JP2008120957A - Sulfonic acid group-containing polyarylene ether based compound, and method for preparation thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polymeric material which can be used for forming an ionic conductive membrane being excellent in heat resistance, ionic conductivity, dimensional stability, especially excellent in processability. <P>SOLUTION: The invention relates to the sulfonic acid group-containing polyarylene ether based compound having a structural unit represented by general formula (1) and a structural unit represented by general formula (2) in the molecule chain. In the formulae, X is hydrogen or a monovalent cation species, Y is a sulfone group or a ketone group, Z is a sulfone group, a ketone or a direct bonding, V is hydrogen or fluorine, m, n are each an optional number selected from integers of two or more. When V is fluorine, then Z may be oxygen. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a sulfonic acid group-containing polyarylene ether compound, and more particularly to a sulfonic acid group-containing polyarylene ether compound useful as an adhesive for polymer electrolyte membranes and electrolyte membrane / electrode composites. is there.

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. Polymer membranes and membrane / electrode composite resins used in these materials must be sufficiently stable chemically, thermally, electrochemically and mechanically with proton conductivity as cation exchange membranes. . For this reason, a perfluorocarbon sulfonic acid membrane has been used as one that can be used for a long time.
However, if the perfluorocarbon sulfonic acid membrane is to be operated at a temperature of 100 ° C. or higher, the moisture content of the membrane is drastically lowered and the membrane is also softened. 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. Furthermore, it is pointed out as an obstacle to the establishment of fuel cell technology that the cost of the membrane is too high even in a fuel cell that operates near 80 ° C. using hydrogen as a fuel. The same problem has been pointed out when perfluorocarbon sulfonic acid resin is used as the adhesive resin.

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 the polymer skeleton, polyarylene ether compounds such as polyarylene ether ketones and polyarylene ether sulfones can be considered as promising structures in consideration of heat resistance and chemical stability. (For example, see Non-Patent Document 1), 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 films are also required to have even better characteristics. In addition, when used as an adhesive resin in the production of a membrane / electrode composite, a resin having a stronger bondability with a polymer electrolyte membrane is required.

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 provide a sulfonic acid group-containing polyarylene ether-based compound having a phenylene ether oligomer structure, and further, it is useful as a polymer electrolyte membrane, a resin for bonding membrane electrode assemblies, and the like. It is to obtain molecular materials.

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 sulfonic acid group-containing polyarylene ether having a structural unit represented by general formula (1) and general formula (2) in a molecular chain and having a logarithmic viscosity of 0.1 to 5 Compounds.

（ただし、式中、Ｘは水素又は１価のカチオン種、Ｙはスルホン基又はケトン基、Ｚはスルホン基、ケトン基、直接結合のうちのいずれか、Ｖは水素又はフッ素、ｍ、ｎは２以上の整数から選ばれる任意の数を示す。Ｖがフッ素の場合、Ｚは酸素であってもよい。）

(Wherein, X is hydrogen or a monovalent cation species, Y is a sulfone group or ketone group, Z is any one of a sulfone group, a ketone group, and a direct bond, V is hydrogen or fluorine, and m and n are Represents an arbitrary number selected from an integer of 2 or more, and when V is fluorine, Z may be oxygen.)

(2) The sulfonic acid group-containing polyarylene ether compound according to the first invention, further comprising a structural unit represented by the general formula (3).

（ただし、式中、ｏは２以上の整数から選ばれる任意の数を示す。）
（３）スルホン酸基含有量が、０．３〜５．０ｍｅｑ／ｇの範囲にある第１の発明又は第２の発明に記載のスルホン酸基含有ポリアリーレンエーテル系化合物。
（４）スルホン酸基含有ポリアリーレンエーテル系化合物におけるポリフェニレンエーテル単位が、一般式（４）で表される化合物で、ｐが異なる複数の成分を含み、ｐの平均値が１＜ｐ≦１０の範囲にある末端ジヒドロキシ化合物を原料モノマーの一部として使用することにより導入されてなる第１〜第３の発明のいずれかに記載のスルホン酸基含有ポリアリーレンエーテル系化合物。

(In the formula, o represents an arbitrary number selected from an integer of 2 or more.)
(3) The sulfonic acid group-containing polyarylene ether compound according to the first invention or the second invention, wherein the sulfonic acid group content is in the range of 0.3 to 5.0 meq / g.
(4) The polyphenylene ether unit in the sulfonic acid group-containing polyarylene ether compound is a compound represented by the general formula (4), and includes a plurality of components having different p, and the average value of p is 1 <p ≦ 10 The sulfonic acid group-containing polyarylene ether compound according to any one of the first to third inventions, which is introduced by using a terminal dihydroxy compound in a range as a part of a raw material monomer.

