JP2006261110A - Composition containing oxocarbon acid and/or its derivative and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new composition useful for a polymer electrolyte of a polymer electrolyte fuel cell. <P>SOLUTION: This composition contains an oxocarbon acid represented by the general formula (1) and/or its derivative and a polymer electrolyte. In the formula (1), X<SP>1</SP>and X<SP>2</SP>are each -O-, -S- or -NR'; Z is -CO-, -C(S)-, -C(NR'')-, an alkylene group or an arylene group; n is an integer of 0-10; R is -OH, -SH, -NHR''', an alkyl group, an aryl group or aralkyl group; R', R'' and R''' are each an hydrogen atom, an alkyl group or an aryl group; and B is a hydrogen atom or a monovalent metal atom. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a composition comprising an oxocarbonic acid and / or a derivative thereof and use thereof.

It is known that an oxocarbonic acid represented by squaric acid (square acid) or a derivative thereof has high acidity because a state in which hydrogen in an oxocarbon group is dissociated has a stable structure due to resonance (non-patent literature). 1) (Non-patent document 2).
On the other hand, polymer compounds having a sulfonic acid group are known to be useful as polymer electrolytes for polymer electrolyte fuel cells and the like. For example, fluorinated polymers such as Nafion (registered trademark of DuPont), polymers obtained by introducing sulfonic acid groups into polyether ketones (Patent Document 1), polymers obtained by introducing sulfonic acid groups into polyether sulfones (Non-patent Document 3), Polymers with sulfonic acid groups introduced into polyimides (Patent Document 2), Polymers with sulfonic acid groups introduced into polyphenylenes (Patent Document 3), and sulfonic acid groups introduced into polyphosphazenes The polymer (Non-patent Document 4) has been proposed as a polymer electrolyte for a polymer electrolyte fuel cell or the like.
Further, in a fuel cell that is repeatedly started and stopped, it is known that the polymer electrolyte membrane undergoes a dimensional change such as swelling with generated water during operation, and drying and shrinking when stopped.

Oxocarbons, p. 45 (Edited by Robert West), Academic Press (1980), (ISBN: 0-12-744580-3). Journal of the American Chemical Society, 95, 8703 (1973) J. et al. Membrane Science, 83, 211 (1993) Chemical Material, 3, 1120 (1991) US Pat. No. 5,438,082 JP 2003-277501 A US Pat. No. 5,403,675

However, there is no known composition containing oxocarbonic acid and / or a derivative thereof and a polymer electrolyte.
An object of the present invention is to provide a novel composition useful as a material for a proton conducting membrane of a polymer electrolyte fuel cell, that is, a polymer electrolyte. When a proton conducting membrane is used, the proton conductivity is lowered. It is another object of the present invention to provide a composition that provides a film having higher flexibility than a single polymer electrolyte.

（式中、Ｘ¹、Ｘ²はそれぞれ独立に−Ｏ−、−Ｓ−又は−ＮＲ’−を表し、Ｚは−ＣＯ−、−Ｃ（Ｓ）−、−Ｃ（ＮＲ’’）−、置換基を有していても良い炭素数１〜６のアルキレン基又は置換基を有していても良い炭素数６〜１０のアリーレン基を表す。ｎは、繰り返しの数を表わし、０〜１０の整数を表わす。ｎ個あるＺは、互いに同じであっても良く、異なっていても良い。Ｒは、−ＯＨ、−ＳＨ、−ＮＨＲ’’’、置換基を有していても良い炭素数１〜１８のアルキル基、置換基を有していても良い炭素数６〜１８のアリール基又は置換基を有していても良い炭素数７〜１６のアラルキル基を表す。Ｒ’、Ｒ’’、Ｒ’’’は、それぞれ独立に水素原子、置換基を有していてもよい炭素数１〜６のアルキル基又は置換基を有していてもよい炭素数６〜１０のアリール基を表す。Ｂは、水素原子又は１価の金属原子を表す。）
〔３〕Ｚが、−ＣＯ−、−Ｃ（Ｓ）−又は−Ｃ（ＮＨ）−であることを特徴とする〔２〕記載の組成物、
〔４〕Ｘ₁とＸ₂が−Ｏ−、Ｚが−ＣＯ−、ｎが０〜２であることを特徴とする〔２〕又は〔３〕記載の組成物、
〔５〕高分子電解質が、（Ａ）主鎖が脂肪族炭化水素からなる高分子であり、イオン交換基が導入された形の高分子電解質；（Ｂ）主鎖の一部又は全部の水素原子がフッ素で置換された脂肪族炭化水素からなる高分子であり、イオン交換基が導入された形の高分子電解質；（Ｃ）主鎖が芳香環を有する高分子であり、イオン交換基が導入された形の高分子電解質；（Ｄ）主鎖に実質的に炭素原子を含まない無機物からなる高分子であり、イオン交換基が導入された形の高分子電解質；（Ｅ）主鎖あるいは側鎖に窒素原子を含み、酸性化合物がイオン結合により導入された形の高分子電解質；（Ｆ）（Ａ）〜（Ｅ）の共重合体及び／又は混合物からなる高分子電解質からなる群から選ばれる少なくとも１種であることを特徴とする〔１〕〜〔４〕いずれかに記載の組成物、
〔６〕［高分子電解質中のイオン交換基の物質量（ｍｍｏｌ）］／［高分子電解質の重量（ｇ）］が０．０５〜５ｍｍｏｌ／ｇであることを特徴とする〔１〕〜〔５〕いずれかに記載の組成物、
〔７〕高分子電解質が主鎖に芳香環を有する高分子であり、イオン交換基が導入された形の高分子電解質であることを特徴とする〔１〕〜〔６〕いずれかに記載の組成物、
〔８〕高分子電解質が主鎖に実質的に炭素原子を含まない無機物からなる高分子であり、イオン交換基が導入された形の高分子電解質であることを特徴とする〔１〕〜〔６〕いずれかに記載の組成物、
〔９〕高分子電解質が実質的にイオン交換基を有するセグメントと実質的にイオン交換基を有さないセグメントから成ることを特徴とする〔１〕〜〔８〕いずれかに記載の組成物、
〔１０〕イオン交換基が陽イオン交換基であることを特徴とする〔１〕〜〔９〕いずれかに記載の組成物、
〔１１〕陽イオン交換基がスルホン酸基及び／又はホスホン酸基であることを特徴とする〔１〕〜〔１０〕いずれかに記載の組成物、
〔１２〕［オキソカーボン酸及び／又はその誘導体の物質量（ｍｍｏｌ）］／［高分子電解質の重量（ｇ）＋オキソカーボン酸及び／又はその誘導体の重量（ｇ）］が０．０５〜８ｍｍｏｌ／ｇであることを特徴とする〔１〕〜〔１１〕いずれかに記載の組成物、
〔１３〕前記〔１〕〜〔１２〕いずれかに記載の組成物を用いることを特徴とする高分子電解質膜、
〔１４〕前記〔１３〕記載の高分子電解質膜を用いることを特徴とする高分子電解質膜−電極接合体、
〔１５〕前記〔１３〕に記載の高分子電解質膜又は〔１４〕に記載の高分子電解質膜−電極接合体の少なくとも一つを用いることを特徴とする電池、
〔１６〕前記〔１３〕に高分子電解質膜又は〔１４〕に記載の高分子電解質膜−電極接合体の少なくとも一つを用いることを特徴とする燃料電池、
を提供するものである。 The inventors of the present invention have produced a composition containing oxocarbonic acid and / or a derivative thereof in a polymer electrolyte, and as a result of various studies, the composition containing the oxocarbonic acid and / or the derivative thereof is It is found useful as a proton conductive membrane material for a polymer electrolyte fuel cell using a gas fuel such as gas or a liquid fuel such as methanol or dimethyl ether, that is, a polymer electrolyte, and an oxocarbon acid and / or a derivative thereof is added. As a result, it has been found that flexibility can be imparted without lowering proton conductivity as compared with a membrane of a polymer electrolyte alone, and the present invention has been completed.
That is, the present invention provides [1] a composition comprising oxocarbonic acid and / or a derivative thereof and a polymer electrolyte,
[2] The composition according to [1], wherein the oxocarbonic acid or derivative thereof is represented by the following general formula (1):

