dried, redissolved in THF / NMP (200/300 ml of each), and 1500 ml of a large excess of methanol was coagulated and precipitated. After air drying, 47.0 g (yield 99%) of a copolymer (PolyAB-S0 ₃ neo-Pe) composed of a sulfone brewer derivative protected with a target yellow fibrous neopentyl group was obtained by heat drying. Regarding the molecular weight by GPC, the number average molecular weight (Mn) was 47,600, and the weight average molecular weight (Mw) was 15,9000.

5.1 g of the obtained PolyAB-S0 ₃ neo-Pe was dissolved in 60 ml of NMP and heated to 90 ° C. To the reaction system, a mixture of 50 ml of methanol and 8 ml of concentrated hydrochloric acid was added at a time to form a suspended state and reacted for 10 hours under mild reflux conditions. A distillation apparatus was installed, and excess methanol was distilled off to obtain a light green transparent liquid. This solution was poured into a large amount of water / methanol (1: 1 weight ratio) to solidify the polymer, and then the polymer was washed with ion-exchanged water until the pH of the washing water became 6 or more. From the quantitative analysis of the IR spectrum and ion exchange capacity of the polymer thus obtained, it was found that the sulfonic acid ester group (-S0 ₃ R ^a ) was quantitatively converted to the sulfonic acid group (-S0 ₃ H). . The obtained polyarylene copolymer having a sulfonic acid group had a molecular weight of GPC of Mn of 53,200, Mw of 185,000, and a sulfonic acid equivalent of 1.9 meq / g.

(Preparation of oligomer)
To a 1 L three-necked flask equipped with a stirrer, thermometer, Dean-stark tube, nitrogen inlet tube, and condenser tube, 48.8 g (284 mmol) of 2,6-dichloropentonitrile, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-Hexafluoropropane 89.5 g (266 mmol) and potassium carbonate 47,8 g (346 mmol) were weighed. After nitrogen substitution, 346 mL of sulfolane and 173 mL of toluene were added and stirred. The reaction solution was heated to reflux at 150 ° C. in an oil bath. Water produced by the reaction was trapped in a Dean-stark tube. After 3 hours, when almost no water was observed, toluene was removed from the Dean-stark tube out of the system. The reaction temperature was gradually raised to 200 ° C. and stirring was continued for 3 hours. Then, 9.2 g (53 mmol) of 2,6-dichlorobenzonitrile was added, and the reaction was further continued for 5 hours. The reaction solution was diluted with a cooler and 100 mL of toluene. Inorganic salts insoluble in the reaction solution were filtered, and the filtrate was poured into 2 L of methanol to precipitate the product. The precipitated product was filtered and dried, then dissolved in 250 mL of tetrahydrofuran, and poured into 2 L of methanol for reprecipitation. The precipitated white powder was filtered and dried to obtain 109 g of the desired product. The number average molecular weight (Mn) measured by GPC was 9,500. From the ¹ H-NMR spectrum of this compound, it was confirmed that the obtained compound was an oligomer represented by the following formula.

[Synthesis Example 4]
(Synthesis of sulfonated polymer)
In a 1 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 135.2 g (337 mmol) of neoventil 3- (2,5-dichlorobenzoyl) benzenesulfonate, hydrophobicity of Mn 9,500 obtained in Example 1 Sex unit 48.7 g (5.1 mmol), pis (triphenylphosphine) nickel dichloride 6.71 g (10.3 mmol), sodium iodide 1.54 g (10.3 mmol), triphenylphosphine 35.9 g (137 mmol), Zinc 53.7 g (821 mmol) was weighed and purged with dry nitrogen. 430 mL of N, N-dimethylacetamide (DMAc) was added thereto, and stirring was continued for 3 hours while maintaining the reaction temperature at 80 ° C. Then, 730 mL of DMAc was added for dilution, and insoluble matters were filtered off. The obtained solution was put into a 2 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube. The mixture was heated and stirred at 115 ° C., and 44 g (506 mmol) of lithium bromide was added. After stirring for 7 hours, the product was precipitated by pouring into 5 L of acetone. Subsequently, it was washed with 1N hydrochloric acid and pure water in this order, and then dried to obtain 122 g of the target polymer. From the ¹ H-NMR spectrum in which the weight average molecular weight (Mw) of the obtained polymer was 135,000, the obtained polymer is estimated to be a sulfonated polymer represented by the following formula. The sulfonic acid equivalent was 2.4 meq / g.

<Example 1>
60 g of polyarylene having sulfonic acid obtained in Synthesis Example 2, 136 g of methanol and 204 g of N-methyl-2-pyrrolidone were placed in a 1000 cc plastic bottle and stirred to obtain a uniform polymer solution. To this was added 0.6 g (1% by weight) of carbon black (trade name; Ketjen EC, manufactured by Mitsubishi Chemical Corporation) that had been subjected to ozone treatment for 60 minutes, and mixed with a disperser for 20 minutes for uniform dispersion. . The above solution was cast on a PET film by a percoater method and dried at 80 ° C. for 30 minutes and then at 140 ° C. for 60 minutes to obtain a uniform solid electrolyte membrane having a thickness of 40 μm.