（５）ガラス転移温度が１３０℃から２２０℃の間にある第１〜第４の発明のいずれかに記載のスルホン酸基含有ポリアリーレンエーテル系化合物。

(5) The sulfonic acid group-containing polyarylene ether compound according to any one of the first to fourth inventions having a glass transition temperature between 130 ° C and 220 ° C.

(6) A polymer electrolyte membrane using the sulfonic acid group-containing polyarylene ether compound according to any one of the first to fifth inventions.
(7) A polymer electrolyte membrane / electrode composite obtained by joining the polymer electrolyte membrane according to the sixth invention and an electrode.
(8) A fuel cell using the polymer electrolyte membrane / electrode composite according to the seventh invention.
(9) The fuel cell according to the eighth invention, wherein methanol is used as fuel.
(10) An adhesive containing the sulfonic acid group-containing polyarylene ether compound according to any one of the first to fifth inventions.

(11) A step of casting the solvent solution of the sulfonic acid group-containing polyarylene ether compound according to any one of the first to fifth inventions so that the cast thickness is in the range of 10 to 1500 μm, and the cast solution A method for producing a polymer electrolyte membrane comprising a step of drying the material.

  The sulfonic acid group-containing polyarylene ether compound of the present invention can provide a material excellent in ion conductivity, heat resistance, and processability and exhibiting outstanding performance as a polymer electrolyte such as a fuel cell. The sulfonic acid group-containing polyarylene ether compound of the present invention is also useful as a binder resin for a membrane / electrode assembly exhibiting good bonding properties with a polymer electrolyte membrane.

Hereinafter, the present invention will be described in detail.
The present invention provides a polymer electrolyte material excellent in heat resistance, workability, and ion conductivity, particularly useful as an ion conductive membrane, by a specific polyarylene ether compound having a sulfonic acid group introduced on an aromatic ring. Is. That is, it is a sulfonic acid group-containing polyarylene ether compound having a structural unit represented by the general formula (1) and the general formula (2) in the molecular chain and having a logarithmic viscosity of 0.1 or more and 5 or less.

（ただし、式中、Ｘは水素又は１価のカチオン種、Ｙはスルホン基又はケトン基、Ｚはスルホン基、ケトン基、直接結合のうちのいずれか、Ｖは水素又はフッ素、ｍ、ｎは２以上の整数から選ばれる任意の数を示す。Ｖがフッ素の場合、Ｚは酸素であってもよい。）

(Wherein, X is hydrogen or a monovalent cation species, Y is a sulfone group or ketone group, Z is any one of a sulfone group, a ketone group, and a direct bond, V is hydrogen or fluorine, and m and n are Represents an arbitrary number selected from an integer of 2 or more, and when V is fluorine, Z may be oxygen.)

  Examples of the monovalent cation species in X include monovalent metal salts such as sodium and potassium, salts with organic base compounds such as ammonium salts, and the like. The structural unit of the general formula (1) is composed of 3,3′-disulfo-4,4′-dihalogenated diphenylsulfone, 3,3′-disulfo-4,4′-dihalogenated benzophenone or a derivative thereof and a terminal hydroxyl group. It is a structural unit formed from a group-containing phenylene ether oligomer by an aromatic nucleophilic substitution reaction.

  The structure of the general formula (2) is a structural unit formed by an aromatic nucleophilic substitution reaction from a bishalogenoaromatic compound activated for an aromatic nucleophilic substitution reaction and a terminal hydroxyl group-containing phenylene ether oligomer. . Specific examples of bishalogenoaromatic compounds include 4,4′-dichlorodiphenylsulfone, 4,4′-difluorodiphenylsulfone, 4,4′-dichlorobenzophenone, 4,4′-difluorobenzophenone, decafluorobiphenyl, decafluoro Examples include diphenyl ether, decafluorobenzophenone, decafluorodiphenyl sulfone and the like.

  The part comprised from the phenylene ether oligomer in the said General formula (1) and (2) is shown by the arbitrary numbers chosen from the integer more than 2 in the said formula. n may be a single compound composed of specific numbers, but may be a mixture of a plurality of n. In addition, as long as it includes a component where n is 2 or more, a diphenyl ether unit or a diphenoxybenzene unit corresponding to n = 0 or n = 1 may be included. In order to effectively contain the amount of sulfonic acid group in the molecular chain, it is preferable that n is mainly selected from 10 or less.

