JP2006344589A - Polyelectrolyte and its manufacturing method, electrode for fuel cell, and electrode membrane assembly as well as fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyelectrolyte or the like which is superior in gas permeability and ion conductivity. <P>SOLUTION: This is the polyelectrolyte in which at least one substituent with the total carbon number of 3 or more is substituted by the substituent containing at least one acid residue to any position of a polymer main chain including a repeating unit expressed by a general formula (1). In the general formula (1), Ar<SP>11</SP>and Ar<SP>12</SP>respectively denote a divalent aromatic group. R<SP>11</SP>denotes a single bond or a divalent aliphatic group. X<SP>11</SP>denotes a divalent electron-attracting group. X<SP>12</SP>denotes a divalent electron-donating group, and n<SP>11</SP>denotes an integer of 5 to 1,500. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polymer electrolyte, particularly a polymer electrolyte having proton conductivity, an electrode for a fuel cell, an electrode membrane assembly, a fuel cell, and a method for producing the polymer electrolyte.

  In recent years, lithium-ion batteries and fuel cells that can be used as power sources for portable devices and the like have been actively researched, and active research has also been conducted on polymer electrolytes such as lithium-ion conductive materials and proton-conductive materials that are members thereof. .

Further, it is preferable that the power source is small as long as it has the same output. In particular, fuel cells are being actively studied because of their features such as quietness and cleanness of exhaust gas with respect to internal combustion engines such as engines, and the possibility of high energy efficiency exceeding that of internal combustion engines.
In general, a sulfonic acid group-containing perfluorocarbon polymer represented by Nafion (registered trademark) is used as a polymer electrolyte that is a proton conductive material. This material is used as a solid polymer membrane for a fuel cell and as a binder for an electrode. However, although its ionic conductivity is high, its rigidity is low, so that sufficient durability is not obtained under high temperature and long time conditions. Moreover, although there is an example of research on a proton conductive material exhibiting reaction gas permeability, sufficient durability cannot be expected because of low rigidity like Nafion (Patent Document 1).

  In recent years, there have been many development examples of polymer electrolytes using high-rigidity polymer materials, and research on polymer electrolytes using resin materials with high solvent resistance among polymer materials has been conducted. In Nos. 2 to 6, polymer electrolytes mainly composed of sulfonated polyether ether ketone, sulfonated polysulfone, and sulfonated polyether ketone have been developed.

JP 2004-164857 A JP-A-6-49202 JP-A-6-93114 JP-A-8-20716 JP 2003-257451 A JP 2003-292609 A

  As described above, the development of polymer electrolytes has been promoted. However, when this is used for an electrode of a fuel cell or a gas sensor, a new problem occurs. In fuel cells and gas sensors, it is essential that gas accompanying a detection reaction permeate, and a polymer electrolyte having high gas permeability is required. Conventional materials have low gas permeability, and particularly low hydrogen and oxygen permeability, making them unsuitable for fuel cell electrodes. In particular, non-fluorine polymer electrolytes have a high polarity, and the gas permeability, which is a low polarity molecule, tends to decrease. In the present invention, a polymer electrolyte having a high gas permeability in a highly durable high-rigidity polymer material, in particular, having both a high ion conductivity (proton conductivity) and a high gas permeability, and a fuel cell using the same It is a problem to provide a working electrode, an electrode membrane assembly, and a fuel cell.

（一般式（１）において、Ａｒ¹¹およびＡｒ¹²はそれぞれ２価の芳香族基を表す。Ｒ¹¹は単結合または２価の脂肪族基を表し、Ｘ ¹²は２価の電子吸引性基を表し、Ｘ¹¹は２価の電子供与性基を表す。ｎ１１は５〜１５００の整数を表す。）
（２）前記高分子化合物は、下記一般式（２）で表される繰り返し単位および一般式（３）で表される繰り返し単位の少なくとも１種を含む、（１）に記載の高分子電解質。
一般式（２）

（一般式（２）において、Ａｒ²¹およびＡｒ²²はそれぞれ２価の芳香族基を表す。Ｒ²¹は単結合または２価の脂肪族基を表す。Ｒ²²は酸残基またはその塩を含む１価の置換基を表す。Ｒ²³は総炭素数３以上の１価の置換基を表す。Ｘ²¹は２価の電子吸引性基を表す。Ｘ²²は２価の電子供与性基を表す。ｎ２１は５〜１５００の整数を表す。ｎ２２は、０、１または２を表し、１の繰り返し単位中のｎ２２の和が１以上である。ｎ２３は、０、１または２を表し、１の繰り返し単位中のｎ２３の和が１以上である。)
一般式（３）

（一般式（３）において、Ａｒ³¹およびＡｒ³²はそれぞれ２価の芳香族基を表す。Ｒ³¹は単結合または２価の脂肪族基を表す。Ｒ³²は酸残基またはその塩を含む１価の置換基を表す。Ｒ³³は総炭素数３以上の１価の置換基を表す。Ｘ³¹は２価の電子吸引性基を表す。Ｘ³²は２価の電子供与性基を表す。ｎ３１は５〜１５００の整数を表す。ｎ３２は、０、１または２を表し、１の繰り返し単位中のｎ３２の和が１以上である。ｎ３３は、０、１または２を表し、１の繰り返し単位中のｎ３３の和が１以上である。)
（３）前記高分子主鎖が、ポリスルホン、ポリエーテルスルホン、ポリエーテルケトンまたはポリイミドである、（１）または（２）に記載の高分子電解質。
（４）酸残基を水素原子に置き換えて計算したパーマコール値が０〜２０である、（１）〜（３）のいずれか１項に記載の高分子電解質。
（５）前記高分子化合物の酸素透過係数は、３ｘ１０―¹²ｍｏｌ／ｃｍ・ｓ以上である（１）〜（４）のいずれか１項に記載の高分子電解質。
（６）０．１〜７ｍｅｑ／ｇの濃度で酸残基を含む、（１）〜（５）のいずれか１項に記載の高分子電解質。
（７）前記高分子化合物の重量平均分子量が５，０００以上である、（１）〜（６）のいずれか１項に記載の高分子電解質。
（８）前記酸残基が、スルホン酸基である、（１）〜（７）のいずれか１項に記載の高分子電解質。
（９）前記酸残基がスルホン酸基であり、前記高分子主鎖が炭化水素系高分子化合物であり、かつ、前記高分子化合物の酸素透過係数は、３ｘ１０―¹²ｍｏｌ／ｃｍ・ｓ以上である（１）〜（８）のいずれか１項に記載の高分子電解質。
（１０）下記一般式（４）で表される化合物および下記一般式（６）で表される化合物からなる群から選択される少なくとも１種と、下記一般式（５）で表される化合物および下記一般式（７）で表される化合物からなる群から選択される少なくとも１種とを重合することを含む、（１）〜（９）のいずれか１項に記載の高分子電解質の製造方法。
一般式（４）

(一般式（４）中、Ａｒ⁴¹は２価の芳香族基を表し、Ｒ⁴²は酸残基またはその塩を含む１価の置換基を表し、Ｘ⁴¹は２価の電子吸引性基を表し、Ｙ⁴¹は芳香族求核置換反応における脱離基を表す。ｎ４２は０、１または２を表し、１つの化合物中のｎ４２の和が１以上である。)
一般式（５）

(一般式（５）において、Ａｒ⁵¹は２価の芳香族基を表し、Ｒ⁵³は総炭素数３以上の１価の置換基を表す。Ｘ⁵¹は２価の電子吸引性基を表し、Ｙ⁵¹は芳香族求核置換反応における脱離基を表す。ｎ５３は０、１または２を表し、１つの化合物中のｎ５３の和が１以上である。)
一般式（６）

(一般式（６）において、Ａｒ⁶²は２価の芳香族基を表し、Ｒ⁶¹は単結合または２価の脂肪族基を表し、Ｒ⁶²は酸残基またはその塩を含む１価の置換基を表し、Ｙ⁶²は芳香族求核置換反応における求核性基を表す。ｎ６２は０、１または２を表し、１つの化合物中のｎ６２の和が１以上である。)
一般式（７）

(一般式（７）において、Ａｒ⁷²は２価の芳香族基を表し、Ｒ⁷¹は単結合または２価の脂肪族基を表し、Ｒ⁷³は総炭素数３以上の１価の置換基を表す。Ｙ⁷²は芳香族求核置換反応における求核性基を表す。ｎ７３は０、１または２を表し、１つの化合物中のｎ７３の和が１以上である。)
（１１）（１）〜（９）のいずれか１項に記載の高分子電解質を含む、燃料電池用電極。
（１２）（１）〜（９）のいずれか１項に記載の高分子電解質を含む、電極膜接合体。
（１３）（１）〜（９）のいずれか１項に記載の高分子電解質を含む、燃料電池。 (1) A substituent containing at least one acid residue and at least one substituent having 3 or more total carbon atoms at any position of the polymer main chain containing the repeating unit represented by the following general formula (1) A polymer electrolyte comprising a polymer compound in which a group is substituted.
General formula (1)

(In the general formula (1), Ar ¹¹ and Ar ¹² each represent a divalent aromatic group, R ¹¹ represents a single bond or a divalent aliphatic group, and X ¹² represents a divalent electron-withdrawing group. represents, X ¹¹ is .n11 representing a divalent electron donating group represents an integer of 5 to 1,500.)
(2) The polymer electrolyte according to (1), wherein the polymer compound includes at least one of a repeating unit represented by the following general formula (2) and a repeating unit represented by the general formula (3).
General formula (2)

(In the general formula (2), Ar ²¹ and Ar ²² each represent a divalent aromatic group. R ²¹ represents a single bond or a divalent aliphatic group. R ²² includes an acid residue or a salt thereof. Represents a monovalent substituent, R ²³ represents a monovalent substituent having 3 or more carbon atoms, X ²¹ represents a divalent electron-withdrawing group, and X ²² represents a divalent electron-donating group. N21 represents an integer of 5 to 1500. n22 represents 0, 1 or 2, and the sum of n22 in the repeating unit of 1 is 1 or more, n23 represents 0, 1 or 2 and 1 (The sum of n23 in the repeating unit is 1 or more.)
General formula (3)