Wherein X ¹ and X ² each independently represent —O—, —S— or —NR′—, Z represents —CO—, —C (S) —, —C (NR ″) —, Represents an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms, n represents the number of repetitions, and 0 to 10 The n Zs may be the same or different from each other.R is —OH, —SH, —NHR ′ ″, a carbon which may have a substituent. An alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms which may have a substituent, or an aralkyl group having 7 to 16 carbon atoms which may have a substituent. '', R '''each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an optionally substituted carbon group having 6 carbon atoms. .B representing the 10 aryl group represents a hydrogen atom or a monovalent metal atom.)
[3] The composition according to [2], wherein Z is —CO—, —C (S) — or —C (NH) —.
[4] The composition according to [2] or [3], wherein X ₁ and X ₂ are —O—, Z is —CO—, and n is 0 to 2,
[5] The polymer electrolyte is a polymer electrolyte in which (A) the main chain is a polymer composed of an aliphatic hydrocarbon and an ion exchange group is introduced; (B) part or all of the hydrogen in the main chain A polymer composed of an aliphatic hydrocarbon in which an atom is substituted with fluorine, and a polymer electrolyte in which an ion exchange group is introduced; (C) a polymer having a main chain having an aromatic ring, and an ion exchange group A polyelectrolyte in an introduced form; (D) a polymer composed of an inorganic substance substantially free of carbon atoms in the main chain and having an ion exchange group introduced therein; (E) a main chain or A polymer electrolyte in which a side chain contains a nitrogen atom and an acidic compound is introduced by ionic bonding; (F) from the group consisting of a polymer electrolyte comprising a copolymer and / or a mixture of (A) to (E) [1]-[4 characterized by being at least one selected A composition according to any one,
[6] [Material amount of ion exchange group in polymer electrolyte (mmol)] / [Weight of polymer electrolyte (g)] is 0.05 to 5 mmol / g [1] to [ 5] The composition according to any one of the above,
[7] The polymer electrolyte is a polymer having an aromatic ring in the main chain, and is a polymer electrolyte having an ion exchange group introduced therein [1] to [6] Composition,
[8] The polymer electrolyte is a polymer made of an inorganic substance substantially free of carbon atoms in the main chain, and is a polymer electrolyte having an ion exchange group introduced therein [1] to [1] 6] The composition according to any one of the above,
[9] The composition according to any one of [1] to [8], wherein the polymer electrolyte comprises a segment having substantially an ion exchange group and a segment having substantially no ion exchange group,
[10] The composition according to any one of [1] to [9], wherein the ion exchange group is a cation exchange group,
[11] The composition according to any one of [1] to [10], wherein the cation exchange group is a sulfonic acid group and / or a phosphonic acid group,
[12] [Amount of substance of oxocarbonic acid and / or derivative thereof (mmol)] / [weight of polymer electrolyte (g) + weight of oxocarbonic acid and / or derivative thereof (g)] is 0.05 to 8 mmol / G according to any one of [1] to [11],
[13] A polymer electrolyte membrane comprising the composition according to any one of [1] to [12],
[14] A polymer electrolyte membrane-electrode assembly using the polymer electrolyte membrane according to [13],
[15] A battery comprising at least one of the polymer electrolyte membrane according to [13] or the polymer electrolyte membrane-electrode assembly according to [14],
[16] A fuel cell using at least one of the polymer electrolyte membrane according to [13] or the polymer electrolyte membrane-electrode assembly according to [14],
Is to provide.

  The composition containing the polymer electrolyte of the present invention and oxocarbonic acid and / or a derivative thereof is used for a proton conducting membrane of a polymer electrolyte fuel cell using a gaseous fuel such as hydrogen gas or a liquid fuel such as methanol or dimethyl ether. It is useful as a material, that is, a polymer electrolyte. In particular, the composition of the present invention not only has proton conductivity comparable to that of a single polymer electrolyte, but is also a flexible film that is effective in relieving stress as compared with a single polymer electrolyte. Also, it is advantageous in practical aspects such as durability.

（式中、Ｘ¹、Ｘ²はそれぞれ独立に−Ｏ−、−Ｓ−又は−ＮＲ’−を表し、Ｚは−ＣＯ−、−Ｃ（Ｓ）−、−Ｃ（ＮＲ’’）−、置換基を有していても良い炭素数１〜６のアルキレン基又は置換基を有していても良い炭素数６〜１０のアリーレン基を表す。ｎは、繰り返しの数を表わし、０〜１０の整数を表わす。ｎ個あるＺは、互いに同じであっても良く、異なっていても良い。Ｒは、−ＯＨ、−ＳＨ、−ＮＨＲ’’’、置換基を有していても良い炭素数１〜１８のアルキル基、置換基を有していても良い炭素数６〜１８のアリール基又は置換基を有していても良い炭素数７〜１６のアラルキル基を表す。Ｒ’、Ｒ’’、Ｒ’’’は、それぞれ独立に水素原子、置換基を有していてもよい炭素数１〜６のアルキル基又は置換基を有していてもよい炭素数６〜１０のアリール基を表す。Ｂは、水素原子又は１価の金属原子を表す。） Hereinafter, the present invention will be described in detail.
The composition of the present invention comprises oxocarbonic acid and / or a derivative thereof and a polymer electrolyte. The form of the composition is not particularly limited, but may be compatible at the molecular level or incompatible, and when the polymer electrolyte is in the form of a membrane, oxocarbonic acid and It may also be in a state where a derivative thereof is applied. A form that is compatible at the molecular level is preferable because the effect of imparting flexibility is high.
Here, as a typical example of the oxocarbonic acid or a derivative thereof, a compound represented by the following general formula (1) can be given.

Wherein X ¹ and X ² each independently represent —O—, —S— or —NR′—, Z represents —CO—, —C (S) —, —C (NR ″) —, Represents an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms, n represents the number of repetitions, and 0 to 10 The n Zs may be the same or different from each other.R is —OH, —SH, —NHR ′ ″, a carbon which may have a substituent. An alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms which may have a substituent, or an aralkyl group having 7 to 16 carbon atoms which may have a substituent. '', R '''each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an optionally substituted carbon group having 6 carbon atoms. .B representing the 10 aryl group represents a hydrogen atom or a monovalent metal atom.)

で表わされる平衡反応をとりうる。この平衡反応の極限構造は下記式

のように表わされ、プロトンが解離した時のカチオンが分子内に広く非局在化するために安定な構造である。そのために式（１）で表される化合物は酸性度が高い化合物になるものと考えられる。 In the oxocarbons represented by the formula (1), when B is a hydrogen atom, that is, in the form of a free acid, the following formula

The equilibrium reaction represented by can be taken. The ultimate structure of this equilibrium reaction is

This is a stable structure because the cations when protons dissociate are widely delocalized in the molecule. Therefore, it is considered that the compound represented by the formula (1) becomes a compound having a high acidity.