  Since the sulfonated polyarylene ether of the present invention is characterized in that the polymer chain contains the structures of the above general formula (1) and general formula (2), the above general formula (1) and general formula ( 2), it may consist of only the structure represented by the general formula (1) and the general formula (2), but other aromatic dihydroxy compounds and aromatic dihalogenated compounds may be used. A copolymerized form may be used. Moreover, the structure which gives the said General formula (1) and General formula (2) may not only be 1 type, but 2 or more types of structures may exist, Other than the said General formula (1) and General formula (2) There may also be a plurality of structural components. In any case, since the structure represented by the general formula (1) and the general formula (2) is present in the sulfonated polyarylene ether, the compound having excellent ion conductivity, heat resistance, and workability Become. In the present invention, by including the structures of the above general formula (1) and general formula (2) in which n is 2 or more, the polyarylene ether molecular chain is more flexible, and thus features are exhibited. In the sulfonic acid group-containing polyarylene ether, the proportion of the structural unit represented by the above structural formula is preferably 30% by mass or more, and more preferably 50% by mass or more.

  As described above, it is important that the sulfonic acid group-containing polyarylene ether compound of the present invention contains the structural units represented by the general formula (1) and the general formula (2) in the structure thereof, The method for introducing the structures of the general formula (1) and the general formula (2) is not particularly limited. As a general method, 4,4′-dihalogenated benzophenone and / or 4,4′-dihalogenated diphenylsulfone containing a sulfonic acid group or a sulfonic acid group derivative capable of giving the general formula (1) and the above general It can be synthesized by an aromatic nucleophilic substitution reaction using a bishalogenoaromatic compound that can give formula (2) and a terminal hydroxyl group-containing phenylene ether oligomer as at least part of the monomer.

  Specific examples of 4,4′-dihalogenated benzophenone and / or 4,4′-dihalogenated diphenylsulfone containing a sulfonic acid group or a sulfonic acid group derivative include 3,3′-disulfo-4,4′-dichloro Diphenyl sulfone, 3,3′-disulfo-4,4′-difluorodiphenyl sulfone, 3,3′-disulfo-4,4′-dichlorobenzophenone, 3,3′-disulfo-4,4′-difluorobenzophenone, and Examples thereof include those in which those sulfonic acid groups are converted to salts with monovalent cation species. The monovalent cation species may be sodium, potassium, other metal species, various amines, or the like, but is not limited thereto. Specific examples of bishalogenoaromatic compounds include 4,4′-dichlorobenzophenone, 4,4′-difluorobenzophenone, decafluorobiphenyl, decafluorodiphenyl ether, decafluorobenzophenone, decafluorodiphenyl sulfone, etc. You are not limited to these.

  In addition, the sulfonic acid group-containing polyarylene ether compound of the present invention includes a structural unit represented by the following general formula (3) together with the structures represented by the general formula (1) and the general formula (2). It is preferable.

ただし、一般式（３）において、ｏは２以上の整数から選ばれる任意の数で示される。ｏは特定の数字からなる単独化合物でも良いが、複数のｎが混合されたものであっても良い。一般式（３）で表される構成単位はフェニレンエーテルオリゴマーが占める割合が大きいため、本発明のポリアリーレンエーテルの分子鎖をより柔軟にするのに有効である。本発明のスルホン化ポリアリーレンエーテルが上記一般式（１）及び一般式（２）とともに一般式（３）で表される構成単位を含む場合は、本発明のスルホン化ポリアリーレンエーテルの全構成単位中にそれらの構成単位が５０質量％以上含有されていれば好ましく、７０質量％以上であればさらに好ましい。

However, in General formula (3), o is shown by the arbitrary numbers chosen from 2 or more integers. Although o may be a single compound consisting of specific numbers, it may be a mixture of a plurality of n. The constitutional unit represented by the general formula (3) is effective in making the molecular chain of the polyarylene ether of the present invention more flexible because the proportion of the phenylene ether oligomer is large. When the sulfonated polyarylene ether of the present invention includes the structural unit represented by the general formula (3) together with the general formula (1) and the general formula (2), all the structural units of the sulfonated polyarylene ether of the present invention It is preferable that those structural units are contained in an amount of 50% by mass or more, and more preferably 70% by mass or more.

  Examples of the dihalogenated compound that can give the general formula (3) include 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, and the like.

