JP4048063B2 - Proton-conducting polymer solid electrolyte, method for producing the electrolyte, electrolyte membrane made of the electrolyte, method for producing the electrolyte membrane, electrochemical element using the electrolyte and / or electrolyte membrane, and method for producing the electrochemical element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly proton conductive polymeric solid electrolyte having superior strength, heat resistance, acid resistance, and oxidation and reduction resistance stability, its producing method, an electrolytic membrane consisting thereof, its producing method, an electrochemical element having durability, reliability and current property using the electrolyte and/or the electrolytic membrane, and its producing method. <P>SOLUTION: The highly proton conductive polymeric solid electrolyte comprising a polymer containing quinoxaline skeletons and an acid compound, its producing method, the electrolytic membrane consisting thereof, its producing method, the electrochemical element using the electrolyte and/or the electrolytic membrane, and its producing method. <P>COPYRIGHT: (C)2003,JPO

Description

【００１４】
（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基及び／又は少なくとも二つは重合体の主鎖を形成する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００１５】
また、本発明（ＩＩ）は、本発明（Ｉ）のプロトン伝導性高分子固体電解質の製造方法である。
【００１６】
また、本発明（ＩＩＩ）は、本発明（Ｉ）のプロトン伝導性高分子固体電解質を含むことを特徴とするプロトン伝導性高分子固体電解質膜である。
【００１７】
また、本発明（ＩＶ）は、本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜の製造方法である。
【００１８】
さらにまた、本発明（Ｖ）は、本発明（Ｉ）のプロトン伝導性高分子固体電解質及び／又は本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜を用いることを特徴とする電気化学素子である。
【００１９】
さらに、本発明（ＶＩ）は、本発明（Ｖ）の電気化学素子の製造方法である。
【００２０】
さらに本発明は、例えば以下の事項からなる。
〔１〕 Ａ）一般式（１）で表されるキノキサリン構造を含む重合体
及び
Ｂ）酸性化合物
とを含有することを特徴とするプロトン伝導性高分子固体電解質。
【００２１】
一般式（１）
【化３３】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基及び／又は少なくとも二つは重合体の主鎖を形成する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００２２】
〔２〕 Ａ）一般式（１）で表されるキノキサリン構造を側鎖に含む重合体
及び
Ｂ）酸性化合物
とを含有することを特徴とするプロトン伝導性高分子固体電解質。
【００２３】
一般式（１）
【化３４】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００２４】
〔３〕 Ａ）一般式（２）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
及び
Ｂ）酸性化合物
とを含有することを特徴とするプロトン伝導性高分子固体電解質。
【００２５】
一般式（２）
【化３５】

（式中、Ｒ⁷〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００２６】
〔４〕 Ａ）一般式（１）で表されるキノキサリン構造を側鎖に含み、且つ一般式（２）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
及び
Ｂ）酸性化合物
とを含有することを特徴とするプロトン伝導性高分子固体電解質。
【００２７】
一般式（１）
【化３６】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００２８】
一般式（２）
【化３７】

（式中、Ｒ⁷〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００２９】
〔５〕 Ａ）一般式（２）で表されるキノキサリン構造が、一般式（３）で表されるキノキサリン構造であることを特徴とする〔３〕又は〔４〕のいずれかに記載のプロトン伝導性高分子固体電解質。
【００３０】
一般式（３）
【化３８】

（式中、Ｒ¹¹〜Ｒ¹⁴はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００３１】
〔６〕 Ａ）一般式（２）で表されるキノキサリン構造が、一般式（４）で表されるキノキサリン構造であることを特徴とする〔３〕〜〔５〕のいずれかに記載のプロトン伝導性高分子固体電解質。
【００３２】
一般式（４）
【化３９】

（式中、Ｒ¹⁵〜Ｒ³⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表し、Ｘはそれぞれ独立に置換基を有しても良いアリール基を表し、Ｙはそれぞれ独立にヘテロ原子、ヘテロ原子を有しても良い炭素数が４以上２０以下の置換基を有しても良いアリール基を表し、ｎは０〜５の整数を表す。）
【００３３】
〔７〕 Ｂ）酸性化合物が、硫酸、硝酸、酢酸、フッ化酢酸、プロピオン酸、フッ化プロピオン酸、酪酸及びフッ化酪酸からなる群から選ばれる少なくとも一種以上であることを特徴とする〔１〕〜〔６〕のいずれかに記載のプロトン伝導性高分子固体電解質。
【００３４】
〔８〕 Ｂ）酸性化合物が、酸型モノマーであることを特徴とする〔１〕〜〔６〕のいずれかに記載のプロトン伝導性高分子固体電解質。
【００３５】
〔９〕 酸型モノマーが、アクリル酸、フッ化アクリル酸、メタクリル酸、フッ化メタクリル酸、スチレンスルホン酸、フッ化スチレンスルホン酸、ビニルスルホン酸及びビニルリン酸からなる群から選ばれる少なくとも一種以上であることを特徴とする〔８〕に記載のプロトン伝導性高分子固体電解質。
【００３６】
〔１０〕 Ｂ）酸性化合物が、酸型高分子であることを特徴とする〔１〕〜〔６〕のいずれかに記載のプロトン伝導性高分子固体電解質。
【００３７】
〔１１〕 酸型高分子が、カルボン酸系高分子、スルホン酸系高分子及びリン酸系高分子からなる群から選ばれる少なくとも一種以上であることを特徴とする〔１０〕に記載のプロトン伝導性高分子固体電解質。
【００３８】
〔１２〕 以下の工程を含むことを特徴とする〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質の製造方法。
工程
Ａ）一般式（１）で表されるキノキサリン構造を含む重合体
及び
Ｂ）酸性化合物
を混合して、プロトン伝導性高分子固体電解質を得る工程
【００３９】
一般式（１）
【化４０】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基及び／又は少なくとも二つは重合体の主鎖を形成する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００４０】
〔１３〕 以下の第一工程〜第二工程を含むことを特徴とする〔１〕〜〔６〕、〔８〕又は〔９〕のいずれかに記載のプロトン伝導性高分子固体電解質の製造方法。
第一工程
Ａ）一般式（１）で表されるキノキサリン構造を含む重合体
及び
Ｂ）アクリル酸、フッ化アクリル酸、メタクリル酸、フッ化メタクリル酸、スチレンスルホン酸、フッ化スチレンスルホン酸、ビニルスルホン酸及びビニルリン酸からなる群から選ばれる少なくとも一種以上の重合性官能基を有する酸性化合物
を混合して、プロトン伝導性高分子固体電解質製造用組成物を得る工程
【００４１】
第二工程
第一工程で得たプロトン伝導性高分子固体電解質製造用組成物に含まれる酸性化合物を重合して、プロトン伝導性高分子固体電解質を得る工程
【００４２】
一般式（１）
【化４１】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基及び／又は少なくとも二つは重合体の主鎖を形成する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００４３】
〔１４〕 以下の第一工程〜第二工程を含むことを特徴とする〔１〕〜〔６〕、〔８〕又は〔９〕のいずれかに記載のプロトン伝導性高分子固体電解質の製造方法。
第一工程
Ａ）一般式（１）で表されるキノキサリン構造を側鎖に含む重合体
及び
Ｂ）アクリル酸、フッ化アクリル酸、メタクリル酸、フッ化メタクリル酸、スチレンスルホン酸、フッ化スチレンスルホン酸、ビニルスルホン酸及びビニルリン酸からなる群から選ばれる少なくとも一種以上の重合性官能基を有する酸性化合物
を混合して、プロトン伝導性高分子固体電解質製造用組成物を得る工程
【００４４】
第二工程
第一工程で得たプロトン伝導性高分子固体電解質製造用組成物に含まれる酸性化合物を重合して、プロトン伝導性高分子固体電解質を得る工程
一般式（１）
【化４２】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００４５】
〔１５〕 以下の第一工程〜第二工程を含むことを特徴とする〔１〕〜〔６〕、〔８〕又は〔９〕のいずれかに記載のプロトン伝導性高分子固体電解質の製造方法。
第一工程
Ａ）一般式（２）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
及び
Ｂ）アクリル酸、フッ化アクリル酸、メタクリル酸、フッ化メタクリル酸、スチレンスルホン酸、フッ化スチレンスルホン酸、ビニルスルホン酸及びビニルリン酸からなる群から選ばれる少なくとも一種以上の重合性官能基を有する酸性化合物
を混合して、プロトン伝導性高分子固体電解質製造用組成物を得る工程
【００４６】
第二工程
第一工程で得たプロトン伝導性高分子固体電解質製造用組成物に含まれる酸性化合物を重合して、プロトン伝導性高分子固体電解質を得る工程
【００４７】
一般式（２）
【化４３】

（式中、Ｒ⁷〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００４８】
〔１６〕 以下の第一工程〜第二工程を含むことを特徴とする〔１〕〜〔６〕、〔８〕又は〔９〕のいずれかに記載のプロトン伝導性高分子固体電解質の製造方法。
第一工程
Ａ）一般式（１）で表されるキノキサリン構造を側鎖に含み、且つ一般式（２）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
及び
Ｂ）アクリル酸、フッ化アクリル酸、メタクリル酸、フッ化メタクリル酸、スチレンスルホン酸、フッ化スチレンスルホン酸、ビニルスルホン酸及びビニルリン酸からなる群から選ばれる少なくとも一種以上の重合性官能基を有する酸性化合物
を混合して、プロトン伝導性高分子固体電解質製造用組成物を得る工程
【００４９】
第二工程
第一工程で得たプロトン伝導性高分子固体電解質製造用組成物に含まれる酸性化合物を重合して、プロトン伝導性高分子固体電解質を得る工程
一般式（１）
【化４４】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００５０】
一般式（２）
【化４５】

（式中、Ｒ⁷〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００５１】
〔１７〕 以下の第一工程〜第二工程を含むことを特徴とする〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質の製造方法。
第一工程
Ａ）一般式（１）で表されるキノキサリン構造を含む重合性化合物
及び
Ｂ）酸性化合物
を混合して、プロトン伝導性高分子固体電解質製造用組成物を得る工程
【００５２】
第二工程
第一工程で得たプロトン伝導性高分子固体電解質製造用組成物に含まれる重合性化合物を重合して、プロトン伝導性高分子固体電解質を得る工程
【００５３】
一般式（１）
【化４６】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基及び／又は少なくとも二つは重合体の主鎖を形成する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００５４】
〔１８〕 以下の第一工程〜第二工程を含むことを特徴とする〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質の製造方法。
第一工程
Ａ）一般式（１）で表されるキノキサリン構造を含む重合性化合物
及び
Ｂ）酸型高分子
を混合して、プロトン伝導性高分子固体電解質製造用組成物を得る工程
【００５５】
第二工程
第一工程で得たプロトン伝導性高分子固体電解質製造用組成物に含まれる重合性化合物を重合して、プロトン伝導性高分子固体電解質を得る工程
一般式（１）
【化４７】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基及び／又は少なくとも二つは重合体の主鎖を形成する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００５６】
〔１９〕 〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質を含むことを特徴とするプロトン伝導性高分子固体電解質膜。
【００５７】
〔２０〕 膜の厚みが５μｍ〜２００μｍの範囲であることを特徴とする〔１９〕に記載のプロトン伝導性高分子固体電解質膜。
【００５８】
〔２１〕 非電子伝導性補強剤が添加されていることを特徴とする〔１９〕又は〔２０〕のいずれかに記載のプロトン伝導性高分子固体電解質膜。
【００５９】
〔２２〕 非電子伝導性補強剤が酸化物粒子であることを特徴とする〔２１〕に記載のプロトン伝導性高分子固体電解質膜。
【００６０】
〔２３〕 酸化物粒子がＡｌ、Ｓｉ及びＴｉから選ばれる少なくとも一種以上の元素の酸化物であることを特徴とする〔２２〕に記載のプロトン伝導性高分子固体電解質膜。
【００６１】
〔２４〕 酸化物粒子の粒子径が０．００１μｍ〜１０μｍの範囲であることを特徴とする〔２２〕又は〔２３〕のいずれかに記載のプロトン伝導性高分子固体電解質膜。
【００６２】
〔２５〕 以下の第一工程〜第二工程を含むことを特徴とする〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜の製造方法。
第一工程
基材に以下の（ａ）〜（ｄ）で表される、いずれかの重合体の少なくとも一種以上の溶液を塗布した後に溶媒を留去して重合体膜を得る工程
（ａ） 一般式（１）で表されるキノキサリン構造を含む重合体
（ｂ） 一般式（２）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
（ｃ） 一般式（３）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
（ｄ） 一般式（４）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
【００６３】
一般式（１）
【化４８】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基及び／又は少なくとも二つは重合体の主鎖を形成する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００６４】
一般式（２）
【化４９】

（式中、Ｒ⁷〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００６５】
一般式（３）
【化５０】

（式中、Ｒ¹¹〜Ｒ¹⁴はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００６６】
一般式（４）
【化５１】

（式中、Ｒ¹⁵〜Ｒ³⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表し、Ｘはそれぞれ独立に置換基を有しても良いアリール基を表し、Ｙはそれぞれ独立にヘテロ原子単独、ヘテロ原子を有しても良い炭素数が４以上２０以下のアリール基を表し、ｎは０〜５の整数を表す。）
【００６７】
第二工程
第一工程で得た重合体膜に、Ｂ）酸性化合物を付加してプロトン伝導性高分子固体電解質膜を得る工程
【００６８】
〔２６〕 以下の第一工程〜第三工程を含むことを特徴とする〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜の製造方法。
第一工程
基材に以下の（ａ）〜（ｄ）で表される、いずれかの重合体の少なくとも一種以上の溶液を塗布した後に溶媒を留去して重合体膜を得る工程
（ａ） 一般式（１）で表されるキノキサリン構造を含む重合体
（ｂ） 一般式（２）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
（ｃ） 一般式（３）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
（ｄ） 一般式（４）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
【００６９】
一般式（１）
【化５２】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基及び／又は少なくとも二つは重合体の主鎖を形成する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００７０】
一般式（２）
【化５３】

（式中、Ｒ⁷〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００７１】
一般式（３）
【化５４】

（式中、Ｒ¹¹〜Ｒ¹⁴はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００７２】
一般式（４）
【化５５】

（式中、Ｒ¹⁵〜Ｒ³⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表し、Ｘはそれぞれ独立に置換基を有しても良いアリール基を表し、Ｙはそれぞれ独立にヘテロ原子単独、ヘテロ原子を有しても良い炭素数が４以上２０以下のアリール基を表し、ｎは０〜５の整数を表す。）
【００７３】
第二工程
第一工程で得た重合体膜に、酸型モノマーを付加してプロトン伝導性高分子固体電解質前駆体膜を得る工程
【００７４】
第三工程
第二工程で得たプロトン伝導性高分子固体電解質前駆体膜中に含まれる酸型モノマーを重合して、プロトン伝導性高分子固体電解質膜を得る工程
【００７５】
〔２７〕 酸型モノマーが、アクリル酸、フッ化アクリル酸、メタクリル酸、フッ化メタクリル酸、スチレンスルホン酸、フッ化スチレンスルホン酸、ビニルスルホン酸及びビニルリン酸からなる群から選ばれる少なくとも一種以上の重合性官能基を有する酸性化合物であることを特徴とする〔２６〕に記載のプロトン伝導性高分子固体電解質膜の製造方法。
【００７６】
〔２８〕 以下の第一工程〜第二工程を含むことを特徴とする〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜の製造方法。
第一工程
Ａ）以下の（ａ）〜（ｄ）で表される、いずれかの重合体の少なくとも一種以上の重合体
（ａ） 一般式（１）で表されるキノキサリン構造を含む重合体
（ｂ） 一般式（２）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
（ｃ） 一般式（３）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
（ｄ） 一般式（４）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
【００７７】
一般式（１）
【化５６】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基及び／又は少なくとも二つは重合体の主鎖を形成する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００７８】
一般式（２）
【化５７】

（式中、Ｒ⁷〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００７９】
一般式（３）
【化５８】

（式中、Ｒ¹¹〜Ｒ¹⁴はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００８０】
一般式（４）
【化５９】

（式中、Ｒ¹⁵〜Ｒ³⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表し、Ｘはそれぞれ独立に置換基を有しても良いアリール基を表し、Ｙはそれぞれ独立にヘテロ原子単独、ヘテロ原子を有しても良い炭素数が４以上２０以下のアリール基を表し、ｎは０〜５の整数を表す。）
及び
Ｂ）酸性化合物
を含むプロトン伝導性高分子固体電解質膜製造用組成物を得る工程
【００８１】
第二工程
第一工程で得たプロトン伝導性高分子固体電解質膜製造用組成物を、加圧及び／または加熱成型してプロトン伝導性高分子固体電解質膜を得る工程
【００８２】
〔２９〕 以下の第一工程〜第二工程を含むことを特徴とする〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜の製造方法。
第一工程
Ａ）以下の（ａ）〜（ｄ）で表される、いずれかの重合体の少なくとも一種以上の重合体
（ａ） 一般式（１）で表されるキノキサリン構造を含む重合体
（ｂ） 一般式（２）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
（ｃ） 一般式（３）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
（ｄ） 一般式（４）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体
【００８３】
一般式（１）
【化６０】

（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基及び／又は少なくとも二つは重合体の主鎖を形成する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００８４】
一般式（２）
【化６１】

（式中、Ｒ⁷〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００８５】
一般式（３）
【化６２】

（式中、Ｒ¹¹〜Ｒ¹⁴はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【００８６】
一般式（４）
【化６３】

（式中、Ｒ¹⁵〜Ｒ³⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表し、Ｘはそれぞれ独立に置換基を有しても良いアリール基を表し、Ｙはそれぞれ独立にヘテロ原子単独、ヘテロ原子を有しても良い炭素数が４以上２０以下のアリール基を表し、ｎは０〜５の整数を表す。）
及び
Ｂ）酸型モノマー
を含むプロトン伝導性高分子固体電解質膜製造用組成物を得る工程
【００８７】
第二工程
第一工程で得たプロトン伝導性高分子固体電解質膜製造用組成物中の酸型モノマーを重合しながら加圧加熱成型して、プロトン伝導性高分子固体電解質膜を得る工程
【００８８】
〔３０〕 酸型モノマーが、アクリル酸、フッ化アクリル酸、メタクリル酸、フッ化メタクリル酸、スチレンスルホン酸、フッ化スチレンスルホン酸、ビニルスルホン酸及びビニルリン酸からなる群から選ばれる少なくとも一種以上の重合性官能基を有する酸性化合物であることを特徴とする〔２９〕に記載のプロトン伝導性高分子固体電解質膜の製造方法。
【００８９】
〔３１〕 〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質及び／又は〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜を用いることを特徴とする電気化学素子。
【００９０】
〔３２〕 〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質及び／又は〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜を用いることを特徴とする電池。
【００９１】
〔３３〕 〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質及び／又は〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜を用いることを特徴とする燃料電池。
【００９２】
〔３４〕 〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質及び／又は〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜を用いることを特徴とする電気二重層コンデンサ。
【００９３】
〔３５〕 〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質及び／又は〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜を用いることを特徴とするエレクトロクロミック素子。
【００９４】
〔３６〕 正極と負極の間に〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質及び／又は〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜を設置することを特徴とする電池の製造方法。
【００９５】
〔３７〕 燃料極と空気極の間に〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質及び／又は〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜を設置することを特徴とする燃料電池の製造方法。
【００９６】
〔３８〕 ２つの分極性電極の間に〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質及び／又は〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜を設置することを特徴とする電気二重層コンデンサの製造方法。
【００９７】
〔３９〕 変色電極と対極の間に〔１〕〜〔１１〕のいずれかに記載のプロトン伝導性高分子固体電解質及び／又は〔１９〕〜〔２４〕のいずれかに記載のプロトン伝導性高分子固体電解質膜を設置することを特徴とするエレクトロクロミック素子の製造方法。
【００９８】
【発明の実施の形態】
以下、本発明についてより詳細に説明する。
【００９９】
本発明（Ｉ）は、Ａ）一般式（１）で表されるキノキサリン構造を含む重合体、及びＢ）酸性化合物とを含有することを特徴とするプロトン伝導性高分子固体電解質である。
【０１００】
一般式（１）
【化６４】

【０１０１】
（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基及び／又は少なくとも二つは重合体の主鎖を形成する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【０１０２】
まず、本発明（Ｉ）のプロトン伝導性高分子固体電解質における「Ａ）一般式（１）で表されるキノキサリン構造を含む重合体」について説明する。
【０１０３】
本発明（Ｉ）の「キノキサリン構造を含む重合体」とは、重合体の主鎖であっても側鎖であっても少なくとも一部にキノキサリン構造を含むものであれば、いかなる構造の物でも使用することができる。例えば、重合体の主鎖を形成する構造に直接キノキサリン構造が含まれるのではなく、キノキサリン構造の一部が主鎖に結合した例えば構造式（１）で表される構造を有する物であっても良く、また、重合体の主鎖を形成する構造の一部としてキノキサリン構造を有する一般式（２）で表される構造を繰り返し単位として有する物でも良い。
【０１０４】
構造式（１）
【化６５】

【０１０５】
一般式（２）
【化６６】

【０１０６】
（式中、Ｒ⁷〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【０１０７】
また、キノキサリン構造の一部が主鎖に結合した例えば構造式（１）で表される構造を有する部分と、一般式（２）で表される構造を有する部分との両方を含む重合体であっても良く、さらに、キノキサリン構造とは異なる繰り返し単位を含む物であっても良い。さらにはこれらの混合物であっても良い。
【０１０８】
本発明（Ｉ）の「キノキサリン構造を含む重合体」での一般式（１）における「式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基であり」とは、例えば構造式（１）で表されるような構造を含むことを意味する。
【０１０９】
構造式（１）
【化６７】

【０１１０】
ここで主鎖とキノキサリン構造は、構造式（１）に示したように直接結合する物だけでなく、間に他の官能基を有していても良い。例えば、構造式（２）に示すようなキノキサリン構造を有するアルコールのアクリル酸エステルを原料として用いた場合の重合体の場合は、主鎖とキノキサリン構造との間にエステル構造を有する構造式（３）に示す繰り返し単位を有する重合体となるが、いっこうに差し支えない。
【０１１１】
構造式（２）
【化６８】

【０１１２】
構造式（３）
【化６９】

【０１１３】
一般式（１）における「式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基であり」とは、ここで一例としてあげたエステル結合はもちろんのこと、どの様な形態でも主鎖とキノキサリン構造が結合していれば良いということはいうまでもない。
【０１１４】
また、本発明（Ｉ）における、「一般式（２）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体」とは、重合体の主鎖の少なくとも一部にキノキサリン構造を有する物であればいかなる物であっても良い。
【０１１５】
ここでいう「キノキサリン構造を繰り返し単位の一部として含む重合体」とは、キノキサリン構造のみからなる重合体であっても、キノキサリン構造に加えて他の一種以上の異なる構造を繰り返し単位として含む物であっても良い。この場合、キノキサリン構造と他の構造とが交互にあってもよく、またキノキサリン構造のみを繰り返した部分と他の構造が繰り返す部分が交互に存在する構造であっても良い。
【０１１６】
さらにまた、キノキサリン構造が直接に繰り返す構造であってもなくても良く、例えばキノキサリン構造に他の構造が結合した構造を繰り返し単位の基本構造とするような、一般式（４）で表されるような物も含む。
【０１１７】
一般式（４）
【化７０】