(In the general formula (3), Ar ³¹ and Ar ³² each represent a divalent aromatic group. R ³¹ represents a single bond or a divalent aliphatic group. R ³² includes an acid residue or a salt thereof. Represents a monovalent substituent, R ³³ represents a monovalent substituent having a total carbon number of 3 or more, X ³¹ represents a divalent electron-withdrawing group, and X ³² represents a divalent electron-donating group. N31 represents an integer of 5 to 1500. n32 represents 0, 1 or 2, and the sum of n32 in the repeating unit of 1 is 1 or more, n33 represents 0, 1 or 2; (The sum of n33 in the repeating unit is 1 or more.)
(3) The polymer electrolyte according to (1) or (2), wherein the polymer main chain is polysulfone, polyethersulfone, polyetherketone, or polyimide.
(4) The polymer electrolyte according to any one of (1) to (3), wherein the permacol value calculated by replacing the acid residue with a hydrogen atom is 0 to 20.
(5) oxygen permeability coefficient of the polymer compound, 3x10- ¹² mol / cm · s or more at a (1) to a polymer electrolyte according to any one of (4).
(6) The polymer electrolyte according to any one of (1) to (5), comprising an acid residue at a concentration of 0.1 to 7 meq / g.
(7) The polymer electrolyte according to any one of (1) to (6), wherein the polymer compound has a weight average molecular weight of 5,000 or more.
(8) The polymer electrolyte according to any one of (1) to (7), wherein the acid residue is a sulfonic acid group.
(9) the acid residue is a sulfonic acid group, the polymer main chain is hydrocarbon-based polymer compound, and an oxygen permeability coefficient of the polymer compound, 3x10- ¹² mol / cm · s or more The polymer electrolyte according to any one of (1) to (8).
(10) at least one selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (6), a compound represented by the following general formula (5) and The method for producing a polymer electrolyte according to any one of (1) to (9), comprising polymerizing at least one selected from the group consisting of compounds represented by the following general formula (7): .
General formula (4)

(In the general formula (4), Ar ⁴¹ represents a divalent aromatic group, R ⁴² represents a monovalent substituent containing an acid residue or a salt thereof, and X ⁴¹ represents a divalent electron-withdrawing group. represents, Y ⁴¹ is .n42 representing a leaving group in nucleophilic aromatic substitution represents 0, 1 or 2, the sum of n42 in one compound is one or more.)
General formula (5)

(In the general formula (5), Ar ⁵¹ represents a divalent aromatic group, R ⁵³ represents a monovalent substituent having a total carbon number of 3 or more, X ⁵¹ represents a divalent electron-withdrawing group, Y ⁵¹ represents a leaving group in the aromatic nucleophilic substitution reaction, n53 represents 0, 1 or 2, and the sum of n53 in one compound is 1 or more.)
General formula (6)

(In General Formula (6), Ar ⁶² represents a divalent aromatic group, R ⁶¹ represents a single bond or a divalent aliphatic group, and R ⁶² represents a monovalent substituent containing an acid residue or a salt thereof. Y ⁶² represents a nucleophilic group in the aromatic nucleophilic substitution reaction, n62 represents 0, 1 or 2, and the sum of n62 in one compound is 1 or more.
General formula (7)

(In the general formula (7), Ar ⁷² represents a divalent aromatic group, R ⁷¹ represents a single bond or a divalent aliphatic group, and R ⁷³ represents a monovalent substituent having 3 or more carbon atoms in total. Y ⁷² represents a nucleophilic group in the aromatic nucleophilic substitution reaction, n73 represents 0, 1 or 2, and the sum of n73 in one compound is 1 or more.)
(11) A fuel cell electrode comprising the polymer electrolyte according to any one of (1) to (9).
(12) An electrode membrane assembly comprising the polymer electrolyte according to any one of (1) to (9).
(13) A fuel cell comprising the polymer electrolyte according to any one of (1) to (9).

  In the present invention, it has become possible to provide a polymer electrolyte having both high ion conductivity and high oxygen permeability. By employing the polymer electrolyte of the present invention, it can be preferably employed as a solid electrolyte used in fuel cells and the like.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the present specification, the membrane-shaped polymer electrolyte is sometimes referred to as “polymer electrolyte membrane”.

The polyelectrolyte according to the present invention includes a substituent containing at least one acid residue and at least one total carbon number at any position of the polymer main chain containing the repeating unit represented by the general formula (1). It includes a polymer compound in which three or more substituents are substituted.
Here, the repeating units represented by the general formula (1) contained in the polymer compound may be the same or different.
Further, Ar ¹¹ , Ar ¹² and X ¹² in the repeating unit represented by the general formula (1) in the present invention, Ar ²¹ , Ar ²² , R ²² , R in the repeating unit represented by the general formula (2) ²³ , X ²² , n22 and n23, Ar ³¹ , Ar ³² , R ³² , R ³³ , X ³² , n32 and n33 in the repeating unit represented by the general formula (3) are each in one repeating unit. When multiple are included, they may be the same or different from each other, but are preferably the same.
Furthermore, Ar ⁴¹ , R ⁴² , Y ⁴¹ and n42 in the compound represented by the general formula (4), Ar ⁵¹ , R ⁵³ , Y ⁵¹ and n53 in the compound represented by the general formula (5), the general formula Ar ⁶² , R ⁶² , Y ⁶² and n62 in the compound represented by (6), and Ar ⁷² , R ⁷³ , Y ⁷² and n73 in the compound represented by the general formula (7) are each one compound. When a plurality of them are contained, they may be the same or different from each other, but are preferably the same.

In the repeating unit represented by the general formula (1), Ar ¹¹ and Ar ¹² each represent a divalent aromatic group, and each may be the same or different. The total carbon number of Ar ¹¹ and Ar ¹² is preferably 6-30, more preferably 6-20, and still more preferably 6-12. Ar ¹¹ and Ar ¹² are each preferably a divalent aromatic group having one or more benzene rings (including those in which the benzene ring is condensed), and the following (A1) to (A20) Or a combination thereof, more preferably (A1), (A2), (A3), (A4) or (A6), and (A1), (A2). Or (A4) is more preferable.

In General Formula (A19), Q ¹ represents —O—, —S—, or —NR ²¹ —, and is preferably —S—.
In the formula (A20), Q ^{2 is, -O -, - CR 22 R} 23 -, - CO- or -NR ²⁴ - ^{represents, -CR 22 R 23 -, -} CO- is preferred. Here, R ^{21 to} R ²⁴ each represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and preferably a hydrogen atom, a methyl group or an ethyl group.
The positions of the binders of (A4) to (A16), (A19) and (A20) are not particularly defined, but the positions of the binders in the case of (A4) are particularly preferably 4-position and 4'-position, In the case of (A5), the 4-position and the 4 ″ -position are particularly preferred. In the case of (A6), the position of the binder is particularly preferably the 2-position and the 6-position. The position of the binder in the case of (A7) Is particularly preferably 2-position and 3-position, the position of the binder in the case of (A8) is particularly preferably 2-position and 6-position, and the position of the binder in the case of (A9) is particularly preferably 2-position and 3-position, The position of the bond in the case of (A12) is particularly preferably the 3rd and 6th positions, and the position of the bond in the cases of (A13), (A14), (A15) and (A16) is at the 4th and 4 'positions. Particularly preferred, the position of the connector in the case of (A19) is particularly preferably the 2nd and 5th positions. In the case of (A20), the position of the binder is particularly preferably the 2nd and 7th positions.

Ar ¹¹ and Ar ¹² are preferably the same.

In the repeating unit represented by the general formula (1), R ¹¹ represents a single bond or a divalent aliphatic group, and the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, 3 is more preferable.
R ¹¹ represents an alkylene group (methylene group, ethylene group, methylethylene group, propylene group, methylpropylene group, butylene group, pentylene group, hexylene group, octylene group), cycloalkylene group (cyclopropylene group, cyclobutylene group, cyclopentylene group). Ene group, cyclohexylene group, cyclooctylene group), halogen-substituted alkylene group (difluoromethylene group, tetrafluoroethylene group, hexafluorohexylene group, tetrafluorohexylene group, dichloromethylene group), alkenylene group (ethenylene group) , Propenylene group, butadienylene group), halogen-substituted alkynylene group (difluoroethenylene group, tetrafluoropropenylene group, dichloroethenylene group), alkynylene group (ethynylene group, propynylene group) are preferable, alkylene , A cycloalkylene group, a halogen-substituted alkylene group are more preferable.

In the repeating unit represented by the general formula (1), X ¹¹ represents a divalent electron-withdrawing group, preferably —CO—, —SO— or —SO ₂ —, more preferably —SO ₂ —.

In the repeating unit represented by the general formula (1), X ¹² represents a divalent electron donating group. X ¹² is preferably —S— or —O—, more preferably —O—.

In the repeating unit represented by the general formula (1), n11 represents an integer of 5 to 1500, preferably 10 to 1000, and more preferably 20 to 500. The polymer compound contained in the polymer electrolyte of the present invention is preferably not crosslinkable.
The polymer aromatic compound used for the main chain is preferably one having high heat resistance, such as a polyethersulfone-based polymer compound, a polyetherethersulfone-based polymer compound, a polyetheretherketone-based polymer compound, a polyphenylene sulfide-based compound. More preferred are molecular compounds, polyphenylene ether polymer compounds, polysulfone polymer compounds or polyether ketone polymer compounds, and polyether ether ketone polymer compounds and polyether sulfone compounds from the viewpoint of resistance to oxidation degradation of the main chain. More preferred are polymer compounds and polyether ether sulfone polymer compounds. Although the preferable example of the repeating structure represented by General formula (1) below is illustrated below, this invention is not limited to these. As for the examples of the repeating unit represented by the general formula (1), the monovalent substituent including the acid residue and the salt thereof may be located at any position of the left benzene ring / right benzene ring, respectively. The number is not particularly limited.

ｎ１１個の一般式（１）で表される繰り返し単位は、それぞれ、同一であってもよいし、異なっていてもよいが、好ましくは同一の場合である。
また、一般式（１）で表される繰り返し単位を含む高分子主鎖は、一般式（１）で表される繰り返し単位が、ｎ１１回繰り返している必要はなく、間に他のモノマーが含まれていてもよい。

The n11 repeating units represented by the general formula (1) may be the same or different, but are preferably the same.
In addition, the polymer main chain containing the repeating unit represented by the general formula (1) does not need to be repeated n11 times for the repeating unit represented by the general formula (1), and other monomers are included therebetween. It may be.