  In the aromatic nucleophilic substitution reaction for obtaining the sulfonic acid group-containing polyarylene ether compound of the present invention, the terminal hydroxyl group-containing phenylene ether oligomer giving the above general formulas (1) to (3) is represented by the following general formula (4). Can be expressed as

ただし、一般式（４）において、ｐは２以上の整数から選ばれる任意の数を示す。一般式（４）で表される末端ヒドロキシル基含有フェニレンエーテルオリゴマーはｐが単一の化合物からなるものを使用しても良いが、ｐの異なる複数の成分を含んでいても良い。ｐの異なる複数の成分を含んでいる場合には、ｐの平均値が１＜ｐ≦１０の範囲にあるものをモノマー成分の一部として使用することが好ましい。また、より好ましくは平均組成が２≦ｐ≦１０の範囲にあるものをモノマー成分の一部として使用することが好ましい。平均値としてのｐが１より小さいと得られるポリマーのガラス転移温度が高くなり、燃料電池用材料としての加工性が低下する傾向にあり、ｐ＞１０であるとガラス転移温度が低くなり燃料電池材料として使用する際の耐熱性が不十分となる傾向が現れるためである。なお、一般式（４）で表される末端ヒドロキシル基含有フェニレンエーテルオリゴマーがｐの異なる複数の成分を含んでいる場合、その平均組成はＮＭＲ等により、ｐの異なる成分の存在率はＧＰＣ等により決定することができる。

However, in General formula (4), p shows the arbitrary numbers chosen from 2 or more integers. As the terminal hydroxyl group-containing phenylene ether oligomer represented by the general formula (4), p may be composed of a single compound, but may contain a plurality of components having different p. When a plurality of components having different p are included, it is preferable to use a component having an average value of p in the range of 1 <p ≦ 10 as a part of the monomer component. More preferably, the monomer having an average composition in the range of 2 ≦ p ≦ 10 is used as a part of the monomer component. When p as an average value is smaller than 1, the glass transition temperature of the obtained polymer tends to be high, and the processability as a fuel cell material tends to decrease. When p> 10, the glass transition temperature becomes low and the fuel cell becomes low. This is because the heat resistance when used as a material tends to be insufficient. In addition, when the terminal hydroxyl group-containing phenylene ether oligomer represented by the general formula (4) includes a plurality of components having different p, the average composition is determined by NMR, and the abundance of components having different p is determined by GPC, etc. Can be determined.

  In the aromatic nucleophilic substitution reaction for obtaining the sulfonic acid group-containing polyarylene ether compound of the present invention, an activated difluoroaromatic compound or dichloroaromatic compound that gives a structure other than the above general formulas (1) to (3) Can be used together as monomers. Examples include compounds such as 2,4-dichlorobenzonitrile and 2,4-difluorobenzonitrile, but are not limited thereto, and other aromatic dihalogenated compounds that are active in aromatic nucleophilic substitution reactions Aromatic dinitro compounds, aromatic dicyano compounds, and the like can also be used. These compounds may be used alone or as a mixture of two or more.

  Moreover, the aromatic diol component which gives structural units other than the general formula (1)-(3) in the sulfonic acid group-containing polyarylene ether compound of the present invention is also the sulfonic acid group-containing polyarylene ether compound of the present invention. Can be used in aromatic nucleophilic substitution reactions to obtain. Examples of these are 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) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydride) Xylphenyl) 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, bis (4-hydroxyphenoxy) -1,4-benzene, bis (4-hydroxyphenoxy) -1,3-benzene, etc. may be used. Yes, but this It may be used various aromatic diols which can be used for the polymerization of polyarylene ether-based compound according to aromatic nucleophilic substitution reaction. In addition, a substituent such as a methyl group, a halogen, a cyano group, a sulfonic acid group, and a salt compound thereof may be bonded to these aromatic diols. The kind of substituent is not particularly limited, and is preferably 0 to 2 per aromatic ring. Furthermore, diphenylthioether-4,4'-dithiol etc. which can react like an aromatic diol can also be used. These aromatic diols can be used alone, or a plurality of aromatic diols can be used in combination.

  In the polymerization of the sulfonic acid group-containing 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, 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 ethylenically unsaturated groups, photopolymerization of benzophenones, α-diketones, acyloins, acyloin ethers, benzyl alkyl ketals, acetophenones, polynuclear quinones, thioxanthones, acylphosphines It is preferable to add an initiator.

  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, -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-H Loxyphenyl) 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.

  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 5.0 meq / g as an ion exchange capacity. When it is less than 0.3 meq / g, there is a tendency that it does not show sufficient ionic conductivity when used as a polymer electrolyte membrane. Tend to be. 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. In addition, Preferably it is 0.5-3.5 meq / g.