【０１１８】
（式中、Ｒ¹⁵〜Ｒ³⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表し、Ｘはそれぞれ独立に置換基を有しても良いアリール基を表し、Ｙはそれぞれ独立にヘテロ原子単独、ヘテロ原子を有しても良い炭素数が４以上２０以下のアリール基を表し、ｎは０〜５の整数を表す。）
【０１１９】
また、「一般式（１）で表されるキノキサリン構造を側鎖に含み、且つ一般式（２）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体」とは、その重合体の一部分がキノキサリン構造の一部が主鎖に結合した例えば構造式（１）で表される構造を有し、且つ他の部分では重合体の主鎖の一部にキノキサリン構造を有する物であればいかなる物であっても良い。
【０１２０】
この場合、キノキサリン構造を側鎖に含む部分と、キノキサリン構造を主鎖の構造として含む部分とは、それぞれ交互に存在しても、また、キノキサリン構造を側鎖に含む部分を繰り返した後に、キノキサリン構造を主鎖の構造として含む部分を繰り返した物であっても良い。さらに、キノキサリン構造とは異なる繰り返し単位を有する物であっても良く、その場合は各構造がそれぞれ任意の順に結合していてもかまわない。
【０１２１】
本発明（Ｉ）の一般式（１）〜一般式（４）でのＲ¹〜Ｒ³⁰は、それぞれ独立に水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。
【０１２２】
ここでいう「それぞれ独立に」とは、Ｒ¹〜Ｒ³⁰のいずれもが独立であると言うことのみならず、重合体のそれぞれのキノキサリン構造においても独立であることを示している。すなわち、例えばキノキサリン構造の任意のＲ^α（αは１〜３０の整数）がメチル基である場合、他のキノキサリン構造の相似の位置であるＲ^αではメチル基でも良いしメチル基以外の他の官能基であっても良いことを示している。従って、一つの重合体にｎ個のキノキサリン構造が存在する場合、任意のＲ^αはｎ個のキノキサリン構造において各々独立の官能基であることを示している。
【０１２３】
一般式（１）〜一般式（４）におけるＲ¹〜Ｒ³⁰として具体的には例えば水素原子、メチル基、トリフルオロメチル基、エチル基等のアルキル基、エテニル基、２−プロペニル基、１，３−ブタジエニル基、４−メトキシ−２−ブテニル基等のアルケニル基、エチニル基、２−プロピニル基等のアルキニル基、フェニル基、チエニル基、ピロリル基、４−メトキシフェニル基、３−トリフルオロメチルフェニル基、ナフチル基、３−メチルチエニル基等のアリール基、フッ素、塩素等のハロゲン原子、カルボン酸基、カルボン酸エステル基、ニトロ基、ニトリル基、スルホン酸基、スルホン酸エステル基等を挙げることができる。
【０１２４】
好ましくは水素原子、メチル基、トリフルオロメチル基、フェニル基、３−トリフリオロメチルフェニル基、ナフチル基、フッ素、カルボン酸基、カルボン酸エステル基、ニトロ基、ニトリル基、スルホン酸基、スルホン酸エステル基であり、より好ましくは水素原子、メチル基、トリフルオロメチル基、フェニル基、ナフチル基、フッ素、ニトロ基、ニトリル基、スルホン酸基、スルホン酸エステル基である。
【０１２５】
Ｒ¹〜Ｒ³⁰の組み合わせとしては、水素原子とメチル基、フェニル基等の電子供与性基の組み合わせ、または水素原子とフッ素、トリフルオロメチル基、ニトロ基、ニトリル基等の電子吸引性基の組み合わせが好ましい。また、これら好ましい要素単独、たとえばすべて水素原子、すべてメチル基、すべてフッ素等の場合も好ましい。
【０１２６】
本発明（Ｉ）の「一般式（１）で表されるキノキサリン構造を含む重合体」として、好ましくは一般式（２）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体である。
【０１２７】
一般式（２）
【化７１】

【０１２８】
（式中、Ｒ⁷〜Ｒ¹⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【０１２９】
より好ましくは一般式（３）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体、又は一般式（４）で表されるキノキサリン構造を繰り返し単位の一部として含む重合体である。
【０１３０】
一般式（３）
【化７２】

【０１３１】
（式中、Ｒ¹¹〜Ｒ¹⁴はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【０１３２】
一般式（４）
【化７３】

【０１３３】
（式中、Ｒ¹⁵〜Ｒ³⁰はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表し、Ｘはそれぞれ独立に置換基を有しても良いアリール基を表し、Ｙはそれぞれ独立にヘテロ原子単独、ヘテロ原子を有しても良い炭素数が４以上２０以下のアリール基を表し、ｎは０〜５の整数を表す。）
【０１３４】
一般式（３）におけるＲ¹¹〜Ｒ¹⁴として好ましくは水素原子、メチル基、トリフルオロメチル基、フェニル基、３−トリフリオロメチルフェニル基、ナフチル基、フッ素、カルボン酸基、カルボン酸エステル基、ニトロ基、ニトリル基、スルホン酸基、スルホン酸エステル基であり、より好ましくは水素原子、メチル基、トリフルオロメチル基、フェニル基、ナフチル基、フッ素、ニトロ基、ニトリル基、スルホン酸基、スルホン酸エステル基である。
【０１３５】
Ｒ¹¹〜Ｒ¹⁴の組み合わせとしては、水素原子とメチル基、フェニル基等の電子供与性基の組み合わせ、または水素原子とフッ素、トリフルオロメチル基、ニトロ基、ニトリル基等の電子吸引性基の組み合わせが好ましい。また、これら好ましい要素単独、たとえばすべて水素原子、すべてメチル基、すべてフッ素等の場合も好ましい。
【０１３６】
また、一般式（４）におけるＲ¹⁵〜Ｒ³⁰として好ましくは水素原子、メチル基、トリフルオロメチル基、フェニル基、３−トリフリオロメチルフェニル基、ナフチル基、フッ素、カルボン酸基、カルボン酸エステル基、ニトロ基、スルホン酸基、スルホン酸エステル基であり、より好ましくは水素原子、メチル基、トリフルオロメチル基、フェニル基、ナフチル基、フッ素、ニトロ基、スルホン酸基、スルホン酸エステル基である。
【０１３７】
Ｒ¹⁵〜Ｒ³⁰の組み合わせとしては、水素原子とメチル基、フェニル基等の電子供与性基の組み合わせ、または水素原子とフッ素、トリフルオロメチル基、ニトロ基、ニトリル基等の電子吸引性基の組み合わせが好ましい。また、これら好ましい要素単独、たとえばすべて水素原子、すべてメチル基、すべてフッ素等の場合も好ましい。
【０１３８】
また、一般式（４）におけるＸはそれぞれ独立に置換基を有しても良いアリーレン基を表し、Ｙはそれぞれ独立にヘテロ原子単独、ヘテロ原子を有しても良い炭素数が６以上２０以下のアリーレン基を表し、ｎはそれぞれ独立に０〜５の整数を表す。
【０１３９】
ここで言うＸ、Ｙ及びｎの「それぞれ独立に」とは、各繰り返し単位においてすべてが同じでも良く、また、すべてが異なっても良いと言うことを意味する。すなわち、例えば一般式（４）で示される繰り返し単位をｍ個有する重合体の場合、ｍ個のＸ、Ｙ或いはｎすべて同じでも良いし、すべて異なっても良いし、一部が同じで一部が違っていてもかまわないことを意味する。
【０１４０】
一般式（４）におけるＸとしては、具体的には例えばフェニレン基、４−メチルフェニレン基、３−ニトロフェニレン基、３−トリフリオロメチルフェニレン基、ナフチレン基、５−メチルナフチレン基、４−ニトロナフチレン基等を挙げることができる。好ましくはフェニレン基、３−ニトロフェニレン基、３−トリフリオロメチルフェニレン基、ナフチレン基、４−ニトロナフチレン基であり、より好ましくはフェニレン基、３−トリフリオロメチルフェニレン基、ナフチレン基である。
【０１４１】
また、一般式（４）におけるＹとしては、具体的には酸素、イオウ、セレン、ＮＲ（ＲはＨまたは炭素数１０以下のアルキル基）、フェニレン基、３−ニトロフェニレン基、２，５−ジメトキシフェニレン基、ナフチレン基等を挙げることができる。好ましくは酸素、フェニレン基、３−ニトロフェニレン基、ナフチレン基であり、より好ましくは酸素、フェニレン基である。
【０１４２】
ＸとＹの組み合わせとしては、フェニレン基と酸素、ナフチレン基等の電子供与性基の組み合わせ、または３−トリフルオロメチルフェニレン基等の電子吸引性基の組み合わせが好ましい。また、フェニレン基やナフチレン基のようなＸ、Ｙのどちらでも使用可能な基はＸ、Ｙ両方が同じ場合も好ましい。
【０１４３】
また、ｎは０〜５の整数を表すが、好ましい範囲はＹにより異なる。
【０１４４】
本発明（Ｉ）の一般式（１）で表されるキノキサリン構造を含む重合体の具体例としては、ポリフェニルキノキサリン（以下、「ＰＰＱ」と略す。）、ポリ−２，２’−（ｐ，ｐ’−オキシジフェニレン)−６，６’−オキシジ（３−フェニルキノキサリン)（以下、「ＰＯＰＱ」と略す。）等を挙げることができるが、これに限定されるわけではない。詳しくは「Ｊ．Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ：ｐａｒｔ Ａ１、第５巻、１４５３頁、１９６７年」に記載がある。
【０１４５】
本発明（Ｉ）の一般式（１）で表されるキノキサリン構造を含む重合体のキノキサリン構造は、核磁気共鳴スペクトル（以下、「ＮＭＲ」と略す。）、赤外スペクトル（以下、「ＩＲ」と略す。）、元素分析、質量分析法（以下、「ＭＳ」と略す。）等の方法で分析、同定することが可能である。
【０１４６】
具体的には例えば、本発明（Ｉ）のプロトン伝導性高分子固体電解質より、中和、洗浄等の方法により一般式（１）で表されるキノキサリン構造を含む重合体を分離し、さらに熱重量分析−質量分析法（以下、「ＴＧ−ＭＳ」と略す。）で分解物の構造からキノキサリン骨格を同定、元素分析で元素の組成比を定量、ＮＭＲ、ＩＲで結合状態を同定等の方法でキノキサリン構造を同定することが可能である。詳しくは「Ｊ．Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ：ｐａｒｔ Ａ１、第５巻、１４５３頁、１９６７年」に記載がある。
【０１４７】
本発明（Ｉ）の一般式（１）で表されるキノキサリン構造を含む重合体の分子量は、例えばゲルパーミエーションクロマトグラフィー（以下、「ＧＰＣ」と略す。）等の液体クロマトグラフィーにより測定することができる。具体的には例えばヘキサイソプロパノール等の溶媒に溶解し、ＧＰＣにより測定することが一般的である。例えば「Ｊ．Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ：ｐａｒｔ Ｂ：Ｐｏｌｙｍｅｒ Ｐｈｙｓｉｃｓ、第３８巻、１３４８頁、２０００年」、又は「Ｃｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ、１０４９頁、１９９９年」にその記載がある。
【０１４８】
本発明（Ｉ）の一般式（１）で表されるキノキサリン構造を含む重合体の分子量としては、特に制限はない。一般的にはプロトンの挿入放出への耐久性、フィルム化したときの強度の点から高い方が好ましい。具体的にはＧＰＣによる絶対分子量測定での重量平均分子量で５０００以上が好ましく、１００００以上がより好ましい。
【０１４９】
また、本発明（Ｉ）の一般式（１）で表されるキノキサリン構造を含む重合体は、低分子量体の存在量が少ない方が好ましい。具体的には前述の光散乱法による絶対分子量測定での重量平均分子量における１０００未満の分子量を有する低分子量体が重合体全体に対して５質量％以下であることが好ましく、より好ましくは１質量％以下である。
【０１５０】
この際の低分子量体の存在量の測定は、具体的には例えば上記ＧＰＣ等の方法を用いて測定することができる。
【０１５１】
次に、本発明（Ｉ）のプロトン伝導性高分子固体電解質における「Ｂ）酸性化合物」について説明する。
【０１５２】
本発明（Ｉ）のプロトン伝導性高分子固体電解質における「Ｂ）酸性化合物」としては、乖離してプロトンを放出するものであればいかなるものでも使用することができる。いかなる無機酸及び有機酸であっても良く、またプロトンを放出することが可能な高分子であっても良い。これらは、各々単独で用いても良いし、二種類以上を併用してもかまわない。
【０１５３】
無機酸の具体例としては、例えば硫酸及び硝酸等を挙げることができる。また、有機酸の具体例としては、酢酸、フッ化酢酸、プロピオン酸、フッ化プロピオン酸、酪酸、フッ化酪酸、アクリル酸、フッ化アクリル酸、メタクリル酸、フッ化メタクリル酸、スチレンスルホン酸、フッ化スチレンスルホン酸、ビニルスルホン酸、及びビニルリン酸等を挙げることができる。
【０１５４】
ここでいう「フッ化酢酸」等の「フッ化〜」の記載は、その有機酸の水素原子のすくなくとも一つ以上がフッ素に置換されているものを指す。具体的には、トリフルオロ酢酸、ヘプタフルオロプロピオン酸、ヘキサフルオロスチレンスルホン酸等が挙げられる。
【０１５５】
本発明（Ｉ）の「Ｂ）酸性化合物」として、好ましくはプロトンを放出することが可能な高分子である「酸型高分子」である。ここでいう「酸型高分子」とは高分子の側鎖、主鎖及び／または末端等にプロトン放出可能な基が結合したものを意味する。具体的にはポリスチレンスルホン酸、ポリリン酸、ポリアクリル酸及びこれらのフッ化物等を指す。
【０１５６】
本発明（Ｉ）の「Ｂ）酸性化合物」として用いることができるものの例としては、カルボン酸系高分子、スルホン酸系高分子及びリン酸系高分子等を挙げることができる。具体的には例えばポリアクリル酸、ポリメタクリル酸、ポリスチレンスルホン酸、ポリビニルスルホン酸、ポリリン酸、ポリビニルリン酸及びこれらのフッ化物等を挙げることができる。好ましくはポリスチレンスルホン酸、ポリビニルスルホン酸、ポリリン酸、ポリビニルリン酸及びこれらのフッ化物であり、より好ましくはポリスチレンスルホン酸、ポリビニルスルホン酸、ポリビニルリン酸及びこれらのフッ化物である。これらは一種のみを単独で用いても、二種以上を併用して用いてもかまわない。
【０１５７】
酸型高分子の分子量はＧＰＣ等の方法で測定することができる。具体的には酸型高分子を水溶液等の溶液状態にし、ＧＰＣで測定することで可能である。
【０１５８】
本発明（Ｉ）の「Ｂ）酸性化合物」として用いることができる酸型高分子の好ましい分子量としては、特に制限はないが、好ましくは前記のＧＰＣによる分子量測定での重量平均分子量が５００〜１００００００の範囲であり、より好ましくは１０００〜１００００００の範囲である。
【０１５９】
次に、本発明（Ｉ）のプロトン伝導性高分子固体電解質について説明する。
本発明（Ｉ）のプロトン伝導性高分子固体電解質は、Ａ）一般式（１）で表されるキノキサリン構造を含む重合体、及びＢ）酸性化合物とを含有することを特徴とする。
【０１６０】
一般式（１）
【化７４】

【０１６１】
（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【０１６２】
本発明（Ｉ）のプロトン伝導性高分子固体電解質における、Ａ）一般式（１）で表されるキノキサリン構造を含む重合体、及びＢ）酸性化合物の比率には特に制限はない。好ましくはプロトン伝導性及び熱的安性の点からＡ）一般式（１）で表されるキノキサリン構造を含む重合体の窒素の量に対して、Ｂ）酸性化合物のアニオンの量がモル比で、

の範囲であり、より好ましくは

の範囲である。
【０１６３】
本発明（Ｉ）のプロトン伝導性高分子固体電解質における、Ａ）一般式（１）で表されるキノキサリン構造を含む重合体、及びＢ）酸性化合物の比率は元素分析、熱分析等により測定することができる。具体的には例えば元素分析により窒素と酸成分の元素の比を測定する、ＴＧで酸性分の揮発重量を測定する等の方法を挙げることができる。
【０１６４】
本発明（Ｉ）のプロトン伝導性高分子固体電解質のプロトン伝導度としては特に制限はない。当該プロトン伝導性高分子固体電解質を使用して作成する電気化学素子に求められる性能により好ましい範囲は異なる。一般には２５℃で０．１ｍＳ／ｃｍ以上であり、且つ８０℃で１ｍＳ／ｃｍ以上であれば良い。好ましくは２５℃で１ｍＳ／ｃｍ以上であり、且つ８０℃で１０ｍＳ／ｃｍ以上である。プロトン伝導度の測定方法としては交流インピーダンス法を挙げることができる。具体的には膜状等に加工したプロトン伝導性高分子固体電解質サンプルを白金等の不活性電極ではさみ、これに交流を印加し、インピーダンスの周波数依存性で測定する等の方法を挙げることができる。詳しくは「電気化学測定法」（電気化学会編、１９８４年１１月１５日１版１刷発行）等に記載がある。
【０１６５】
次に、本発明（ＩＩ）について説明する。本発明（ＩＩ）は、本発明（Ｉ）のプロトン伝導性高分子固体電解質の製造方法である。
【０１６６】
本発明（Ｉ）の一般式（１）で表されるキノキサリン構造を有する重合体の製造方法は特に限定されないが、以下の製造方法Ａ、製造方法Ｂ及び製造方法Ｃの方法を具体例として挙げることができる。
【０１６７】
＜製造方法Ａ＞
本発明（Ｉ）の一般式（１）で表されるキノキサリン構造を有する重合体の製造方法のひとつめの例としては、一般式（１）で表されるキノキサリン骨格を有する化合物のＲ¹〜Ｒ⁶の少なくともいずれかひとつがビニル基等の重合性官能基である化合物をラジカル重合等で重合することにより得られる。
【０１６８】
この方法で一般式（１）で表されるキノキサリン骨格を有する化合物に重合性官能基を付与することが可能であれば、その官能基を重合すればよいので、材料設計が容易で、重合体も比較的容易に得ることができる。例えば、Ｐｈｏｔｏｃｈｅｍ．Ｐｈｏｔｏｂｉｏｌ．、第５４巻、１号、７頁、１９９１年には、スチリルキノキサリンの重合の記載がある。しかしながらこの方法は、特定の官能基しか付与が難しく、また得られた重合体の官能基部分の化学的安定性が問題となる場合がある。
【０１６９】
このような重合性官能基が付与されたキノキサリン骨格を有する化合物としては、例えば一般式（５）で表される。
【０１７０】
一般式（５）
【化７５】

【０１７１】
（式中、Ｒ³¹〜Ｒ³⁷は、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表し、Ｘはそれぞれ独立に置換基を有しても良いアリーレン基を表し、Ｙはそれぞれ独立にヘテロ原子単独、ヘテロ原子を有しても良い炭素数が４以上２０以下のアリーレン基を表し、ｎは０〜５の整数を表す。）
【０１７２】
これらの具体例としては、５−ビニルキノキサリン、２−スチリルキノキサリン、５−（メタ）アクリロイルキノキサリン及びこれらの置換基誘導体を挙げることができる。
【０１７３】
＜製造方法Ｂ＞
本発明（Ｉ）の一般式（１）で表されるキノキサリン構造を有する重合体の製造法のふたつめの例としては、一般式（１）で表されるキノキサリン骨格を有する化合物のＲ¹〜Ｒ⁶の少なくともいずれか２つがブロム基等のハロゲン原子である化合物をＣｕやＮｉ等の金属触媒で脱ハロゲン重合する方法も挙げられる。
【０１７４】
この方法で一般式（１）で表されるキノキサリン骨格を有する化合物にハロゲンを付与することが可能であれば、脱ハロゲン化重合すればよいので、材料設計が容易で、重合体も比較的容易に得ることができる。例えば、特開平９−３１７１号公報には、キノキサリン等の各種ジハライド誘導体をビス（１，５−シクロオクタジエン）ニッケル等のニッケル（０）価触媒で重合した例が記載されている。
【０１７５】
しかしながらこの方法は、キノキサリン骨格の特定の部分にハロゲンを導入する方法が難しく、脱ハロゲン化触媒も比較的高価で製造コスト的に問題となる場合がある。また、重合後の重合体中に、触媒の金属残やハロゲン残が不純物として残る可能性が高く、重合体の化学的安定性に影響する場合もある。
【０１７６】
このようなハロゲン置換キノキサリン化合物としては、２，６−ジブロモキノキサリン、２，５−ジブロモキノキサリン及びこれらの置換基誘導体が挙げられる。
【０１７７】
＜製造方法Ｃ＞
本発明（Ｉ）の一般式（１）で表されるキノキサリン構造を有する重合体の製造方法の三つめの例としては、テトラミン誘導体とビスベンジル及びまたはこの誘導体とを脱水重縮合する方法が挙げられる。例えば、Ｊ．Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ：ｐａｒｔ Ａ１、第５巻、１４５３頁、１９６７年に各種キノキサリン系重合物を脱水重縮合で重合することが記載されている。
【０１７８】
本発明（Ｉ）の一般式（１）で表されるキノキサリン骨格を有する重合体を製造する方法としては、この方法が重合工程的に簡易で、高収率で、高分子量のものが得られ好ましい。しかしながら、化合物の設計多様性が製造方法Ａ、製造方法Ｂよりやや劣るという欠点を有する。
【０１７９】
以下、本発明（Ｉ）の一般式（１）で表されるキノキサリン骨格を有する重合体を製造する最も好ましい製造方法と考えられる製造方法Ｃ、即ち各種テトラミンとビスベンジル及びまたはビスベンジル誘導体との脱水重縮合についてより詳細に説明する。
【０１８０】
＜テトラミン誘導体＞
製造方法Ｃで用いる化合物のひとつであるテトラミンは、一般式（６）で表される。
【０１８１】
一般式（６）
【化７６】

【０１８２】
（式中、Ｒ³⁸〜Ｒ⁴³は、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。Ｚはそれぞれ独立にヘテロ原子単独、ヘテロ原子を有しても良い炭素数が４以上２０以下のアリール基を表し、ｍは０〜５の整数を表す。）
【０１８３】
この具体例としては、一般式（７）で表される３，３−ジアミノベンジジン及びその誘導体
一般式（７）
【化７７】