The repeating unit represented by the general formula (1) has a substituent containing at least one acid residue and at least one substituent having a total carbon number of 3 or more. These substituents are preferably bonded to any one or more of Ar ¹¹ , Ar ^{12 and} R ¹¹ , respectively.
The substituent containing an acid residue is preferably a substituent represented by the following general formula (8). In general formula (8), L ⁸ represents a single bond or a divalent linking group, and A represents an acid residue. Or represents a salt thereof.
L ⁸ may be any linking group, but is preferably an alkylene group (preferably an alkylene group having 1 to 20 carbon atoms such as methylene group, ethylene group, methylethylene group, propylene group, methylpropylene group, butylene group, pentylene. Group, hexylene group, octylene group), halogen-substituted alkylene group (preferably C1-C20 halogen-substituted alkylene group, for example, difluoromethylene group, tetrafluoroethylene group, hexafluorohexylene group, tetrafluorohexylene group, Dichloromethylene group), arylene group (preferably an arylene group having 6 to 26 carbon atoms, such as 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 4-phenylenemethylene group, 1, 4-naphthylene group), halogen-substituted arylene group (preferably having 6 to 6 carbon atoms) 6 halogen-substituted arylene groups such as 2,3,5,6-tetrafluoro-1,4-phenylene group, 2,6-difluoro-1,4-phenylene group, 2,3,5,6-tetrachloro group -1,4-phenylene group, 3,4,5,6-tetrabromophenylene group), alkenylene group (preferably an alkenylene group having 2 to 20 carbon atoms, such as ethenylene group, propenylene group, butadienylene group), halogen substitution Alkynylene groups (preferably C2-C20 halogen-substituted alkynylene groups such as difluoroethenylene group, tetrafluoropropenylene group, dichloroethenylene group), alkynylene groups (preferably C2-C20 alkynylene groups such as Ethynylene group, propynylene group), amide group, ester group, sulfoamide group, sulfonic acid ester group, Ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, heterylene group (preferably a C1-C26 heterylene group such as 6-chloro-1,3,5-triazyl-2,4- One diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group), —C (CF ₃ ) ₂ —O—, —S—, —CO—, —SO ₂ — It represents a linking group having 0 to 100 carbon atoms, preferably 1 to 20 carbon atoms, which is configured in combination. More preferred are an alkylene group, a halogen-substituted alkylene group, an arylene group, an alkenylene group, and a halogen-substituted alkynylene group.
The acid residue is preferably an acid residue having a pKa of 5 or less, and more preferably an acid residue having a pka of 2 or less. Specifically, a sulfonic acid residue, a phosphonic acid residue, and a carboxylic acid residue are preferable, and a sulfonic acid residue is more preferable.

General formula (8)

  The average number of substitutions of substituents including acid residues that are substituted with the repeating unit represented by the general formula (1) is preferably in the range of 1 to 4, more preferably in the range of 1 to 2. It is more preferable.

 When the substituent containing the acid residue forms a salt, the acid residue proton is preferably substituted with the following cation, and the substitution ratio (cation / acid residue ratio) is in the range of 0 to 1. It is preferable that it is, and it is more preferable that it is the range of 0-0.1. Cations that form salts include alkali metal (lithium, sodium, potassium) cation, alkaline earth metal (potassium, strontium, barium) cation, quaternary ammonium (trimethylammonium, triethylammonium, tributylammonium, benzyltrimethylammonium) Protonates of cations and organic bases (triethylamine, pyridine, methylimidazole, morpholine, tributylammonium, tris (2-hydroxyethyl) amine) are preferred, alkali metal cations and ammonium cations are more preferred, and alkali metal cations are more preferred.

In the general formula (8), when L ⁸ is a linking group, any linking group can be used. Preferably, an alkylene group (preferably an alkylene group having 1 to 20 carbon atoms (hereinafter referred to as C number), for example, methylene group, ethylene group, methylethylene group, propylene group, methylpropylene group, butylene group, pentylene group, hexylene. Group, octylene group), halogen-substituted alkylene group (preferably C1-C20 halogen-substituted alkylene group such as difluoromethylene group, tetrafluoroethylene group, hexafluorohexylene group, tetrafluorohexylene group, dichloroamethylene group) Group), an arylene group (preferably an arylene group having 6 to 26 carbon atoms such as 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 4-phenylenemethylene group, 1,4- Naphthylene group), halogen-substituted arylene group (preferably having 6 to 26 carbon atoms) Logen-substituted arylene groups such as 2,3,5,6-tetrafluoro-1,4-phenylene group, 2,6-difluoro-1,4-phenylene group, 2,3,5,6-tetrachloro-1 , 4-phenylene group, 3,4,5,6-tetrabromophenylene group), alkenylene group (preferably having 2 to 20 carbon atoms, such as ethenylene, propenylene, butadienylene), halogen-substituted alkynylene group (preferably having 2 to 2 carbon atoms). 20 halogen-substituted alkynylene groups such as difluoroethenylene group, tetrafluoropropenylene group and dichloroethenylene group), alkynylene groups (preferably alkynylene groups having 2 to 20 carbon atoms such as ethynylene group and propynylene group), amides Group, ester group, sulfonamide group, sulfonic acid ester group, ureido group, sulfonyl group, Rufinyl group, thioether group, ether group, carbonyl group, heterylene group (preferably a C1-C26 heterylene group such as 6-chloro-1,3,5-triazyl-2,4-diyl group, pyrimidine-2 , 4-diyl group, quinoxaline-2,3-diyl group), more preferably a single bond, or an alkylene group, a halogen-substituted alkylene group, an arylene group, a halogen-substituted arylene group, a sulfonamide group, an ether group, or a carbonyl group. More preferably, a single bond, or a group having 0 to 100 carbon atoms (more preferably having 1 to 20 carbon atoms), which is composed of one or two or more alkylene groups, halogen-substituted alkylene groups, and ether groups. Group).

  3-100 are preferable, as for the total carbon number of the substituent of total carbon number 3 or more substituted by the repeating unit represented by General formula (1), 5-60 are more preferable, and 6-36 are more preferable. . Examples of the substituent include an alkyl group (n-propyl group, isopropyl group, n-butyl group, n-pentyl group, benzyl group, 3-sulfopropyl group, 4-sulfobutyl group, carboxymethyl group, carboxypentyl group). ), Alkenyl group (allyl group, 2-butenyl group, 1,3-butadienyl group), cycloalkyl group (cyclopentyl group, cyclohexyl group), aryl group (phenyl group, 2-chlorophenyl group, 4-methoxyphenyl group, 3 -Methylphenyl group, 1-naphthyl group, 2-nitrophenyl group), heterocyclic group (pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, pyrazolyl group, pyrrolidino group, piperidino group, morpholino group), alkynyl Group (2-propynyl group, 1,3-butadiynyl group, 2-phenylethynyl group) And the like. An alkyl group, an alkenyl group or a cycloalkyl group is preferable, and an alkyl group or a cycloalkyl group is more preferable. Among these substituents, those having an ether structure or a silicon atom in a methylene chain (ethoxymethyl group, propoxymethyl group, butoxymethyl group, hexyloxymethyl group, trimethylsilyl group, triethylsilyl group, tributylsilyl group, 3 -Trimethylsilylpropyl group, 2-trimethylsilylethyl group, 6-triethylsilylhexyl group, triethylsilylpropyl group) are particularly preferred.

These substituents may further have a substituent.
Examples of the substituent include a halogen atom (for example, F, Cl, Br, I), an amino group (preferably a C number of 0 to 20, for example, an amino group, a dimethylamino group, a diethylamino group, a dibutylamino group or an anilino group), A cyano group, a nitro group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfonic acid group, a phosphonic acid group, an acyl group (preferably having 1 to 20 carbon atoms, such as an acetyl group, a benzoyl group, a salicyloyl group, a pivaloyl group, 3, 5-dimethoxybenzoyl group, 4-methoxybenzoyl group), alkoxy group (preferably C number 1-20, for example, methoxy group, butoxy group, cyclohexyloxy group), aryloxy group (preferably C number 6-26, for example, , Phenoxy group, 1-naphthoxy group), alkylthio group (preferably having 1 to 20 carbon atoms, for example, Ruthio group, ethylthio group), arylthio group (preferably C6-20, for example, phenylthio group, 4-chlorophenylthio group), alkylsulfonyl group (preferably C1-20, for example, methanesulfonyl group, butanesulfonyl) Group), arylsulfonyl group (preferably C number 6-20, for example, benzenesulfonyl group, paratoluenesulfonyl group), sulfamoyl group (preferably C number 0-20, such as sulfamoyl group, N-methylsulfamoyl group) N-phenylsulfamoyl group), carbamoyl group (preferably having 1 to 20 carbon atoms, for example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-phenylcarbamoyl group), acylamino group ( Preferably it has 1 to 20 carbon atoms, such as acetylamino group, Zoylamino group), imino group (preferably C number 2-20, for example, phthalimino group), acyloxy group (preferably C number 1-20, for example, acetyloxy group, benzoyloxy group), alkoxycarbonyl group (preferably C And a carbamoylamino group (preferably having a C number of 1-20, such as a carbamoylamino group, an N-methylcarbamoylamino group, and an N-phenylcarbamoylamino group).

The polymer compound contained in the polymer electrolyte of the present invention preferably contains a repeating unit represented by the general formula (2) and / or a repeating unit represented by the general formula (3).
Here, Ar ²¹ , Ar ²² , X ²¹ , X ²² , R ²¹ in the repeating unit represented by the general formula (2) are respectively Ar ¹¹ in the repeating unit represented by the general formula (1). , Ar ¹² , X ¹¹ , X ¹² and R ¹¹ , and the preferred range is also the same.
In the repeating unit represented by the general formula (2), R ²² has the same meaning as the substituent containing the acid residue, and preferred examples thereof are also the same. In the repeating unit represented by the general formula (2), n22 is 0, 1 or 2, and the sum of n22 in one repeating unit is 1 or more, and 1 or 2 is preferable.
In the repeating unit represented by the general formula (2), R ²³ has the same meaning as the substituent having 3 or more carbon atoms, and preferred examples thereof are also the same.
In the repeating unit represented by the general formula (2), n23 is 0, 1 or 2, and the sum of n23 in one repeating unit is 1 or more, and 1 or 2 is preferable.

In the repeating unit represented by the general formula (3), Ar ³¹ , Ar ³² , X ³¹ , X ³² , and R ³¹ are, respectively, the repeating unit represented by the general formula (1), Ar ¹¹ , Ar ¹² , X ^11, X ^12, R ¹¹ in the above formula, the same applies to its preferable range. In the repeating unit represented by the general formula (3), R ³² has the same meaning as the substituent containing the acid residue, and preferred examples thereof are also the same. In the repeating unit represented by the general formula (3), n32 is 0, 1 or 2, and the sum of n32 in one repeating unit is 1 or more, and 1 or 2 is preferable.
In the repeating unit represented by the general formula (3), R ³³ has the same meaning as the substituent having 3 or more carbon atoms, and preferred examples thereof are also the same.
In the repeating unit represented by the general formula (3), n33 is 0, 1 or 2, and the sum of n33 in one repeating unit is 1 or more, and 1 or 2 is preferable.

  Specific examples of the repeating unit represented by the general formula (1) include at least one selected from the group consisting of a compound represented by the general formula (4) and a compound represented by the general formula (6), Examples thereof include at least one polymer selected from the group consisting of a compound represented by the general formula (5) and a compound represented by the general formula (7). Of course, the polymer compound contained in the polymer electrolyte of the present invention is not limited to this. In the present invention, these compounds are subjected to condensation polymerization, whereby the polymer becomes an alternating copolymer. Furthermore, other components may be copolymerized.

  The polymer compound contained in the polymer electrolyte of the present invention preferably has a polymer main chain of polysulfone, polyethersulfone, polyetherketone or polyimide, more preferably polysulfone or polyethersulfone.

  The polymer electrolyte of the present invention preferably has a permacol value calculated by replacing an acid residue with a hydrogen atom of 0 to 20, more preferably 0 to 15, and still more preferably 0 to 10. . The permacol value is used as an indicator of gas permeability. It is a value calculated from the table described in Salame by ACS Polymer Preprints 8, 137 (1967).