In the oxocarbonic acid or derivative (1) thereof, X ¹ and X ² each independently represent —O—, —S— or —NR′—. R ′ is a C 1-6 alkyl group which may have a substituent represented by a hydrogen atom, a methyl group, a trifluoromethyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and the like. Alternatively, it represents an aryl group having 6 to 10 carbon atoms which may have a substituent represented by a phenyl group, a pentafluorophenyl group, a naphthyl group, or the like. R ′ is preferably a hydrogen atom. X ¹ and X ² are preferably —O— and —S—, and particularly preferably —O—.
Z may be —CO—, —C (S) —, —C (NR ″) —, an optionally substituted alkylene group having 1 to 6 carbon atoms, or a substituent. A good arylene group having 6 to 10 carbon atoms is represented. R ″ represents a hydrogen atom, a methyl group, a trifluoromethyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and the like, which may have a substituent having 1 to 6 carbon atoms. Alternatively, it represents an aryl group having 6 to 10 carbon atoms which may have a substituent represented by a phenyl group, a pentafluorophenyl group, a naphthyl group, or the like. R ″ is preferably a hydrogen atom.
Here, as a C1-C6 alkylene group, a methylene, ethylene, propylene, i-propylene, butylene, pentylene etc. are mentioned, for example. Examples of the arylene group having 6 to 10 carbon atoms include phenylene and naphthylene. In the case of having a substituent, examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, etc. Among them, fluorine is preferably used.
Z is preferably —CO—, —C (S) —, —C (NR ″) —, methylene, difluoromethylene, phenylene, tetrafluorophenylene, etc., more preferably —CO—, —C (S )-And the like, particularly preferably -CO- and the like.
n represents the number of repetitions of Z, and represents a number of n = 0 to 10. When n is 0, it means a single bond. The n Zs may be the same or different. n is preferably 0 to 4, more preferably 0 to 2, and particularly preferably 1.

R is —OH, —SH, —NHR ′ ″, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, or An aralkyl group having 7 to 16 carbon atoms which may have a substituent is represented. R ′ ″ represents a hydrogen atom; optionally having a substituent represented by a methyl group, a trifluoromethyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, etc. It represents an aryl group having 6 to 10 carbon atoms which may have a substituent represented by an alkyl group, a phenyl group, a pentafluorophenyl group, a naphthyl group or the like. R ′ ″ is preferably a hydrogen atom.
Here, examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, a pentyl group, Examples include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like.
Examples of the substituent when the alkyl group having 1 to 18 carbon atoms has a substituent include halogeno groups such as a fluoro group, a chloro group, and a bromo group; a nitro group; a cyano group; a methoxy group, an ethoxy group, and a propoxy group. C1-C5 alkoxy groups; C1-C5 fluoroalkyl groups, such as a trifluoromethyl group and a pentafluoromethyl group, etc. are mentioned.

  Moreover, as a C6-C18 aryl group, a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group etc. are mentioned, for example. Examples of the substituent when the aryl group having 6 to 18 carbon atoms has a substituent include a halogeno group such as a fluoro group, a chloro group, and a bromo group, a nitro group, a cyano group, a methoxy group, an ethoxy group, and a propoxy group. C1-C5 fluoroalkyl group such as C1-C5 alkoxy group, trifluoromethyl group, pentafluoromethyl group, etc., C1-C5 alkyl such as methyl group, ethyl group, propyl group, butyl group Etc.

が挙げられる。
式中、Ｙ¹〜Ｙ⁵はそれぞれ独立にハロゲノ基を表す。ｐは１〜５の整数を表す。ｑは０〜３の整数、ｒは０〜４の整数を表し、かつ（ｑ＋ｒ）の値が１〜７である。ｓは０〜４の整数、ｔは０〜５の整数を表し、かつ（ｓ＋ｔ）の値が１〜９である。Ｙ¹〜Ｙ⁵がそれぞれ複数あるときにはこれらは同じであっても良いし異なっていても良い。
ハロゲノ基として好ましくはフルオロ基、クロロ基であり、特に好ましくはフルオロ基である。（２ａ）〜（２ｃ）の中で特に好ましくは（２ａ）である。 More specifically, examples of the aryl group having 6 to 18 carbon atoms having a halogeno group as a substituent include, for example, the following general formulas (2a) to (2c):

Is mentioned.
Wherein, Y ¹ to Y ⁵ each independently represent a halogeno group. p represents an integer of 1 to 5. q represents an integer of 0 to 3, r represents an integer of 0 to 4, and (q + r) has a value of 1 to 7. s represents an integer of 0 to 4, t represents an integer of 0 to 5, and (s + t) has a value of 1 to 9. When there are a plurality of Y ^{1 to} Y ⁵ , these may be the same or different.
The halogeno group is preferably a fluoro group or a chloro group, and particularly preferably a fluoro group. (2a) is particularly preferable among (2a) to (2c).

Examples of the aralkyl group having 7 to 16 carbon atoms include benzyl group, phenylethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group and the like. Examples of the substituent when the aralkyl group having 7 to 16 carbon atoms has a substituent include a halogeno group such as a fluoro group, a chloro group, and a bromo group, a nitro group, a cyano group, a methoxy group, an ethoxy group, and a propoxy group. C1-C5 fluoroalkyl group such as C1-C5 alkoxy group, trifluoromethyl group, pentafluoromethyl group, etc., C1-C5 alkyl such as methyl group, ethyl group, propyl group, butyl group Groups and the like.
R is preferably —OH, —SH, methyl group, ethyl group, trifluoromethyl group, phenyl group, naphthyl group, pentafluorophenyl group, benzyl group, and more preferably —OH, phenyl group, penta A fluorophenyl group and the like;

B represents a hydrogen atom or a monovalent metal atom. Examples of the monovalent metal atom include a lithium atom, a sodium atom, a potassium atom, a cesium atom, and a silver atom. B is preferably a hydrogen atom, lithium atom, sodium atom, potassium atom or cesium atom, more preferably a lithium atom, sodium atom or potassium atom, still more preferably a hydrogen atom or lithium atom, particularly preferably. Is a hydrogen atom.
When the composition of the present invention is used as an electrolyte for a lithium secondary battery, lithium is used as B.
When the composition of the present invention is used in a polymer electrolyte fuel cell, it is preferable that substantially all functional groups are in the form of free acid. The composition of the present invention is more suitably used for a polymer electrolyte fuel cell.

Specific examples of the oxocarbonic acid or derivative (1) in the present invention include the following compounds. Here, the case where B is a hydrogen atom is illustrated.

  In the present invention, the above oxocarbonic acid and / or its derivative is used. Among these, (a1) to (a66) are preferable. More preferably (a2), (a5) (a8), (a11), (a14), (a17), (a20), (a23), (a26), (a29), (a32), (a35), (A38), (a41), (a44), (a47), (a50), (a53), (a56), (a59), (a62), (a65), and more preferably (a2), (A5), (a17), (a26), (a29), (a41), (a44), (a50), (a53), (a59), (a62), (a65), particularly preferably ( a2), (a41), (a50), and (a53).