  The sulfonic acid group-containing polyarylene ether compound of the present invention preferably has a glass transition temperature between 130 ° C and 220 ° C. When the glass transition temperature is lower than 130 ° C., the heat resistance when used as a polymer electrolyte membrane tends to be insufficient, and when the glass transition temperature is higher than 220 ° C., the electrolyte membrane / electrode composite This is because a tendency for processability to decrease when a body is produced begins to appear. When the glass transition temperature is between 130 ° C. and 220 ° C., the processability when producing the electrolyte membrane / electrode composite is excellent, and the heat resistance when used as a fuel cell is particularly good. In addition, the glass transition temperature said here can be determined by the dynamic viscoelasticity measurement mentioned later.

  When the sulfonic acid group-containing polyarylene ether compound of the present invention is polymerized by an aromatic nucleophilic substitution reaction, the activated difluoroaromatic compound and / or the dichloroaromatic compound and the aromatic diol in the presence of a basic compound. A polymer can be obtained by reacting. 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 agent 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 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 has a polymer logarithmic viscosity of 0.1 or more and 5 or less measured by a method described later. When the logarithmic viscosity is less than 0.1, the membrane tends to become brittle when molded as a polymer electrolyte membrane. The logarithmic viscosity is preferably 0.3 or more. On the other hand, when the logarithmic 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 66, nylon 610, and nylon 12, polymethyl methacrylate, polymethacrylates, and polymethyl. Acrylate resins such as acrylates and polyacrylates, polyacrylic acid resins, polymethacrylic acid resins, polyethylene, polypropylene, various polyolefins including polystyrene and diene polymers, polyurethane resins, cellulose acetate, cellulose such as ethyl cellulose Resin, polyarylate, aramid, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polysulfone, polyethers Thermal curing of aromatic polymers such as phon, polyetheretherketone, polyetherimide, polyimide, polyamideimide, 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 polymer electrolyte membrane containing this resin composition has a low sulfonic acid group concentration, which is favorable. There is a tendency that ion conductivity cannot be obtained, and a unit containing a 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, and an antifoam as necessary. Various additives such as an agent, a dispersant, and a polymerization inhibitor may be included.

  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 any 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, alcohols such as methanol and ethanol, A mixed solvent selected from a combination of ketones, water and the like can be used, 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.

  A polymer electrolyte 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 polymer electrolyte membrane is casting from a solution, and the polymer electrolyte 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 in some cases alcohols, ketones, water, etc. Examples thereof include a mixed solvent selected from combinations. The removal of the solvent is preferably performed by drying in view of 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 shape as a polymer electrolyte 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 by making the thickness constant by using an applicator, a doctor blade, or the like, and making the cast area constant by using a frame that prevents the solution from flowing out. The cast solution can be formed into 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 polymer electrolyte membrane of the present invention can have any film thickness depending on the purpose, but 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 polymer electrolyte membrane is less than 5 μm, it is difficult to handle the polymer electrolyte membrane and a short circuit or the like tends to occur when a fuel cell is manufactured. If the thickness is greater than 250 μm, the electric resistance value of the ion conductive membrane increases. The power generation performance of the fuel cell 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 ionic conductivity of the polymer electrolyte membrane is preferably 1.0 × 10 ⁻³ S / cm or more. When the ionic conductivity is 1.0 × 10 ⁻³ S / cm or more, there is a tendency that a good output is obtained in a fuel cell using the polymer electrolyte membrane, and 1.0 × 10 ⁻³ S If it is less than / cm, the output of the fuel cell tends to decrease.

The polymer electrolyte membrane of the present invention is also useful for direct methanol fuel cells using methanol as fuel. A polymer electrolyte membrane in which a membrane with an average thickness of 50 μm is prepared and the methanol permeation rate measured at 25 ° C. using a 5 M aqueous methanol solution is 7 mmol / m ² · sec or less is preferred. The methanol permeation rate is further 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. A film having an average thickness of 50 μm substantially indicates a film having an average thickness in the range of 48 to 52 μm.

In the polymer electrolyte membrane from the sulfonic acid group-containing polyarylene ether compound of the present invention and the resin composition thereof, when it contains a component that crosslinks by heat and / or light, it is crosslinked by heat treatment and / or light irradiation treatment. By introducing the structure, the dimensional stability can be further improved. 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 0.01 to 50 hours, preferably 0.02 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 polymer electrolyte membrane or film of the present invention and the electrode can be obtained by joining the above-described polymer electrolyte membrane 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, a method of applying an adhesive to the electrode surface and bonding the polymer electrolyte membrane and the electrode, or a polymer electrolyte membrane and the electrode There is a method of heating and pressurizing. Among these, the 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 the adhesion between the polymer electrolyte membrane and the electrode is improved, and it is considered that the ion conductivity of the polymer electrolyte membrane is less impaired.