<Example 2>
A uniform solid electrolyte membrane having a thickness of 42 μm was obtained in the same manner as in Example 1 except that the amount of carbon black added was 2.4 g (4 wt%) in Example 1.

<Example 3>
In Example 1, a uniform collective electrolyte membrane having a thickness of 41 μm was obtained in the same manner as in Example 1 except that the amount of carbon black added was 0.006 g (0.01 wt%).

<Example 4>
In Synthesis Example 4, 60 g of polyarylene having sulfonic acid obtained, 136 g of methanol and 204 g of N-methyl-2-pyrrolidone were placed in a 1000 cc plastic bottle and stirred to obtain a uniform polymer solution. Carbon black (trade name; Ketjen EC, manufactured by Mitsubishi Chemical Corporation), which was subjected to ozone treatment for 60 minutes, was added thereto, mixed for 20 minutes with a disperser, and uniformly dispersed. The above solution was cast on a PET film by a bar coater method and dried at 80 ° C. for 30 minutes and then at 140 ° C. for 60 minutes to obtain a uniform solid electrolyte membrane having a thickness of 41 μm.

<Example 5>
A uniform solid electrolyte membrane having a thickness of 39 μm was obtained in the same manner as in Example 1 except that the amount of carbon black added was 3 g (5 wt%) in Example 1.

<Example 6>
A uniform solid electrolyte membrane having a thickness of 43 μm was obtained in the same manner as in Example 1 except that the amount of carbon black added was 0.003 g (0.005 wt%) in Example 1.

<Comparative Example 1>
A uniform solid electrolyte membrane having a thickness of 41 μm was obtained in the same manner as in Example 1 except that carbon black was not added.

<Comparative Example 2>
In Example 4, a uniform solid electrolyte membrane having a thickness of 40 μm was obtained in the same manner as in Example 1 except that carbon black was not added.

<Comparative Example 3>
Evaluation similar to Examples 1-6 and Comparative Examples 1-3 was implemented using Nafion112 (made by DuPont).

  Table 1 shows the evaluation results of the electrolyte membranes obtained in Examples 1 to 6 and Comparative Examples 1 to 3.

  According to this example, the carbon material subjected to the ozone treatment is added in an amount of 0.01 to 4 parts by mass, particularly in a high temperature region of 100 ° C. or higher, with respect to 100 parts by mass of the polyarylene having a sulfonic acid group. It can also be seen that a proton conductive membrane having sufficiently high mechanical strength and excellent durability can be obtained.

  Moreover, as shown in Table 1, the polymer (particularly Examples 1 to 4) to which carbon black was added to the polymer to which the carbon black subjected to ozone treatment was not added (Comparative Examples 1, 2 and 3), It was found that the strength to withstand strong oxidation was high.

Claims (6)

  A proton conductor composition comprising a polyarylene having a sulfonic acid group and a carbon material subjected to ozone treatment.   The proton conductor composition according to claim 1, wherein the carbon material is contained in an amount of 0.01 to 4 parts by mass with respect to 100 parts by mass of the polyarylene having the sulfonic acid group.   The proton conductor composition according to claim 1 or 2, wherein the carbon material is at least one selected from the group consisting of carbon black, activated carbon, carbon nanotubes, and carbon nanohorns. The proton conductor composition according to any one of claims 1 to 3, wherein the polyarylene having a sulfonic acid group includes at least a repeating unit represented by the following general formula (1).

(In formula (1), Y represents a divalent electron-withdrawing group, Z represents a divalent electron-donating group or a direct bond, and Ar represents an aromatic having a substituent represented by —SO ₃ H. Represents a group, k represents an integer of 0 to 10, 1 represents an integer of 0 to 10, and j represents an integer of 1 to 4.) The polyarylene having the sulfonic acid group includes a repeating unit represented by the following general formula (1) and at least one of the repeating units represented by the following general formulas (2) and (3). Item 4. The proton conductor composition according to any one of Items 1 to 3.

(In formula (1), Y represents a divalent electron-withdrawing group, Z represents a divalent electron-donating group or a direct bond, and Ar represents an aromatic having a substituent represented by —SO ₃ H. Represents a group, k represents an integer of 0 to 10, 1 represents an integer of 0 to 10, and j represents an integer of 1 to 4.)

(In Formula (2), R ^{1 to} R ⁸ may be the same as or different from each other, and are selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, a fluorine-substituted alkyl group, an allyl group, an aryl group, and a nitrile group. Represents an atom or group, W represents a divalent electron-withdrawing group or a single bond, T represents a single bond or a divalent organic group, and p represents 0 or a positive integer.)

(In the formula (3), B is independently an oxygen atom or a sulfur atom, and R ^{9 to} R ¹¹ may be the same or different from each other, and are selected from the group consisting of a hydrogen atom, a fluorine atom, a nitrile group and an alkyl group. And n represents an integer of 2 or more, and Q represents a structure represented by the following general formula (q).)

(In the formula (q), A is independently a divalent atom, a divalent organic group or a direct bond, and R ^{12 to} R ¹⁹ may be the same as or different from each other, a hydrogen atom, fluorine Represents an atom or group selected from the group consisting of an atom, a nitrile group, an alkyl group and an aromatic group.)   A proton conducting membrane comprising the proton conductor composition according to claim 1.