The oxocarbonic acid or derivative thereof can be produced, for example, according to the following method. Moreover, you may obtain from a reagent maker.
(I) A method for producing a compound in which R in the oxocarbonic acid or derivative (1) thereof is alkyl or aryl using a lithium reagent (Journal of Organic Chemistry, 53 , 2482, 2477 (1988)).
(II) A method for producing a compound in which R in the oxocarbonic acid or derivative (1) thereof is alkyl or aryl using a Grignard reagent (Heterocycles, 27 (5), 1191 (1988)).
(III) A method for producing a compound in which R in the oxocarbonic acid or derivative (1) thereof is alkyl or aryl using a tin reagent (Journal of Organic Chemistry, 55 , 5359 (1990), Tetrahedron Letters, 31 (30 ), 4293 (1990)).
(IV) A method of synthesis using Friedel Crafts reaction (Synthesis, page 46 (1974)).
Various derivatives can be synthesized by complying with these methods.

（式中、Ｘ¹、Ｘ²、Ｚ、ｎは前記（１）と同じ意味を示す。）
で示されるオキソカーボン基等の陽イオン交換基、−ＮＨ₂、−ＮＨＲ、−ＮＲＲ’、−ＮＲＲ’Ｒ’’⁺、−ＮＨ₃ ⁺など（Ｒはアルキル基、シクロアルキル基、アリール基等を表す）等の陰イオン交換基を有する高分子である。イオン交換基は、その一部又は全部が対イオンとの塩を形成していても良い。
イオン交換基として、好ましくは陽イオン交換基であり、さらに好ましくは−ＳＯ₃Ｈ、−ＰＯ（ＯＨ）₂、−ＰＯＨ（ＯＨ）、−ＳＯ₂ＮＨＳＯ₂−、オキソカーボン基であり、特に好ましくは−ＳＯ₃Ｈ、−ＰＯ（ＯＨ）₂、オキソカーボン基であり、最も好ましくは−ＳＯ₃Ｈである。 The polymer electrolyte in the present invention is not particularly limited as long as it is a polymer that can be used as an electrolyte, and a polymer electrolyte containing an ion exchange group, a blend of a strong inorganic acid and a polymer, etc. can be used. Preferably it is.
As ion exchange groups, for _{example, -SO 3 H, -COOH, -PO} (OH) 2, -POH (OH), - SO 2 NHSO 2 -, - Ph (OH) (Ph represents a phenylene group), the following General formula (2)

(In the formula, X ¹ , X ² , Z and n have the same meaning as in the above (1).)
A cation exchange group such as an oxocarbon group represented by the formula: —NH ₂ , —NHR, —NRR ′, —NRR′R ″ ⁺ , —NH ₃ ^{+ and the} like (R represents an alkyl group, a cycloalkyl group, an aryl group, etc. And a polymer having an anion exchange group. Some or all of the ion exchange groups may form a salt with a counter ion.
The ion exchange group is preferably a cation exchange group, more preferably —SO ₃ H, —PO (OH) ₂ , —POH (OH), —SO ₂ NHSO ₂ —, an oxocarbon group, and particularly preferably. Are —SO ₃ H, —PO (OH) ₂ , and an oxocarbon group, and most preferably —SO ₃ H.

  Representative examples of the polymer electrolyte include, for example, (A) a polymer electrolyte in which the main chain is an aliphatic hydrocarbon and an ion exchange group is introduced; (B) a part of the main chain or A polymer electrolyte comprising an aliphatic hydrocarbon in which all hydrogen atoms are substituted with fluorine, and a polymer electrolyte in which an ion exchange group is introduced; (C) a polymer having an aromatic ring in its main chain, and an ion A polyelectrolyte in a form in which an exchange group is introduced; (D) a polymer electrolyte made of an inorganic substance substantially free of carbon atoms in the main chain and in a form in which an ion exchange group is introduced; (E) A polymer electrolyte in which a main chain or a side chain contains a nitrogen atom and an acidic compound is introduced by ionic bonding; a polymer electrolyte comprising a copolymer and / or a mixture of (F) (A) to (E), etc. Is mentioned.

Examples of the polymer electrolyte (A) include polyvinyl sulfonic acid, polystyrene sulfonic acid, poly (α-methylstyrene) sulfonic acid, and the like.
In addition, as the polymer electrolyte (B), a polymer having perfluoroalkylsulfonic acid in the side chain represented by Nafion (registered trademark of DuPont, the same shall apply hereinafter) and having a main chain of perfluoroalkane. A sulfonic acid type polystyrene-graft-ethylene-tetrafluoroethylene copolymer composed of a main chain made by copolymerization of a fluorocarbon vinyl monomer and a hydrocarbon vinyl monomer and a hydrocarbon side chain having a sulfonic acid group. A film made by copolymerization of a polymer (ETFE, for example, JP-A-9-102322) or a fluorine-based vinyl monomer and a hydrocarbon-based vinyl monomer, α, β, β-trifluorostyrene is graft-polymerized, A sulfonic acid type poly (trifluorostyrene) -glass was obtained by introducing a sulfonic acid group into the polymer electrolyte membrane. Doo -ETFE film (e.g., U.S. Patent No. 4,012,303 and U.S. Pat. No. 4,605,685), and the like.

  The polymer electrolyte (C) may be one in which the main chain is interrupted by a hetero atom such as an oxygen atom. For example, polyether ether ketone, polysulfone, polyether sulfone, poly (arylene ether) , Polyimide, poly ((4-phenoxybenzoyl) -1,4-phenylene), polyphenylene sulfide, polyphenylquinoxalene and other polymers each having an ion exchange group introduced therein, sulfoarylated polybenzimidazole, Sulfoalkylated polybenzimidazole, phosphoalkylated polybenzimidazole (for example, JP-A-9-110882), phosphonated poly (phenylene ether) (for example, J. Appl. Polym. Sci., 18, 1969 (1974)) and the like. Is mentioned.

Examples of the polymer electrolyte (D) include those obtained by introducing an ion exchange group into polyphosphazene, polysiloxane having a phosphonic acid group described in Polymer Prep., 41, no. 1, 70 (2000), and the like. Is mentioned.
Examples of the polymer electrolyte (E) include polybenzimidazole containing phosphoric acid described in JP-A-11-503262.
As the polymer electrolyte of the above (F), an ion exchange group is introduced into a random copolymer, an ion exchange group is introduced into an alternating copolymer, or an ion exchange group is introduced into a block copolymer. It may be introduced. As what introduce | transduced the sulfonic acid group into the random copolymer, the thing etc. which are described in Unexamined-Japanese-Patent No. 10-021943 etc. are mentioned, for example. Specific examples of the block having a sulfonic acid group in the block copolymer include those described in JP-A No. 2001-250567.
The distribution of the ion exchange groups introduced into the polymer electrolyte is not particularly limited, but a polymer electrolyte comprising a segment having an ion exchange group and a segment having substantially no ion exchange group is preferable.

The weight average molecular weight of the polymer electrolyte used in the present invention is preferably about 1,000 to 1,000,000, more preferably about 5,000 to 200,000.
In the present invention, [substance amount of ion exchange groups in polymer electrolyte (mmol)] / [weight of polymer electrolyte (g)], that is, the ion exchange group equivalent of the polymer electrolyte is preferably 0.05 to 5 mmol. / G, more preferably about 0.5-4.
Among the polymer electrolytes of the above (A) to (F), a polymer electrolyte in which the main chain of (C) has an aromatic ring and a sulfonic acid group and / or phosphonic acid group is introduced is preferable. Used.
The composition of the present invention containing the polymer compound as described above and the oxocarbon acid and / or derivative thereof as described above is [substance amount (mmol) of oxocarbon acid and / or derivative thereof] / [high Molecular electrolyte weight (g) + oxocarbonic acid and / or derivative weight (g)], that is, the equivalent weight of oxocarbonic acid and / or derivative thereof in the composition is preferably 0.05 to 8 mmol / g. More preferably, it is 0.1-7 mmol / g, Most preferably, it is 0.3-6 mmol / g, Most preferably, it is 0.5-5 mmol / g.
Here, the equivalent of the oxocarbonic acid and / or derivative thereof in the composition is preferably 0.05 mmol / g or more because the effect of imparting flexibility tends to be further improved, and is preferably 8 mmol / g or less. It is more preferable in terms of water resistance.
The oxocarbonic acid and / or derivative thereof is usually used so that the total equivalent amount in the composition falls within the above range. The equivalent weight of the oxocarbonic acid and / or derivative thereof in the composition of the present invention is determined using an NMR method.