  A fuel cell can also be produced using the assembly of the polymer electrolyte membrane or film described above and an electrode. The polymer electrolyte membrane or film of the present invention is excellent in heat resistance, processability, ion conductivity and dimensional stability, and therefore can withstand operation at high temperature, easy to produce, and good output 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, and the viscosity was measured using a Ubbelohde viscometer in a constant temperature bath at 30 ° C., and the logarithmic viscosity ln [ta / tb] / c) Evaluation was made (ta is the number of seconds for dropping the sample solution, tb is the number of seconds for dropping only the solvent, and c is the polymer concentration).
<TGA>
Using a thermogravimetry meter (TGA-50) manufactured by Shimadzu Corporation, measurement was carried out in an argon atmosphere at a temperature rising rate of 10 ° C./min (while being kept at 150 ° C. for 30 minutes to sufficiently remove moisture).
<Ion conductivity measurement>
A platinum wire (diameter: 0.2 mm) was pressed against the surface of the strip-shaped film sample on a probe for self-made measurement (made of tetrafluoroethylene), and a constant temperature / humidity oven at 80 ° C. and 95% RH (Nagano Science Machinery Co., Ltd., The sample was held in 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]

<Ion exchange capacity>
Weigh the sample dried overnight under a nitrogen atmosphere, and after stirring with aqueous sodium hydroxide, measure the sulfonic acid group content by back titration with aqueous hydrochloric acid to determine the ion exchange capacity (IEC: meq / g). Asked.
<Methanol permeation rate>
A membrane immersed in an aqueous methanol solution with a concentration of 5 M (mol / liter) adjusted to 25 ° C. for 24 hours is sandwiched in an H-type cell, 100 ml of an aqueous methanol solution with a concentration of 5 M is added to one side of the cell, and an excess of 100 ml is added to the other cell. Calculated by injecting pure 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 was 2.0 cm ² ).
<Glass transition temperature>
Using a Rheogel-E4000 manufactured by Orientec Corp., a tensile sine wave was applied to a film sample having a sample width of 5 mm and an effective sample length of 15 mm, and dynamic viscoelasticity measurement was performed at a temperature rising rate of 2 ° C./min. The temperature at which the elastic modulus begins to decrease with increasing temperature is defined as the glass transition point.
<HNMR measurement>
Samples were dissolved in deuterated dimethyl sulfoxide and measured at 80 ° C. using a Varian GEMINI 200 NMR spectrometer.

<Evaluation of power generation>
After adding and dampening a small amount of ultrapure water and isopropyl alcohol to Pt / Ru catalyst-supporting carbon (Tanaka Kikinzoku Kogyo TEC61E54), a DuPont 20% Nafion (registered trademark) solution (product number: SE-20192) is used. The Pt / Ru catalyst-supported carbon and Nafion were added so that the mass ratio was 2.5: 1. Next, stirring was performed to prepare an anode catalyst paste. This catalyst paste is applied to a carbon paper (TGPH-060 manufactured by Toray Industries, Inc.) serving as a gas diffusion layer by screen printing so that the amount of platinum deposited is 2 mg / cm ^2, and carbon paper with an electrode catalyst layer for anode Was made. 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, a 20% Nafion solution (product number: SE-20192) manufactured by DuPont is used. And a Nafion mass ratio of 2.5: 1 were added and stirred to prepare a cathode catalyst paste. This catalyst paste was applied and dried on carbon paper (TGPH-060 manufactured by Toray Industries, Inc.) that had been subjected to water repellent treatment so that the amount of platinum deposited was 1 mg / cm ^2. Produced. 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 Technica). 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) 8.3450 g (0.016987 mole), 4,4′-dichlorodiphenylsulfone (abbreviation: DCDPS) 9.8984 g (0.034489 mole), terminal hydroxyl group-containing phenylene ether oligomer (abbreviation: DPE) (Dainippon Ink & Co., Ltd. SPECIANOL DPE-PL, lot C008) (in formula (4), a mixture containing a plurality of p components. NMR) The average composition was p = 2.3) 21.1054 g (0.051477 mole) and potassium carbonate 8.1817 g (0.05920 mole) 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 9 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 1.14.
20 g of the polymer was dissolved in 80 ml of NMP, cast to a thickness of about 500 μm on the upper glass plate of the hot plate, NMP was distilled off until a film was formed, 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 ionic conductivity of this film was measured, it was 0.08 S / cm at 80 ° C. and 95% RH, and 0.025 S / cm in 25 ° C. water. The IEC determined by titration was 0.94 meq / g. The methanol permeation rate was 2.7 mmol / m ² · sec. The glass transition temperature measured by dynamic viscoelasticity was 164 ° C.