  The acid residue (for example, sulfonic acid group) concentration in the polymer electrolyte of the present invention can be measured as an ion exchange capacity, preferably 0.1 to 7 meq / g, more preferably 0.5 to 5 meq / g. Preferably, 1 to 3 meq / g is more preferable. By setting it to 0.1 meq / g or more, proton conductivity becomes higher, and by setting it to 7 meq / g or less, durability or mechanical strength can be improved, and water solubility can be improved. It can be made lower, which is preferable.

  The molecular weight of the precursor polymer before sulfonation of the polymer compound of the present invention thus obtained is a polystyrene-equivalent weight average molecular weight, preferably 1,000 to 1,000,000, more preferably 1. 500 to 200,000, more preferably 5,000 to 200,000. By setting it to 1,000 or more, it is possible to more effectively prevent the coating properties from becoming insufficient due to the occurrence of cracks in the molded film, and the strength properties are more preferable. On the other hand, by setting it to 1,000,000 or less, it is possible to more effectively suppress problems such as sufficient solubility, high solution viscosity, and poor processability.

  Hereinafter, at least one selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (6), a compound represented by the following general formula (5) and the following A method for producing a polymer compound contained in the polymer electrolyte of the present invention using at least one selected from the group consisting of compounds represented by formula (7) will be described.

Compound represented by the general formula (4) In the general formula (4), Ar ⁴¹ , X ⁴¹ , R ⁴² , and n42 have the same meaning as Ar ²¹ , X ²¹ , R ²² , and n22 in the general formula (2), respectively. The preferred range is also the same. Y ⁴¹ represents a leaving group in the aromatic nucleophilic substitution reaction, and is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), nitro group, sulfonyloxy group (tosyloxy group, phenylsulfonyloxy group, methyl group). A sulfonyloxy group) is preferred, a halogen atom is more preferred, and a fluorine atom and a chlorine atom are particularly preferred.

Specific examples of the compound represented by the general formula (4) include the compounds represented below.

  These compounds can be synthesized, for example, by sulfonation of di (halogenophenyl) sulfones, which is a known synthesis method.

 These compounds can be synthesized, for example, by haloalkylation and sulfonation using a metal reagent of dibromo (halogenophenyl) sulfones, which is a known synthesis method.

In the general formula (5), Ar ⁵¹ , X ⁵¹ , R ⁵³ and n53 have the same meanings as Ar ³¹ , X ³¹ , R ³³ and n33 in the general formula (3), respectively, and preferred ranges thereof are also the same. Y ⁵¹ represents a leaving group in the aromatic nucleophilic substitution reaction, and is synonymous with Y ⁴¹ in the general formula (4), and its preferred range is also the same.

Specific examples of the compound represented by the general formula (5) include the compounds represented below.

  These compounds can be synthesized, for example, by halomethylation and etherification of di (halogenophenyl) sulfones, which are known synthesis methods.

In General Formula (6), Ar ⁶² , R ⁶¹ , R ⁶² , and n62 have the same meanings as Ar ²² , R ²¹ , R ²² , and n22 in General Formula (3), respectively, and preferred ranges thereof are also the same. Y ⁶² represents a nucleophilic group in the aromatic nucleophilic substitution reaction, an amino group, an alkylamino group, an arylamino group, a hydroxyl group, a mercapto group are preferable, a hydroxyl group is particularly preferred.

  Specific examples of the compound represented by the general formula (6) include the compounds represented below.

  These compounds can be synthesized, for example, by sulfonation of bisphenols, which is a known synthesis method.

  These compounds can be synthesized, for example, by haloalkylation and sulfonation of bisphenols, which are known synthesis methods.

In the general formula (7), Ar ⁷² , R ⁷¹ , R ⁷³ and n73 have the same meanings as Ar ²² , R ²¹ , R ²³ and n23 in the general formula (2), respectively, and preferred ranges thereof are also the same. Y ⁷² represents a nucleophilic group in the aromatic nucleophilic substitution reaction, and is synonymous with Y ⁶² in the general formula (6), and its preferred range is also the same.

  Specific examples of the compound represented by the general formula (7) include the compounds represented below.

  These compounds can be synthesized, for example, by alkylation of bisphenols or condensation of alkylphenols and ketones, which is a known synthesis method.

In the present invention, at least one compound represented by the general formula (4), at least one compound represented by the general formula (7), or at least one compound represented by the general formula (5). And at least one of the compounds represented by the general formula (6) is preferably used.
Further, in the production method of the present invention, the compound represented by the general formula (4) which is an aromatic electrophilic compound is a compound wherein n42 is 0, the compound wherein n53 is 0 in the general formula (5), and the general formula which is an aromatic nucleophilic compound. It is preferable to use a mixture of at least one of a compound having n62 of 0 in (6) and a compound having n73 of 0 in General Formula (7).

  Specific examples of the general formulas (5) and (7) that can be used for the synthesis of the condensed polymer include di (4-chlorophenyl) sulfone, di (4-fluorophenyl) sulfone, and aromatic compounds as aromatic electrophilic compounds. Hydroquinone, resorcin, 2-methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-hexylhydroquinone, 2-octylhydroquinone, 2-decanylhydroquinone, 2,3-dimethyl as group nucleophilic compounds Hydroquinone, 2,3-diethylhydroquinone, 2,5-dimethylhydroquinone, 2,5-diethylhydroquinone, 2,6-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, 2,3,5,6-tetramethylhydroquinone , 4,4'- Hydroxybiphenyl, 2,2′-dihydroxybiphenyl, 3,3′-dimethyl-4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, 3,3 '-Dichloro-4,4'-dihydroxybiphenyl, 3,3', 5,5'-tetrachloro-4,4'-dihydroxybiphenyl, 3,3'-dibromo-4,4'-dihydroxybiphenyl, 3, 3 ', 5,5'-tetrabromo-4,4'-dihydroxybiphenyl, 3,3'-difluoro-4,4'-dihydroxybiphenyl, 3,3', 5,5'-tetrafluoro-4,4 ' -Dihydroxybiphenyl, 4,4'-dihydroxydiphenylmethane, 2,2'-dihydroxydiphenylmethane, 3,3'-dimethyl-4,4'-dihydroxydiphenylmethane, 3,3 ', 5 , 5′-tetramethyl-4,4′-dihydroxydiphenylmethane, 3,3′-dichloro-4,4′-dihydroxydiphenylmethane, 3,3 ′, 5,5′-tetrachloro-4,4′-dihydroxydiphenylmethane 3,3′-dibromo-4,4′-dihydroxydiphenylmethane, 3,3 ′, 5,5′-tetrabromo-4,4′-dihydroxydiphenylmethane, 3,3′-difluoro-4,4′-dihydroxydiphenylmethane 3,3′5,5′-tetrafluoro-4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,2′-dihydroxydiphenyl ether, 3,3′-dimethyl-4,4′-dihydroxy Diphenyl ether, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl ether, 3,3′-di Chloro-4,4′-dihydroxydiphenyl ether, 3,3 ′, 5,5′-tetrachloro-4,4′-dihydroxydiphenyl ether, 3,3′-dibromo-4,4′-dihydroxydiphenyl ether, 3,3 ′ , 5,5′-tetrabromo-4,4′-dihydroxydiphenyl ether, 3,3′-difluoro-4,4′-dihydroxydiphenyl ether, 3,3 ′, 5,5′-tetrafluoro-4,4′-dihydroxy Diphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 2,2′-dihydroxydiphenyl sulfide, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, 3,3 ′, 5,5′-tetramethyl-4 , 4′-dihydroxydiphenyl sulfide, 3,3′-dichloro-4,4′-dihydroxydiphenylsulfide 3,3 ′, 5,5′-tetrachloro-4,4′-dihydroxydiphenyl sulfide, 3,3′-dibromo-4,4′-dihydroxydiphenyl sulfide, 3,3 ′, 5,5′-tetrabromo -4,4'-dihydroxydiphenyl sulfide, 3,3'-difluoro-4,4'-dihydroxydiphenyl sulfide, 3,3 ', 5,5'-tetrafluoro-4,4'-dihydroxydiphenyl sulfide, 4, 4'-dihydroxydiphenylsulfone, 2,2'-dihydroxydiphenylsulfone, 3,3'-dimethyl-4,4'-dihydroxydiphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,4'- Dihydroxydiphenylsulfone, 3,3′-dichloro-4,4′-dihydroxydiphenylsulfone, 3,3 ′, 5,5′-tetrachloro-4,4′-di Droxydiphenylsulfone, 3,3′-dibromo-4,4′-dihydroxydiphenylsulfone, 3,3 ′, 5,5′-tetrabromo-4,4′-dihydroxydiphenylsulfone, 3,3′-difluoro-4 , 4′-dihydroxydiphenylsulfone, 3,3 ′, 5,5′-tetrafluoro-4,4′-dihydroxydiphenylsulfone, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (2 -Hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5- Dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-didibu Mo-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, α, α′-bis (2-hydroxyphenyl) -1,4 -Diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -1,3-diisopropylbenzene, α, α'-bis (2-hydroxyphenyl) -1,3-diisopropylbenzene, α, α'-bis (3-Methyl-4-hydroxyphenyl) -1,4-diisopropylbenzene, α, α′-bis (3,5-dimethyl-4-hydroxyphenyl) -1,4 -Diisopropylbenzene, α, α'-bis (3-methyl-4-hydroxyphenyl) -1,3-diisopropylbenzene, α, α'-bis (3,5-dimethyl-4-hydroxyphenyl) -1,3 -Diisopropyl benzene etc. are mentioned. These aromatic compounds can be used alone or in admixture of two or more.

  In the compound represented by the general formula (4), the compound represented by the general formula (5), the sum of the number of moles of the aromatic electrophilic compound and the compound represented by the general formula (6), the general formula (7) The ratio of the sum of the number of moles of the compound represented by the aromatic nucleophilic compound is preferably 1: 0.8 to 1.2, more preferably 1: 0.9 to 1.1, and 1: 0.95 to 1.05 is particularly preferred.

  The polymer compound contained in the polymer electrolyte of the present invention can be synthesized according to a known method (4th edition, Experimental Science Course, Vol. 28, P.355), and in particular, an aromatic electrophilic compound and an aromatic nucleophilic compound. A method in which one or a plurality of compounds selected from is polycondensed under basic conditions is preferably used.

  The type of reaction agent, reaction conditions, and the like are not particularly defined, and known reaction agents, reaction conditions, and the like can be applied. Reactants include alkali metals (lithium, sodium, potassium), alkaline earth metals (potassium, strontium, barium), basic metal compounds such as zinc oxide, various metal carbonates (sodium carbonate, lithium carbonate, potassium carbonate, Cesium carbonate), acetate (sodium acetate, lithium acetate, potassium acetate, cesium acetate), hydroxide (lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide), quaternary ammonium salt (Trimethylammonium hydroxide, triethylammonium hydroxide, tributylammonium hydroxide, benzyltrimethylammonium hydroxide), organic bases (triethylamine, pyridine, methylimidazole, morpholine, tributylammonium, (2-hydroxyethyl) amine) and the like.