The composition of the present invention is characterized by containing a polymer electrolyte and oxocarbonic acid and / or a derivative thereof, and the production method thereof is not particularly limited. For example, (1) a polymer electrolyte and A method obtained by dissolving, dispersing or suspending oxocarbonic acid and / or a derivative thereof in a solvent and mixing them, and then removing the solvent; (2) dissolving, dispersing or dispersing the oxocarbon in a solvent that does not dissolve the polymer electrolyte; For example, a method of impregnating and / or adhering oxocarbonic acid and / or a derivative thereof by suspending and immersing the polymer electrolyte in this solution may be used.
Here, examples of the solvent include water, alcohol solvents, ketone solvents, ether solvents, halogen solvents, sulfoxide solvents, sulfone solvents, amide solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents. , And a mixed solvent thereof.
Examples of alcohol solvents include methanol, ethanol, isopropanol, butanol, and examples of ketone solvents include acetone, methyl isobutyl ketone, methyl ethyl ketone, and benzophenone. Examples of ether solvents include diethyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran (hereinafter abbreviated as THF), dioxane, dioxolane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and the like. It is done.

Examples of the halogen-based solvent include chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, and dichlorobenzene. Examples of the sulfoxide-based solvent include dimethyl sulfoxide (hereinafter abbreviated as DMSO). It is done. Examples of the sulfone solvent include diphenyl sulfone and sulfolane, and examples of the amide solvent include N, N-dimethylacetamide (hereinafter abbreviated as DMAc), N-methylacetamide, N, N-dimethylformamide (hereinafter abbreviated as DMF), N-methylformamide, formamide, N-methylpyrrolidone (hereinafter abbreviated as NMP) and the like. Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, and octane, and examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and the like.
Among these, it is preferable to select from water, alcohol solvents, ether solvents, halogen solvents, amide solvents, and mixed solvents thereof. More preferably, it is selected from water, methanol, THF, dichloromethane, DMAc, and mixed solvents thereof.

  Examples of the method for removing the solvent include a method of evaporating and evaporating the solvent of the mixed solution, dispersion or suspension, and in the case of the production method (1), the solvent casting method described later is used. It can be formed into a film by using it.

Next, the case where the composition of the present invention is used as a diaphragm of an electrochemical device such as a fuel cell will be described.
In this case, the composition of the present invention is usually used in the form of a film, but there is no particular limitation on the method of converting into a film, and for example, a method of forming a film from a solution state (solvent casting method) is preferably used.
Specifically, a film is formed by dissolving the composition in an appropriate solvent, applying the solution onto a glass plate, and removing the solvent. The solvent used for film formation is not particularly limited as long as it can dissolve the composition and can be removed thereafter, and is an aprotic polar solvent such as DMF, DMAc, NMP, DMSO, or dichloromethane, chloroform, Chlorinated solvents such as 1,2-dichloroethane, chlorobenzene and dichlorobenzene, alcohols such as methanol, ethanol and propanol, alkylenes such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether Glycol monoalkyl ether, THF, 1,3-dioxolane, 1,4-dioxane, 1,3-dioxane, tetrahydropyran, dibutyl ether, tert-butyl methyl ether, dipheny Ether, ether solvents such as crown ethers are preferably used. These can be used singly, but two or more solvents can be mixed and used as necessary.
Among these, DMSO, DMF, DMAc, NMP, THF, 1,3-dioxolane and the like are preferable because of high solubility of the polymer composition.

  Although there is no restriction | limiting in particular in the thickness of a film, 10-300 micrometers is preferable and 20-100 micrometers is especially preferable. A film having a thickness of 10 μm or more is preferable because practical strength is more excellent, and a film having a thickness of 300 μm or less is preferable because the membrane resistance becomes smaller and the characteristics of the electrochemical device are further improved. The film thickness can be controlled by the concentration of the solution and the coating thickness on the substrate.

In addition, for the purpose of improving various physical properties of the film, a plasticizer, a stabilizer, a mold release agent, and the like used in ordinary polymer compounds can be contained in the composition of the present invention. Also, other polymers can be combined with the polymer composition of the present invention by a method such as co-casting in the same solvent.
In addition, in fuel cell applications, it is also known to add inorganic or organic fine particles as a water retention agent in order to facilitate water management. Any of these known methods can be used as long as they are not contrary to the object of the present invention.
Further, for the purpose of improving the mechanical strength of the film, it can also be crosslinked by irradiating with an electron beam, radiation or the like (for example, JP-A-11-111310). Furthermore, a porous film or sheet is impregnated and composited (Japanese Patent Laid-Open No. 6-29032), or a method of reinforcing a film by mixing fibers or pulp is known. Can be used as long as the object of the present invention is not violated.

The polymer electrolyte membrane of the present invention is characterized by using the above polymer electrolyte.
The polymer electrolyte membrane-electrode assembly of the present invention is characterized by using at least one selected from the above-mentioned polymer electrolytes and polymer electrolyte membranes.
The battery of the present invention is characterized by using at least one of the polymer electrolyte, the polymer electrolyte membrane, or the polymer electrolyte membrane-electrode assembly.
Here, examples of the battery include a fuel cell, a lithium ion secondary battery, and the like, and a fuel cell is particularly preferable. Among the fuel cells, a polymer electrolyte fuel cell is most preferable.
The fuel cell of the present invention is characterized by using at least one of the polymer electrolyte, the polymer electrolyte membrane, or the polymer electrolyte membrane-electrode assembly.
Next, the fuel cell of the present invention will be described.
The fuel cell of the present invention can be produced by bonding a catalyst and a conductive material as a current collector to both surfaces of a film.
The catalyst is not particularly limited as long as it can activate the oxidation-reduction reaction with hydrogen or oxygen, and a known catalyst can be used, but platinum fine particles are preferably used. The fine particles of platinum are often used by being supported on particulate or fibrous carbon such as activated carbon or graphite.
A known material can be used for the conductive material as the current collector, but porous carbon woven fabric, carbon non-woven fabric or carbon paper is preferable for efficiently transporting the raw material gas to the catalyst.
For a method of bonding platinum fine particles or carbon carrying platinum fine particles to a porous carbon non-woven fabric or carbon paper, and a method of bonding it to a polymer electrolyte film, see, for example, J. Org. Electrochem. Soc. : Known methods such as those described in Electrochemical Science and Technology, 1988, 135 (9), 2209 can be used.
The composition of the present invention can also be used as a proton conductive material that is a component of a catalyst composition constituting a catalyst layer of a polymer electrolyte fuel cell.
The fuel cell of the present invention thus produced can be used in various forms using hydrogen gas, reformed hydrogen gas, methanol, dimethyl ether, etc. as fuel.