【０１８４】
或いは、一般式（８）で表される３，３’，４，４’−テトラアミノジフェニルエーテル及びその誘導体
一般式（８）
【化７８】

等が挙げられる。
【０１８５】
＜ビスベンジル及び／またはビスベンジル誘導体＞
製造方法Ｃで用いるのもうひとつの化合物であるビスベンジル及び／またはビスベンジル誘導体は、一般式（９）で表される。
【０１８６】
一般式（９）
【化７９】

【０１８７】
（式中、Ｒ⁴⁴〜Ｒ⁵⁷は、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【０１８８】
この具体例としては一般式（１０）、又は一般式（１１）で表される１，４−ビスベンジル（パラ体）、１，３−ビスベンジル(メタ体) 及びこれらの置換体等を挙げることができる。
【０１８９】
一般式（１０）
【化８０】

【０１９０】
一般式（１１）
【化８１】

【０１９１】
＜脱水重縮合条件＞
製造方法Ｃでの脱水重縮合する条件について説明する。
反応温度には特に制限はない。好ましい反応温度は、使用するモノマーの種類や溶媒によって異なり一概に限定できないが、一般的には使用する溶媒の環流温度付近である。
【０１９２】
また、反応時間にも特に制限はない。好ましい反応時間は、使用するモノマーの種類や溶媒によって異なり一概に限定できないが、脱水重縮合であることから一般的には高分子化するには少なくとも１０時間程度は必要である。好ましい範囲としては、２５時間以上１００時間以内であり、３０時間以上７０時間以下が特に好ましい。
【０１９３】
使用する溶媒としては、使用するモノマーが溶解しやすく、また反応しないものなら特に限定されない。例えばＮ，Ｎ−ジメチルホルムアミド（以下、「ＤＭＦ」とも記す。）、Ｎ−メチルピロリドン等の含窒素極性溶媒、テトラヒドロフラン、１，２−ジメトキシエタン、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル等のエーテル類が挙げられる。たとえば溶媒がＮ，Ｎ−ジメチルホルムアミドの場合は１３０℃以上１５０℃以下で反応することが好ましい。
【０１９４】
重合時の溶媒中のモノマー濃度としては、ビスベンジル及びまたはビスベンジル誘導体とテトラミンの質量の総計が５質量％以上４０質量％以下が好ましく、８質量％以上３０質量％以下が特に好ましい。モノマー濃度が低すぎると重合が進みにくく分子量が伸びない。モノマー濃度が高すぎると重合溶液の粘度が上がり、混合しづらくなり、重合体の析出が早期に起こり分子量が伸びにくくなる恐れがある。
【０１９５】
次に、キノキサリン構造を含む重合体への酸性化合物の付加について説明する。ここでいう「付加」とは本発明のキノキサリン構造を含む重合体に各種反応で結合することを意味する。例えば塩基性の高いキノキサリン中の窒素原子に酸塩基反応で酸が結合することを「付加」すると表す。他にキノキサリン構造を含む重合体の側鎖にある窒素原子やリン原子に酸塩基反応で酸が結合することを「付加」すると表す。またキノキサリン構造を含む重合体中のフェニル基等の不飽和結合に酸が反応し、共有結合することも「付加」すると表す。
【０１９６】
本発明（Ｉ）のプロトン伝導性高分子固体電解質は、Ａ）一般式（１）で表されるキノキサリン構造を含む重合体、及びＢ）酸性化合物とを含有することを特徴とする。
【０１９７】
一般式（１）
【化８２】

【０１９８】
（式中、Ｒ¹〜Ｒ⁶の内、少なくとも一つは重合体の主鎖に結合する基であり、他はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ニトロ基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基、置換基を有してもよい炭素数１〜炭素数２０のアルキル基、置換基を有してもよい炭素数２〜炭素数２０のアルケニル基、置換基を有してもよい炭素数２〜炭素数２０のアルキニル基又は置換基を有してもよいアリール基を表す。）
【０１９９】
本発明（Ｉ）のプロトン伝導性高分子固体電解質における、Ａ）一般式（１）で表されるキノキサリン構造を含む重合体への、Ｂ）酸性化合物の付加方法に特に制限はない。例えばキノキサリン骨格の窒素と酸との酸塩基反応で窒素上に酸を付加させることができる。付加させる方法としては粉末状や膜状の重合体を酸溶液に浸漬する方法が挙げられる。但し、硫酸等の低分子酸化合物はこの方法でＰＰＱ膜中に含浸、付加しやすいが、ポリスチレンスルホン酸等の高分子は膜内部まで含浸しにくいという問題点を有する。また未置換のキノキサリン骨格を有する重合体は一般的に疎水性であり、酸溶液を水溶液、非水溶液等に変更し、濡れ性を制御する必要がある。
【０２００】
高分子酸を効率よく付加には、例えば以下の２通りの方法を挙げることができる。
（イ）高分子酸の存在する媒体中でキノキサリン骨格を有する重合体を合成する方法
（ロ）キノキサリン骨格を有する重合体を重合性官能基を有する酸性化合物の溶液に浸漬含浸した後に、該酸性化合物を重合する方法
【０２０１】
（イ）の方法としては、例えばポリスチレンスルホン酸の溶液中で一般式（６）で表される各種テトラミンと、一般式（９）で表されるビスベンジル及び／またはビスベンジル誘導体とを、前述した脱水重縮合する方法が例示できる。
【０２０２】
一般式（６）
【化８３】

【０２０３】
一般式（９）
【化８４】

【０２０４】
（ロ）の方法としては、重合性官能基を有する酸性化合物として、例えばスチレンスルホン酸モノマー水溶液中にキノキサリン骨格を有する重合体を浸漬含浸し、キノキサリンの窒素にスチレンスルホン酸を付加させた後、スチレンスルホン酸を重合させるという方法が例示できる。
【０２０５】
ここで例示したスチレンスルホン酸の重合は、一般的なラジカル重合の条件で行うことができる。即ち、光及び／または熱重合開始剤を添加した後、加熱や紫外光照射、電子線照射を行うことにより、重合させることができる。このような重合性官能基を有する酸性化合物としては、他にビニルスルホン酸、ビニルリン酸、アクリル酸及びこれらのフッ化物等の誘導体が挙げられる。
【０２０６】
次に、本発明（ＩＩＩ）について説明する。本発明（ＩＩＩ）は、本発明（Ｉ）のプロトン伝導性高分子固体電解質を含むことを特徴とするプロトン伝導性高分子固体電解質膜である。
【０２０７】
本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜は、本発明（Ｉ）のプロトン伝導性高分子固体電解質を含む膜状の物であればいかなる物でもかまわない。
【０２０８】
本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜の厚みには特に制限はないが、通常５μｍ以上２００μｍ以下が好ましく、１０μｍ以上８０μｍ以下が特に好ましい。膜の厚みの測定は、ダイヤルゲージを用いることで可能である。
【０２０９】
一般に、各種素子に本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜を用いる場合、膜の厚みにバラツキが少ないことも重要である。従って、一枚の膜での厚みの好ましい範囲としては、膜の面積にもよるが、通常平均厚みに対してプラスマイナス１０％の範囲が好ましく、プラスマイナス５％の範囲が特に好ましい。
【０２１０】
また、膜の強度には特に制限はないが、各種素子へ用いる場合の取扱性から、引張り強度として１００ｋｇ／ｃｍ²以上が好ましく、５００ｋｇ／ｃｍ²以上が特に好ましい。この場合の引張り強度とは、ＪＩＳ規格：ＪＫ７１２７により測定した値である。
【０２１１】
本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜には、その物性を損なわない範囲で、特に膜の強度を向上することを目的として補強剤を添加することが出来る。補強剤の添加により膜の強度が上がる、或いは膜の保存安定性が向上し、その取り扱い性が増すことでひいては各種素子の生産性を向上することが可能である。
【０２１２】
添加する補強剤としては、非電子伝導性で電気化学的に安定で、耐熱、耐酸／アルカリ性であることが好ましい。具体的には例えば、アルミナ等の酸化物粒子、ポリプロピレン等のポリオレフィン性繊維、テフロン（イー アイ デュポンドゥ ヌムール アンド カンパニー登録商標）等のフルオロハイドロカーボンファイバー等が挙げられる。
【０２１３】
中でも特に酸化物微粒子を添加すると、膜の強度のみならず、膜の安定性が向上し保液性等も増加することから好ましい。この酸化物微粒子としては、より大きな比表面積を有する物が好ましい。一般的には、ＢＥＴ比表面積で１０ｍ²／ｇ以上のものが好ましく、より好ましくはＢＥＴ比表面積５０ｍ²／ｇ以上である。
【０２１４】
酸化物微粒子（凝集して二次粒子を形成する場合は一次粒子）のサイズとしては、本発明の一般式(１)で表されるキノキサリン骨格を有する重合体と混合できれば特に限定はないが、最大粒径が１０μｍ以下のものが好ましい。さらに好ましくは最大径が０．００１μｍ〜１μｍの微粒子である。
【０２１５】
また、形状としては球形、卵形、立方体状、直方体状、円筒ないし棒状等の種々の形状のものを用いることができる。
【０２１６】
このような酸化物微粒子の具体例としては、α、β、γ−アルミナ等のアルミナ系微粒子、シリカ系微粒子、チタニア系微粒子、マグネシア系微粒子、及びこれらの複合酸化物微粒子等のイオン伝導性または非電導性酸化物微粒子が挙げられる。これらの中では、アルミナ系微粒子、シリカ系微粒子が安定性に優れ、好ましい。特にアルミナ系微粒子の表面はアニオンとの親和性が高く、特にプロトンの束縛を減少させ、プロトンの移動を促進する効果がある。アルミナ系微粒子の具体例としては、固相法、気相法等の種々の製法で得られる、α、β、γ型Ａｌ₂Ｏ₃微粒子やこれらと他の金属とのアルミナ系複合酸化物微粒子が挙げられる。この中で比表面積が大きく、表面活性の大きいアルミニウムオキサイドＣ（商品名；デグサ社製）、ＵＡ-５８０５（昭和電工（株）製）のγ型Ａｌ₂Ｏ₃微粒子等が適している。シリカ系微粒子の具体例としては、比表面積が大きく、表面活性の大きいアエロジル（商品名；デグサ社製）、コロイダルシリカ等が挙げられる。
【０２１７】
補強剤の好ましい添加量は、高分子固体電解質膜の単位質量あたり、０．１質量％〜５０質量％の範囲が好ましく、１質量％〜３０質量％の範囲が特に好ましい。補強剤の添加量が０．１％以下では十分な効果を発揮することが困難である。また５０質量％を越えると、膜のイオン伝導性を低下させる恐れがあり好ましくない。
【０２１８】
本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜に含まれる補強剤の量は熱重量分析での重量残や元素分析等の方法で測定することが出来る。
【０２１９】
次に、本発明（ＩＶ）について説明する。本発明（ＩＶ）は、本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜の製造方法である。
【０２２０】
本発明（ＩＶ）のプロトン伝導性高分子固体電解質膜の製造方法は、本発明（Ｉ）のプロトン伝導性高分子固体電解質を含む物質を膜状に形成できる方法であればいかなる方法でもかまわない。
【０２２１】
具体的には、例えば重合体を可溶な溶剤に溶解させたあとキャスティングにより成膜する従来公知の方法が挙げられる。例えば、高分子論文集、１９８７年、Ｖｏｌ．４４，Ｎｏ．４，３１７頁、特開平９−２４５８１８号公報等に記載がある。
【０２２２】
また、軟化点をもっている重合体の場合は、加熱ロールプレス、押し出し器等で加圧加熱成型するという一般的な汎用熱可塑性樹脂の成膜方法を用いることができる。例えば、特開平２−１４２０６３号公報に記載がある。
【０２２３】
さらに、一般式（１）で表されるキノキサリン構造を有する重合性化合物またはモノマー溶液を支持体にキャスト後やモノマー溶液を補強剤と混合後にキャストした後に重合するという方法も挙げられる。この方法は他の支持体、補強剤との複合フィルムを作成する場合に特に有用である。
【０２２４】
一般にキャステイング法で得られる膜は、膜の厚みが５μｍ〜１０μｍ程度の薄い膜の製造には好適であるが、この方法で得られた膜は一般的に強度的に弱い。また、厚みのバラツキも大きくなる傾向がある。従って、ロールプレス等の加熱加圧成型法を併用して強度、厚みを改善することも可能であり、好ましい。
【０２２５】
本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜には補強剤を添加することが可能であるが、添加する方法に特に制限はない。例えば、成膜前の高分子を加熱溶融しながら補強剤を添加した後、成膜する方法や、キャステイング成膜前の高分子溶液に補強剤を添加し、成膜する方法等が例示できる。また、補強剤を先に支持体の上で膜状に伸ばしておき、そこに上述した高分子溶融体や高分子溶液を塗布成膜する方法も挙げられる。
【０２２６】
次に本発明（Ｖ）及び本発明（ＶＩ）について説明する。本発明（Ｖ）は、本発明（Ｉ）のプロトン伝導性高分子固体電解質及び／又は本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜を用いることを特徴とする電気化学素子であり、本発明（ＶＩ）は、本発明（Ｖ）の電気化学素子の製造方法である。
【０２２７】
本発明（Ｉ）のプロトン伝導性高分子固体電解質及び／又は本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜は、各種電気化学素子の電解質として使用することができる。素子の具体例としては、例えば二次電池や燃料電池等の電池、電気二重層コンデンサ、エレクトロクロミック素子等を挙げることができるが、これらに限定されるわけではない。
【０２２８】
以下、各種電気化学素子の一例として二次電池、燃料電池及びエレクトロクロミック素子に関して、その構成と製造方法の具体例に関して説明する。
【０２２９】
＜二次電池の構成及び製造方法＞
本発明（Ｖ）の電気化学素子の一例として、プロトン移動型二次電池の構成の概念を、図１のようなシート型で示す。基本として、該二次電池は正極／プロトン伝導性高分子固体電解質膜／負極の積層構造をとっている。これらの二次電池及びその製造方法に関しては、特開平１１−１２６６１０公報、特開平１１−１４４７３２公報等に記載がある。
【０２３０】
負極には、ポリピリジン及びその誘導体に代表されるｎ-型プロトンドーピングが可能な高分子に対して、カーボンブラックのような導電助剤及びテフロン（イー アイ デュポン ドゥ ヌムール アンド カンパニー登録商標）のようなバインダーを加え、０．１ｍｍから１ｍｍ程度の厚みの板状に成型したものを用いることができる。成型には、例えば加圧プレス機や加熱加圧プレス機等を用いることができる。電極の面積はプロトン移動型二次電池の形状、容量等により様々な大きさのものが用いることができる。
【０２３１】
ｎ−型プロトンドーピングが可能な他の材料の具体例としては、ポリピリミジン及びその誘導体、ポリキノリン及びその誘導体等の窒素含有芳香族系高分子、ポリキノン及びポリアントラキノン及びこれらの誘導体等のキノン系高分子、ポリフェニレン及びポリフェニレンビニレン及びこれらの誘導体等を挙げることができる。
【０２３２】
正極には、ポリアニリン及びその誘導体のようなｐ-型プロトンドーピングが可能な導電性高分子に対して、カーボンブラックのような導電助剤及びテフロン（イー アイ デュポン ドゥ ヌムール アンド カンパニー登録商標）のようなバインダーを加え、０．１ｍｍから１ｍｍ程度の厚みの板状に成型したものを用いることができる。成型には、例えば加圧プレス機や加熱加圧プレス機等を用いることができる。電極の面積はプロトン移動型二次電池の形状、容量等により様々な大きさのものが用いることができる。
【０２３３】
ｐ−型プロトンドーピングが可能な他の材料の具体例としては、ポリインドール、ポリイソインドール、ポリピロール及びこれらの誘導体等の含アミン窒素芳香族系高分子、ポリチオフェン及び誘導体等の含イオウ芳香族高分子、ポリフラン及び誘導体等の含酸素芳香族高分子等を挙げることができる。
【０２３４】
上記の正極及び負極を本発明のプロトン伝導性高分子固体電解質膜を介して積層させ、積層体全体をアルミラミネート体、ポリオレフィン樹脂等の電池外装体に収納し、ポリオレフィン樹脂、エポキシ樹脂等の絶縁樹脂で封止することにより本発明（Ｖ）の一種であるプロトン移動型二次電池を製造することができる。より詳しくは、特開平１１−１２６６１０号公報、特開平１１−１４４７３２号公報に記載がある。
【０２３５】
本発明（Ｖ）のプロトン移動型二次電池の構成は図１に示すシ−ト型に限らず、チップ型、コイン型、角型、円筒型等いかなる形状でもよいこと、さらにその大きさにも特に制限はなく各種の大きさのものを製造することができることは言うまでもない。
【０２３６】
＜燃料電池の構成及びその製造方法＞
本発明（Ｖ）の電気化学素子の一例として、燃料電池の構成の概念を図２に示す。基本として、単セルはセパレータ／多孔質支持体＋カソード触媒／プロトン伝導性高分子固体電解質膜／アノード触媒＋多孔質支持体／セパレータの積層構造をとっている。燃料電池の構成及び及びその製造方法に関しては、「固体高分子型燃料電池の開発と実用化」（技術情報協会編、１９９９年第１刷発行）、特開平７−２２０３４号公報、特開平７−３２６３６３号公報に記載がある。各部材のサイズは燃料電池のサイズによって様々のものが用いられる。
【０２３７】
ここでいう「セパレータ」とは、単セルを直列につなぐ導電材料であり、触媒層にガス供給孔を加工しなければならず加工性が要求される。また耐酸性が必要な為、導電性炭素材料が用いられる。具体的には例えばグラファイトシートやグラファイトと各種樹脂の複合シート等が用いられる。
【０２３８】
触媒層は、一般に触媒と多孔質支持体からなる。水素に代表される燃料を空気極で酸素と反応させ、電荷を取り出す層で触媒には通常、白金が用いられ、効率を挙げる為に白金を多孔質炭素上に薄く被覆する等の工夫がなされる。多孔質支持体は触媒を固定する役目をなし、強度が必要であるが、ガス拡散性も重要で通常カーボン繊維シート等の導電性炭素多孔質シートが用いられる。これら触媒層とプロトン伝導性高分子固体電解質膜の接触が電池特性に重要であり、膜と触媒層を膜の軟化点以上の温度で加熱加圧プレス等を行い積層させる。
【０２３９】
触媒層／高分子固体電解質膜積層体の両側にセパレータを燃料極、空気極として貼り合わせ、パッケージ化しすることで燃料電池を製造することができる。得られた燃料電池は、燃料極から燃料を供給することにより電池として作動する。また、この単電池をセパレータ部分で積層していくことにより、積層型燃料電池パックを製造することもできる。
【０２４０】
本発明（Ｖ）の高分子固体電解質型燃料電池の構成は図２に示すシート型に限らず、チップ型、コイン型、角型、円筒型等いかなる形状でもよいこと、さらにその大きさにも特に制限はなく各種の大きさのものを製造することができることは言うまでもない。
【０２４１】
＜エレクトロクロミック素子の構成及びその製造方法＞
本発明（Ｖ）の電気化学素子の一例として、エレクトロクロミック素子の構成を図３に示す。基本として、透明電極／変色極材料／プロトン伝導性高分子固体電解質膜／対極材料／電極の積層構造をとっている。エレクトロクロミック素子及びその製造方法に関しては、「高分子」（１９８９年、３８号、９７０頁）、特開平３−２３１２２９号公報、特開平７−１５２０５０号公報等に記載がある。
【０２４２】
エレクトロクロミック素子の色変化は材料の酸化還元反応で起こる。電解質にプロトン伝導性高分子固体電解質膜を用いる場合は、プロトンもしくは対アニオンの移動による可逆性の良好な酸化還元反応を起こし色変化する材料が用いられる。これを「変色極材料」という。
【０２４３】
そのような材料の具体例としては、タングステン酸化物、イリジウム酸化物等の金属酸化物、ポリアニリン、ポリピロール等の導電性高分子、ビオロゲン、ビオロゲン系重合体等の酸化還元性有機物等を挙げることができる。これらの材料を透明電極上にキャスティング法や蒸着法で０．１μｍ〜１μｍ程度の厚みに成膜して変色電極として用いる。
【０２４４】
対極材料には変色極材料の酸化還元反応を補償できるプロトンもしくは対アニオンの移動による可逆性の良好な酸化還元を起こす材料が用いられる。この場合、色変化は必要としない。このような材料具体例としては、各種金属酸化物、導電性高分子等を挙げることができる。これら対極材料も電極上にキャスティング法や蒸着法で０．１μｍ〜１μｍ程度の厚みに成膜して電極として用いる。
【０２４５】
透明電極には、ガラス基盤上にＩＴＯや酸化錫等をスパッタリング等で成膜したものや、薄く金蒸着したものを用いることができる。
【０２４６】
本発明（Ｉ）のプロトン伝導性高分子固体電解質、或いは本発明（ＩＩＩ）のプロトン伝導性高分子固体電解質膜を所望の大きさに切り出し、その両側に上記の変色電極、対極電極をお互いが接触しないように貼り合わせ、場合によっては酸等のプロトン伝導性電解液を添加し、封止することにより、図３に示すような、本発明（Ｖ）のエレクトロクロミック素子を作製することができる。
【０２４７】
本発明（Ｖ）のエレクトロクロミック素子の構成は図３に示すシ−ト型に限らず、チップ型、コイン型、角型等の形状でもよいこと、さらにその大きさにも特に制限はなく各種の大きさのものを製造することができることは言うまでもない。
【０２４８】
【実施例】
以下に本発明について代表的な例を示し具体的に説明する。尚これらは説明のための単なる例示であって、本発明はこれらに何ら制限されるものではない。
【０２４９】
実施例１：ポリフェニルキノキサリン ( 以下、「ＰＰＱ」と略す。 ) の合成
反応は下記スキーム（１）に従って実施した。
スキーム（１）
【０２５０】
【化８５】

【０２５１】
即ち、ＤＭＦ(含水量２００ｐｐｍ)６００ｃｃを加えた１Ｌのガラス製四口フラスコ（長さ４ｃｍの撹拌はね及び冷却管付き）に、１，４−ビスベンジル（以下、「ＢＢＺ」と略す。）（Ｍｗ３４２．４、昭和電工製、ＧＣ純度９８％）４１．５２ｇ、３，３−ジアミノベンジジン（以下、「ＤＡＢＺ」と略す。）（Ｍｗ２１４．３、アルドリッチ製ＬＣ純度９８％）２５．９８ｇを添加し、室温窒素雰囲気下で３０分撹拌し、ＢＢＺ及びＤＡＢＺを完全に溶解させた。その後、窒素雰囲気下、１３０℃まで１時間で昇温した後、１３０℃で攪拌しながら４０時間反応させた。
【０２５２】
得られた黄色沈殿を濾過、メタノール洗浄、乾燥後１２０℃で１２時間、真空乾燥することにより、５４．０３ｇのＰＰＱ粉末を得た。
【０２５３】
この粉末の元素分析値及びＩＲスペクトルから目的通りの構造と推定された。また、ヘキサフルオロイソプロパノール（以下、「ＨＦＩＰ」と略す。）を溶離液としたＧＰＣからの光散乱法による絶対絶対重量平均分子量は５１０００であった。
【０２５４】
実施例２：ＰＰＱフィルムの製造
実施例１で製造したＰＰＱ粉末の５質量％ＨＦＩＰ溶液を調製した。これをスクリーン印刷機で成膜後、常温／常圧でＨＦＩＰをゆっくり揮発させ、平均膜厚み５０μｍの均一な黄色フィルムを製造した。このフィルムの引っ張り強度（ＪＩＳ規格:ＪＫ７１２７、サンプル幅１０ｍｍ）は７５０ｋｇ／ｃｍ²であった。このフィルムを空気中で熱重量分析したところ、５３０℃付近で重量減少が起こり、ＰＰＱ自身に何らかの変化があることが示唆された。
【０２５５】
実施例３：硫酸付加ＰＰＱフィルムの製造
実施例２で製造したＰＰＱフィルムに硫酸を付加するために４０％硫酸水溶液中に浸積し、５０℃で１０時間放置したところ、黄赤色に変化した。ＣＨＮＳの元素分析から硫酸イオンはＰＰＱのＮ原子に約３個に対して１個付加していることが推定された。
【０２５６】
このフィルムの９０％加湿下のイオン伝導率を交流インピーダンス法で測定したところ、２５℃で３．０ｍＳ／ｃｍ、８０℃で３５ｍＳ／ｃｍであった。このフィルムの引っ張り強度（ＪＩＳ規格：ＪＫ７１２７、サンプル幅１０ｍｍ）は７２０ｋｇ／ｃｍ²で硫酸付加前よりわずかに減少した。
【０２５７】
このフィルムの空気中の熱重量分析を行ったところ、１８０℃付近から硫酸イオンの脱離と思われる重量減少があり、５１０℃付近からＰＰＱ自身の変化と思われる重量減少があった。
【０２５８】
実施例４：ポリリン酸付加ＰＰＱフィルムの製造
実施例２で製造したＰＰＱフィルムにポリリン酸を付加するために、５０％ポリリン酸（重量平均分子量８０００）水溶液中で、８０℃で２０時間放置したところ、黄赤色に変化した。ＣＨＮＰの元素分析からポリリン酸中のリン酸イオンはＰＰＱのＮ原子約４個に対して１個付加していることが推定された。このフィルムの９０％加湿下のイオン伝導率を交流インピーダンス法で測定したところ、２５℃で０．８ｍＳ／ｃｍ、８０℃で２０ｍＳ／ｃｍであった。このフィルムの引っ張り強度(ＪＩＳ規格：ＪＫ７１２７、サンプル幅１０ｍｍ)は８３０ｋｇ／ｃｍ2でポリリン酸付加前よりわずかに増加した。
【０２５９】
このフィルムの空気中の熱重量分析を行ったところ、５１０℃付近からＰＰＱ自身の変化及びポリリン酸の脱離と思われる質量減少があった。
【０２６０】
実施例５：ポリスチレンスルホン酸付加ＰＰＱフィルムの製造
実施例２で製造したＰＰＱフィルムにポリスチレンスルホン酸を付加するために、３０％ポリスチレンスルホン酸（重量平均分子量１２０００）水溶液中で８０℃で２０時間放置したところ、黄赤色に変化した。ＣＨＮＳの元素分析からポリスチレンスルホン酸中のスルホン酸イオンはＰＰＱのＮ原子約５個に対して１個付加していることが推定された。このフィルムの９０％加湿下のイオン伝導率を交流インピーダンス法で測定したところ、２５℃で１．０ｍＳ／ｃｍ、８０℃で２３ｍＳ／ｃｍであった。このフィルムの引っ張り強度（ＪＩＳ規格:ＪＫ７１２７、サンプル幅１０ｍｍ)は１０００ｋｇ／ｃｍ²でポリスチレンスルホン酸付加前より増加した。
【０２６１】
このフィルムの空気中の熱重量分析を行ったところ、２００℃付近からスルホン酸イオンの脱離と思われる質量減少があり、５００℃付近からＰＰＱ自身の変化によると思われる質量減少があった。
【０２６２】
実施例６ : 各種重合性官能基を有する酸性化合物を付加したＰＰＱフィルムの製造及びその重合
実施例２で製造したＰＰＱフィルムを表１に示す各種重合性官能基を有する酸性化合物水溶液中で実施例３と同様にして、３０℃で２０時間放置したところ、各溶液中のＰＰＱフィルムが黄赤色に変化した。ＣＨＮＳＰの元素分析から各種酸中のアニオンはいずれもＰＰＱのＮ原子約３個に対して１個付加していることが推定された。これらフィルムの９０％加湿下のイオン伝導率を交流インピーダンス法で測定したところ、表１のごとくなった。またフィルム引張り強度(ＪＩＳ規格:ＪＫ７１２７、サンプル幅１０ｍｍ）は表１のごとくなった。また、このフィルムの空気中の熱重量分析を行ったところ、表１のごとくなった。
【０２６３】
これら重合性官能基を有する酸性化合物付加したＰＰＱフィルムを窒素雰囲気下、表１に示す温度で２時間放置することにより、重合性官能基を有する酸性化合物を重合させた。これらフィルムの９０％加湿下のイオン伝導率、引張り強度、熱重量分析を重合前と同様に行ったところ、表１のような結果となった。
【０２６４】
【表１】

【０２６５】
実施例７：ポリフェニルキノキサリンエーテル ( 以下、「ＰＰＱＥ」と略す。）の合成
反応は下記スキーム（２）に従って実施した。
スキーム（２）
【０２６６】
【化８６】

【０２６７】
即ち、実施例１で用いたＤＡＢＺ２５．９８ｇの代わりに、３，３‘，４，４’−テトラアミノジフェニルエーテル（以下、「ＴＡＤＥ」と略す。）（Ｍｗ２３０．２７、ＬＣ純度９８％）２７．９２ｇを用いた以外は実施例１と同様の方法で、５５．８３ｇの黄色のＰＰＱＥ粉末を得た。
【０２６８】
この粉末の元素分析値及びＩＲスペクトルから得られた粉末は目的通りの構造と推定された。また、ＨＦＩＰを溶離液としたＧＰＣからの光散乱法による絶対分子量（重量平均）は４８０００であった。
【０２６９】
実施例８：ＰＰＱＥフィルムの製造
実施例７で製造したＰＰＱＥ粉末の５質量％ＨＦＩＰ溶液を調製した。これをスクリーン印刷機で成膜後、常温／常圧でＨＦＩＰをゆっくり揮発させ、平均膜厚５０μｍの均一な黄色フィルムを製造した。このフィルムの引っ張り強度（ＪＩＳ規格：ＪＫ７１２７、サンプル幅１０ｍｍ）は１０５０ｋｇ／ｃｍ²であった。このフィルムを空気中で熱重量分析したところ、４６０℃付近で質量減少が起こり、ＰＰＱＥ自身に何らかの変化があることが示唆された。
【０２７０】
実施例９：パラスチレンスルホン酸付加ＰＰＱフィルム及びその重合物の製造
実施例８で製造したＰＰＱフィルムを２０％パラスチレンスルホン酸水溶液中に浸積し、８０℃で２０時間放置したところ、黄赤色に変化した。ＣＨＮＳの元素分析からパラスチレンスルホン酸イオンはＰＰＱＥのＮ原子に約３個に対して１個付加していることが推定された。このフィルムの９０％加湿下のイオン伝導率を交流インピーダンス法で測定したところ、２５℃で３．０ｍＳ／ｃｍ、８０℃で５０ｍＳ／ｃｍであった。このフィルムの引っ張り強度（ＪＩＳ規格:ＪＫ７１２７、サンプル幅１０ｍｍ）は９８０ｋｇ／ｃｍ²で酸付加前よりわずかに減少した。このフィルムの空気中の熱重量分析を行ったところ、２４０℃付近からパラスチレンスルホン酸イオンの脱離と思われる質量減少があり、４５０℃付近からＰＰＱＥ自身の変化と思われる質量減少があった。
【０２７１】
このパラスチレンスルホン酸付加したＰＰＱＥフィルムを窒素雰囲気下、１２０℃で２時間放置することにより、パラスチレンスルホン酸を重合させた。このフィルムの９０％加湿下のイオン伝導率は２５℃で２．８ｍＳ／ｃｍ、８０℃で７０ｍＳ／ｃｍであった。このフィルムの引っ張り強度（ＪＩＳ規格:ＪＫ７１２７、サンプル幅１０ｍｍ）は１２５０ｋｇ／ｃｍ²と重合前や酸付加前より上昇した。
【０２７２】
実施例１０：ポリメトキシフェニルキノキサリン（以下、「ＰＰＱＯＭ」と略す。）の合成
反応は下記スキーム（３）に従って実施した。
スキーム（３）
【０２７３】
【化８７】

【０２７４】
即ち、実施例１で用いたＢＢＺ４１．５２ｇの代わりに、ＢＢＺメトキシ体（以下、「ＢＢＺＯＭ」と略す。）（Ｍｗ４０４．４１、ＬＣ純度９８％）４９．０４ｇを用いた以外は実施例１と同様の方法で、黄赤色の６０．３３ｇのＰＰＱＯＭ粉末を得た。
【０２７５】
この粉末の元素分析値及びＩＲスペクトルから目的通りのＰＰＱＯＭが得られていると推定された。また、ＨＦＩＰを溶離液としたＧＰＣからの光散乱法による絶対分子量(重量平均)は３８０００であった。
【０２７６】
実施例１１：ＰＰＱＯＭフィルムの製造
実施例１０で製造したＰＰＱＯＭ粉末の５質量％ＨＦＩＰ溶液を調製した。これをスクリーン印刷機で成膜後、常温／常圧でＨＦＩＰをゆっくり揮発させ、平均膜厚５０μｍの均一な黄色フィルムを製造した。このフィルムの引っ張り強度（ＪＩＳ規格:ＪＫ７１２７、サンプル幅１０ｍｍ）は７８０ｋｇ／ｃｍ²であった。このフィルムを空気中で熱重量分析したところ、３８０℃付近と５００℃付近と２段の質量減少が起こり、ＰＰＱＯＭ自身に何らかの変化があることが示唆された。
【０２７７】
実施例１２ : ビニルスルホン酸付加ＰＰＱＯＭフィルム及びその重合物の製造
実施例１１で製造したＰＰＱＯＭフィルムを２０％ビニルスルホン酸水溶液中に浸積し、８０℃で２０時間放置したところ、赤色に変化した。ＣＨＮＳの元素分析からパラスチレンスルホン酸イオンはＰＰＱＯＭのＮ原子に約３個に対して１個付加していることが推定された。このフィルムの９０％加湿下のイオン伝導率を交流インピーダンス法で測定したところ、２５℃で３．２ｍＳ／ｃｍ、８０℃で４３ｍＳ／ｃｍであった。このフィルムの引っ張り強度（ＪＩＳ規格:ＪＫ７１２７、サンプル幅１０ｍｍ）は７２０ｋｇ／ｃｍ²で酸付加前よりわずかに減少した。このフィルムの空気中の熱重量分析を行ったところ、１９０℃付近からパラスチレンスルホン酸イオンの脱離と思われる質量減少があり、３７０℃付近と５００℃付近にＰＰＱＯＭ自身の変化と思われる質量減少があった。
【０２７８】
このビニルスルホン酸付加したＰＰＱＯＭフィルムを窒素雰囲気下、１２０℃で３時間放置することにより、ビニルスルホン酸を重合させた。このフィルムの９０％加湿下のイオン伝導率は２５℃で２．３ｍＳ／ｃｍ、８０℃で６０ｍＳ／ｃｍであった。このフィルムの引っ張り強度（ＪＩＳ規格:ＪＫ７１２７、サンプル幅１０ｍｍ）は８３０ｋｇ／ｃｍ²と重合前や酸付加前より上昇した。
【０２７９】
実施例１３：ポリピリジン−２，５−ジイル（以下、「Ｐｐｙ」と略す。）電極の製造
Ｓｙｎｔｈ．Ｍｅｔａｌｓ（２５ １０３ １９８８）に従い、Ｎｉ(０)法でＰｐｙ粉末を得た（ＨＦＩＰ溶液での重量平均分子量はポリスチレン換算で１８０００）。
【０２８０】
このＰｐｙ粉末とアセチレンブラック(以下、「ＡＢ」と略す。）（電気化学工業製)、ポリフッ化ビニリデン(以下、「ＰＶＤＦ」と略す。）（クレハ製)を質量比７０：２５：５の混合物に過剰のＮ−メチルピロリドン（以下、「ＮＭＰ」と略す。）を加え、ゲル状電極組成物を得た。この組成物を塗布後、大気中１ｔｏｎ加圧することにより、１×１ｃｍ、５００μｍの厚さのＰｐｙ電極を数個作製した。これら電極の平均重量は４０ｍｇであった。
【０２８１】
実施例１４：ポリアニリン（以下、「ＰＡｎ」と略す。）電極の製造
特開昭６２−１０８４５９号公報記載の方法に従い、過硫酸アンモニウムを酸化剤として１Ｎ塩酸中でアニリンを酸化重合後、アンモニア水溶液で中和することにより濃紫色の塩基型ＰＡｎ粉末、１００ｇを得た。元素分析、ＩＲから本ＰＡｎはほぼ目的の構造であると推定された。ＮＭＰ中でのＧＰＣの結果から、ＰＡｎの分子量（ＰＭＭＡ換算）は重量平均で約１２００００であった。
【０２８２】
このＰＡｎ粉末とＡＢ（電気化学製）、ＶＧＣＦ(昭和電工製)、ＰＶＤＦ（クラレ製）の８５：７：１：７の混合物に過剰のＮＭＰを加え、ゲル状組成物を得た。この組成物を導電性フィルム集電体１ｃｍ×１ｃｍ上に塗布後、１ｔｏｎ加圧成型し、８０℃で８時間真空乾燥することにより、０．５ｍｍの厚さのＰＡｎ電極（平均３８ｍｇ）を数個作成した。
【０２８３】
実施例１５：二次電池の製造
実施例１４で製造したＰＡｎ電極、実施例６で製造したＰＰＱ／パラスチレンスルホン酸重合膜（５０μｍ、１．２ｃｍ×１．２ｃｍ）を重ねた。実施例１３で製造したＰｐｙ電極を重ね、実施例１４で用いたと同様の導電性フィルム（１ｃｍ×１ｃｍ）をさらに集電体として重ねた。これら積層体を加圧して密着させたあと、ポリイミドテープ（カプトンテープ）で両端部を固定した。ついで正極、負極側の導電性フィルム集電体に白金箔をリード線として銀ぺーストで取り付け、この積層体をアルミラミネート外装体の中にいれ、２つの白金リード線を短絡しないように外部に取り出した。ついで電解液として２０％硫酸水溶液を外装体内部に注入し、減圧で余分な硫酸水溶液を抜き出しながら、外装体内を密着させた後、加熱融着で封止し、Ｐｐｙ／ＰＡｎ系二次電池(各ｎ＝３、計１８個)を作成した。図１に外装体内の電池構成を示した。
【０２８４】
この電池を２５℃、作動電圧０〜０．８Ｖ、電流２ｍＡ、１０ｍＡで充放電を行ったところ、最大放電容量は１．５ｍＡｈ、１．２ｍＡｈであった。また、２ｍＡで、０℃及び−１０℃において放電させたところ１．４ｍＡｈ、１．０ｍＡｈであった。また、１０ｍＡで充放電サイクルを繰り返したところ、２００サイクル後の容量は１．５ｍＡｈであった。
【０２８５】
実施例１６：燃料電池の製造
実施例６で製造したＰＰＱ／ビニルスルホン酸重合膜（５０μｍ、１．２ｃｍ×１．２ｃｍ）の両側に常法に従い、白金触媒及び多孔質導電性炭素電極（１ｃｍ×１ｃｍ）を取り付けることにより、燃料電池用積層体を製造した。この積層体の両側に水素供給室、空気室を作り、水素供給極に水素を供給することにより、８０℃、２００ｍＡで０．８Ｖの起電力が得られた。また、１Ａでは０．５Ｖであった。
【０２８６】
実施例１７：三酸化タングステン（以下、「ＷＯ ³ 」と略す。）エレクトロクロミック層の製造
松崎真空（株）製のインジウムチンオキサイド（以下、「ＩＴＯ」と略す。）ガラスを１．２ｃｍ×１．２ｃｍに切断したものの端部を被覆し、ＩＴＯ露出部が１ｃｍ×１ｃｍになった電極上に、抵抗加熱法でＷＯ³の真空蒸着を行った。得られた膜の厚みは約１５００Å、密度は約５ｇ／ｃｃであった。
【０２８７】
実施例１８：エレクトロクロミック素子の作製
松崎真空（株）製のＩＴＯガラス１．２ｃｍ×１．２ｃｍ上に０．５Ｍアニリンを含む１Ｍ塩酸水溶液を電解液として、−０．２から０．８ＶｖｓＳＣＥの範囲の電位走査法で約５０００Åの電解重合ポリアニリン（以下、「ＰＡｎ」と略す。）膜をＩＴＯガラス上に形成させた。
【０２８８】
このＰＡｎ／ＩＴＯ電極に実施例６で製造したＰＰＱ／パラスチレンスルホン酸重合膜（５０μｍ、１．２ｃｍ×１．２ｃｍ）を重ねた。次いで実施例１７で製造したＷＯ³／ＩＴＯ電極を重ね、これら積層体を加圧して密着させたあと、ポリイミドテープ（カプトンテープ）で両端部を固定した。ついで電解液として２０％硫酸水溶液を外装体内部に注入し、減圧で余分な硫酸水溶液を抜き出しながら、外装体内を密着させた後、電極端部全体をエポキシ樹脂で封止し、ＷＯ³／ＰＰＱ膜／ＰＡｎ系エレクトロクロミック素子を作製した。
【０２８９】
このエレクトロクロミック素子に注入電気量６ｍＣで発色／消色駆動を繰り返したところ、濃青色/淡青色のエレクトロクロミズムを示した。応答速度は１００ｍｓｅｃであった。またこの条件で駆動を１００回繰り返しても色調、応答速度に変化は見られなかった。
【０２９０】
【発明の効果】
以上のように、Ａ）一般式（１）で表されるキノキサリン構造を含む重合体、及びＢ）酸性化合物とを含有することを特徴とするプロトン伝導性高分子固体電解質及び該電解質からなる電解質膜は、プロトン親和性が高いキノキサリン骨格を有しているために、従来の高プロトン伝導性高分子固体電解質及び該電解質からなる電解質膜に比べて強度、耐熱性、耐酸性、耐酸化還元安定性に優れていることは明かである。
【０２９１】
また、該電解質及び／又は該電解質膜をその構成に含む電気化学素子は、耐久性、信頼性、高速電流特性、応答速度に優れ、特に二次電池や燃料電池などの電池、コンデンサ、エレクトロクロミック素子は従来のものより優れていることは明かである。
【０２９２】
【図面の簡単な説明】
【図１】本発明のプロトン移動型電池の一例として示す、シート型電池の実施例の概略断面図である。
【図２】本発明の燃料電池の一例として示す、実施例の概略断面図である。
【図３】本発明のエレクトロクロミック素子の一例として示す、シート型エレクトロクロミック素子の実施例の概略断面図である。
【符号の説明】
１ 正極
２ プロトン伝導性高分子固体電解質＋セパレータ
３ 負極
４ 集電体シート
５ リード線
６ 外装体
７ 燃料極セパレータ
８ 燃料極触媒層
９ プロトン伝導性高分子固体電解質膜
１０ 空気極触媒層
１１ 空気極セパレータ
１２ ガラス
１３ 透明導電膜
１４ エレクトロクロミック層
１５ プロトン伝導性高分子固体電解質＋セパレータ
１６ 対極層
１７ 絶縁性フィルムスペーサー
１８ 絶縁性樹脂封止剤
１９ リード線[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a high proton conductive polymer solid electrolyte excellent in strength, heat resistance, acid resistance and oxidation-reduction stability, a method for producing the electrolyte, an electrolyte membrane comprising the electrolyte, and a method for producing the electrolyte membrane.
[0002]
Furthermore, the present invention relates to an electrochemical device excellent in durability, reliability, and current characteristics using the high proton conductive polymer solid electrolyte and / or the electrolyte membrane, and a method for producing the device.
[0003]
[Prior art]
Proton-conducting electrolytes such as sulfuric acid take advantage of the high electrical conductivity due to the small ionic radius of protons, so batteries and electric double-layer capacitors that require high output, and displays that require high-speed response It is often used for so-called electrochemical devices such as devices.
[0004]
Specifically, “Electrochemistry” 1998, Vol. 66, No. On pages 9 and 884, a carbon material having a large specific surface area such as activated carbon or carbon black is used as a polarizable electrode material for a memory backup power source, and a proton conductive electrolyte is used as an organic or aqueous liquid (so-called electrolyte). The electric double layer capacitor disposed in (1) is exemplified. Further, for example, “Electronic Technology” 1999, No. On pages 11 and 58, an electric double layer capacitor using a sulfuric acid aqueous solution is described.
[0005]
However, these all use an electrolyte in a liquid state. Conventionally, electrolyte materials for electrochemical elements such as batteries and capacitors have been used in liquid form in many cases including proton conducting electrolytes. On the other hand, in recent years, electrolytes have been used to improve the processability of devices, meet the demands for lighter and smaller devices and devices that incorporate them, and meet the increasing requirements for device reliability and safety. There is an increasing demand for solidification of materials, and various developments are being made to meet this demand. The same applies to proton conductive electrolytes, and various developments have been made for solidification of electrolyte materials.
[0006]
For example, JP-A-7-22034 and JP-A-7-326363 describe proton conductive polymer solid electrolytes such as Nafion. However, the proton-conducting polymer solid electrolyte disclosed here is expensive in raw material and difficult to produce, and there are still problems in the thermal stability and water retention of the electrolyte membrane made of the electrolyte.
[0007]
On the other hand, Japanese Patent Application Laid-Open No. 2000-273159 describes a proton conductive polymer solid electrolyte made of a complex of polyquinoline or polyquinoxaline and phosphoric acid or phosphate esters. However, the degree of dissociation of phosphoric acid is low and the conductivity is insufficient, and there are also problems with the heat resistance of the electrolyte itself and the strength of the membrane made of the electrolyte.
[0008]
As described above, the performance of electrolyte materials for electrochemical elements such as batteries and capacitors that have been demanded in recent years is not sufficient, and a more excellent proton conductive polymer solid electrolyte and an electrolyte membrane comprising the electrolyte are provided. It has been demanded.
[0009]
[Problems to be solved by the invention]
One of the objects of the present invention is a problem of conventional proton conductive polymer solid electrolytes and electrolyte membranes composed of the electrolytes, and proton conductivity excellent in strength, heat resistance, acid resistance, and redox stability. To provide a polymer solid electrolyte, a method for producing the electrolyte, an electrolyte membrane made of the electrolyte, and a method for producing the electrolyte membrane.
[0010]
Furthermore, one of the objects of the present invention is to provide an electrochemical element excellent in durability, reliability, and current characteristics using the proton conductive polymer solid electrolyte and / or the electrolyte membrane, and a method for producing the element. There is.
[0011]
[Means for Solving the Problems]
The inventors of the present invention have made extensive studies to solve the above problems. As a result, the proton conductive polymer solid electrolyte composed of a polymer containing a quinoxaline skeleton and an acidic compound has high proton conductivity, heat resistance under the conditions required for the solid electrolyte, and acidic conditions, redox The present invention was completed by finding that the electrolyte membrane is stable with respect to the conditions and that the electrolyte membrane made of the electrolyte is excellent in strength.
[0012]
That is, the present invention (I) is a proton conductive polymer solid electrolyte comprising A) a polymer containing a quinoxaline structure represented by the general formula (1) and B) an acidic compound.
General formula (1)
[0013]
Embedded image

[0014]
(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a nitro group. Group, carboxylic acid group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent -An alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[0015]
Moreover, this invention (II) is a manufacturing method of the proton-conductive polymer solid electrolyte of this invention (I).
[0016]
The present invention (III) is a proton conductive polymer solid electrolyte membrane comprising the proton conductive polymer solid electrolyte of the present invention (I).
[0017]
Moreover, this invention (IV) is a manufacturing method of the proton-conductive polymer solid electrolyte membrane of this invention (III).
[0018]
Furthermore, the present invention (V) uses the proton conductive polymer solid electrolyte of the present invention (I) and / or the proton conductive polymer solid electrolyte membrane of the present invention (III), and an electrochemical device It is.
[0019]
Furthermore, this invention (VI) is a manufacturing method of the electrochemical element of this invention (V).
[0020]
Furthermore, this invention consists of the following matters, for example.
[1] A) Polymer containing a quinoxaline structure represented by the general formula (1)
as well as
B) Acidic compounds
And a proton conductive polymer solid electrolyte.
[0021]
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a nitro group. Group, carboxylic acid group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent -An alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[0022]
[2] A) Polymer containing quinoxaline structure represented by general formula (1) in the side chain
as well as
B) Acidic compounds
And a proton conductive polymer solid electrolyte.
[0023]
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfone group. It may have an acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent. An alkynyl group having 2 to 20 carbon atoms or an aryl group which may have a substituent is represented. )
[0024]
[3] A) A polymer containing a quinoxaline structure represented by the general formula (2) as a part of repeating units
as well as
B) Acidic compounds
And a proton conductive polymer solid electrolyte.
[0025]
General formula (2)
Embedded image

(Wherein R⁷~ R^TenAre each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0026]
[4] A) Polymer containing a quinoxaline structure represented by the general formula (1) in the side chain and a quinoxaline structure represented by the general formula (2) as a part of the repeating unit
as well as
B) Acidic compounds
And a proton conductive polymer solid electrolyte.
[0027]
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfone group. It may have an acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent. An alkynyl group having 2 to 20 carbon atoms or an aryl group which may have a substituent is represented. )
[0028]
General formula (2)
Embedded image

(Wherein R⁷~ R^TenAre each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0029]
[5] A) The proton according to any one of [3] or [4], wherein the quinoxaline structure represented by the general formula (2) is a quinoxaline structure represented by the general formula (3) Conductive polymer solid electrolyte.
[0030]
General formula (3)
Embedded image

(Wherein R¹¹~ R¹⁴Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0031]
[6] A) The proton according to any one of [3] to [5], wherein the quinoxaline structure represented by the general formula (2) is a quinoxaline structure represented by the general formula (4) Conductive polymer solid electrolyte.
[0032]
General formula (4)
Embedded image

(Wherein R¹⁵~ R³⁰Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent X represents an aryl group which may independently have a substituent, and Y represents a heteroatom or a substituent having 4 to 20 carbon atoms which may have a heteroatom independently. Represents an aryl group which may be substituted, and n represents an integer of 0 to 5. )
[0033]
[7] B) The acidic compound is at least one selected from the group consisting of sulfuric acid, nitric acid, acetic acid, fluorinated acetic acid, propionic acid, fluorinated propionic acid, butyric acid and fluorinated butyric acid [1] ] The proton-conductive polymer solid electrolyte according to any one of [6] to [6].
[0034]
[8] The proton conductive polymer solid electrolyte according to any one of [1] to [6], wherein B) the acidic compound is an acid type monomer.
[0035]
[9] The acid-type monomer is at least one selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid, and vinyl phosphoric acid. The proton conductive polymer solid electrolyte according to [8], which is characterized in that it exists.
[0036]
[10] The proton conductive polymer solid electrolyte according to any one of [1] to [6], wherein the B) acidic compound is an acid polymer.
[0037]
[11] The proton conduction according to [10], wherein the acid type polymer is at least one selected from the group consisting of a carboxylic acid polymer, a sulfonic acid polymer, and a phosphoric acid polymer. Polymer solid electrolyte.
[0038]
[12] The method for producing a proton-conductive polymer solid electrolyte according to any one of [1] to [11], comprising the following steps.
Process
A) A polymer containing a quinoxaline structure represented by the general formula (1)
as well as
B) Acidic compounds
To obtain a proton conductive polymer solid electrolyte
[0039]
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a nitro group. Group, carboxylic acid group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent -An alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[0040]
[13] The method for producing a proton conductive polymer solid electrolyte according to any one of [1] to [6], [8] or [9], comprising the following first step to second step: .
First step
A) A polymer containing a quinoxaline structure represented by the general formula (1)
as well as
B) having at least one polymerizable functional group selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid Acidic compounds
To obtain a composition for producing a proton conductive polymer solid electrolyte
[0041]
Second step
A step of polymerizing an acidic compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a proton conductive polymer solid electrolyte
[0042]
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a nitro group. Group, carboxylic acid group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent -An alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[0043]
[14] The method for producing a proton conductive polymer solid electrolyte according to any one of [1] to [6], [8] or [9], comprising the following first step to second step: .
First step
A) A polymer containing a quinoxaline structure represented by the general formula (1) in the side chain
as well as
B) having at least one polymerizable functional group selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid Acidic compounds
To obtain a composition for producing a proton conductive polymer solid electrolyte
[0044]
Second step
A step of polymerizing an acidic compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a proton conductive polymer solid electrolyte
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfone group. It may have an acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent. An alkynyl group having 2 to 20 carbon atoms or an aryl group which may have a substituent is represented. )
[0045]
[15] The method for producing a proton conductive polymer solid electrolyte according to any one of [1] to [6], [8] or [9], comprising the following first step to second step: .
First step
A) A polymer containing a quinoxaline structure represented by the general formula (2) as a part of repeating units
as well as
B) having at least one polymerizable functional group selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid Acidic compounds
To obtain a composition for producing a proton conductive polymer solid electrolyte
[0046]
Second step
A step of polymerizing an acidic compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a proton conductive polymer solid electrolyte
[0047]
General formula (2)
Embedded image

(Wherein R⁷~ R^TenAre each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0048]
[16] The method for producing a proton conductive polymer solid electrolyte according to any one of [1] to [6], [8] or [9], comprising the following first step to second step: .
First step
A) A polymer containing a quinoxaline structure represented by the general formula (1) in the side chain and a quinoxaline structure represented by the general formula (2) as a part of the repeating unit.
as well as
B) having at least one polymerizable functional group selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid Acidic compounds
To obtain a composition for producing a proton conductive polymer solid electrolyte
[0049]
Second step
A step of polymerizing an acidic compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a proton conductive polymer solid electrolyte
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfone group. It may have an acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent. An alkynyl group having 2 to 20 carbon atoms or an aryl group which may have a substituent is represented. )
[0050]
General formula (2)
Embedded image

(Wherein R⁷~ R^TenAre each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0051]
[17] The method for producing a proton conductive polymer solid electrolyte according to any one of [1] to [11], comprising the following first step to second step.
First step
A) Polymerizable compound containing a quinoxaline structure represented by the general formula (1)
as well as
B) Acidic compounds
To obtain a composition for producing a proton conductive polymer solid electrolyte
[0052]
Second step
A step of polymerizing a polymerizable compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a proton conductive polymer solid electrolyte
[0053]
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a nitro group. Group, carboxylic acid group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent -An alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[0054]
[18] The method for producing a proton conductive polymer solid electrolyte according to any one of [1] to [11], comprising the following first step to second step.
First step
A) Polymerizable compound containing a quinoxaline structure represented by the general formula (1)
as well as
B) Acid type polymer
To obtain a composition for producing a proton conductive polymer solid electrolyte
[0055]
Second step
A step of polymerizing a polymerizable compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a proton conductive polymer solid electrolyte
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a nitro group. Group, carboxylic acid group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent -An alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[0056]
[19] A proton conductive polymer solid electrolyte membrane comprising the proton conductive polymer solid electrolyte according to any one of [1] to [11].
[0057]
[20] The proton conductive polymer solid electrolyte membrane according to [19], wherein the membrane has a thickness in the range of 5 μm to 200 μm.
[0058]
[21] The proton conductive solid polymer electrolyte membrane according to any one of [19] or [20], wherein a non-electron conductive reinforcing agent is added.
[0059]
[22] The proton conductive polymer solid electrolyte membrane according to [21], wherein the non-electron conductive reinforcing agent is an oxide particle.
[0060]
[23] The proton conductive polymer solid electrolyte membrane according to [22], wherein the oxide particles are oxides of at least one element selected from Al, Si and Ti.
[0061]
[24] The proton conductive polymer solid electrolyte membrane according to any one of [22] or [23], wherein the particle diameter of the oxide particles is in the range of 0.001 μm to 10 μm.
[0062]
[25] The method for producing a proton conductive polymer solid electrolyte membrane according to any one of [19] to [24], comprising the following first step to second step.
First step
The process of obtaining the polymer film by distilling off the solvent after applying at least one solution of any polymer represented by the following (a) to (d) to the substrate
(A) A polymer containing a quinoxaline structure represented by the general formula (1)
(B) A polymer containing the quinoxaline structure represented by the general formula (2) as a part of the repeating unit
(C) A polymer containing a quinoxaline structure represented by the general formula (3) as a part of repeating units
(D) a polymer containing the quinoxaline structure represented by the general formula (4) as a part of the repeating unit
[0063]
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a nitro group. Group, carboxylic acid group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent -An alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[0064]
General formula (2)
Embedded image

(Wherein R⁷~ R^TenAre each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0065]
General formula (3)
Embedded image

(Wherein R¹¹~ R¹⁴Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0066]
General formula (4)
Embedded image

(Wherein R¹⁵~ R³⁰Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent X represents an aryl group that may independently have a substituent, and Y represents a hetero atom alone or an aryl group having 4 to 20 carbon atoms that may have a hetero atom. N represents an integer of 0 to 5. )
[0067]
Second step
B) A step of adding an acidic compound to the polymer membrane obtained in the first step to obtain a proton conductive polymer solid electrolyte membrane
[0068]
[26] The method for producing a proton conductive polymer solid electrolyte membrane according to any one of [19] to [24], comprising the following first to third steps.
First step
The process of obtaining the polymer film by distilling off the solvent after applying at least one solution of any polymer represented by the following (a) to (d) to the substrate
(A) A polymer containing a quinoxaline structure represented by the general formula (1)
(B) A polymer containing the quinoxaline structure represented by the general formula (2) as a part of the repeating unit
(C) A polymer containing a quinoxaline structure represented by the general formula (3) as a part of repeating units
(D) a polymer containing the quinoxaline structure represented by the general formula (4) as a part of the repeating unit
[0069]
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a nitro group. Group, carboxylic acid group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent -An alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[0070]
General formula (2)
Embedded image

(Wherein R⁷~ R^TenAre each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0071]
General formula (3)
Embedded image

(Wherein R¹¹~ R¹⁴Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0072]
General formula (4)
Embedded image

(Wherein R¹⁵~ R³⁰Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent X represents an aryl group which may independently have a substituent, Y represents a hetero atom alone, or an aryl group having 4 to 20 carbon atoms which may have a hetero atom. N represents an integer of 0 to 5. )
[0073]
Second step
A step of adding an acid-type monomer to the polymer membrane obtained in the first step to obtain a proton conductive polymer solid electrolyte precursor membrane
[0074]
Third process
A step of polymerizing the acid type monomer contained in the proton conductive polymer solid electrolyte precursor membrane obtained in the second step to obtain a proton conductive polymer solid electrolyte membrane
[0075]
[27] The acid type monomer is at least one selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid, and vinyl phosphoric acid. The method for producing a proton conductive polymer solid electrolyte membrane according to [26], wherein the method is an acidic compound having a polymerizable functional group.
[0076]
[28] The method for producing a proton conductive polymer solid electrolyte membrane according to any one of [19] to [24], comprising the following first step to second step.
First step
A) At least one polymer selected from the polymers represented by the following (a) to (d):
(A) A polymer containing a quinoxaline structure represented by the general formula (1)
(B) A polymer containing the quinoxaline structure represented by the general formula (2) as a part of the repeating unit
(C) A polymer containing a quinoxaline structure represented by the general formula (3) as a part of repeating units
(D) a polymer containing the quinoxaline structure represented by the general formula (4) as a part of the repeating unit
[0077]
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a nitro group. Group, carboxylic acid group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent -An alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[0078]
General formula (2)
Embedded image

(Wherein R⁷~ R^TenAre each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0079]
General formula (3)
Embedded image

(Wherein R¹¹~ R¹⁴Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0080]
General formula (4)
Embedded image

(Wherein R¹⁵~ R³⁰Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent X represents an aryl group that may independently have a substituent, and Y represents a hetero atom alone or an aryl group having 4 to 20 carbon atoms that may have a hetero atom. N represents an integer of 0 to 5. )
as well as
B) Acidic compounds
For obtaining a composition for producing a proton conductive polymer solid electrolyte membrane comprising
[0081]
Second step
A step of obtaining a proton conductive polymer solid electrolyte membrane by pressurizing and / or thermoforming the composition for producing a proton conductive polymer solid electrolyte membrane obtained in the first step
[0082]
[29] The method for producing a proton conductive polymer solid electrolyte membrane according to any one of [19] to [24], comprising the following first step to second step.
First step
A) At least one polymer selected from the polymers represented by the following (a) to (d):
(A) A polymer containing a quinoxaline structure represented by the general formula (1)
(B) A polymer containing the quinoxaline structure represented by the general formula (2) as a part of the repeating unit
(C) A polymer containing a quinoxaline structure represented by the general formula (3) as a part of repeating units
(D) a polymer containing the quinoxaline structure represented by the general formula (4) as a part of the repeating unit
[0083]
General formula (1)
Embedded image

(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a nitro group. Group, carboxylic acid group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent -An alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[0084]
General formula (2)
Embedded image

(Wherein R⁷~ R^TenAre each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0085]
General formula (3)
Embedded image

(Wherein R¹¹~ R¹⁴Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0086]
General formula (4)
Embedded image

(Wherein R¹⁵~ R³⁰Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent X represents an aryl group that may independently have a substituent, and Y represents a hetero atom alone or an aryl group having 4 to 20 carbon atoms that may have a hetero atom. N represents an integer of 0 to 5. )
as well as
B) Acid type monomer
For obtaining a composition for producing a proton conductive polymer solid electrolyte membrane comprising
[0087]
Second step
A step of obtaining a proton conductive polymer solid electrolyte membrane by pressurizing and heating while polymerizing the acid type monomer in the composition for producing a proton conductive polymer solid electrolyte membrane obtained in the first step
[0088]
[30] The acid-type monomer is at least one selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid, and vinyl phosphoric acid. [29] The method for producing a proton conductive polymer solid electrolyte membrane according to [29], which is an acidic compound having a polymerizable functional group.
[0089]
[31] Use of the proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or the proton conductive polymer solid electrolyte membrane according to any one of [19] to [24]. An electrochemical element characterized by the above.
[0090]
[32] Use of the proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or the proton conductive polymer solid electrolyte membrane according to any one of [19] to [24]. A battery characterized by.
[0091]
[33] Use of the proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or the proton conductive polymer solid electrolyte membrane according to any one of [19] to [24]. A fuel cell.
[0092]
[34] Use of the proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or the proton conductive polymer solid electrolyte membrane according to any one of [19] to [24]. Electric double layer capacitor characterized by
[0093]
[35] Use of the proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or the proton conductive polymer solid electrolyte membrane according to any one of [19] to [24]. An electrochromic device characterized by.
[0094]
[36] The proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or the proton conductive polymer according to any one of [19] to [24], between the positive electrode and the negative electrode. A method for producing a battery, comprising installing a solid electrolyte membrane.
[0095]
[37] The proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or the proton conductivity according to any one of [19] to [24], between the fuel electrode and the air electrode. A method for producing a fuel cell, comprising installing a solid polymer electrolyte membrane.
[0096]
[38] The proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or the proton conductivity according to any one of [19] to [24], between two polarizable electrodes. A method for producing an electric double layer capacitor, comprising installing a solid polymer electrolyte membrane.
[0097]
[39] The proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or the proton conductive high according to any one of [19] to [24], between the color changing electrode and the counter electrode. A method for producing an electrochromic device, comprising installing a molecular solid electrolyte membrane.
[0098]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0099]
The present invention (I) is a proton conductive polymer solid electrolyte comprising A) a polymer having a quinoxaline structure represented by the general formula (1), and B) an acidic compound.
[0100]
General formula (1)
Embedded image

[0101]
(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, or a nitro group. Group, carboxylic acid group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent -An alkenyl group having 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[0102]
First, “A) a polymer containing a quinoxaline structure represented by the general formula (1)” in the proton conductive polymer solid electrolyte of the present invention (I) will be described.
[0103]
The “polymer having a quinoxaline structure” in the present invention (I) is any polymer having a quinoxaline structure at least partially including a main chain or a side chain of the polymer. Can be used. For example, the structure forming the main chain of the polymer does not include the quinoxaline structure directly, but has a structure represented by the structural formula (1) in which a part of the quinoxaline structure is bonded to the main chain. Moreover, the thing which has as a repeating unit the structure represented by General formula (2) which has a quinoxaline structure as a part of structure which forms the principal chain of a polymer may be sufficient.
[0104]
Structural formula (1)
Embedded image

[0105]
General formula (2)
Embedded image

[0106]
(Wherein R⁷~ R^TenAre each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0107]
In addition, a polymer including both a part having a structure represented by, for example, the structural formula (1) and a part having a structure represented by the general formula (2) in which a part of the quinoxaline structure is bonded to the main chain. Further, it may be a substance containing a repeating unit different from the quinoxaline structure. Furthermore, a mixture thereof may be used.
[0108]
In the general formula (1) in the “polymer containing a quinoxaline structure” of the present invention (I),¹~ R⁶"At least one is a group bonded to the main chain of the polymer" means that it includes a structure represented by, for example, the structural formula (1).
[0109]
Structural formula (1)
Embedded image

[0110]
Here, the main chain and the quinoxaline structure may have not only a direct bond as shown in the structural formula (1) but also other functional groups therebetween. For example, in the case of a polymer in which an acrylate ester of an alcohol having a quinoxaline structure as shown in the structural formula (2) is used as a raw material, the structural formula (3) having an ester structure between the main chain and the quinoxaline structure. ), The polymer having the repeating unit shown in FIG.
[0111]
Structural formula (2)
Embedded image

[0112]
Structural formula (3)
Embedded image

[0113]
In the general formula (1), “wherein R¹~ R⁶Of these, at least one is a group that binds to the main chain of the polymer '' means that the main chain and the quinoxaline structure may be bonded in any form as well as the ester bond exemplified here. Needless to say, it should be.
[0114]
In the present invention (I), the “polymer containing the quinoxaline structure represented by the general formula (2) as a part of the repeating unit” means a substance having a quinoxaline structure in at least a part of the main chain of the polymer. Any object can be used.
[0115]
The “polymer containing a quinoxaline structure as a part of a repeating unit” as used herein refers to a polymer containing only a quinoxaline structure as a repeating unit in addition to the quinoxaline structure. It may be. In this case, the quinoxaline structure and other structures may be alternated, or a structure in which only the quinoxaline structure is repeated and a part in which the other structure is repeated may be present.
[0116]
Furthermore, the quinoxaline structure may or may not repeat directly. For example, the quinoxaline structure is represented by the general formula (4) such that a structure in which another structure is bonded to the quinoxaline structure is used as the basic structure of the repeating unit. Such a thing is also included.
[0117]
General formula (4)
Embedded image

[0118]
(Wherein R¹⁵~ R³⁰Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent X represents an aryl group that may independently have a substituent, and Y represents a hetero atom alone or an aryl group having 4 to 20 carbon atoms that may have a hetero atom. N represents an integer of 0 to 5. )
[0119]
Further, “a polymer containing a quinoxaline structure represented by the general formula (1) in a side chain and a quinoxaline structure represented by the general formula (2) as a part of a repeating unit” If a part of the quinoxaline structure has a structure represented by, for example, the structural formula (1) in which a part of the quinoxaline structure is bonded to the main chain, and the other part has a quinoxaline structure in a part of the main chain of the polymer Any thing is acceptable.
[0120]
In this case, the portion containing the quinoxaline structure in the side chain and the portion containing the quinoxaline structure as the main chain structure are alternately present, or after repeating the portion containing the quinoxaline structure in the side chain, The thing which repeated the part which contains a structure as a structure of a principal chain may be sufficient. Furthermore, the thing which has a different repeating unit from a quinoxaline structure may be sufficient, and in that case, each structure may be couple | bonded in arbitrary orders, respectively.
[0121]
R in the general formulas (1) to (4) of the present invention (I)¹~ R³⁰Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent having 1 to 20 carbon atoms. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group.
[0122]
Here, “independently” means R¹~ R³⁰These are not only independent of each other, but are also independent in each quinoxaline structure of the polymer. That is, for example, any R of a quinoxaline structure^αWhen (α is an integer of 1 to 30) is a methyl group, R is a position similar to other quinoxaline structures.^αShows that it may be a methyl group or a functional group other than a methyl group. Therefore, when n quinoxaline structures are present in one polymer, any R^αIndicates that each is an independent functional group in n quinoxaline structures.
[0123]
R in general formula (1) to general formula (4)¹~ R³⁰Specifically, for example, an alkyl group such as a hydrogen atom, a methyl group, a trifluoromethyl group, and an ethyl group, an alkenyl such as an ethenyl group, a 2-propenyl group, a 1,3-butadienyl group, and a 4-methoxy-2-butenyl group Group, ethynyl group, alkynyl group such as 2-propynyl group, phenyl group, thienyl group, pyrrolyl group, 4-methoxyphenyl group, 3-trifluoromethylphenyl group, naphthyl group, aryl group such as 3-methylthienyl group, Examples thereof include halogen atoms such as fluorine and chlorine, carboxylic acid groups, carboxylic acid ester groups, nitro groups, nitrile groups, sulfonic acid groups, and sulfonic acid ester groups.
[0124]
Preferably hydrogen atom, methyl group, trifluoromethyl group, phenyl group, 3-trifluoromethylphenyl group, naphthyl group, fluorine, carboxylic acid group, carboxylic acid ester group, nitro group, nitrile group, sulfonic acid group, sulfone An acid ester group, more preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a phenyl group, a naphthyl group, a fluorine, a nitro group, a nitrile group, a sulfonic acid group, or a sulfonic acid ester group.
[0125]
R¹~ R³⁰As the combination, a combination of a hydrogen atom and an electron-donating group such as a methyl group or a phenyl group, or a combination of a hydrogen atom and an electron-withdrawing group such as a fluorine, trifluoromethyl group, nitro group or nitrile group is preferable. In addition, these preferable elements alone, for example, all hydrogen atoms, all methyl groups, all fluorine and the like are also preferable.
[0126]
The “polymer containing a quinoxaline structure represented by the general formula (1)” of the present invention (I) is preferably a polymer containing the quinoxaline structure represented by the general formula (2) as a part of the repeating unit. .
[0127]
General formula (2)
Embedded image

[0128]
(Wherein R⁷~ R^TenAre each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0129]
More preferred is a polymer containing the quinoxaline structure represented by the general formula (3) as a part of the repeating unit, or a polymer containing the quinoxaline structure represented by the general formula (4) as a part of the repeating unit.
[0130]
General formula (3)
Embedded image

[0131]
(Wherein R¹¹~ R¹⁴Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent Represents a group. )
[0132]
General formula (4)
Embedded image

[0133]
(Wherein R¹⁵~ R³⁰Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a C 1-20 carbon atom which may have a substituent. An alkyl group, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, or an aryl optionally having a substituent X represents an aryl group that may independently have a substituent, and Y represents a hetero atom alone or an aryl group having 4 to 20 carbon atoms that may have a hetero atom. N represents an integer of 0 to 5. )
[0134]
R in the general formula (3)¹¹~ R¹⁴Preferably a hydrogen atom, methyl group, trifluoromethyl group, phenyl group, 3-trifluoromethylphenyl group, naphthyl group, fluorine, carboxylic acid group, carboxylic acid ester group, nitro group, nitrile group, sulfonic acid group, A sulfonic acid ester group, more preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a phenyl group, a naphthyl group, a fluorine, a nitro group, a nitrile group, a sulfonic acid group, or a sulfonic acid ester group.
[0135]
R¹¹~ R¹⁴As the combination, a combination of a hydrogen atom and an electron-donating group such as a methyl group or a phenyl group, or a combination of a hydrogen atom and an electron-withdrawing group such as a fluorine, trifluoromethyl group, nitro group or nitrile group is preferable. In addition, these preferable elements alone, for example, all hydrogen atoms, all methyl groups, all fluorine and the like are also preferable.
[0136]
Further, R in the general formula (4)¹⁵~ R³⁰Preferably, a hydrogen atom, methyl group, trifluoromethyl group, phenyl group, 3-trifluoromethylphenyl group, naphthyl group, fluorine, carboxylic acid group, carboxylic acid ester group, nitro group, sulfonic acid group, sulfonic acid ester More preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a phenyl group, a naphthyl group, a fluorine, a nitro group, a sulfonic acid group, or a sulfonic acid ester group.
[0137]
R¹⁵~ R³⁰As the combination, a combination of a hydrogen atom and an electron-donating group such as a methyl group or a phenyl group, or a combination of a hydrogen atom and an electron-withdrawing group such as a fluorine, trifluoromethyl group, nitro group or nitrile group is preferable. In addition, these preferable elements alone, for example, all hydrogen atoms, all methyl groups, all fluorine and the like are also preferable.
[0138]
Moreover, X in General formula (4) represents the arylene group which may respectively independently have a substituent, and Y is respectively independently a hetero atom, and carbon number which may have a hetero atom is 6-20. N represents an integer of 0 to 5 each independently.
[0139]
Here, “independently” of X, Y, and n means that all may be the same in each repeating unit, or all may be different. That is, for example, in the case of a polymer having m repeating units represented by the general formula (4), m X, Y or n may all be the same, or all may be different, and some may be the same and part. Means that they can be different.
[0140]
Specific examples of X in the general formula (4) include a phenylene group, a 4-methylphenylene group, a 3-nitrophenylene group, a 3-trifluoromethylphenylene group, a naphthylene group, a 5-methylnaphthylene group, 4 -A nitronaphthylene group etc. can be mentioned. Preferred are a phenylene group, a 3-nitrophenylene group, a 3-trifluoromethylphenylene group, a naphthylene group, and a 4-nitronaphthylene group, and more preferred are a phenylene group, a 3-trifluoromethylphenylene group, and a naphthylene group.
[0141]
As Y in the general formula (4), specifically, oxygen, sulfur, selenium, NR (R is H or an alkyl group having 10 or less carbon atoms), phenylene group, 3-nitrophenylene group, 2,5- A dimethoxyphenylene group, a naphthylene group, etc. can be mentioned. Preferred are oxygen, a phenylene group, a 3-nitrophenylene group, and a naphthylene group, and more preferred are oxygen and a phenylene group.
[0142]
The combination of X and Y is preferably a combination of a phenylene group and an electron donating group such as oxygen or naphthylene group, or a combination of an electron withdrawing group such as a 3-trifluoromethylphenylene group. Further, a group that can be used for either X or Y, such as a phenylene group or a naphthylene group, is also preferred when both X and Y are the same.
[0143]
N represents an integer of 0 to 5, but a preferable range varies depending on Y.
[0144]
Specific examples of the polymer containing the quinoxaline structure represented by the general formula (1) of the present invention (I) include polyphenylquinoxaline (hereinafter abbreviated as “PPQ”), poly-2,2 ′-(p , P′-oxydiphenylene) -6,6′-oxydi (3-phenylquinoxaline) (hereinafter abbreviated as “POPQ”) and the like, but is not limited thereto. Details are described in “J. Polymer Science: part A1, Vol. 5, p. 1453, 1967”.
[0145]
The quinoxaline structure of the polymer containing the quinoxaline structure represented by the general formula (1) of the present invention (I) has a nuclear magnetic resonance spectrum (hereinafter abbreviated as “NMR”), an infrared spectrum (hereinafter referred to as “IR”). And elemental analysis, mass spectrometry (hereinafter abbreviated as “MS”), and the like.
[0146]
Specifically, for example, the polymer containing the quinoxaline structure represented by the general formula (1) is separated from the proton conductive polymer solid electrolyte of the present invention (I) by a method such as neutralization and washing, and further heated. Methods such as identifying the quinoxaline skeleton from the structure of the decomposition product by gravimetric analysis-mass spectrometry (hereinafter abbreviated as “TG-MS”), quantifying the composition ratio of elements by elemental analysis, and identifying the binding state by NMR and IR It is possible to identify the quinoxaline structure. Details are described in “J. Polymer Science: part A1, Vol. 5, p. 1453, 1967”.
[0147]
The molecular weight of the polymer containing the quinoxaline structure represented by the general formula (1) of the present invention (I) is measured by liquid chromatography such as gel permeation chromatography (hereinafter abbreviated as “GPC”). Can do. Specifically, for example, it is generally dissolved in a solvent such as hexaisopropanol and measured by GPC. For example, “J. Polymer Science: part B: Polymer Physics, Vol. 38, p. 1348, 2000” or “Chemistry Letters, p. 1049, 1999”.
[0148]
There is no restriction | limiting in particular as molecular weight of the polymer containing the quinoxaline structure represented by General formula (1) of this invention (I). In general, a higher one is preferable from the viewpoint of durability against insertion and release of protons and strength when formed into a film. Specifically, the weight average molecular weight in the absolute molecular weight measurement by GPC is preferably 5000 or more, and more preferably 10,000 or more.
[0149]
Moreover, it is preferable that the polymer containing the quinoxaline structure represented by the general formula (1) of the present invention (I) has a small amount of low molecular weight. Specifically, the low molecular weight material having a molecular weight of less than 1000 in the weight average molecular weight in the absolute molecular weight measurement by the light scattering method described above is preferably 5% by mass or less, more preferably 1% by mass. % Or less.
[0150]
In this case, the abundance of the low molecular weight substance can be specifically measured by using a method such as GPC as described above.
[0151]
Next, “B) acidic compound” in the proton conductive polymer solid electrolyte of the present invention (I) will be described.
[0152]
As the “B) acidic compound” in the proton conducting polymer solid electrolyte of the present invention (I), any compound can be used as long as it is dissociated to release protons. Any inorganic acid and organic acid may be used, and a polymer capable of releasing protons may be used. These may be used alone or in combination of two or more.
[0153]
Specific examples of the inorganic acid include sulfuric acid and nitric acid. Specific examples of organic acids include acetic acid, fluorinated acetic acid, propionic acid, fluorinated propionic acid, butyric acid, fluorinated butyric acid, acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, Examples thereof include fluorinated styrene sulfonic acid, vinyl sulfonic acid, and vinyl phosphoric acid.
[0154]
The description of “fluorination˜” such as “fluorinated acetic acid” herein refers to a compound in which at least one hydrogen atom of the organic acid is substituted with fluorine. Specific examples include trifluoroacetic acid, heptafluoropropionic acid, hexafluorostyrene sulfonic acid and the like.
[0155]
The “B) acidic compound” of the present invention (I) is preferably an “acid type polymer” which is a polymer capable of releasing protons. As used herein, “acid-type polymer” means a polymer in which a proton-releasable group is bonded to the side chain, main chain, and / or terminal of the polymer. Specifically, it refers to polystyrene sulfonic acid, polyphosphoric acid, polyacrylic acid, and fluorides thereof.
[0156]
Examples of what can be used as “B) acidic compound” of the present invention (I) include carboxylic acid polymers, sulfonic acid polymers, and phosphoric acid polymers. Specific examples include polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyphosphoric acid, polyvinyl phosphoric acid, and fluorides thereof. Preferred are polystyrene sulfonic acid, polyvinyl sulfonic acid, polyphosphoric acid, polyvinyl phosphoric acid and their fluorides, and more preferred are polystyrene sulfonic acid, polyvinyl sulfonic acid, polyvinyl phosphoric acid and their fluorides. These may be used alone or in combination of two or more.
[0157]
The molecular weight of the acid type polymer can be measured by a method such as GPC. Specifically, the acid type polymer can be in a solution state such as an aqueous solution and measured by GPC.
[0158]
Although there is no restriction | limiting in particular as a preferable molecular weight of the acid type polymer | macromolecule which can be used as "B) acidic compound" of this invention (I), Preferably the weight average molecular weight in the molecular weight measurement by said GPC is 500-1 million. More preferably, it is the range of 1000-1 million.
[0159]
Next, the proton conductive polymer solid electrolyte of the present invention (I) will be described.
The proton conductive polymer solid electrolyte of the present invention (I) is characterized by containing A) a polymer containing a quinoxaline structure represented by the general formula (1), and B) an acidic compound.
[0160]
General formula (1)
Embedded image

[0161]
(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfone group. It may have an acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent. An alkynyl group having 2 to 20 carbon atoms or an aryl group which may have a substituent is represented. )
[0162]
The ratio of A) the polymer containing a quinoxaline structure represented by the general formula (1) and B) the acidic compound in the proton conductive polymer solid electrolyte of the present invention (I) is not particularly limited. Preferably, from the viewpoint of proton conductivity and thermal safety, A) the amount of the anion of the acidic compound is in molar ratio with respect to the amount of nitrogen of the polymer containing the quinoxaline structure represented by the general formula (1). ,

And more preferably

Range.
[0163]
In the proton conductive polymer solid electrolyte of the present invention (I), the ratio of A) a polymer containing a quinoxaline structure represented by the general formula (1) and B) an acidic compound is measured by elemental analysis, thermal analysis, or the like. be able to. Specifically, for example, a method of measuring a ratio of nitrogen to an acid component by elemental analysis or measuring a volatile weight of an acidic component by TG can be used.
[0164]
There is no restriction | limiting in particular as proton conductivity of the proton-conductive polymer solid electrolyte of this invention (I). The preferable range varies depending on the performance required for the electrochemical device prepared using the proton conductive polymer solid electrolyte. Generally, it may be 0.1 mS / cm or more at 25 ° C. and 1 mS / cm or more at 80 ° C. Preferably, it is 1 mS / cm or more at 25 ° C. and 10 mS / cm or more at 80 ° C. An AC impedance method can be used as a method for measuring proton conductivity. Specifically, a proton conductive polymer solid electrolyte sample processed into a membrane or the like is sandwiched between inert electrodes such as platinum, an alternating current is applied to the sample, and measurement is performed based on impedance frequency dependence. it can. Details are described in “Electrochemical Measurement Method” (Electrical Society of Japan, November 15, 1984, 1st edition, 1 issue).
[0165]
Next, the present invention (II) will be described. The present invention (II) is a method for producing the proton conductive polymer solid electrolyte of the present invention (I).
[0166]
Although the manufacturing method of the polymer which has quinoxaline structure represented by General formula (1) of this invention (I) is not specifically limited, The method of the following manufacturing method A, manufacturing method B, and manufacturing method C is mentioned as a specific example. be able to.
[0167]
<Production method A>
As a first example of the method for producing a polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I), R of a compound having a quinoxaline skeleton represented by the general formula (1)¹~ R⁶It is obtained by polymerizing a compound in which at least one of these is a polymerizable functional group such as a vinyl group by radical polymerization or the like.
[0168]
If a polymerizable functional group can be imparted to the compound having the quinoxaline skeleton represented by the general formula (1) by this method, the functional group may be polymerized, and thus the material design is easy, and the polymer Can also be obtained relatively easily. For example, Photochem. Photobiol. 54, No. 1, p. 7, 1991 describes the polymerization of styrylquinoxaline. However, in this method, it is difficult to impart only a specific functional group, and chemical stability of the functional group portion of the obtained polymer may be a problem.
[0169]
Such a compound having a quinoxaline skeleton provided with a polymerizable functional group is represented, for example, by the general formula (5).
[0170]
General formula (5)
Embedded image

[0171]
(Wherein R³¹~ R³⁷Is a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an optionally substituted alkyl group having 1 to 20 carbon atoms, An alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. , X each independently represents an arylene group which may have a substituent, Y represents each independently a heteroatom, or an arylene group having 4 to 20 carbon atoms which may have a heteroatom, n Represents an integer of 0 to 5. )
[0172]
Specific examples thereof include 5-vinylquinoxaline, 2-styrylquinoxaline, 5- (meth) acryloylquinoxaline and substituent derivatives thereof.
[0173]
<Production method B>
As a second example of the method for producing a polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I), R of a compound having a quinoxaline skeleton represented by the general formula (1)¹~ R⁶A method of dehalogenating a compound in which at least any two of these are halogen atoms such as a bromo group with a metal catalyst such as Cu or Ni is also included.
[0174]
If halogen can be imparted to the compound having the quinoxaline skeleton represented by the general formula (1) by this method, dehalogenation polymerization may be performed, so that material design is easy and the polymer is relatively easy. Can get to. For example, JP-A-9-3171 describes an example in which various dihalide derivatives such as quinoxaline are polymerized with a nickel (0) valent catalyst such as bis (1,5-cyclooctadiene) nickel.
[0175]
However, in this method, it is difficult to introduce a halogen into a specific part of the quinoxaline skeleton, and the dehalogenation catalyst is relatively expensive and may cause a problem in production cost. In addition, there is a high possibility that the metal residue or halogen residue of the catalyst remains as an impurity in the polymer after polymerization, which may affect the chemical stability of the polymer.
[0176]
Examples of such halogen-substituted quinoxaline compounds include 2,6-dibromoquinoxaline, 2,5-dibromoquinoxaline, and substituent derivatives thereof.
[0177]
<Manufacturing method C>
A third example of the method for producing a polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I) includes a method of dehydrating polycondensation of a tetramine derivative and bisbenzyl and / or this derivative. . For example, J. et al. Polymer Science: part A1, Vol. 5, page 1453, 1967 describes that various quinoxaline polymers are polymerized by dehydration polycondensation.
[0178]
As a method for producing a polymer having a quinoxaline skeleton represented by the general formula (1) of the present invention (I), this method is simple in the polymerization process, and can be obtained in high yield and high molecular weight. preferable. However, there is a drawback that the design diversity of the compound is slightly inferior to the production method A and the production method B.
[0179]
Hereinafter, production method C, which is considered as the most preferred production method for producing a polymer having a quinoxaline skeleton represented by the general formula (1) of the present invention (I), that is, dehydration weight of various tetramines with bisbenzyl and / or bisbenzyl derivatives. The condensation will be described in more detail.
[0180]
<Tetramine derivative>
Tetramine, which is one of the compounds used in production method C, is represented by general formula (6).
[0181]
General formula (6)
Embedded image

[0182]
(Wherein R³⁸~ R⁴³Is a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an optionally substituted alkyl group having 1 to 20 carbon atoms, An alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. . Z represents each independently a heteroatom, an aryl group having 4 to 20 carbon atoms that may have a heteroatom, and m represents an integer of 0 to 5. )
[0183]
Specific examples thereof include 3,3-diaminobenzidine represented by general formula (7) and derivatives thereof.
General formula (7)
Embedded image

[0184]
Alternatively, 3,3 ′, 4,4′-tetraaminodiphenyl ether represented by the general formula (8) and derivatives thereof
General formula (8)
Embedded image

Etc.
[0185]
<Bisbenzyl and / or bisbenzyl derivative>
Another compound used in Production Method C, bisbenzyl and / or bisbenzyl derivative, is represented by the general formula (9).
[0186]
General formula (9)
Embedded image

[0187]
(Wherein R⁴⁴~ R⁵⁷Is a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an optionally substituted alkyl group having 1 to 20 carbon atoms, An alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. . )
[0188]
Specific examples thereof include 1,4-bisbenzyl (para form), 1,3-bisbenzyl (meta form) represented by general formula (10) or general formula (11), and substituted products thereof. it can.
[0189]
General formula (10)
Embedded image