  The amount of these reactants used is preferably 0.05 to 10.0 moles per mole of the sum of the number of moles of the compound of the general formula (6), the compound of the general formula (7), and the aromatic nucleophilic compound. 0.1 to 4.0 mol is more preferable, and 0.5 to 2.5 mol is more preferable.

  The reaction for producing the polymer compound contained in the polymer electrolyte of the present invention is usually carried out in a solvent. The following are mentioned as a preferable solvent.

1) Ether solvent 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane and the like.
2) Aprotic amide solvents N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N -Methylcaprolactam, hexamethylphosphorotriamide and the like.
3) Amine solvents Pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine etc.
4) Other solvents Dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisole and the like.

  Among the above-mentioned solvents, particularly preferred solvents include the aprotic amide solvent described in the above item 2) and the dimethyl sulfoxide and sulfolane described in the item 4). N, N-dimethylacetamide, N, N-diethylacetamide, N -Methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane are particularly preferred.

  These solvents may be used alone or in combination of two or more. Moreover, it can also be used by mixing with the solvent shown in the following item 5). When mixed and used, it is not always necessary to select a combination of solvents that are mutually soluble in an arbitrary ratio, and they may be mixed or non-uniform. Further, the solvent may be distilled off and added during the reaction in order to adjust the reaction concentration and the reaction solution viscosity. The concentration profile is preferably a low concentration for dissolution at the time of charging, a high concentration for promoting the reaction in the middle period, and a low concentration again for fluidization in the final period.

  The concentration of the reaction performed in these solvents (hereinafter referred to as polymerization concentration) is not limited, but the reaction rate decreases at low concentrations, and the viscosity becomes too high at high concentrations, making stirring difficult. The appropriate concentration is preferably 1% to 100% (no solvent) as the solid content concentration, more preferably 5% to 70%, and still more preferably 10% to 50%.

  The atmosphere is preferably air, nitrogen, helium, neon, or argon, and more preferably an inert gas (for example, nitrogen or argon).

Moreover, in order to remove the water produced | generated by reaction out of a system, another solvent can also coexist. Examples of the solvent used here include the following 5).
5) Solvent for azeotrope benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromo Examples include benzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, and p-bromotoluene. These solvents may be used alone or in combination of two or more.

  Further, two or more solvents shown in the above items 1) to 5) may be mixed and used. When mixed and used, it is not always necessary to select a combination of solvents that are mutually soluble in an arbitrary ratio, and they may be mixed or non-uniform. There is no limit to the amount of these dehydrating agents used.

  There are no particular limitations on the reaction temperature, reaction time, and reaction pressure, and known conditions can be applied. That is, the reaction temperature is preferably 50 ° C to 300 ° C, more preferably 100 ° C to 270 ° C, and further preferably 130 ° C to 250 ° C. Moreover, although reaction time changes with the kind of monomer to be used, the kind of solvent, and reaction temperature, 1 to 72 hours are preferable. More preferably, it is 3 hours-60 hours, More preferably, it is 5 hours-48 hours. The reaction pressure may be under pressure or under reduced pressure, but may be normal pressure.

As a method for synthesizing the polymer compound contained in the polymer electrolyte of the present invention, in addition to the above polymerization method, a method of introducing a sulfonic acid group into the polymer can also be mentioned.
As the sulfonation method, for example, the polymer having no sulfonic acid group can be sulfonated under known conditions using a known sulfonating agent such as sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, sulfuric acid and the like. .

  As the reaction conditions for the sulfonation, the 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, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. In addition to aprotic polar solvents, halogenated hydrocarbons such as tetrachloroethane, dichloroethane, chloroform, and methylene chloride. Although there is no restriction | limiting in particular in reaction temperature, Preferably it is -50-200 degreeC, More preferably, it is -10-100 degreeC. Moreover, reaction time becomes like this. Preferably it is 0.5 to 100 hours, More preferably, it is 1 to 50 hours.

Furthermore, as a method for introducing a sulfonic acid group into the polymer compound, the following introduction method can be used in addition to the above.
For example, a halogenomethylated polymer using a halogenomethylating agent such as chloromethylmethyl ether described later is used, and then a halogen site is acetylthiolated and then oxidized to a sulfonic acid group. In the case of a sulfoalkyl group having a larger number of carbon atoms, for example, a chloro-substituted acid chloride represented by Cl— (CH ₂ ) _n —COCl (n is, for example, 2 to 6) is used in a conventional manner, such as aluminum chloride or iron chloride. A method in which a chloro-substituted acyl group is introduced by a Friedel-Crafts reaction using a Lewis acid, and then the chloro atom is converted to a sulfonic acid group with dimethylthioether and sodium thiosulfate, and then the carbonyl group is reduced with hydrazine. Org. Chem. 45.2717 (1980), lithiating hydrogen of an aromatic ring, then halogenoalkylating with a dihalogenoalkane, and then converting the chloro atom to a sulfonic acid group by the above method, etc. Is mentioned.

  In order to introduce a preferred halogenomethyl group in the present invention into an aromatic ring (halogenomethylation reaction of an aromatic ring), known reactions can be widely used. For example, as a chloromethylating agent, chloromethyl methyl ether, chloromethyl ethyl ether, chloromethyl octyl ether, 1,4-bis (chloromethoxy) butane, 1-chloromethoxy-4-chlorobutane, etc. are used, and tin chloride is used as a catalyst. A chloromethyl group can be introduced into the aromatic ring by performing a chloromethylation reaction using Lewis acid such as zinc chloride, aluminum chloride, titanium chloride or hydrofluoric acid. The solvent is preferably dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, nitrobenzene, etc., and the reaction is preferably carried out in a homogeneous system. Alternatively, a halogenomethylation reaction can be performed using paraformaldehyde and hydrogen chloride, hydrogen bromide, or the like.

As a general method for introducing a sulfonic acid group, for example, a Friedel-Crafts reaction using a sultone represented by the following general formula (X) and a Lewis acid (for example, AlCl ₃ ) (Journal of Applied Polymer Science, Vol. 36, 1753-1767, 1988) can be used.

  When performing the Friedel-Crafts reaction, α, β unsaturated sultone and the like can be used as the alkyl sulfonating agent. As the solvent, hydrocarbons (benzene, toluene, nitrobenzene, acetophenone, etc.), alkyl halides (methylene chloride, chloroform, dichloroethane, carbon tetrachloride, trichloroethane, dichloroethane, tetrachloroethane, chlorobenzene, trichlorobenzene, etc.) can be used. . The reaction temperature may be selected in the range of room temperature (for example, 18 ° C.) to 250 ° C. In these reactions, a mixture of two or more solvents may be used.

The structure of the sulfonic group-containing polymer compound of the present invention, the infrared absorption spectrum, 1,030~1,045cm ^-1, S = O absorption at 1,160~1,190cm ^-1, 1,130~1 , C-O-C absorption at 250 cm ^-1, can be confirmed by such C = O absorption of 1,640～1,660Cm ^-1, these composition ratio, neutralization titration of sulfonic acid or be known by elemental analysis Can do. Moreover, the structure can be confirmed from the peak of the aromatic proton at 6.8 to 8.0 ppm by nuclear magnetic resonance spectrum ( ¹ H-NMR).

  When the obtained polymer electrolyte is used as a proton conductive material, it needs to be converted into a proton type. This step is performed by immersing the polymer electrolyte in an acidic solution. As the acidic solution, a protonic acid solution is preferable, and as the protonic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, tetrafluoroboric acid, hexafluoroarsenic acid, hydrobromic acid, solid acid (for example, tungstophosphoric acid, tungsten And sulfonic acids (for example, sulfonic acids having 1 to 15 carbon atoms, such as benzenesulfonic acid, toluenesulfonic acid, hexafluorobenzenesulfonic acid, trifluoromethanesulfonic acid, dodecylsulfonic acid, etc.). Two or more of these may be used in combination. Hydrochloric acid and nitric acid are particularly preferable. 10-100 degreeC is preferable and the temperature in this process has more preferable 20-80 degreeC. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. The concentration of the acid solution is preferably 0.1 to 10 N, and more preferably 0.5 to 5 N.

  It is possible to form a film by impregnating the solid electrolyte of the present invention into the pores of the porous substrate. The reaction solution after completion of the second step of the present invention may be applied and impregnated on a substrate having pores, or the substrate may be immersed in the reaction solution to fill the pores with a solid electrolyte to form a film. . Preferable examples of the substrate having pores include porous polypropylene, porous polytetrafluoroethylene, porous cross-linked heat-resistant polyethylene, and porous polyimide.

 Further, if necessary, the modification treatment may be performed by performing a heat treatment in a conditioned environment and a radiation (visible light, ultraviolet ray, γ ray, electron beam, etc.) irradiation treatment.

  For the purpose of removing unnecessary components after the crosslinking step, a washing step and a drying step with water, an organic solvent or the like may be added.

Other components of solid electrolyte To improve the membrane characteristics, the solid electrolyte of the present invention may contain an antioxidant, fibers, fine particles, water-absorbing agent, plasticizer, compatibilizer, and the like, if necessary. The content of these additives is preferably in the range of 1 to 30% by mass with respect to the total amount of the solid electrolyte.

  Antioxidants include (hindered) phenolic, monovalent or divalent sulfur, trivalent and pentavalent phosphorus, benzophenone, benzotriazole, hindered amine, cyanoacrylate, salicylate, oxalic Acid anilide compounds are preferred examples. Specific examples thereof include compounds described in JP-A-8-53614, JP-A-10-101873, JP-A-11-114430, and JP-A-2003-151346.

  Preferred examples of the fibers include perfluorocarbon fibers, cellulose fibers, glass fibers, polyethylene fibers, and the like, and specifically, JP-A-10-31815, JP-A-2000-231828, JP-A-2001-307545. Examples thereof include fibers described in JP-A No. 2003-317748, JP-A No. 2004-63430, and JP-A No. 2004-107461.

  Examples of the fine particles include fine particles made of silica, alumina, titanium oxide, zirconium oxide, and the like. Specifically, Japanese Patent Application Laid-Open Nos. 6-1111834, 2003-178777, and 2004-217921. Fine particles described in the publication can be mentioned.

  Water-absorbing agents (hydrophilic substances) include cross-linked polyacrylate, starch-acrylate, poval, polyacrylonitrile, carboxymethylcellulose, polyvinylpyrrolidone, polyglycol dialkyl ether, polyglycol dialkyl ester, silica gel, synthetic zeolite, alumina gel , Titania gel, zirconia gel, and yttria gel are preferable examples. Specific examples include water absorbing agents described in JP-A Nos. 7-13003, 8-20716, and 9-251857. .

  Plasticizers include phosphate ester compounds, phthalate ester compounds, aliphatic monobasic acid ester compounds, aliphatic dibasic acid ester compounds, dihydric alcohol ester compounds, oxyacid ester compounds, and chlorination. Paraffin, alkylnaphthalene compounds, sulfonalkylamide compounds, oligoethers, carbonates, and aromatic nitriles are preferable examples, and specifically, JP2003-970030A and JP2003-288916A. And plasticizers described in JP-A No. 2003-317539.

Further, the polymer electrolyte of the present invention may contain various polymer compounds for the purpose of (1) increasing the mechanical strength of the film and (2) increasing the acid concentration in the film.
(1) For the purpose of increasing mechanical strength, a polymer compound having a molecular weight of about 10,000 to 1,000,000 and having good compatibility with the solid electrolyte of the present invention is suitable. For example, perfluorinated polymer, polystyrene, polyethylene glycol, polyoxetane, poly (meth) acrylate, polyether ketone, polyether sulfone, and two or more polymers thereof are preferable, and the content is 1 to 30 based on the total. A range of mass% is preferred.

The compatibilizer preferably has a boiling point or sublimation point of 250 ° C. or higher, more preferably 300 ° C. or higher.
(2) For the purpose of increasing the acid concentration, perfluorocarbon sulfonic acid polymer represented by Nafion, poly (meth) acrylate having a phosphate group in the side chain, sulfonated polyetheretherketone, sulfonated polyethersulfone, sulfone Polymer compounds having a ptronic acid moiety in a sulfonated product of a heat-resistant aromatic polymer such as sulfonated polysulfone and sulfonated polybenzimidazole are preferred, and the content is preferably in the range of 1 to 30% by mass.

As the characteristics of the polymer electrolyte of the present invention, those having the following performances are preferred.
The ionic conductivity is, for example, preferably 0.005 S / cm or more at 25 ° C. and 95% relative humidity, and more preferably greater than 0.01 S / cm.
The oxygen permeability coefficient is preferably 1.0 × 10 ⁻¹² mol / cm · s or more, and particularly preferably 3.0 × 10 ⁻¹² mol / cm · s or more. Furthermore, the oxygen permeability coefficient is what is preferably 5x10- ¹² mol / cm · s or more. In particular, those satisfying these requirements at 25 ° C. are preferred, and those satisfying these requirements at 75 ° C. are more preferred.
As the strength, for example, the tensile strength is preferably 10 MPa or more, and more preferably 20 MPa or more.
Regarding durability, the rate of change in weight, ion exchange capacity and oxygen diffusion coefficient before and after aging at a constant temperature in boiling water is preferably 20% or less, more preferably 10% or less, More preferably, the weight, ion exchange capacity, and oxygen diffusion coefficient change rate are all 10% or less.
Further, the rate of change is preferably 20% or less, more preferably 10% or less, before and after aging in hydrogen peroxide. Further, the volume swelling rate at a constant temperature in water is preferably 50% or less, and more preferably 30% or less.
The polymer electrolyte of the present invention preferably has a stable water absorption and water content. Further, it is preferable that the solubility in water is substantially negligible. Moreover, the thing which is a grade which can be substantially disregarded in the weight reduction and shape change when immersed in water is preferable.
When formed into a film, the ion conduction direction is preferably such that the direction from the front surface to the back surface is higher than the other directions.
When the polymer electrolyte of the present invention is formed in a film shape, the thickness is preferably 10 to 300 μm. The heat resistant temperature of the polymer electrolyte of the present invention is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher. The heat resistant temperature can be defined as, for example, the time when the weight loss reaches 5% when heated at a rate of 1 ° C./min. This weight loss is calculated excluding evaporation such as moisture.

The polymer electrolyte of the present invention can be used for an electrode for a fuel cell, an electrode membrane assembly (hereinafter referred to as “MEA”), and a fuel cell using the electrode membrane assembly.
FIG. 1 shows an example of a schematic cross-sectional view of the electrode membrane assembly of the present invention. The MEA 10 includes a membrane-shaped polymer electrolyte membrane 11 and an anode electrode 12 and a cathode electrode 13 that are opposed to each other with the membrane electrolyte membrane 11 interposed therebetween. The polymer electrolyte membrane here is a perfluorocarbon sulfonic acid polymer represented by Nafion (registered trademark), poly (meth) acrylate having a phosphate group in the side chain, sulfonated polyetheretherketone, sulfonated polyethersulfone, Examples include heat-resistant aromatic polymer membranes such as sulfonated polysulfone.
The anode electrode 12 and the cathode electrode 13 are composed of porous conductive sheets (for example, carbon paper) 12a and 13a and catalyst layers 12b and 13b. The catalyst layers 12b and 13b are made of a dispersion in which carbon particles (for example, ketjen black, acetylene black, carbon nanotubes, etc.) carrying a catalyst metal such as platinum particles are dispersed in the polymer electrolyte of the present invention.

  A method for manufacturing the electrode will be described. The polymer electrolyte of the present invention is dissolved in a solvent and mixed and dispersed with platinum-supporting carbon. Solvents at this time are heterocyclic compounds (3-methyl-2-oxazolidinone, N-methylpyrrolidone, etc.), cyclic ethers (dioxane, tetrahydrofuran, etc.), chain ethers (diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl). Ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.), alcohols (methanol, ethanol, isopropanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, etc.), many Polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene glycol, poly Pyrene glycol, glycerin, etc.), nitrile compounds (acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, etc.), nonpolar solvents (toluene, xylene, etc.), chlorinated solvents (methylene chloride, ethylene chloride, etc.), Amides (N, N-dimethylformamide, N, N-dimethylacetamide, acetamide, etc.), water and the like are preferably used, and among these, heterocyclic compounds, alcohols, polyhydric alcohols and amides are preferably used.

  The dispersion method may be a method using stirring, but ultrasonic dispersion, ball mill, or the like can also be used. The resulting dispersion can be applied using the following application method.

  Application of the dispersion will be described. In the coating step, the dispersion may be used to form a film by extrusion molding, or these dispersions may be cast or applied to form a film. Although a support body is not specifically limited, As a preferable example, a glass substrate, a metal substrate, a polymer film, a reflecting plate, etc. can be mentioned. Polymer films include cellulose polymer films such as TAC (triacetyl cellulose), ester polymer films such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate), and fluorine such as PTFE (polytrifluoroethylene). Examples thereof include a polymer film and a polyimide film. The coating method may be a known method, for example, curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, etc. it can. In particular, when a conductive porous body (carbon paper, carbon cloth) is used as a support, a catalyst electrode can be directly produced.

  These operations can be performed with a film forming machine using a roll such as a calender roll or a cast roll or a T die, or can be press forming using a press machine. Further, a stretching process may be added to control film thickness and improve film characteristics.

  The drying temperature of the coating process is related to the drying speed and can be selected according to the properties of the material. Preferably it is -20 degreeC-150 degreeC, More preferably, it is 20 degreeC-120 degreeC, More preferably, it is 50 degreeC-100 degreeC. A short drying time is preferable from the viewpoint of productivity. However, if the drying time is too short, defects such as bubbles and surface irregularities are caused. For this reason, the drying time is preferably 1 minute to 48 hours, more preferably 5 minutes to 10 hours, and further preferably 10 minutes to 5 hours. Control of humidity is also important, with 25-100% relative humidity being preferred, and 50% -95% relative humidity being more preferred.

  A thing with little content of metal ions is preferable in the coating liquid in a coating process, and especially a thing with few transition metal ions, especially iron ion, nickel ion, and cobalt ion is preferable. The content is preferably 500 ppm or less, particularly preferably 100 ppm or less. Therefore, the solvent used in the above-mentioned process is also preferably a solvent having a low content of these ions.

  Furthermore, surface treatment may be performed after the film forming step. As the surface treatment, rough surface treatment, surface cutting, removal, and coating treatment may be performed, which may improve adhesion with the polymer electrolyte membrane or the porous conductor.

  The shape of the polymer electrolyte obtained is preferably a membrane, and the thickness is preferably 5 to 200 μm, more preferably 10 to 100 μm.

In order to bring the catalyst layers 12b and 13b into close contact with the polymer electrolyte membrane 11, the porous conductive sheets 12a and 13a coated with the catalyst layers 12b and 13b are applied to the polymer electrolyte (membrane) 11 by a hot press method (preferably Is pressure-bonded at 120 to 130 ° C. and 2 to 100 kg / cm ² ), or a catalyst obtained by coating the catalyst layer 12b or 13b on an appropriate support while being transferred to the polymer electrolyte 11, and then porous. Generally, a method of sandwiching between the conductive sheets 12a and 13a is preferably used.

  FIG. 2 shows an example of a fuel cell structure. The fuel cell includes an MEA 10, a pair of separators 21 and 22 that sandwich the MEA 10, and a current collector 17 and a packing 14 made of a stainless steel net attached to the separators 21 and 22. An anode pole side opening 15 is provided in the anode pole side separator 21, and a cathode pole side opening 16 is provided in the cathode pole side separator 22. Gas fuel such as hydrogen and alcohols (such as methanol) or liquid fuel such as an alcohol aqueous solution is supplied from the anode electrode side opening 15, and oxidant gas such as oxygen gas and air is supplied from the cathode electrode side opening 16. Is supplied.

  For the anode electrode and the cathode electrode, a catalyst in which active metal particles such as platinum are supported on a carbon material is used. The particle size of the active metal that is usually used is in the range of 2 to 10 nm. The smaller the particle size, the greater the surface area per unit mass and the greater the activity, which is advantageous. It is said that the limit is about 2 nm.

  The active polarization in the hydrogen-oxygen fuel cell is larger in the cathode electrode (air electrode) than in the anode electrode (hydrogen electrode). This is because the cathode electrode reaction (oxygen reduction) is slower than the anode electrode. For the purpose of improving the activity of the oxygen electrode, various platinum-based binary metals such as Pt—Cr, Pt—Ni, Pt—Co, Pt—Cu, and Pt—Fe can be used. In a direct methanol fuel cell using an aqueous methanol solution as an anode fuel, it is important to suppress catalyst poisoning due to CO that occurs during the oxidation process of methanol. For this purpose, platinum-based binary metals such as Pt—Ru, Pt—Fe, Pt—Ni, Pt—Co, Pt—Mo, Pt—Ru—Mo, Pt—Ru—W, Pt—Ru—Co Platinum-based ternary metals such as Pt—Ru—Fe, Pt—Ru—Ni, Pt—Ru—Cu, Pt—Ru—Sn, and Pt—Ru—Au can be used.

  As the carbon material for supporting the active metal, acetylene black, Vulcan XC-72, ketjen black, carbon nanohorn (CNH), and carbon nanotube (CNT) are preferably used.

  The function of the catalyst layer was caused by (1) transporting the fuel to the active metal, (2) providing a field for fuel oxidation (anode electrode) and reduction (cathode electrode) reaction, and (3) redox. (4) transporting protons generated by the reaction to the polymer electrolyte. For (1), the catalyst layer needs to be porous so that liquid and gaseous fuel can permeate deeply. (2) is the active metal catalyst described above, and (3) is the same carbon material as described above. In order to fulfill the function (4), a polymer electrolyte is mixed in the catalyst layer.