  While the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and further includes meanings equivalent to the description of the claims and all modifications within the scope.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The ion exchange capacity was measured by a titration method, and the proton conductivity was measured by an AC impedance method. The tensile test was measured at a test speed of 10 mm / min at 23 ° C. and a relative humidity of 50% in accordance with Japanese Industrial Standard (JIS K 7127).

(Reference Example 1)
In a flask equipped with an azeotropic distillation apparatus, 25.0 g (110 mmol) of potassium 2,5-dihydroxybenzenesulfonate and 60.2 g of dipotassium 4,4′-difluorodiphenylsulfone-3,3′-disulfonate in an Ar atmosphere. (123 mmol) and 15.9 g (115 mmol) of potassium carbonate were added, and 341 mL of DMSO and 68 mL of toluene were added. Thereafter, toluene was distilled off by heating at a bath temperature of 150 ° C. to azeotropically dehydrate water, and the mixture was stirred while keeping at 150 ° C. for 6.5 hours to obtain a hydrophilic oligomer solution (a1).
In another flask equipped with an azeotropic distillation apparatus, 78.2 g (312 mmol) of 4,4′-dihydroxydiphenylsulfone, 76.1 g (299 mmol) of 4,4′-difluorodiphenylsulfone, 47. 5 g (344 mmol) was added, and 617 mL DMSO and 123 mL toluene were added. Thereafter, toluene was distilled off with heating at a bath temperature of 150 ° C. to azeotropically dehydrate the water in the system, and the mixture was stirred at 150 ° C. for 6.5 hours to obtain a hydrophobic oligomer solution (a2).
Subsequently, after the reaction solution was sufficiently allowed to cool to room temperature, the obtained hydrophilic oligomer solution (a1) was added to the hydrophobic oligomer solution (a2), and the mixture was stirred while keeping the temperature up to 150 ° C. for a total of 18 hours. The reaction solution was allowed to cool and then added dropwise to a large amount of hydrochloric acid, and the resulting precipitate was collected by filtration. Further, filtration and washing with water was repeated until the washing solution became neutral, followed by washing with hot water at 100 ° C. for 2 hours, filtration and drying to obtain 194 g of Polymer A. The ion exchange capacity of A was 1.36 meq / g.

(Reference Example 2)
Synthesis of 3-Hydroxy-4-phenylcyclobut-3-ene-1,2-dione (Compound B) According to the method described in Journal of Organic Chemistry, 1988, 53 (11), 2482, 3- (1 -Methylethoxy) -4-Phenylcyclobut-3-ene-1,2-dione was prepared. Next, 0.63 g of this product, 12 ml of THF, and 36 ml of 12N hydrochloric acid were placed in a 100 ml flask and stirred at 100 ° C. for 5 hours. Thereafter, the mixture was allowed to cool to room temperature, the aqueous layer was washed with chloroform, and then the aqueous layer was concentrated to obtain 0.24 g of 3-Hydroxy-4-phenylcyclo-3-ene-1,2-dione (Compound B). . The structure was confirmed by ¹ H NMR and ¹³ C NMR.

Example 1
Into a flask, 0.265 g of the polymer A synthesized in Reference Example 1 and 0.142 g of the compound B synthesized in Reference Example 2 and 10 ml of a methylene chloride: methanol = 9: 1 (vol / vol) mixed solution were added and stirred to obtain a uniform solution. This solution was spread on a petri dish, and the solvent was volatilized and dried at room temperature and normal pressure to obtain a film C of the composition. [Amount of substance of oxocarbonic acid and / or derivative thereof (mmol)] / [weight of polyelectrolyte (g) + weight of oxocarbonic acid and / or derivative thereof (g)] of 2.00 (mmol / g). Table 1 shows the C tensile test results and proton conductivity measurement results.

(Comparative Example 1)
The flask was charged with 0.400 g of the polymer A synthesized in Reference Example 1 and 10 ml of a mixed solution of methylene chloride: methanol = 9: 1 (vol / vol) to obtain a uniform solution. This solution was developed in a petri dish, and the solvent was volatilized at room temperature and normal pressure and dried to obtain a polymer electrolyte membrane D. Table 1 shows the tensile test results of D and the proton conductivity measurement results.

(Example 2)
In a flask equipped with an azeotropic distillation apparatus, in an argon atmosphere, 9.32 parts by weight of dipotassium 4,4′-difluorodiphenylsulfone-3,3′-disulfonate, and 4.20% by weight of potassium 2,5-dihydroxybenzenesulfonate. Parts, DMSO 59.6 parts by weight, and toluene 9.00 parts by weight were added, and argon gas was bubbled for 1 hour while stirring them at room temperature. Thereafter, 2.67 parts by weight of potassium carbonate was added to the obtained mixture, and azeotropic dehydration was performed by heating and stirring at 140 ° C. Thereafter, heating was continued while distilling off toluene to obtain a hydrophilic oligomer solution (e1). Total heating time was 14 hours. The resulting solution was allowed to cool at room temperature.
In a separate flask equipped with an azeotropic distillation apparatus, under an argon atmosphere, 8.32 parts by weight of 4,4′-difluorodiphenylsulfone, 5.36 parts by weight of 2,6-dihydroxynaphthalene, 30.2 parts by weight of DMSO, 30% of NMP. 2 parts by weight and 9.81 parts by weight of toluene were added, and argon gas was bubbled for 1 hour while stirring at room temperature. Thereafter, 5.09 parts by weight of potassium carbonate was added to the obtained mixture, and azeotropic dehydration was performed by heating and stirring at 140 ° C. Thereafter, heating was continued while toluene was distilled off. Total heating time was 5 hours. The resulting solution was allowed to cool at room temperature to obtain a hydrophobic oligomer solution (e2).
The total amount of the above hydrophilic oligomer solution (e1), 80.4 parts by weight of NMP and 45.3 parts by weight of DMSO were added to the obtained hydrophobic oligomer solution (e2), and a block copolymerization reaction was performed at 150 ° C. for 40 hours. .
The obtained reaction solution was dropped into a large amount of 2N hydrochloric acid and immersed for 1 hour. Thereafter, the produced precipitate was filtered off and then immersed again in 2N hydrochloric acid for 1 hour. The obtained precipitate was filtered and washed with water, and then immersed in a large amount of hot water at 95 ° C. for 1 hour. Then, the precipitate was dried at 80 ° C. for 12 hours to obtain poly [oxy (2-sulfo-1,4-phenylene) oxy (2-sulfo-1,4-phenylene) sulfonyl (3-sulfo-1,4 -Phenylene)]-block-poly (oxy-2,6-naphthyleneoxy-1,4-phenylenesulfonyl-1,4-phenylene)] (Polymer E) was synthesized. The ion exchange capacity of Polymer E was 1.80 meq / g. Into a flask, 0.266 g of polymer E, 0.135 g of 3,4-dihydroxy-3-cyclobutene-1,2-dione (compound F, purchased from Aldrich) and 5 g of NMP were added and stirred to obtain a homogeneous solution. This solution was spread on a petri dish, and the solvent was evaporated at 80 ° C. and normal pressure to dry the film G of the composition. [Substance amount (mmol) of oxocarbonic acid and / or derivative thereof] / [weight of polyelectrolyte (g) + weight of oxocarbonic acid and / or derivative thereof (g)] of G is 2.95 (mmol / g). Table 1 shows the G tensile test results and proton conductivity measurement results.

(Comparative Example 2)
Polymer E0.400g and NMP5g were put into the flask, and it was set as the uniform solution. This solution was spread on a petri dish, and the solvent was evaporated at 80 ° C. and normal pressure to dry the polymer electrolyte membrane H. Table 1 shows the H tensile test results and proton conductivity measurement results.