[0190]
Formula (11)
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[0191]
<Dehydration polycondensation conditions>
The conditions for dehydrating polycondensation in Production Method C will be described.
There is no particular limitation on the reaction temperature. The preferred reaction temperature varies depending on the type of monomer used and the solvent, and cannot be generally limited, but is generally around the reflux temperature of the solvent used.
[0192]
There is no particular limitation on the reaction time. The preferred reaction time varies depending on the type of monomer used and the solvent, and cannot be generally limited. However, since it is a dehydration polycondensation, it generally requires at least about 10 hours for polymerization. A preferable range is 25 hours or more and 100 hours or less, and 30 hours or more and 70 hours or less is particularly preferable.
[0193]
The solvent to be used is not particularly limited as long as the monomer to be used is easily dissolved and does not react. For example, N, N-dimethylformamide (hereinafter also referred to as “DMF”), nitrogen-containing polar solvent such as N-methylpyrrolidone, ether such as tetrahydrofuran, 1,2-dimethoxyethane, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether Kind. For example, when the solvent is N, N-dimethylformamide, the reaction is preferably carried out at 130 ° C. or higher and 150 ° C. or lower.
[0194]
As the monomer concentration in the solvent during polymerization, the total mass of bisbenzyl and / or bisbenzyl derivative and tetramine is preferably 5% by mass or more and 40% by mass or less, and particularly preferably 8% by mass or more and 30% by mass or less. If the monomer concentration is too low, the polymerization does not proceed easily and the molecular weight does not increase. If the monomer concentration is too high, the viscosity of the polymerization solution will increase, making it difficult to mix, and there is a risk that the polymer will precipitate early and the molecular weight will be difficult to extend.
[0195]
Next, addition of an acidic compound to a polymer containing a quinoxaline structure will be described. As used herein, “addition” means binding to the polymer containing the quinoxaline structure of the present invention by various reactions. For example, it is expressed as “addition” that an acid is bonded to a nitrogen atom in quinoxaline having high basicity by an acid-base reaction. In addition, it is expressed as “addition” that an acid is bonded to a nitrogen atom or a phosphorus atom in a side chain of a polymer containing a quinoxaline structure by an acid-base reaction. In addition, an acid reacts with an unsaturated bond such as a phenyl group in a polymer containing a quinoxaline structure to form a covalent bond, which is referred to as “addition”.
[0196]
The proton conductive polymer solid electrolyte of the present invention (I) is characterized by containing A) a polymer containing a quinoxaline structure represented by the general formula (1), and B) an acidic compound.
[0197]
General formula (1)
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[0198]
(Wherein R¹~ R⁶Among them, at least one is a group bonded to the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfone group. It may have an acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent. An alkynyl group having 2 to 20 carbon atoms or an aryl group which may have a substituent is represented. )
[0199]
There is no particular limitation on the method for adding B) the acidic compound to the polymer containing the quinoxaline structure represented by the general formula (1) in the proton conducting polymer solid electrolyte of the present invention (I). For example, an acid can be added onto nitrogen by an acid-base reaction between a quinoxaline skeleton nitrogen and an acid. As a method of adding, a method of immersing a powdery or film-like polymer in an acid solution can be mentioned. However, low molecular acid compounds such as sulfuric acid are easily impregnated and added into the PPQ film by this method, but polymers such as polystyrene sulfonic acid have a problem that it is difficult to impregnate into the film. In addition, a polymer having an unsubstituted quinoxaline skeleton is generally hydrophobic, and it is necessary to control the wettability by changing the acid solution to an aqueous solution, a non-aqueous solution, or the like.
[0200]
For example, the following two methods can be used for efficiently adding a polymer acid.
(A) Method for synthesizing a polymer having a quinoxaline skeleton in a medium in which a polymer acid is present
(B) A method of polymerizing an acidic compound after immersing and impregnating a polymer having a quinoxaline skeleton in a solution of an acidic compound having a polymerizable functional group
[0201]
As the method (a), for example, various tetramines represented by the general formula (6) and bisbenzyl and / or bisbenzyl derivatives represented by the general formula (9) in a solution of polystyrene sulfonic acid can be dehydrated as described above. A method of polycondensation can be exemplified.
[0202]
General formula (6)
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[0203]
General formula (9)
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[0204]
As the method (b), as an acidic compound having a polymerizable functional group, for example, a polymer having a quinoxaline skeleton is immersed and impregnated in a styrene sulfonic acid monomer aqueous solution, and styrene sulfonic acid is added to nitrogen of quinoxaline, A method of polymerizing styrene sulfonic acid can be exemplified.
[0205]
The polymerization of the styrene sulfonic acid illustrated here can be performed on the conditions of general radical polymerization. That is, after adding a light and / or thermal polymerization initiator, polymerization can be performed by heating, ultraviolet light irradiation, or electron beam irradiation. Other acidic compounds having such a polymerizable functional group include derivatives such as vinyl sulfonic acid, vinyl phosphoric acid, acrylic acid, and fluorides thereof.
[0206]
Next, the present invention (III) will be described. The present invention (III) is a proton conductive polymer solid electrolyte membrane comprising the proton conductive polymer solid electrolyte of the present invention (I).
[0207]
The proton conducting polymer solid electrolyte membrane of the present invention (III) may be any membrane as long as it contains the proton conducting polymer solid electrolyte of the present invention (I).
[0208]
Although there is no restriction | limiting in particular in the thickness of the proton conductive polymer solid electrolyte membrane of this invention (III), Usually, 5 micrometers or more and 200 micrometers or less are preferable, and 10 micrometers or more and 80 micrometers or less are especially preferable. The film thickness can be measured using a dial gauge.
[0209]
In general, when the proton conductive polymer solid electrolyte membrane of the present invention (III) is used for various elements, it is also important that there is little variation in the thickness of the membrane. Therefore, although the preferred range of the thickness of a single film depends on the area of the film, it is preferably in the range of plus or minus 10%, particularly preferably in the range of plus or minus 5% with respect to the average thickness.
[0210]
Further, the strength of the film is not particularly limited, but the tensile strength is 100 kg / cm from the handling property when used for various elements.²Or more, preferably 500 kg / cm²The above is particularly preferable. The tensile strength in this case is a value measured according to JIS standard: JK7127.
[0211]
A reinforcing agent can be added to the proton conductive polymer solid electrolyte membrane of the present invention (III) for the purpose of improving the strength of the membrane as long as the physical properties are not impaired. By adding a reinforcing agent, the strength of the film is increased, or the storage stability of the film is improved, and the handleability is increased, so that the productivity of various elements can be improved.
[0212]
The reinforcing agent to be added is preferably non-electron conductive, electrochemically stable, heat resistant and acid / alkali resistant. Specific examples include oxide particles such as alumina, polyolefin fibers such as polypropylene, and fluorohydrocarbon fibers such as Teflon (registered trademark of EI DuPont de Nemours and Company).
[0213]
In particular, addition of oxide fine particles is preferable because not only the strength of the film but also the stability of the film is improved and the liquid retention property is increased. The oxide fine particles are preferably those having a larger specific surface area. Generally, 10m in BET specific surface area²/ G or more is preferred, more preferably a BET specific surface area of 50 m²/ G or more.
[0214]
The size of the oxide fine particles (primary particles when agglomerated to form secondary particles) is not particularly limited as long as it can be mixed with the polymer having a quinoxaline skeleton represented by the general formula (1) of the present invention. Those having a maximum particle size of 10 μm or less are preferred. More preferably, the fine particles have a maximum diameter of 0.001 μm to 1 μm.
[0215]
In addition, various shapes such as a spherical shape, an oval shape, a cubic shape, a rectangular parallelepiped shape, a cylindrical shape or a rod shape can be used.
[0216]
Specific examples of such oxide fine particles include ion conductivity such as alumina fine particles such as α, β, and γ-alumina, silica fine particles, titania fine particles, magnesia fine particles, and composite oxide fine particles thereof. Non-conductive oxide fine particles are exemplified. Among these, alumina-based fine particles and silica-based fine particles are preferable because of excellent stability. In particular, the surface of the alumina-based fine particles has a high affinity with anions, and in particular, has an effect of reducing proton binding and promoting proton movement. Specific examples of the alumina-based fine particles include α, β, and γ type Al obtained by various production methods such as a solid phase method and a gas phase method.₂O_ThreeExamples thereof include fine particles and alumina-based composite oxide fine particles of these and other metals. Among these, aluminum oxide C (trade name; manufactured by Degussa) having a large specific surface area and large surface activity, and γ-type Al of UA-5805 (manufactured by Showa Denko KK)₂O_ThreeFine particles are suitable. Specific examples of the silica-based fine particles include Aerosil (trade name; manufactured by Degussa), colloidal silica, and the like, which have a large specific surface area and a large surface activity.
[0217]
A preferable addition amount of the reinforcing agent is preferably in the range of 0.1% by mass to 50% by mass and particularly preferably in the range of 1% by mass to 30% by mass per unit mass of the polymer solid electrolyte membrane. If the addition amount of the reinforcing agent is 0.1% or less, it is difficult to exert a sufficient effect. On the other hand, if it exceeds 50% by mass, the ion conductivity of the membrane may be lowered, which is not preferable.
[0218]
The amount of the reinforcing agent contained in the proton conductive polymer solid electrolyte membrane of the present invention (III) can be measured by a method such as weight residue in thermogravimetric analysis or elemental analysis.
[0219]
Next, the present invention (IV) will be described. The present invention (IV) is a method for producing the proton conductive polymer solid electrolyte membrane of the present invention (III).
[0220]
The production method of the proton conductive polymer solid electrolyte membrane of the present invention (IV) may be any method as long as it can form the substance containing the proton conductive polymer solid electrolyte of the present invention (I) into a film shape. .
[0221]
Specifically, for example, a conventionally known method of forming a film by casting after dissolving the polymer in a soluble solvent can be mentioned. For example, Polymer Journals, 1987, Vol. 44, no. 4, page 317, and JP-A-9-245818.
[0222]
In the case of a polymer having a softening point, a general general-purpose thermoplastic resin film forming method in which pressure heating molding is performed with a heated roll press, an extruder, or the like can be used. For example, it is described in JP-A-2-142063.
[0223]
Further, there may be mentioned a method of polymerizing after casting a polymerizable compound or monomer solution having a quinoxaline structure represented by the general formula (1) onto a support or after casting the monomer solution after mixing with a reinforcing agent. This method is particularly useful when preparing a composite film with another support or reinforcing agent.
[0224]
In general, a film obtained by the casting method is suitable for producing a thin film having a thickness of about 5 μm to 10 μm, but the film obtained by this method is generally weak in strength. Moreover, the thickness variation tends to increase. Accordingly, it is possible to improve the strength and thickness by using a heat press molding method such as a roll press in combination, which is preferable.
[0225]
A reinforcing agent can be added to the proton conductive polymer solid electrolyte membrane of the present invention (III), but there is no particular limitation on the method of addition. For example, a method of forming a film after adding a reinforcing agent while heating and melting a polymer before film formation, a method of forming a film by adding a reinforcing agent to a polymer solution before film formation of casting, and the like can be exemplified. In addition, there is a method in which a reinforcing agent is first stretched into a film on a support, and the above-described polymer melt or polymer solution is applied to form a film.
[0226]
Next, the present invention (V) and the present invention (VI) will be described. The present invention (V) is an electrochemical device characterized by using the proton conductive polymer solid electrolyte of the present invention (I) and / or the proton conductive polymer solid electrolyte membrane of the present invention (III), The present invention (VI) is a method for producing the electrochemical device of the present invention (V).
[0227]
The proton conductive polymer solid electrolyte of the present invention (I) and / or the proton conductive polymer solid electrolyte membrane of the present invention (III) can be used as an electrolyte for various electrochemical devices. Specific examples of the element include, but are not limited to, a battery such as a secondary battery and a fuel cell, an electric double layer capacitor, and an electrochromic element.
[0228]
Hereinafter, regarding a secondary battery, a fuel cell, and an electrochromic element as examples of various electrochemical elements, specific examples of the configuration and the manufacturing method will be described.
[0229]
<Configuration and manufacturing method of secondary battery>
As an example of the electrochemical element of the present invention (V), the concept of the structure of a proton transfer type secondary battery is shown in a sheet form as shown in FIG. Basically, the secondary battery has a laminated structure of positive electrode / proton conductive polymer solid electrolyte membrane / negative electrode. These secondary batteries and their manufacturing methods are described in JP-A-11-126610, JP-A-11-144732, and the like.
[0230]
For the negative electrode, for a polymer capable of n-type proton doping represented by polypyridine and its derivatives, a conductive aid such as carbon black and Teflon (registered trademark of EI DuPont de Nemours and Company) What added the binder and shape | molded in the plate shape of the thickness of about 0.1 mm to 1 mm can be used. For the molding, for example, a pressure press machine or a heat press machine can be used. The electrode area can be of various sizes depending on the shape and capacity of the proton transfer secondary battery.
[0231]
Specific examples of other materials capable of n-type proton doping include nitrogen-containing aromatic polymers such as polypyrimidine and its derivatives, polyquinoline and its derivatives, and quinone-based polymers such as polyquinone and polyanthraquinone and their derivatives. Examples thereof include molecules, polyphenylene, polyphenylene vinylene, and derivatives thereof.
[0232]
For the positive electrode, for conductive polymers capable of p-type proton doping such as polyaniline and derivatives thereof, conductive assistants such as carbon black and Teflon (registered trademark of EI DuPont de Nemours and Company) A suitable binder can be added to form a plate having a thickness of about 0.1 mm to 1 mm. For the molding, for example, a pressure press machine or a heat press machine can be used. The electrode area can be of various sizes depending on the shape and capacity of the proton transfer secondary battery.
[0233]
Specific examples of other materials capable of p-type proton doping include amine-containing nitrogen aromatic polymers such as polyindole, polyisoindole, polypyrrole and derivatives thereof, and sulfur-containing aromatic compounds such as polythiophene and derivatives. Examples thereof include oxygen-containing aromatic polymers such as molecules, polyfurans and derivatives.
[0234]
The positive electrode and the negative electrode are laminated via the proton conductive polymer solid electrolyte membrane of the present invention, and the entire laminate is housed in a battery outer package such as an aluminum laminate or a polyolefin resin, and an insulation such as a polyolefin resin or an epoxy resin. By sealing with resin, a proton transfer type secondary battery which is a kind of the present invention (V) can be manufactured. More details are described in JP-A-11-126610 and JP-A-11-144732.
[0235]
The configuration of the proton transfer type secondary battery of the present invention (V) is not limited to the sheet type shown in FIG. 1, but may be any shape such as a chip type, a coin type, a square type, a cylindrical type, and the size thereof. However, there is no particular limitation, and it goes without saying that various sizes can be manufactured.
[0236]
<Configuration of fuel cell and manufacturing method thereof>
As an example of the electrochemical element of the present invention (V), the concept of the structure of a fuel cell is shown in FIG. Basically, a single cell has a laminated structure of separator / porous support + cathode catalyst / proton conductive polymer solid electrolyte membrane / anode catalyst + porous support / separator. Regarding the configuration of the fuel cell and the manufacturing method thereof, “Development and Practical Use of Polymer Electrolyte Fuel Cell” (edited by the Technical Information Association, 1999, first printing), JP-A-7-22034, JP-A-7 There is description in the publication -326363. Various sizes are used depending on the size of the fuel cell.
[0237]
Here, the “separator” is a conductive material that connects single cells in series, and the gas supply holes must be processed in the catalyst layer, and workability is required. Moreover, since acid resistance is required, a conductive carbon material is used. Specifically, for example, a graphite sheet or a composite sheet of graphite and various resins is used.
[0238]
The catalyst layer generally comprises a catalyst and a porous support. Platinum is usually used as the catalyst in the layer where the fuel typified by hydrogen reacts with oxygen at the air electrode and extracts the charge. In order to increase efficiency, measures such as thin coating of platinum on porous carbon have been made. The The porous support serves to fix the catalyst and needs strength, but gas diffusivity is also important, and a conductive carbon porous sheet such as a carbon fiber sheet is usually used. The contact between the catalyst layer and the proton conductive polymer solid electrolyte membrane is important for battery characteristics, and the membrane and the catalyst layer are laminated by heating and pressing at a temperature equal to or higher than the softening point of the membrane.
[0239]
A fuel cell can be manufactured by laminating a separator as a fuel electrode and an air electrode on both sides of the catalyst layer / solid polymer electrolyte membrane laminate and packaging them. The obtained fuel cell operates as a battery by supplying fuel from the fuel electrode. Further, a stacked fuel cell pack can be manufactured by stacking the unit cells at the separator portion.
[0240]
The configuration of the solid polymer electrolyte fuel cell of the present invention (V) is not limited to the sheet type shown in FIG. 2, but may be any shape such as a chip type, a coin type, a square type, a cylindrical type, and the size thereof. Needless to say, there are no particular limitations, and various sizes can be manufactured.
[0241]
<Configuration of Electrochromic Element and Method for Manufacturing the Same>
As an example of the electrochemical element of the present invention (V), the structure of an electrochromic element is shown in FIG. Basically, it has a laminated structure of transparent electrode / color-changing electrode material / proton conductive polymer solid electrolyte membrane / counter electrode material / electrode. The electrochromic device and the production method thereof are described in “Polymer” (1989, 38, 970 pages), JP-A-3-231229, JP-A-7-152050, and the like.
[0242]
The color change of the electrochromic device occurs due to the redox reaction of the material. In the case where a proton conductive polymer solid electrolyte membrane is used as the electrolyte, a material that undergoes a redox reaction with good reversibility due to movement of protons or counter anions and changes color is used. This is called “color-changing electrode material”.
[0243]
Specific examples of such materials include metal oxides such as tungsten oxide and iridium oxide, conductive polymers such as polyaniline and polypyrrole, and redox organic substances such as viologen and viologen-based polymers. it can. These materials are formed on a transparent electrode by casting or vapor deposition to a thickness of about 0.1 μm to 1 μm and used as a color changing electrode.
[0244]
As the counter electrode material, a material capable of compensating for the redox reaction of the discolored electrode material and causing redox with good reversibility due to transfer of a proton or counter anion is used. In this case, no color change is required. Specific examples of such materials include various metal oxides and conductive polymers. These counter electrode materials are also used as electrodes by forming a film on the electrode to a thickness of about 0.1 μm to 1 μm by casting or vapor deposition.
[0245]
As the transparent electrode, a film obtained by forming a film of ITO, tin oxide or the like on a glass substrate by sputtering, or a film obtained by thinly depositing gold can be used.
[0246]
The proton conducting polymer solid electrolyte of the present invention (I) or the proton conducting polymer solid electrolyte membrane of the present invention (III) is cut out to a desired size, and the above-mentioned discoloration electrode and counter electrode are placed on both sides of the membrane. The electrochromic device of the present invention (V) as shown in FIG. 3 can be produced by bonding so as not to contact each other, and adding a proton conductive electrolyte such as acid in some cases and sealing. .
[0247]
The configuration of the electrochromic device of the present invention (V) is not limited to the sheet type shown in FIG. 3, but may be a chip type, a coin type, a square type or the like, and there is no particular limitation on the size thereof. Needless to say, it is possible to manufacture a product of the size of
[0248]
【Example】
Hereinafter, the present invention will be described in detail by way of typical examples. These are merely examples for explanation, and the present invention is not limited to these.
[0249]
Example 1: Polyphenylquinoxaline ( Hereinafter, it is abbreviated as “PPQ”. ) Synthesis of
The reaction was carried out according to the following scheme (1).
Scheme (1)
[0250]
Embedded image

[0251]
That is, 1,4-bisbenzyl (hereinafter abbreviated as “BBZ”) was added to a 1 L glass four-necked flask (with a 4 cm long stirring splash and a cooling tube) to which 600 cc of DMF (water content 200 ppm) was added. Mw 342.4, Showa Denko, GC purity 98%) 41.52 g, 3,3-diaminobenzidine (hereinafter abbreviated as “DABZ”) (Mw 214.3, Aldrich LC purity 98%) 25.98 g was added. The mixture was stirred for 30 minutes under a nitrogen atmosphere at room temperature to completely dissolve BBZ and DABZ. Then, after heating up to 130 degreeC in nitrogen atmosphere for 1 hour, it was made to react for 40 hours, stirring at 130 degreeC.
[0252]
The resulting yellow precipitate was filtered, washed with methanol, dried and then vacuum dried at 120 ° C. for 12 hours to obtain 54.03 g of PPQ powder.
[0253]
It was estimated from the elemental analysis value and IR spectrum of this powder that the structure was as intended. Further, the absolute absolute weight average molecular weight by light scattering from GPC using hexafluoroisopropanol (hereinafter abbreviated as “HFIP”) as an eluent was 51000.
[0254]
Example 2: Production of PPQ film
A 5% by mass HFIP solution of the PPQ powder produced in Example 1 was prepared. After film formation with a screen printer, HFIP was slowly evaporated at room temperature / normal pressure to produce a uniform yellow film having an average film thickness of 50 μm. The tensile strength of this film (JIS standard: JK7127, sample width 10 mm) is 750 kg / cm.²Met. Thermogravimetric analysis of this film in air revealed that weight loss occurred at around 530 ° C., suggesting that PPQ itself had some change.
[0255]
Example 3: Production of PPQ film with sulfuric acid addition
In order to add sulfuric acid to the PPQ film produced in Example 2, it was immersed in a 40% aqueous sulfuric acid solution and allowed to stand at 50 ° C. for 10 hours. From the elemental analysis of CHNS, it was estimated that one sulfate ion was added to about 3 N atoms in PPQ.
[0256]
When the ionic conductivity of the film under 90% humidification was measured by an alternating current impedance method, it was 3.0 mS / cm at 25 ° C. and 35 mS / cm at 80 ° C. The tensile strength of this film (JIS standard: JK7127, sample width 10 mm) is 720 kg / cm.²It decreased slightly before addition of sulfuric acid.
[0257]
As a result of thermogravimetric analysis of the film in the air, there was a weight reduction that seems to be desorption of sulfate ions from around 180 ° C., and a weight reduction that seems to be a change in PPQ itself from around 510 ° C.
[0258]
Example 4: Production of polyphosphate-added PPQ film
In order to add polyphosphoric acid to the PPQ film produced in Example 2, it was left in a 50% polyphosphoric acid (weight average molecular weight 8000) aqueous solution at 80 ° C. for 20 hours, and turned yellowish red. From the elemental analysis of CHNP, it was estimated that one phosphate ion in polyphosphoric acid was added to about 4 N atoms in PPQ. When the ionic conductivity of the film under 90% humidification was measured by an alternating current impedance method, it was 0.8 mS / cm at 25 ° C. and 20 mS / cm at 80 ° C. The tensile strength (JIS standard: JK7127, sample width 10 mm) of this film was 830 kg / cm 2, which was slightly increased before addition of polyphosphoric acid.
[0259]
When the film was subjected to thermogravimetric analysis in the air, there was a change in PPQ itself and a decrease in mass that was considered to be the elimination of polyphosphoric acid from around 510 ° C.
[0260]
Example 5: Production of PPQ film with addition of polystyrene sulfonic acid
In order to add polystyrene sulfonic acid to the PPQ film produced in Example 2, it was allowed to stand at 80 ° C. for 20 hours in an aqueous solution of 30% polystyrene sulfonic acid (weight average molecular weight 12000). From elemental analysis of CHNS, it was estimated that one sulfonate ion in polystyrene sulfonate was added to about 5 N atoms in PPQ. When the ionic conductivity of this film under 90% humidification was measured by an alternating current impedance method, it was 1.0 mS / cm at 25 ° C. and 23 mS / cm at 80 ° C. The tensile strength (JIS standard: JK7127, sample width 10 mm) of this film is 1000 kg / cm.²Increased from before the addition of polystyrene sulfonic acid.
[0261]
As a result of thermogravimetric analysis of the film in the air, there was a mass decrease that seems to be desorption of sulfonate ions from around 200 ° C., and a mass reduction that seems to be due to changes in PPQ itself from around 500 ° C.
[0262]
Example 6 : Production of PPQ film to which acidic compounds having various polymerizable functional groups are added and polymerization thereof
When the PPQ film produced in Example 2 was left in an acidic compound aqueous solution having various polymerizable functional groups shown in Table 1 in the same manner as in Example 3 at 30 ° C. for 20 hours, the PPQ film in each solution was yellow. It turned red. From the elemental analysis of CHNSP, it was presumed that one anion in each acid was added to about 3 N atoms of PPQ. When the ionic conductivity of these films under 90% humidification was measured by the AC impedance method, it was as shown in Table 1. The film tensile strength (JIS standard: JK7127, sample width 10 mm) was as shown in Table 1. Moreover, when thermogravimetric analysis of this film in the air was conducted, it was as shown in Table 1.
[0263]
The PPQ film added with an acidic compound having a polymerizable functional group was allowed to stand at a temperature shown in Table 1 for 2 hours in a nitrogen atmosphere to polymerize the acidic compound having a polymerizable functional group. When the ionic conductivity, tensile strength and thermogravimetric analysis of these films under 90% humidification were performed in the same manner as before polymerization, the results shown in Table 1 were obtained.
[0264]
[Table 1]

[0265]
Example 7: Polyphenylquinoxaline ether ( Hereinafter, it is abbreviated as “PPQE”. ) Synthesis
The reaction was carried out according to the following scheme (2).
Scheme (2)
[0266]
[Chemical Formula 86]

[0267]
That is, instead of 25.98 g of DABZ used in Example 1, 3,3 ′, 4,4′-tetraaminodiphenyl ether (hereinafter abbreviated as “TADE”) (Mw 230.27, LC purity 98%) 55.83 g of yellow PPQE powder was obtained in the same manner as in Example 1 except that 92 g was used.
[0268]
The powder obtained from the elemental analysis value and IR spectrum of this powder was estimated to have the intended structure. Moreover, the absolute molecular weight (weight average) by the light scattering method from GPC using HFIP as an eluent was 48,000.
[0269]
Example 8: Production of PPQE film
A 5% by mass HFIP solution of PPQE powder produced in Example 7 was prepared. After film formation with a screen printer, HFIP was slowly evaporated at room temperature / normal pressure to produce a uniform yellow film having an average film thickness of 50 μm. The tensile strength of this film (JIS standard: JK7127, sample width 10 mm) is 1050 kg / cm.²Met. When this film was thermogravimetrically analyzed in air, mass loss occurred at around 460 ° C., suggesting that PPQE itself had some changes.
[0270]
Example 9: Production of a PPQ film added with parastyrene sulfonic acid and a polymer thereof
When the PPQ film produced in Example 8 was immersed in a 20% parastyrene sulfonic acid aqueous solution and left at 80 ° C. for 20 hours, it turned yellowish red. From the elemental analysis of CHNS, it was estimated that one parastyrene sulfonate ion was added to N atoms of PPQE. When the ionic conductivity of the film under 90% humidification was measured by an alternating current impedance method, it was 3.0 mS / cm at 25 ° C. and 50 mS / cm at 80 ° C. The tensile strength of this film (JIS standard: JK7127, sample width 10 mm) is 980 kg / cm.²It decreased slightly before acid addition. As a result of thermogravimetric analysis of this film in the air, there was a mass decrease that seems to be desorption of parastyrene sulfonate ions from around 240 ° C., and a mass reduction that seems to be a change of PPQE itself from around 450 ° C. .
[0271]
The PPQE film added with parastyrene sulfonic acid was allowed to stand at 120 ° C. for 2 hours in a nitrogen atmosphere to polymerize parastyrene sulfonic acid. The ionic conductivity of the film under 90% humidification was 2.8 mS / cm at 25 ° C. and 70 mS / cm at 80 ° C. The tensile strength of this film (JIS standard: JK7127, sample width 10 mm) is 1250 kg / cm.²Increased before polymerization and before acid addition.
[0272]
Example 10: Synthesis of polymethoxyphenylquinoxaline (hereinafter abbreviated as “PPQOM”)
The reaction was carried out according to the following scheme (3).
Scheme (3)
[0273]
Embedded image