(Example 2)
S-DCDPS 8.4000 g (0.017099 mole), 4,4′-difluorobenzophenone 11.1932 g (0.051298 mole), DPE (Dai Nippon Ink & Co., Ltd. SPECIANOL DPE-PL, lot C008) (28.0428 g (0.068397 mole) ), 10.87711 g (0.078656 mole) of potassium carbonate were weighed into a 200 ml four-necked flask and flushed with nitrogen, 140 ml of N-methyl-2-pyrrolidone was added, and the mixture was stirred with heating to a reaction temperature of 195-200. The mixture was allowed to react for 11 hours by raising the temperature to 0 ° C. After allowing to cool, the polymerization solution was poured into water to precipitate the polymer into strands, and the resulting polymer was immersed in fresh water for one day and dried. The logarithmic viscosity of the polymer was 0.89.
20 g of the polymer was dissolved in 80 ml of NMP, cast to a thickness of about 500 μm on the upper glass plate of the hot plate, NMP was distilled off until a film was formed, 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 ionic conductivity of this film was measured, it showed a value of 0.016 S / cm in 25 ° C. water. The IEC determined by titration was 0.80 meq / g. The methanol permeation rate was 2.2 mmol / m ² · sec. The glass transition temperature measured by dynamic viscoelasticity was 155 ° C.

(Example 3)
S-DCDPS 9.0000 g (0.018321 mole), DCDPS 9.7703 g (0.034023 mole), 2,2-bis (4-hydroxyphenyl) propane 3.5849 g (0.015703 mole), DPE (SPECIANOL DPE manufactured by Dainippon Ink & Chemicals, Inc.) -PL, lot C008) 15.0229 g (0.036641 mole) and potassium carbonate 8.3197 g (0.060196 mole) were weighed into a 200 ml four-necked flask and flushed with nitrogen. 110 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 11 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 1.31.
20 g of the polymer was dissolved in 80 ml of NMP, cast to a thickness of about 500 μm on the upper glass plate of the hot plate, NMP was distilled off until a film was formed, 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 ionic conductivity of this film was measured, it showed a value of 0.033 S / cm in 25 ° C. water. The IEC determined by titration was 1.09 meq / g. The methanol permeation rate was 3.0 mmol / m ² · sec.

Example 4
3,3′-disulfo-4,4′-difluorobenzophenone disodium salt 8.5000 g (0.020128 mole), DCDPS 6.4299 g (0.037381 mole), DPE (SPECIANOL DPE-PL, lot C008, manufactured by Dainippon Ink & Chemicals, Inc.) 23.5789 g (0.05751 mole) and 9.1407 g (0.06614 mole) of potassium carbonate were weighed into a 200 ml four-necked flask and flushed with nitrogen. 110 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 13 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 0.96.
20 g of the polymer was dissolved in 80 ml of NMP, cast to a thickness of about 500 μm on the upper glass plate of the hot plate, NMP was distilled off until a film was formed, 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 ionic conductivity of this film was measured, it showed a value of 0.031 S / cm in 25 ° C. water. The IEC determined by titration was 1.13 meq / g.

(Example 5)
In Example 3, instead of 2,2-bis (4-hydroxyphenyl) propane, 2,798 g (0.01573 mole) of 2,2-bis (4-hydroxyphenyl) hexafluoropropane was used to obtain a polymer. The logarithmic viscosity of the polymer was 0.76.
20 g of the polymer was dissolved in 80 ml of NMP, cast on a glass plate on a hot plate to a thickness of about 500 μm, 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 0.017 S / cm in 25 ° C. water. The IEC determined by titration was 1.00 meq / g.

(Example 6)
S-DCDPS 7.5000 g (0.015267 mole), decafluorobenzophenone 11.2246 g (0.030997 mole), DPE (Dai Nippon Ink & Co., Ltd. SPECIANOL DPE-PL, lot C008) 18.9683 g (0.046264 mole), potassium carbonate 7 3533 g (0.05320 mole) was weighed into a 200 ml four-necked flask and flushed with nitrogen. 120 ml N-methyl-2-pyrrolidone. 30 ml of benzene was added and the mixture was heated and stirred, and the reaction temperature was raised to 100 ° C. for 4 hours, 120 ° C. for 8 hours, and 195 to 200 ° C. for further 8 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.
20 g of the polymer was dissolved in 80 ml of NMP, cast to a thickness of about 500 μm on the upper glass plate of the hot plate, NMP was distilled off until a film was formed, 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 ionic conductivity of this film was measured, it showed a value of 0.08 S / cm at 80 ° C. and 95% RH and 0.011 S / cm in water at 25 ° C. The IEC determined by titration was 0.88 meq / g.