  The proton conductive material of the catalyst layer is not limited as long as it is a solid having a proton donating group, but a polymer compound having an acid residue used for a polymer electrolyte (for example, perfluorocarbon sulfonic acid represented by Nafion, Side chain phosphoric acid group poly (meth) acrylates, sulfonated polyether ether ketones, sulfonated products of heat-resistant aromatic polymers such as sulfonated polybenzimidazoles, etc.) are preferably used. When the polymer electrolyte of the present invention is used for the catalyst layer, the material is the same as that of the polymer electrolyte. Therefore, the electrochemical adhesion between the polymer electrolyte and the catalyst layer is increased, which is more advantageous.

The amount of active metal used is suitably in the range of 0.03 to 10 mg / cm ² from the viewpoint of battery output and economy. The amount of the carbon material supporting the active metal is suitably 1 to 10 times the mass of the active metal. The amount of the proton conductive material is suitably 0.1 to 0.7 times the mass of the active metal-carrying carbon.

  It is also called an electrode base material, a permeable layer, or a backing material, and plays a role of collecting current and preventing water from accumulating and deteriorating gas permeation. Usually, carbon paper or carbon cloth can be used, and polytetrafluoroethylene (PTFE) treated for water repellency can be used.

The following four methods are preferable for the production of MEA.
(1) Proton conductive material coating method: Directly apply catalyst paste (ink) based on active metal-supported carbon, proton conductive material, and solvent on both sides of the polymer electrolyte, and (thermal) pressure-bond the porous conductive sheet A five-layer MEA is manufactured.
(2) Porous conductive sheet coating method: After applying a catalyst paste to the surface of the porous conductive sheet to form a catalyst layer, it is pressure-bonded to a polymer electrolyte to prepare a MEA having a five-layer structure.
(3) Decal method: After applying a catalyst paste on PTFE to form a catalyst layer, only the catalyst layer is transferred to a polymer electrolyte to form a three-layer MEA, and a porous conductive sheet is pressure-bonded. A MEA having a layer structure is manufactured.
(4) Post-catalyst support method: After coating and film-forming an ink in which a platinum non-supported carbon material is mixed with a proton conductive material on a polymer electrolyte, a porous conductive sheet or PTFE, the polymer electrolyte is impregnated with the platinum electrolyte. Then, platinum particles are reduced and precipitated in the film to form a catalyst layer. After forming the catalyst layer, the MEA is produced by the above methods (1) to (3).

  As fuel for the fuel cell using the polymer electrolyte of the present invention, as anode fuel, hydrogen, alcohols (methanol, isopropanol, ethylene glycol, etc.), ethers (dimethyl ether, dimethoxymethane, trimethoxymethane) Etc.), formic acid, borohydride complexes, ascorbic acid and the like. Examples of the cathode fuel include oxygen (including oxygen in the atmosphere) and hydrogen peroxide.

  The methods for supplying the anode fuel and the cathode fuel to the respective catalyst layers include (1) a method of forced circulation using an auxiliary device such as a pump (active type), and (2) a method not using an auxiliary device ( For example, in the case of a liquid, there are two types, ie, a passive type in which a catalyst layer is exposed to the atmosphere and supplied to the atmosphere in the case of a gas due to capillary action or natural fall, and these can be combined. An active type capable of obtaining high output is preferable.

  Since the single cell voltage of the fuel cell is generally 1 V or less, the single cells are used by stacking in series according to the required voltage of the load. As the stacking method, “planar stacking” in which single cells are arranged on a plane and “bipolar stacking” in which single cells are stacked via separators having fuel flow paths formed on both sides thereof are used. The latter is suitable for a fuel cell because of its high thermal efficiency and a compact battery. In addition to this, a method of applying MEMS technology, performing fine processing on a silicon wafer, and stacking has been proposed.

  The fuel cell is considered for various uses such as transportation, home use, and portable equipment. For example, preferable transportation applications include automobiles (passenger cars, freight cars, motorcycles, personal beagles), ships, For home use, cogeneration systems, vacuum cleaners, robots, and portable devices include mobile phones, notebook computers, electronic still cameras, PDAs, video cameras, and portable game machines. Furthermore, it can be used for portable generators, outdoor lighting devices, and the like. Moreover, it can be preferably used as a power source for industrial or household robots or other toys. Furthermore, it is also useful as a power source for charging secondary batteries and capacitors mounted on these devices.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Ionic conductivity]
The polymer electrolyte membrane was punched into a circle having a diameter of 5 mm, sandwiched between two stainless steel plates, and the ionic conductivity at 25 ° C. and relative humidity of 95% was measured by an alternating current impedance method.

[Oxygen permeability]
50 mg of a sample was dissolved in 250 μl of DMAc, and 20 μl of this electrolyte solution was applied on the platinum electrode of the rotating disk electrode. After drying at 40 ° C. for 24 hours and further at 120 ° C. for 2 hours, oxygen permeability at 25 ° C. and 75 ° C. was calculated according to Journal of power Sources 149 (2005) 66 using this rotating disk electrode.

Fabrication of fuel cell (1) Fabrication of catalyst membrane 2 g of platinum-supported carbon (50% by mass of platinum is supported on Vulcan XC72) and 15 g of polymer electrolyte solution (5% N-methylpyrrolidone aqueous solution) are mixed with an ultrasonic disperser. Dispersed for minutes. The obtained dispersion was coated on carbon paper (thickness 350 μm), dried by heating, and then punched out to a predetermined size to prepare a catalyst film.

(2) Production of MEA The catalyst film obtained above was bonded to both surfaces of Nafion 117 so that the coated surface was in contact with Nafion 117, and thermocompression bonded at 125 ° C. and 3 MPa for 2 minutes to produce MEA.

(3) Fuel cell characteristics The MEA obtained in (2) was set in the fuel cell shown in FIG. 2, and hydrogen gas was flowed into the anode side opening 15. At this time, the cathode side opening 16 flowed air. A potentiostat was connected between the anode electrode 12 and the cathode electrode 13, and the current value at 700 mV was recorded.

  The MEA was set in the fuel cell shown in FIG. 2, and hydrogen gas was flowed into the anode side opening 15. At this time, the cathode side opening 16 flowed air. A potentiostat was connected between the anode electrode 12 and the cathode electrode 13, and the current value at 700 mV was recorded. The results are shown in Table 1.

[Comparative example]
In accordance with Journal of Membrane Science 239 (2004) 119, 120 ml of fuming nitric acid was dissolved in 56.86 g (0.198 mol) of 4,4′-dichlorodiphenylsulfone under a nitrogen atmosphere, and the mixture was stirred at 110 ° C. for 6 hours. The mixture was cooled to room temperature, added to 800 ml of ice water, and salted out by adding 360 g of NaCl. After filtration, it was dissolved in 800 ml of water and neutralized with 2N aqueous sodium hydroxide solution to pH 6-7. Further, 200 g of NaCl was added, filtered, and recrystallized with an aqueous solution of methanol / water = 7/3 to synthesize 52.6 g of 3,3′-disulfo-4,4′-dichlorodiphenylsulfone. 3,3′-Disulfo-4,4′-dichlorodiphenylsulfone 0.7897 g (2.75 mmol): 4,4′-dichlorodiphenylsulfone 1.3509 g (2.75 mmol): 4,4′-isopropylidenediphenol 1 Polymerization was carried out in accordance with this document in a ratio of 0.5556 g (5.5 mmol) = 0.5: 0.5: 1 to obtain 1.46 g of polymer A. The weight average molecular weight was 87.000. The polymer A was formed into a film by a casting method and immersed in a 2 mol / l aqueous hydrochloric acid solution overnight to perform salt exchange, thereby converting it into a proton type. Ion conductivity of this proton type of the film was 0.023S / cm, the oxygen permeability coefficient at ^{25 ℃ 2.82x10- 12 mol / cm ·} s, 75 at ℃ 3.44x10- ¹² mol / cm · s . Further, the membrane converted to the proton type was redissolved, and the catalyst membrane, MEA, and fuel cell were prepared by the above method, and the cell characteristics were recorded. The obtained current value was 159 mA. The permacall value was 42.

[Example 1]
Instead of 4,4′-isopropylidenediphenol of comparative example, 4,4 ′-(1-methylethylden) -bis (2,6-dimethylphenol) manufactured by Wako Pure Chemical Industries, Ltd. was used, and 3,3 ′ -Disulfo-4,4'-dichlorodiphenylsulfone 0.7897 g (2.75 mmol): 4,4'-dichlorodiphenylsulfone 1.3509 g (2.75 mmol): 4,4 '-(1-methylethylden) -bis Polymer B1 was synthesized in the same manner as in the comparative example at a ratio of 1.5642 g (5.5 mmol) = 0.5: 0.5: 1 (2,6-dimethylphenol). The weight average molecular weight was 31,000. The polymer B1 was formed into a film by a casting method, immersed in a 2 mol / l hydrochloric acid aqueous solution overnight and subjected to salt exchange to convert it into a proton type. Ion conductivity of this proton type of the film was 0.028S / cm, the oxygen permeability coefficient at ^{25 ℃ 7.95x10- 12 mol / cm ·} s, 75 at ℃ 1.32x10- ¹¹ mol / cm · s . Further, the membrane converted to the proton type was redissolved, and the catalyst membrane, MEA, and fuel cell were prepared by the above method, and the cell characteristics were recorded. The obtained current value was 189 mA. The permacall value was estimated to be 6.5 or less.

[Example 2]
According to a known method, 24.67 g (80 mmol) of 2,2′-diallylbisphenol A (Aldrich) was dissolved in 150 ml of toluene in a nitrogen atmosphere, and 28 ml (175 mmol) of triethylsilane and 250 mg of chloroplatinic acid 250 mg were dissolved at 0 ° C. 4 ml of nitrile solution was added and hydrosilylation was performed for 1 hour at room temperature. The reaction solution was concentrated and purified by silica gel chromatography to synthesize 24.7 g of 3,3′-bis (triethylsilylpropyl) bisphenol A. The synthesized 3,3′-bis (triethylsilylpropyl) bisphenol A was used in place of the comparative 4,4′-isopropylidene diphenol, and 3,3′-disulfo-4,4′-dichlorodiphenylsulfone 0.7897 g (2.75 mmol): 4,4′-dichlorodiphenylsulfone 1.3509 g (2.75 mmol): 3,3′-bis (triethylsilylpropyl) bisphenol A 2.9754 g (5.5 mmol) = 0.5: 0 Polymer B2 was synthesized in a ratio of 5: 1 as in the comparative example. The weight average molecular weight was 59,000. The polymer B2 was formed into a film by a casting method and immersed in a 2 mol / l hydrochloric acid aqueous solution overnight to perform salt exchange, thereby converting it into a proton type. Ion conductivity of this proton type of the film was 0.027s / cm, the oxygen permeability coefficient at ^{25 ℃ 7.75x10- 12 mol / cm ·} s, 75 at ℃ 1.90x10- ¹¹ mol / cm · s . Further, the membrane converted to the proton type was redissolved, catalyst membrane, MEA, and fuel cell were prepared by the above-mentioned method, and the cell characteristics were recorded. The obtained current value was 196 mA. The permacall value was estimated to be 6.5 or less.