[0274]
That is, in place of 41.52 g of BBZ used in Example 1, BBZ methoxy compound (hereinafter abbreviated as “BBZOM”) (Mw 404.41, LC purity 98%) 49.04 g was used, except that 49.04 g was used. In the same manner, 60.33 g of PPQOM powder of yellowish red color was obtained.
[0275]
From the elemental analysis values and IR spectrum of this powder, it was estimated that PPQOM was obtained as intended. Further, the absolute molecular weight (weight average) by light scattering from GPC using HFIP as an eluent was 38000.
[0276]
Example 11: Production of PPQOM film
A 5% by mass HFIP solution of PPQOM powder produced in Example 10 was prepared. After film formation with a screen printer, HFIP was slowly evaporated at room temperature / normal pressure to produce a uniform yellow film having an average film thickness of 50 μm. The tensile strength of this film (JIS standard: JK7127, sample width 10 mm) is 780 kg / cm.²Met. The thermogravimetric analysis of this film in air revealed that there was some change in PPQOM itself, with a two-stage mass loss around 380 ° C. and around 500 ° C.
[0277]
Example 12 : Production of vinyl sulfonic acid-added PPQOM film and its polymer
When the PPQOM film produced in Example 11 was immersed in a 20% aqueous vinyl sulfonic acid solution and left at 80 ° C. for 20 hours, it turned red. From the elemental analysis of CHNS, it was estimated that one per parastyrene sulfonate ion was added to N atoms of PPQOM. When the ionic conductivity of the film under 90% humidification was measured by an alternating current impedance method, it was 3.2 mS / cm at 25 ° C. and 43 mS / cm at 80 ° C. The tensile strength (JIS standard: JK7127, sample width 10 mm) of this film is 720 kg / cm.²It decreased slightly before acid addition. As a result of thermogravimetric analysis of the film in the air, there was a mass decrease that seemed to be desorption of parastyrene sulfonate ions from around 190 ° C., and a mass that seemed to change PPQOM itself at around 370 ° C. and around 500 ° C. There was a decrease.
[0278]
The vinyl sulfonic acid-added PPQOM film was allowed to stand at 120 ° C. for 3 hours in a nitrogen atmosphere to polymerize the vinyl sulfonic acid. The ionic conductivity of this film under 90% humidification was 2.3 mS / cm at 25 ° C. and 60 mS / cm at 80 ° C. The tensile strength of this film (JIS standard: JK7127, sample width 10 mm) is 830 kg / cm.²Increased before polymerization and before acid addition.
[0279]
Example 13: Production of polypyridine-2,5-diyl (hereinafter abbreviated as “Ppy”) electrode
Synth. Metals (25  103 1988), Ppy powder was obtained by Ni (0) method (weight average molecular weight in HFIP solution is 18000 in terms of polystyrene).
[0280]
Mixture of this Ppy powder and acetylene black (hereinafter abbreviated as “AB”) (manufactured by Denki Kagaku Kogyo) and polyvinylidene fluoride (hereinafter abbreviated as “PVDF”) (manufactured by Kureha) in a mass ratio of 70: 25: 5. An excess of N-methylpyrrolidone (hereinafter abbreviated as “NMP”) was added to the mixture to obtain a gel electrode composition. After applying this composition, several Ppy electrodes having a thickness of 1 × 1 cm and a thickness of 500 μm were produced by applying 1 ton pressure in the air. The average weight of these electrodes was 40 mg.
[0281]
Example 14: Production of polyaniline (hereinafter abbreviated as “PAn”) electrode
According to the method described in JP-A-62-210859, aniline was oxidatively polymerized in 1N hydrochloric acid using ammonium persulfate as an oxidizing agent, and then neutralized with an aqueous ammonia solution to obtain 100 g of a deep purple basic PAn powder. From the elemental analysis and IR, it was estimated that this PAn is almost the target structure. From the result of GPC in NMP, the molecular weight of PAn (in terms of PMMA) was about 120,000 on a weight average basis.
[0282]
Excess NMP was added to a 85: 7: 1: 7 mixture of this PAn powder, AB (manufactured by Electrochemical), VGCF (manufactured by Showa Denko), and PVDF (manufactured by Kuraray) to obtain a gel-like composition. After coating this composition on a conductive film current collector 1 cm × 1 cm, pressure-molding it for 1 ton, and vacuum-drying it at 80 ° C. for 8 hours, several 0.5 mm-thick PAn electrodes (average 38 mg) were obtained. Created.
[0283]
Example 15: Production of secondary battery
The PAn electrode manufactured in Example 14 and the PPQ / parastyrenesulfonic acid polymer film (50 μm, 1.2 cm × 1.2 cm) manufactured in Example 6 were stacked. The Ppy electrode manufactured in Example 13 was stacked, and the same conductive film (1 cm × 1 cm) as used in Example 14 was further stacked as a current collector. After pressurizing and adhering these laminates, both ends were fixed with a polyimide tape (Kapton tape). Next, attach the platinum foil to the positive and negative electrode conductive film collectors with silver paste as lead wires, put this laminate in an aluminum laminate outer package, and externally prevent the two platinum lead wires from short-circuiting I took it out. Next, 20% sulfuric acid aqueous solution was injected into the outer package as an electrolytic solution, and after the excess sulfuric acid aqueous solution was extracted under reduced pressure, the outer package was brought into close contact, and then sealed by heat fusion, and Ppy / PAn secondary battery ( Each n = 3, a total of 18). FIG. 1 shows a battery configuration in the outer package.
[0284]
When this battery was charged and discharged at 25 ° C., an operating voltage of 0 to 0.8 V, a current of 2 mA, and 10 mA, the maximum discharge capacity was 1.5 mAh and 1.2 mAh. Moreover, when it discharged at 0 degreeC and -10 degreeC at 2 mA, they were 1.4 mAh and 1.0 mAh. When the charge / discharge cycle was repeated at 10 mA, the capacity after 200 cycles was 1.5 mAh.
[0285]
Example 16: Production of a fuel cell
By attaching a platinum catalyst and a porous conductive carbon electrode (1 cm × 1 cm) on both sides of the PPQ / vinyl sulfonic acid polymer membrane (50 μm, 1.2 cm × 1.2 cm) produced in Example 6 according to a conventional method, A laminate for a fuel cell was produced. An electromotive force of 0.8 V was obtained at 80 ° C. and 200 mA by forming hydrogen supply chambers and air chambers on both sides of the laminate and supplying hydrogen to the hydrogen supply electrode. Moreover, in 1A, it was 0.5V.
[0286]
Example 17: Tungsten trioxide (hereinafter referred to as “WO ^Three Abbreviated. ) Manufacture of electrochromic layers
An indium tin oxide (hereinafter abbreviated as “ITO”) glass manufactured by Matsuzaki Vacuum Co., Ltd., covered with an end of 1.2 cm × 1.2 cm, and an ITO exposed portion of 1 cm × 1 cm. On top of that, the resistance heating method^ThreeVacuum deposition was performed. The obtained film had a thickness of about 1500 mm and a density of about 5 g / cc.
[0287]
Example 18: Production of an electrochromic device
Using a 1 M hydrochloric acid aqueous solution containing 0.5 M aniline on an ITO glass 1.2 cm × 1.2 cm manufactured by Matsuzaki Vacuum Co., Ltd. as an electrolyte, a potential scanning method in the range of −0.2 to 0.8 Vvs SCE is about 5000 mm. An electropolymerized polyaniline (hereinafter abbreviated as “PAn”) film was formed on ITO glass.
[0288]
The PPQ / parastyrene sulfonic acid polymer film (50 μm, 1.2 cm × 1.2 cm) produced in Example 6 was superimposed on this PAn / ITO electrode. Next, the WO produced in Example 17^ThreeAfter the ITO electrodes were stacked and these laminates were pressed and adhered, both ends were fixed with polyimide tape (Kapton tape). Next, a 20% sulfuric acid aqueous solution was injected into the exterior body as an electrolytic solution, and after removing the excess sulfuric acid aqueous solution under reduced pressure, the exterior body was brought into close contact, and the entire electrode end was sealed with an epoxy resin.^ThreeA / PPQ film / PAn-based electrochromic device was produced.
[0289]
When this electrochromic device was repeatedly colored / decolored at an injection charge of 6 mC, it showed dark blue / light blue electrochromism. The response speed was 100 msec. Further, even when the driving was repeated 100 times under these conditions, no change was observed in the color tone and response speed.
[0290]
【The invention's effect】
As described above, a proton-conducting polymer solid electrolyte containing A) a polymer containing a quinoxaline structure represented by the general formula (1), and B) an acidic compound, and an electrolyte comprising the electrolyte Since the membrane has a quinoxaline skeleton with high proton affinity, it has higher strength, heat resistance, acid resistance, and oxidation-reduction stability compared to conventional high proton conductive polymer solid electrolytes and electrolyte membranes composed of the electrolytes. It is clear that it is excellent in performance.
[0291]
In addition, the electrochemical element including the electrolyte and / or the electrolyte membrane in its configuration is excellent in durability, reliability, high-speed current characteristics, and response speed, and particularly, batteries such as secondary batteries and fuel cells, capacitors, electrochromic It is clear that the device is superior to the conventional one.
[0292]
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an embodiment of a sheet type battery shown as an example of a proton transfer type battery of the present invention.
FIG. 2 is a schematic sectional view of an example shown as an example of the fuel cell of the present invention.
FIG. 3 is a schematic cross-sectional view of an example of a sheet type electrochromic device shown as an example of the electrochromic device of the present invention.
[Explanation of symbols]
1 Positive electrode
2 Proton conductive polymer solid electrolyte + separator
3 Negative electrode
4 Current collector sheet
5 Lead wire
6 exterior body
7 Fuel electrode separator
8 Fuel electrode catalyst layer
9 Proton conducting polymer solid electrolyte membrane
10 Air electrode catalyst layer
11 Air electrode separator
12 Glass
13 Transparent conductive film
14 Electrochromic layer
15 Proton conductive polymer solid electrolyte + separator
16 Counter electrode layer
17 Insulating film spacer
18 Insulating resin sealant
19 Lead wire

Claims (34)

A proton conductive polymer solid electrolyte comprising: A) a polymer containing a quinoxaline structure represented by the general formula (4) as part of a repeating unit; and B) an acidic compound.
General formula (4)

(Wherein R ^{15 to} R ³⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent. A good C1-C20 alkyl group, a C2-C20 alkenyl group that may have a substituent, a C2-C20 alkynyl group that may have a substituent, or Represents an aryl group that may have a substituent, X represents an aryl group that may independently have a substituent, and Y represents a heteroatom or a hetero atom that may have a heteroatom independently. Represents an aryl group which may have 4 or more and 20 or less substituents, and n represents an integer of 0 to 5.) A) a polymer containing a quinoxaline structure represented by the general formula (1) in the side chain and a quinoxaline structure represented by the general formula (4) as part of a repeating unit, and B) an acidic compound. A proton conductive polymer solid electrolyte characterized by the above.
General formula (1)

(In the formula, at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, An acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkenyl group having 2 to 20 carbon atoms which may have a substituent And represents an alkynyl group having 2 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent.)
General formula (4)

(Wherein R ^{15 to} R ³⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent. A good C1-C20 alkyl group, a C2-C20 alkenyl group that may have a substituent, a C2-C20 alkynyl group that may have a substituent, or Represents an aryl group that may have a substituent, X represents an aryl group that may independently have a substituent, and Y represents a heteroatom or a hetero atom that may have a heteroatom independently. Represents an aryl group which may have 4 or more and 20 or less substituents, and n represents an integer of 0 to 5.)  B) The acidic compound is at least one selected from the group consisting of sulfuric acid, nitric acid, acetic acid, fluorinated acetic acid, propionic acid, fluorinated propionic acid, butyric acid and fluorinated butyric acid. 2. A proton conductive polymer solid electrolyte according to 1.  The proton conductive polymer solid electrolyte according to claim 1 or 2, wherein the acidic compound is an acid type monomer.  The acid type monomer is at least one selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid, and vinyl phosphoric acid. 5. The proton conductive polymer solid electrolyte according to claim 4, wherein  The proton conductive polymer solid electrolyte according to claim 1 or 2, wherein the acidic compound is an acid polymer.  The proton conductive polymer according to claim 6, wherein the acid type polymer is at least one selected from the group consisting of a carboxylic acid polymer, a sulfonic acid polymer, and a phosphoric acid polymer. Solid electrolyte. The method for producing a proton conductive polymer solid electrolyte according to claim 1, comprising the following first step to second step.
First step A) a polymer containing a quinoxaline structure represented by the general formula (1) and B) acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl A step of mixing an acidic compound having at least one polymerizable functional group selected from the group consisting of sulfonic acid and vinyl phosphoric acid to obtain a composition for producing a proton conductive polymer solid electrolyte.
Second step A step of polymerizing an acidic compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a proton conductive polymer solid electrolyte.
General formula (1)

(In the formula, at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the others are each independently, A hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an optionally substituted alkyl group having 1 to 20 carbon atoms, a substituent Represents an alkenyl group having 2 to 20 carbon atoms, which may have an alkenyl group, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. The method for producing a proton conductive polymer solid electrolyte according to claim 1, comprising the following first step to second step.
First step A) Polymer containing quinoxaline structure represented by general formula (1) in side chain and B) Acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfone A step of mixing an acidic compound having at least one polymerizable functional group selected from the group consisting of acid, vinyl sulfonic acid and vinyl phosphoric acid to obtain a composition for producing a proton conductive polymer solid electrolyte.
Second step A step of polymerizing an acidic compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a proton conductive polymer solid electrolyte.
General formula (1)

(In the formula, at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, An acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkenyl group having 2 to 20 carbon atoms which may have a substituent And represents an alkynyl group having 2 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent.) The method for producing a proton conductive polymer solid electrolyte according to claim 1, comprising the following first step to second step.
First Step A) A polymer containing the quinoxaline structure represented by the general formula (2) as a part of the repeating unit, and B) acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorine A step of mixing at least one acidic compound having a polymerizable functional group selected from the group consisting of fluorinated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid to obtain a composition for producing a proton conductive polymer solid electrolyte.
Second step A step of polymerizing an acidic compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a proton conductive polymer solid electrolyte.
General formula (2)

(Wherein R ^{7 to} R ¹⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent. A good C1-C20 alkyl group, a C2-C20 alkenyl group that may have a substituent, a C2-C20 alkynyl group that may have a substituent, or Represents an aryl group which may have a substituent. The method for producing a proton conductive polymer solid electrolyte according to claim 1, comprising the following first step to second step.
First step A) a polymer containing a quinoxaline structure represented by the general formula (1) in the side chain and a quinoxaline structure represented by the general formula (2) as part of the repeating unit, and B) acrylic acid, An acidic compound having at least one polymerizable functional group selected from the group consisting of fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid is mixed. Step for obtaining a composition for producing a proton conductive polymer solid electrolyte Second step Polymerizing an acidic compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a high proton conductivity A step of obtaining a molecular solid electrolyte.
General formula (1)

(In the formula, at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the other is independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, An acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkenyl group having 2 to 20 carbon atoms which may have a substituent And represents an alkynyl group having 2 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent.)
General formula (2)

(Wherein R ^{7 to} R ¹⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent. A good C1-C20 alkyl group, a C2-C20 alkenyl group that may have a substituent, a C2-C20 alkynyl group that may have a substituent, or Represents an aryl group which may have a substituent. The method for producing a proton conductive polymer solid electrolyte according to claim 1, comprising the following first step to second step.
First step A) A step of mixing a polymerizable compound containing a quinoxaline structure represented by the general formula (1) and B) an acidic compound to obtain a composition for producing a proton conductive polymer solid electrolyte.
Second step A step of polymerizing a polymerizable compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a proton conductive polymer solid electrolyte.
General formula (1)

(In the formula, at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the others are each independently, A hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an optionally substituted alkyl group having 1 to 20 carbon atoms, a substituent Represents an alkenyl group having 2 to 20 carbon atoms, which may have an alkenyl group, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. The method for producing a proton conductive polymer solid electrolyte according to any one of claims 1 to 2 and claims 6 to 7, comprising the following first step to second step.
First step A) Step of obtaining a composition for producing a proton conductive polymer solid electrolyte by mixing a polymerizable compound having a quinoxaline structure represented by the general formula (1) and B) an acid type polymer A step of polymerizing a polymerizable compound contained in the composition for producing a proton conductive polymer solid electrolyte obtained in the first step to obtain a proton conductive polymer solid electrolyte.
General formula (1)

(In the formula, at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the others are each independently, A hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an optionally substituted alkyl group having 1 to 20 carbon atoms, a substituent Represents an alkenyl group having 2 to 20 carbon atoms, which may have an alkenyl group, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.  A proton conductive polymer solid electrolyte membrane comprising the proton conductive polymer solid electrolyte according to claim 1.  The proton conductive polymer solid electrolyte membrane according to claim 14, wherein the thickness of the membrane is in the range of 5 µm to 200 µm.  The proton conductive polymer solid electrolyte membrane according to claim 14, wherein a non-electron conductive reinforcing agent is added.  The proton conductive polymer solid electrolyte membrane according to claim 16, wherein the non-electron conductive reinforcing agent is an oxide particle.  The proton conductive polymer solid electrolyte membrane according to claim 17, wherein the oxide particles are oxides of at least one element selected from Al, Si and Ti.  The proton conductive polymer solid electrolyte membrane according to claim 17 or 18, wherein the particle diameter of the oxide particles is in the range of 0.001 µm to 10 µm. The method for producing a proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19, comprising the following first step to second step.
1st process The process of obtaining a polymer film by distilling a solvent off, after apply | coating the polymer solution which contains a quinoxaline structure as a part of repeating unit represented by A) general formula (4) to a base material.
General formula (4)

(Wherein R ^{15 to} R ³⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent. A good C1-C20 alkyl group, a C2-C20 alkenyl group that may have a substituent, a C2-C20 alkynyl group that may have a substituent, or Represents an aryl group that may have a substituent, X represents an aryl group that may independently have a substituent, and Y represents a heteroatom or a hetero atom that may have a heteroatom independently. Represents an aryl group which may have 4 or more and 20 or less substituents, and n represents an integer of 0 to 5.)
Second step B) A step of adding an acidic compound to the polymer membrane obtained in the first step to obtain a proton conductive polymer solid electrolyte membrane. The method for producing a proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19, comprising the following first to third steps.
1st process The process of obtaining a polymer film by distilling a solvent off, after apply | coating the polymer solution which contains a quinoxaline structure as a part of repeating unit represented by A) general formula (4) to a base material.
General formula (4)

(Wherein R ^{15 to} R ³⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent. A good C1-C20 alkyl group, a C2-C20 alkenyl group that may have a substituent, a C2-C20 alkynyl group that may have a substituent, or Represents an aryl group that may have a substituent, X represents an aryl group that may independently have a substituent, and Y represents a heteroatom or a hetero atom that may have a heteroatom independently. Represents an aryl group which may have 4 or more and 20 or less substituents, and n represents an integer of 0 to 5.)
2nd process The process of adding the acid type monomer to the polymer film obtained at the 1st process, and obtaining the proton-conductive polymer solid electrolyte precursor film | membrane.
Third step A step of polymerizing the acid-type monomer contained in the proton conductive polymer solid electrolyte precursor film obtained in the second step to obtain a proton conductive polymer solid electrolyte membrane.  The acid type monomer is at least one polymerizable functional selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid. The method for producing a proton-conducting polymer solid electrolyte membrane according to claim 21, which is an acidic compound having a group. The method for producing a proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19, comprising the following first step to second step.
First Step A) Polymer General Formula (4) Containing a Quinoxaline Structure Represented by General Formula (4) as a Part of Repeating Unit

(Wherein R ^{15 to} R ³⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent. A good C1-C20 alkyl group, a C2-C20 alkenyl group that may have a substituent, a C2-C20 alkynyl group that may have a substituent, or Represents an aryl group that may have a substituent, X represents an aryl group that may independently have a substituent, and Y represents a heteroatom or a hetero atom that may have a heteroatom independently. Represents an aryl group which may have 4 or more and 20 or less substituents, and n represents an integer of 0 to 5.) and B) A composition for producing a proton conductive polymer solid electrolyte membrane containing an acidic compound is obtained. Process.
2nd process The process of obtaining the proton conductive polymer solid electrolyte membrane by pressurizing and / or heat-molding the composition for proton conductive polymer solid electrolyte membrane production obtained in the 1st process. The method for producing a proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19, comprising the following first step to second step.
First Step A) Polymer General Formula (4) Containing a Quinoxaline Structure Represented by General Formula (4) as a Part of Repeating Unit

(Wherein R ^{15 to} R ³⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent. A good C1-C20 alkyl group, a C2-C20 alkenyl group that may have a substituent, a C2-C20 alkynyl group that may have a substituent, or Represents an aryl group which may have a substituent, X represents an aryl group which may independently have a substituent, and Y represents a hetero atom and a carbon atom which may have a hetero atom each independently. 4 represents an aryl group which may have a substituent of 20 or less, and n represents an integer of 0 to 5.) and B) A composition for producing a proton conductive polymer solid electrolyte membrane containing an acid type monomer. Obtaining step.
Second step A step of obtaining a proton conductive polymer solid electrolyte membrane by pressurizing and heating while polymerizing the acid type monomer in the composition for producing a proton conductive polymer solid electrolyte membrane obtained in the first step.  The acid type monomer is at least one polymerizable functional selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid. The method for producing a proton conductive polymer solid electrolyte membrane according to claim 24, wherein the proton conductive polymer solid electrolyte membrane is an acidic compound having a group.  An electrochemical device comprising the proton conductive polymer solid electrolyte according to any one of claims 1 to 7 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19. .  A battery comprising the proton conductive polymer solid electrolyte according to any one of claims 1 to 7 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19.  A fuel cell comprising the proton conductive polymer solid electrolyte according to any one of claims 1 to 7 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19.  An electric double layer comprising the proton conductive polymer solid electrolyte according to any one of claims 1 to 7 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19. Capacitor.  An electrochromic device comprising the proton conductive polymer solid electrolyte according to any one of claims 1 to 7 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19. .  The proton conductive polymer solid electrolyte according to any one of claims 1 to 7 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19 is installed between a positive electrode and a negative electrode. A battery manufacturing method characterized by the above.  The proton conductive polymer solid electrolyte according to any one of claims 1 to 7 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19 is installed between a fuel electrode and an air electrode. A method for manufacturing a fuel cell.  The proton conductive polymer solid electrolyte according to any one of claims 1 to 7 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19 is installed between two polarizable electrodes. A method for manufacturing an electric double layer capacitor.  The proton conductive polymer solid electrolyte according to any one of claims 1 to 7 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 14 to 19 is installed between the color changing electrode and the counter electrode. A method for producing an electrochromic device.

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