(Example 3)
In an argon atmosphere, a flask equipped with an azeotropic distillation apparatus was charged with 145 parts by weight of DMSO, 56.6 parts by weight of toluene, 5.66 parts by weight of sodium 2,5-dichlorobenzenesulfonate, and polyethersulfone having a terminal chloro form (Sumitomo). Chemical Industry Sumika Excel PES5200P) 2.13 parts by weight and 2,2′-bipyridyl 9.35 parts by weight were added and stirred. Thereafter, the bath temperature was raised to 150 ° C., and water in the system was azeotropically dehydrated by distilling off toluene, followed by cooling to 60 ° C. Next, 15.7 parts by weight of bis (1,5-cyclooctadiene) nickel (0) was added thereto, the temperature was raised to 80 ° C., and the mixture was stirred at the same temperature for 5 hours. After allowing to cool, the reaction solution is poured into a large amount of 6 mol / L hydrochloric acid to precipitate a polymer, which is filtered off. Thereafter, washing and filtration with 6 mol / L hydrochloric acid were repeated several times, followed by washing with water until the filtrate became neutral, washing with hot water at 95 ° C., and drying under reduced pressure to obtain poly (sulfo-1,4- Phenylene) -block-poly (oxy-1,4-phenylenesulfonyl-1,4-phenylene) (Polymer I) was synthesized. The ion exchange capacity of Polymer I was 2.20 meq / g. The flask was charged with 0.266 g of polymer I, 0.141 g of compound F and 5 g of NMP, and stirred to obtain a uniform solution. This solution was spread on a petri dish, and the solvent was volatilized and dried at 80 ° C. and normal pressure to obtain a film J of the composition. J [Amount of substance of oxocarbonic acid and / or derivative thereof (mmol)] / [weight of polyelectrolyte (g) + weight of oxocarbonic acid and / or derivative thereof (g)] is 3.04 (mmol / g). Table 1 shows the tensile test results and proton conductivity measurement results for J.

(Comparative Example 3)
The flask was charged with 0.400 g of polymer K and 5 g of NMP to obtain a uniform solution. This solution was developed in a petri dish, and the solvent was volatilized and dried at 80 ° C. and normal pressure to obtain a polymer electrolyte membrane K. Table 1 shows the K tensile test results and proton conductivity measurement results.

Example 4
Poly (diphenoxy) phosphazene (polymer L) was synthesized according to the method described in Polymer Communications, 1984, Vol. 25, 93-96 and Macromolecules, 1980, 13, 1325-1332. 3.10 g of polymer L was dissolved in 30 ml of concentrated sulfuric acid and reacted at 50 ° C. for 8 hours, and then the solution was dropped into ice water to synthesize a sulfonated product of poly (diphenoxy) phosphazene (polymer M). The ion exchange capacity of M was 1.30 meq / g. The flask was charged with 0.503 g of polymer M, 0.146 g of compound F and 10 g of NMP, and stirred to obtain a uniform solution. This solution was developed in a petri dish, and the solvent was volatilized and dried at 80 ° C. and normal pressure to obtain a film N of the composition. [Substance amount (mmol) of oxocarbonic acid and / or derivative thereof] of N / [weight of polyelectrolyte (g) + weight of oxocarbonic acid and / or derivative thereof (g)] is 1.97 (mmol / g). N tensile test results and proton conductivity measurement results are shown in Table 1.

(Comparative Example 4)
The flask was charged with 0.400 g of polymer M and 5 g of NMP to make a uniform solution. This solution was developed in a petri dish, and the solvent was volatilized and dried at 80 ° C. and normal pressure to obtain a polymer electrolyte membrane O. Table 1 shows the O tensile test results and proton conductivity measurement results.

(Example 5)
In a flask, 0.142 g of Compound B was added to 10.36 g (polymer amount 0.518 g) of 5 wt% Nafion solution (manufactured by Aldrich) and stirred to obtain a uniform solution. This solution was spread on a petri dish, and the solvent was volatilized and dried at 80 ° C. and normal pressure to obtain a film R of the composition. [Amount of substance of oxocarbonic acid and / or derivative thereof (mmol)] / [weight of polyelectrolyte (g) + weight of oxocarbonic acid and / or derivative thereof (g)] is 1.24 (mmol / g). Table 1 shows the tensile test results of P and the proton conductivity measurement results.

(Comparative Example 5)
A 5 wt% Nafion solution (manufactured by Aldrich) was developed in a petri dish, and the solvent was volatilized and dried at 80 ° C. and normal pressure to obtain a polymer electrolyte membrane Q. Table 1 shows the Q tensile test results and proton conductivity measurement results.

(Example 6)
In Formula (1), X ¹ , X ² , Z, n, and R are the compounds a, polymers A, and DMAc shown in Table 2 and placed in a flask and stirred to obtain a uniform solution. This solution is spread on a petri dish, and the solvent is volatilized and dried to obtain a film R of the composition. At this time, the compound a and the polymer A are combined with R [amount of substance of oxocarbonic acid and / or derivative thereof (mmol)] / [weight of polymer electrolyte (g) + oxocarbonic acid and / or derivative thereof. When the weight (g)] is selected to be in the range of 0.05 to 8 mmol / g, a membrane having extremely higher flexibility than that of a single polymer electrolyte is preferably obtained without greatly reducing proton conductivity.

(Example 7)
In formula (1), X ¹ , X ² , Z, n, and R are the compounds b, polymer E, and NMP shown in Table 2 and stirred into a uniform solution. This solution is spread on a petri dish, and the solvent is volatilized and dried to obtain a film S of the composition. At this time, the compound b and the polymer E are converted into [the amount of the oxocarbonic acid and / or its derivative (mmol)] / [weight of the polymer electrolyte (g) + the oxocarbonic acid and / or its derivative. When the weight (g)] is selected to be in the range of 0.05 to 8 mmol / g, a membrane having extremely higher flexibility than that of a single polymer electrolyte is preferably obtained without greatly reducing proton conductivity.

(Example 8)
In formula (1), X ¹ , X ² , Z, n, and R are the compounds c, polymer I, and DMSO shown in Table 2 and placed in a flask and stirred to obtain a homogeneous solution. This solution is spread on a petri dish, and the solvent is volatilized and dried to obtain a film T of the composition. At this time, the compound c and the polymer I are combined with the amount of [oxocarbonic acid and / or derivative thereof (mmol)] / [weight of polymer electrolyte (g) + oxocarbonic acid and / or derivative thereof. When the weight (g)] is selected to be in the range of 0.05 to 8 mmol / g, a membrane having extremely higher flexibility than that of a single polymer electrolyte is preferably obtained without greatly reducing proton conductivity.

Example 9
In formula (1), X ¹ , X ² , Z, n, and R are the compounds d, polymer A, and DMAc shown in Table 2 and placed in a flask and stirred to obtain a uniform solution. This solution is spread on a petri dish, and the solvent is volatilized and dried to obtain a film U of the composition. In this case, the compound d and the polymer A are combined with [the amount of substance of oxocarbonic acid and / or its derivative (mmol)] / [weight of polymer electrolyte (g) + oxocarbonic acid and / or its derivative. When the weight (g)] is selected to be in the range of 0.05 to 8 mmol / g, a membrane having extremely higher flexibility than that of a single polymer electrolyte is preferably obtained without greatly reducing proton conductivity.

(Example 10)
In Formula (1), X ¹ , X ² , Z, n, and R are the compounds e, polymers E, and NMP shown in Table 2 and placed in a flask and stirred to obtain a uniform solution. This solution is spread on a petri dish, and the solvent is volatilized and dried to obtain a film V of the composition. At this time, the compound e and the polymer E are converted into the amount of [oxocarbonic acid and / or derivative thereof (mmol)] / [weight of polymer electrolyte (g) + oxocarbonic acid and / or derivative thereof. When the weight (g)] is selected to be in the range of 0.05 to 8 mmol / g, a membrane having extremely higher flexibility than that of a single polymer electrolyte is preferably obtained without greatly reducing proton conductivity.

(Example 11)
In Formula (1), X ¹ , X ² , Z, n, and R are the compounds f, polymers I, and DMSO shown in Table 2 and placed in a flask and stirred to obtain a uniform solution. This solution is spread on a petri dish, and the solvent is volatilized and dried to obtain a film W of the composition. At this time, the compound f and the polymer I are combined with [the amount of substance of oxocarbonic acid and / or its derivative (mmol)] / [weight of polymer electrolyte (g) + oxocarbonic acid and / or its derivative. When the weight (g)] is selected to be in the range of 0.05 to 8 mmol / g, a membrane having extremely higher flexibility than that of a single polymer electrolyte is preferably obtained without greatly reducing proton conductivity.

(Example 12)
In Formula (1), X ¹ , X ² , Z, n, and R are the compounds g, polymer A, and DMAc shown in Table 2 and placed in a flask and stirred to obtain a uniform solution. This solution is spread on a petri dish, and the solvent is volatilized and dried to obtain a film X of the composition. At this time, the compound g and the polymer A are converted into [the amount of the oxocarbonic acid and / or its derivative (mmol)] / [weight of the polymer electrolyte (g) + the oxocarbonic acid and / or its derivative. When the weight (g)] is selected to be in the range of 0.05 to 8 mmol / g, a membrane having extremely higher flexibility than that of a single polymer electrolyte is preferably obtained without greatly reducing proton conductivity.

(Example 13)
In formula (1), X ¹ , X ² , Z, n, and R are the compounds h, polymer E, and NMP shown in Table 2, and are stirred in a flask to obtain a uniform solution. This solution is spread on a petri dish, and the solvent is volatilized and dried to obtain a film Y of the composition. At this time, the compound h and the polymer E are combined with [the amount of the oxocarbonic acid and / or its derivative (mmol)] / [weight of the polyelectrolyte (g) + the oxocarbonic acid and / or its derivative. When the weight (g)] is selected to be in the range of 0.05 to 8 mmol / g, a membrane having extremely higher flexibility than that of a single polymer electrolyte is preferably obtained without greatly reducing proton conductivity.

(Example 14)
In formula (1), X ¹ , X ² , Z, n, and R are the compounds i, polymer I, and DMSO shown in Table 2 and placed in a flask and stirred to obtain a homogeneous solution. This solution is spread on a petri dish, and the solvent is volatilized and dried to obtain a film Z of the composition. At this time, the compound i and the polymer I are combined with [the amount of the oxocarbonic acid and / or its derivative (mmol)] / [weight of the polyelectrolyte (g) + the oxocarbonic acid and / or its derivative. When the weight (g)] is selected to be in the range of 0.05 to 8 mmol / g, a membrane having extremely higher flexibility than that of a single polymer electrolyte is preferably obtained without greatly reducing proton conductivity.

      Tensile test and proton conductivity measurement results

The composition containing the polymer electrolyte of the present invention and oxocarbonic acid and / or a derivative thereof is a material for a proton conducting membrane of a polymer electrolyte fuel cell using a gaseous fuel such as hydrogen gas or a liquid fuel such as methanol or dimethyl ether. That is, it is useful as a polymer electrolyte. In particular, the composition of the present invention not only has proton conductivity comparable to that of a single polymer electrolyte, but is also a flexible film that is effective in relieving stress as compared with a single polymer electrolyte. Also, it is advantageous in practical aspects such as durability.

Claims (16)

  A composition comprising oxocarbonic acid and / or a derivative thereof and a polymer electrolyte. The composition according to claim 1, wherein the oxocarbonic acid or a derivative thereof is represented by the following general formula (1).

Wherein X ¹ and X ² each independently represent —O—, —S— or —NR′—, Z represents —CO—, —C (S) —, —C (NR ″) —, Represents an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 10 carbon atoms, n represents the number of repetitions, and 0 to 10 The n Zs may be the same or different from each other.R is —OH, —SH, —NHR ′ ″, a carbon which may have a substituent. An alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms which may have a substituent, or an aralkyl group having 7 to 16 carbon atoms which may have a substituent. '', R '''each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an optionally substituted carbon group having 6 carbon atoms. .B representing the 10 aryl group represents a hydrogen atom or a monovalent metal atom.)   The composition according to claim 2, wherein Z is -CO-, -C (S)-, or -C (NH)-. X ₁ and X ₂ are -O-, Z is -CO-, n is claim 2 or 3 composition, wherein the 0-2.   The polymer electrolyte is (A) a polymer electrolyte in which the main chain is an aliphatic hydrocarbon and an ion exchange group is introduced; (B) a part or all of the hydrogen atoms in the main chain are fluorine. A polymer composed of an aliphatic hydrocarbon substituted with an ion exchange group introduced into the polymer electrolyte; (C) a polymer having a main chain having an aromatic ring and an ion exchange group introduced therein A polyelectrolyte in the form; (D) a polymer composed of an inorganic substance substantially free of carbon atoms in the main chain, and having a form in which an ion exchange group is introduced; (E) in the main chain or side chain A polymer electrolyte comprising a nitrogen atom and an acidic compound introduced by ionic bonding; (F) at least selected from the group consisting of a polymer electrolyte comprising a copolymer and / or a mixture of (A) to (E) Any one of Claims 1-4 characterized by being 1 type The composition according to. 6. The amount of the ion exchange group in the polymer electrolyte (mmol) / [weight of the polymer electrolyte (g)] is 0.05 to 5 mmol / g. The composition as described. The composition according to any one of claims 1 to 6, wherein the polymer electrolyte is a polymer having an aromatic ring in the main chain, and is a polymer electrolyte having an ion exchange group introduced therein.   7. The polymer electrolyte according to claim 1, wherein the polymer electrolyte is a polymer made of an inorganic substance substantially free of carbon atoms in the main chain, and is a polymer electrolyte in a form in which an ion exchange group is introduced. The composition as described. The composition according to any one of claims 1 to 8, wherein the polymer electrolyte comprises a segment having substantially an ion exchange group and a segment having substantially no ion exchange group.   The composition according to claim 1, wherein the ion exchange group is a cation exchange group.   The composition according to claim 1, wherein the cation exchange group is a sulfonic acid group and / or a phosphonic acid group.   [Amount of substance of oxocarbonic acid and / or derivative thereof (mmol)] / [weight of polyelectrolyte (g) + weight of oxocarbonic acid and / or derivative thereof (g)] is 0.05 to 8 mmol / g The composition according to claim 1, wherein the composition is present.   A polymer electrolyte membrane using the composition according to claim 1.   A polymer electrolyte membrane-electrode assembly comprising the polymer electrolyte membrane according to claim 13.   A battery using at least one of the polymer electrolyte membrane according to claim 13 or the polymer electrolyte membrane-electrode assembly according to claim 14. A fuel cell using at least one of the polymer electrolyte membrane according to claim 13 or the polymer electrolyte membrane-electrode assembly according to claim 14.