[Example 3]
According to a known method, 30.76 g (120 mmol) of 2,2-bis (4-hydroxy-3-methylphenyl) propane, 29.8 g (288 mmol) of potassium carbonate and 100 ml of DMF are mixed and heated to 80 ° C. in a nitrogen atmosphere. did. Subsequently, 32.15 g (265 mmol) of allyl bromide was added dropwise, and the mixture was stirred at 80 ° C. for 3 hours. The mixture was cooled to room temperature, added to water, extracted with ethyl acetate, and washed with saturated NaCl. The reaction mixture was concentrated and purified by silica gel chromatography to synthesize 28.83 g of 2,2-bis (4-allyloxy-3-methylphenyl) propane. Under a nitrogen atmosphere, 24.83 g (73.8 mmol) of the synthesized 2,2-bis (4-allyloxy-3-methylphenyl) propane was heated and stirred at 200 ° C. for 6 hours. After cooling to room temperature, 14.36 g of 2,2-bis (3-allyl-4-hydroxy-5-methylphenyl) propane was synthesized by purification by silica gel chromatography. Furthermore, according to a known method, 5.0 g (14.86 mmol) of 2,2-bis (3-allyl-4-hydroxy-5-methylphenyl) synthesized was dissolved in 25 ml of toluene under a nitrogen atmosphere at 0 ° C. 5.7 ml (35.6 mmol) of triethyl silane and 1 ml of benzonitrile solution of 46 mg of chloroplatinic acid were added, and hydrosilylation was performed at room temperature for 6 hours. The reaction solution was concentrated and purified by silica gel chromatography to synthesize 1.9 g of 2,2-bis (3-methyl-4-hydroxy-5-triethylsilylpropylphenyl) propane. 2,3-bis (3-methyl-4-hydroxy-5-triethylsilylpropylphenyl) propane synthesized in place of the comparative 4,4′-isopropylidenediphenol was used and 3,3′-disulfo-4 , 4′-dichlorodiphenylsulfone 0.7897 g (2.75 mmol): 4,4′-dichlorodiphenylsulfone 1.3509 g (2.75 mmol): 2,2-bis (3-methyl-4-hydroxy-5-triethyl) Silylpropylphenyl) propane 1.5649 (2.75 mmol): bisphenol A 0.6278 (2.75 mmol) = 0.5: 0.5: 0.5: 0.5, a ratio as high as in the comparative example. 1.19 g of molecule B3 was synthesized. The weight average molecular weight was 43,000. The polymer B3 was formed into a film by a casting method, immersed in a 2 mol / l hydrochloric acid aqueous solution overnight and subjected to salt exchange to convert it into a proton type. Ion conductivity of this proton type of the film was 0.029s / cm, the oxygen permeability coefficient at ^{25 ℃ 8.00x10- 12 mol / cm ·} s, 75 at ℃ 2.03x10- ¹¹ mol / cm · s . Further, the membrane converted to the proton type was redissolved, and the catalyst membrane, MEA, and fuel cell were prepared by the above method, and the cell characteristics were recorded. The obtained current value was 209 mA. The permacall value was estimated to be about 6.0 or less.

Instead of the comparative 4,4′-isopropylidenediphenol, 2,2-bis (3-methyl-4-hydroxy-5-triethylsilylpropylphenyl) propane synthesized in Example 3 was used, and 3,3 ′ -Disulfo-4,4'-dichlorodiphenylsulfone 0.7897 g (2.75 mmol): 4,4'-dichlorodiphenylsulfone 1.3509 g (2.75 mmol): 2,2-bis (3-methyl-4-hydroxy- In the same manner as in the comparative example, 1.22 g of polymer B4 was synthesized at a ratio of 3.1297 g (5.5 mmol) = 0.5: 0.5: 1 of 5-triethylsilylpropylphenyl) propane. The weight average molecular weight Mw was 37,000. Polymer B4 was formed into a film by a casting method, immersed in a 2 mol / l hydrochloric acid aqueous solution overnight and subjected to salt exchange to convert it into a proton type. The proton type membrane of ionic conductivity 25 ° C. in 0.026s / cm, the oxygen permeability coefficient at ^{25 ℃ 9.11x10- 12 mol / cm ·} s, 75 at ℃ 2.04x10- ¹¹ mol / cm · s Met. Further, the membrane converted to the proton type was redissolved, catalyst membrane, MEA, and fuel cell were prepared by the above-mentioned method, and the cell characteristics were recorded. The obtained current value was 212 mA. The permacall value was estimated to be about 6.0 or less.

  The carbon material of the present invention has a stable catalyst dispersion, and even when used in a fuel cell, a high output was obtained.

  The polymer electrolyte of the present invention has high ionic conductivity and oxygen permeability. Furthermore, it turned out that a favorable battery characteristic is also shown.

It is a schematic sectional drawing which shows the structure of the catalyst electrode bonding film using the polymer electrolyte of this invention. It is a schematic sectional drawing which shows an example of the structure of the fuel cell of this invention.

Explanation of symbols

10 ... Fuel cell electrode membrane composite (MEA)
11 ... Polymer electrolyte membrane
12 ... Anode electrode
12a ... Anode porous conductive sheet
12b ... Anode electrode catalyst layer
13 ... Cathode electrode
13a ... Cathode porous conductive sheet
13b ... Cathode electrode catalyst layer
14 ... Packing
15 ... Anode pole side opening
16 ... Cathode pole side opening
17 ... current collector
21,22 ... Separator

Claims (13)

A substituent containing at least one acid residue and at least one substituent having 3 or more total carbon atoms are substituted at any position of the polymer main chain containing the repeating unit represented by the following general formula (1) A polymer electrolyte comprising a polymer compound.
General formula (1)

(In the general formula (1), Ar ¹¹ and Ar ¹² each represent a divalent aromatic group, R ¹¹ represents a single bond or a divalent aliphatic group, and X ¹² represents a divalent electron-withdrawing group. represents, X ¹¹ is .n11 representing a divalent electron donating group represents an integer of 5 to 1,500.) The polymer electrolyte according to claim 1, wherein the polymer compound includes at least one of a repeating unit represented by the following general formula (2) and a repeating unit represented by the general formula (3).
General formula (2)

(In the general formula (2), Ar ²¹ and Ar ²² each represent a divalent aromatic group. R ²¹ represents a single bond or a divalent aliphatic group. R ²² includes an acid residue or a salt thereof. Represents a monovalent substituent, R ²³ represents a monovalent substituent having 3 or more carbon atoms, X ²¹ represents a divalent electron-withdrawing group, and X ²² represents a divalent electron-donating group. N21 represents an integer of 5 to 1500. n22 represents 0, 1 or 2, and the sum of n22 in the repeating unit of 1 is 1 or more, n23 represents 0, 1 or 2 and 1 (The sum of n23 in the repeating unit is 1 or more.)
General formula (3)

(In the general formula (3), Ar ³¹ and Ar ³² each represent a divalent aromatic group. R ³¹ represents a single bond or a divalent aliphatic group. R ³² includes an acid residue or a salt thereof. Represents a monovalent substituent, R ³³ represents a monovalent substituent having a total carbon number of 3 or more, X ³¹ represents a divalent electron-withdrawing group, and X ³² represents a divalent electron-donating group. N31 represents an integer of 5 to 1500. n32 represents 0, 1 or 2, and the sum of n32 in the repeating unit of 1 is 1 or more, n33 represents 0, 1 or 2; (The sum of n33 in the repeating unit is 1 or more.) The polymer electrolyte according to claim 1 or 2, wherein the polymer main chain is polysulfone, polyethersulfone, polyetherketone, or polyimide. The polymer electrolyte according to any one of claims 1 to 3, wherein a permacol value calculated by replacing an acid residue with a hydrogen atom is 0 to 20. Oxygen permeability coefficient, the polymer electrolyte according to any one of claims 1 to 4 is 3x10- ¹² mol / cm · s or more of the polymer compound. The polymer electrolyte according to any one of claims 1 to 5, comprising an acid residue at a concentration of 0.1 to 7 meq / g. The polymer electrolyte according to any one of claims 1 to 6, wherein the polymer compound has a weight average molecular weight of 5,000 or more. The polymer electrolyte according to any one of claims 1 to 7, wherein the acid residue is a sulfonic acid group. The acid residue is a sulfonic acid group, the polymer main chain is hydrocarbon-based polymer compound, and an oxygen permeability coefficient of the polymer compound is 3x10- ¹² mol / cm · s or more claims Item 9. The polymer electrolyte according to any one of Items 1 to 8. At least one selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (6), a compound represented by the following general formula (5) and the following general formula The manufacturing method of the polymer electrolyte of any one of Claims 1-9 including superposing | polymerizing with at least 1 sort (s) selected from the group which consists of a compound represented by (7).
General formula (4)

(In the general formula (4), Ar ⁴¹ represents a divalent aromatic group, R ⁴² represents a monovalent substituent containing an acid residue or a salt thereof, and X ⁴¹ represents a divalent electron-withdrawing group. represents, Y ⁴¹ is .n42 representing a leaving group in nucleophilic aromatic substitution represents 0, 1 or 2, the sum of n42 in one compound is one or more.)
General formula (5)

(In the general formula (5), Ar ⁵¹ represents a divalent aromatic group, R ⁵³ represents a monovalent substituent having a total carbon number of 3 or more, X ⁵¹ represents a divalent electron-withdrawing group, Y ⁵¹ represents a leaving group in the aromatic nucleophilic substitution reaction, n53 represents 0, 1 or 2, and the sum of n53 in one compound is 1 or more.)
General formula (6)

(In General Formula (6), Ar ⁶² represents a divalent aromatic group, R ⁶¹ represents a single bond or a divalent aliphatic group, and R ⁶² represents a monovalent substituent containing an acid residue or a salt thereof. Y ⁶² represents a nucleophilic group in the aromatic nucleophilic substitution reaction, n62 represents 0, 1 or 2, and the sum of n62 in one compound is 1 or more.
General formula (7)

(In the general formula (7), Ar ⁷² represents a divalent aromatic group, R ⁷¹ represents a single bond or a divalent aliphatic group, and R ⁷³ represents a monovalent substituent having 3 or more carbon atoms in total. Y ⁷² represents a nucleophilic group in the aromatic nucleophilic substitution reaction, n73 represents 0, 1 or 2, and the sum of n73 in one compound is 1 or more.) The electrode for fuel cells containing the polymer electrolyte of any one of Claims 1-9. The electrode membrane assembly containing the polymer electrolyte of any one of Claims 1-9. A fuel cell comprising the polymer electrolyte according to claim 1.

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