(Example 7)
3,3 ′, 4,4′-tetraaminodiphenylsulfone 1.500 g (5.389 × 10 ⁻³ mole), 1.445 g of 2,5-dicarboxybenzenesulfonic acid (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. The temperature is raised to 100 ° C. while slowly stirring on an oil bath while flowing nitrogen. 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. for 4 hours to polymerize. 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 household mixer. The obtained polymer was dried under reduced pressure at 80 ° C. overnight. The logarithmic viscosity of the polymer was 2.19. 1 g of this polymer was dissolved by heating in 10 ml of N-methyl-2-pyrrolidone, mixed with 40 ml of the film-forming solution prepared in Example 1, and then the thickness was adjusted in the same manner as in Example 1 except that the cast thickness was adjusted. A 50 μm film was prepared. When the ion conductivity of this film was measured, it showed a value of 0.05 S / cm in 25 ° C. water.

(Example 8)
When the power generation evaluation was performed using the film produced in Example 2, a favorable power generation characteristic of 0.31 V was obtained at a current density of 100 mA.

Example 9
In the preparation of the membrane / electrode assembly described above, a membrane / electrode assembly was prepared using a 10% N-methyl-2-pyrrolidone solution of the polymer synthesized in Example 4 instead of the Nafion solution. What was obtained was a good bonded body without electrode peeling.

(Example 10)
In Example 4, polymerization of the polymer and film formation were performed using the same mole number of DPE having an average composition corresponding to p = 4.5, and production of a membrane / electrode assembly was attempted in the same manner as in Example 9. However, a good joined body without electrode peeling was obtained.

(Comparative Example 1)
In Example 4, polymerization of the polymer and film formation were performed using the same mole number of DPE having an average composition corresponding to n = 1.5, and production of a membrane / electrode assembly was attempted in the same manner as in Example 9. However, it showed a phenomenon that the electrode was partially peeled off.

  The sulfonic acid group-containing 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 conductive membranes, but various battery electrolytes, humidifying membranes, humidity adjusting membranes, display elements, sensors, binders, It is expected to be used as an additive.

Claims (11)

A sulfonic acid group-containing polyarylene ether compound having structural units represented by general formulas (1) and (2) in a molecular chain and having a logarithmic viscosity of 0.1 or more and 5 or less.

(Wherein, X is hydrogen or a monovalent cation species, Y is a sulfone group or ketone group, Z is any one of a sulfone group, a ketone group, and a direct bond, V is hydrogen or fluorine, and m and n are Represents an arbitrary number selected from an integer of 2 or more, and when V is fluorine, Z may be oxygen.) The sulfonic acid group-containing polyarylene ether compound according to claim 1, further comprising a structural unit represented by the general formula (3).

(In the formula, o represents an arbitrary number selected from an integer of 2 or more.)   The sulfonic acid group-containing polyarylene ether compound according to claim 1 or 2, wherein the sulfonic acid group content is in the range of 0.3 to 5.0 meq / g. The polyphenylene ether unit in the sulfonic acid group-containing polyarylene ether compound is a compound represented by the general formula (4), includes a plurality of components having different p, and the average value of p is in the range of 1 <p ≦ 10. The sulfonic acid group-containing polyarylene ether compound according to any one of claims 1 to 3, which is introduced by using a terminal dihydroxy compound as a part of a raw material monomer.

  The sulfonic acid group-containing polyarylene ether compound according to any one of claims 1 to 4, wherein the glass transition temperature is between 130 and 220 ° C.   A polymer electrolyte membrane using the sulfonic acid group-containing polyarylene ether compound according to claim 1.   A polymer electrolyte membrane / electrode composite obtained by joining the polymer electrolyte membrane according to claim 6 and an electrode.   A fuel cell using the polymer electrolyte membrane / electrode composite according to claim 7.   The fuel cell according to claim 8, wherein methanol is used as a fuel.   An adhesive containing the sulfonic acid group-containing polyarylene ether compound according to any one of claims 1 to 5.   A step of casting the solvent solution of the sulfonic acid group-containing polyarylene ether compound according to any one of claims 1 to 5 so that a cast thickness is in a range of 10 to 1500 µm, and a step of drying the cast solution. A method for producing a polymer electrolyte membrane comprising: