JP2004331799A - New polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polymer easy to produce at a lower cost, having sufficiently practicable proton conductivity even under high temperature and low humidity. <P>SOLUTION: The new polymer is composed of recurring units of the formula(I)( wherein, R<SB>1</SB>and R<SB>2</SB>are each H, a halogen atom or 1-10C hydrocarbon group and may be joined to each other to form a ring; R<SB>3</SB>is H, a halogen atom, 1-10C hydrocarbon group or carbonyl-containing organic group and may be joined to an atom included in Y to form a ring; R<SB>4</SB>is an electron-attracting group; Y is a bivalent or higher-valent linkage group; k is an integer of ≥1; when k is ≥2, R<SB>4</SB>may be the same as or different from each other ). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００１１】
（式中、Ｒ_１及びＲ_２はそれぞれ独立に、水素原子、ハロゲン原子、またはＣ１〜Ｃ１０炭化水素基を表し、Ｒ_１及びＲ_２は、連結して環を形成してもよく、Ｒ_３は、水素原子、ハロゲン原子、Ｃ１〜Ｃ１０炭化水素基、またはカルボニル基を含む有機基を表し、Ｙに含まれる原子と結合して環を形成してもよく、Ｒ_４は、電子吸引基を表し、Ｙは、２価以上の連結基を表し、ｋは１以上の整数を表し、ｋが２以上の場合、Ｒ_４は同一または相異なっていてもよい。）で表される繰り返し単位を有することを特徴とする新規重合体に関し、
（２）式（Ｉ）中、Ｙが、芳香族炭化水素骨格を有する２価以上の有機連結基であることを特徴とする（１）に記載の新規重合体、
（３）式（Ｉ）中、Ｙが、式（ＩＩ）
【００１２】
【化６】

【００１３】
（式中、Ｘは、酸素原子、硫黄原子、または置換もしくは無置換窒素原子を表し、Ｒ_５は、有機基を表し、ｎは０または１〜４のいずれかの整数を表し、ｎが２以上の場合、同一または相異なっていてもよく、Ｒ_５同士で結合して環を形成してもよく、・は結合点を表し、ｍは１〜５のいずれかの整数を表す。）で表される有機連結基であることを特徴とする（１）または（２）に記載の新規重合体、
（４）式（ＩＩ）中、ＸがＮＲ_６（Ｒ_６は、水素原子または有機基を表す。）であることを特徴とする（３）に記載の新規重合体、
（５）式（Ｉ）で表される繰り返し単位が、式（ＩＩＩ）
【００１４】
【化７】

【００１５】
（式中、Ｒ_１〜Ｒ_４、及びｋは、前記と同じ意味を表し、Ｒ_７は、水素原子または有機基を表し、Ｒ_３とＲ_７、またはＲ_３と窒素原子は結合して環を形成してもよい。）で表される繰り返し単位であることを特徴とする（１）に記載の新規重合体に関する。
（６）式（ＩＶ）
【００１６】
【化８】

【００１７】
（式中、Ｒ_１１及びＲ_１２はそれぞれ独立に、水素原子、ハロゲン原子、またはＣ１〜Ｃ１０炭化水素基を表し、Ｒ_１１及びＲ_１２は、連結して環を形成してもよく、Ｒ_１３は、水素原子、ハロゲン原子、Ｃ１〜Ｃ１０炭化水素基、またはカルボニル基を含む有機基を表し、Ｒ_１３とＲ_１７、またはＲ_１３と窒素原子は結合して環を形成してもよく、Ｒ_１４は、電子吸引基を表し、Ｒ_１７は、水素原子または有機基を表し、ｎは１以上の整数を表し、ｎが２以上の場合、Ｒ_１４は同一または相異なっていてもよい。）で表される化合物に関する。
【００１８】
【発明の実施の形態】
本発明の新規重合体は、式（Ｉ）で表される繰り返し単位を有することを特徴とする。式（Ｉ）中、Ｒ_１及びＲ_２はそれぞれ独立に、水素原子、ハロゲン原子、またはＣ１〜Ｃ１０炭化水素基を表し、具体的には、フッ素原子、クロル原子、ブロム原子等のハロゲン原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、イソブチル基、ｔ−ブチル基、フェニル基、ナフチル基、ベンジル基等の炭素数１〜１０の炭化水素基を表し、Ｒ_１及びＲ_２は、連結して環を形成してもよい。
【００１９】
Ｒ_３は、水素原子、ハロゲン原子、Ｃ１〜Ｃ１０炭化水素基、またはカルボニル基を含む有機基を表し、具体的には、フッ素原子、クロル原子、ブロム原子等のハロゲン原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、イソブチル基、ｔ−ブチル基、フェニル基、ナフチル基、ベンジル基等の炭素数１〜１０の炭化水素基、カルボキシル基、メトキシカルボニル基、エトキシカルボニル基等のエステル基、ホルミル基、アセチル基、ベンゾイル基等のアシル基等のカルボニル基を含む有機基を表し、Ｙに含まれる原子と結合して環を形成してもよく、例えば、Ｙに窒素原子が含まれている場合に、窒素原子とカルボニル基が結合して環状イミド、アルキレン鎖と結合して、環状アミド等を形成することができる。
【００２０】
また、Ｒ_１〜Ｒ_３は、それぞれ独立に、適当な炭素原子上に、置換基を有していてもよく、そのような置換基として、具体的にはフッ素原子、クロル原子、またはブロム原子等ハロゲン原子、メチル基、エチル基、ｎ−プロピル基、フェニル基、ナフチル基、ベンジル基等の炭化水素基、アセチル基、ベンゾイル基等のアシル基、ニトリル基、ニトロ基、メトキシ基、フェノキシ基等の炭化水素オキシ基、メチルチオ基、メチルスルフィニル基、メチルスルホニル基、アミノ基、ジメチルアミノ基、アニリノ基等を例示することができる。
【００２１】
Ｒ_４は、電子吸引基を表し、窒素原子上のプロトンの酸性度をあげ、または窒素原子上の電子を共鳴によって安定化可能な官能基であれな特に制限されず、具体的には、アセチル基、フェニルアセチル基、フェノキシアセチル基、フェニルスルホニルアセチル基、ペンタフルオロフェニルアセチル基、ペンタデカノイル基、ノナノイル基、ノナデカノイル基、ヘキサデカノイル基、３−ペンテノイル基、８−オクタデセノイル基、アセトアセチル基、３−アセチル−２−プロペノイル基、４−ヘキセノイルアセチル基、１１−ペンタノイルウンデカノイル基、９−ノナノイルノナノイル基、６−ドデカノイルヘキサノイル基、４−テトラデカノイルブタノイル基、２−オクチノイル基、２−ノニノイル基、ベンゾイル基、４−メチルベンゾイル基、４−ニトロベンゾイル基、ペンタフルオロベンゾイル基、トリフルオロアセチル基、パーフルオロノナノイル基、パーフルオロプロパノイル基、パーフルオロブタノイル基、パーフルオロデカノイル基、メタンスルホニル基、トリフルオロメタンスルホニル基、パーフルオロノニルスルホニル基、パーフルオロプロピルスルホニル基、パーフルオロブチルスルホニル基、パーフルオロデシルスルホニル基、ｐ−トルエンスルホニル基、テトラフルオロフェニルスルホニル基、フェニル基、４−ニトロフェニル基、２，４−ジニトロフェニル基等を例示することができる。
【００２２】
Ｙは、二価以上の連結基を表し、具体的には、酸素原子、硫黄原子、無置換または置換基を有する窒素原子、または下記式に示す有機基を例示することができる。尚、下記式中の酸素原子は、適宜、硫黄原子、窒素原子、ケイ素原子、ケイ素原子−酸素原子等に交換することができる。また、下記に例示する連結基は、適当な炭素原子上に、置換基を有していてもよく、そのような置換基として、具体的にはフッ素原子、クロル原子、またはブロム原子等ハロゲン原子、メチル基、エチル基、ｎ−プロピル基、フェニル基、ナフチル基、ベンジル基等の炭化水素基、アセチル基、ベンゾイル基等のアシル基、ニトリル基、ニトロ基、メトキシ基、フェノキシ基等の炭化水素オキシ基、メチルチオ基、メチルスルフィニル基、メチルスルホニル基、アミノ基、ジメチルアミノ基、アニリノ基等を例示することができる。
【００２３】
【化９】

【００２４】
【化１０】

【００２５】
Ｙとして、特に、芳香族炭化水素骨格を有する二価以上の有機連結基が好ましく、具体的には、式（ＩＩ）で表される有機連結基を例示することができる。
【００２６】
式（ＩＩ）中、Ｘは、酸素原子、硫黄原子、または置換もしくは無置換窒素原子を表し、Ｒ_５は、メチル基、エチル基、アリール基、プロパルギル基、ベンジル基、またはフェニル基等の炭化水素基、メトキシ基、フェノキシ基、またはアセトキシ基等のアルコキシ基、メチルチオ基、メチルスルフィニル基、またはメチルスルホニル基等の硫黄含有基、ジメチルアミノ基、ピリジル基等の複素環基、エステル基、ニトロ基、シアノ基等の有機基を表し、ｎは０または１〜４のいずれかの整数を表し、ｎが２以上の場合、同一または相異なっていてもよく、Ｒ_５同士で結合して環を形成してもよく、ｍは１〜５のいずれかの整数を表す。尚、・は結合点を表し、結合点において、カルボニル基、またはスルホンアミド基と結合することを表す。
【００２７】
式（Ｉ）で表される繰り返し単位として、特に、式（ＩＩＩ）で表される繰り返し単位を好ましく例示することができる。式（ＩＩＩ）中、Ｒ_１〜Ｒ_４、及びｋは、前記と同じ意味を表し、同様の具体例を例示することができる。また、Ｒ_７は、水素原子、または有機基を表す。この場合、有機基とは、炭素原子を含み、窒素原子に結合できる官能基を表し、具体的には、メチル基、エチル基、アリール基、プロパルギル基、ベンジル基、またはフェニル基等の炭化水素基、メトキシ基、フェノキシ基、またはアセトキシ基等のアルコキシ基、メチルチオ基、メチルスルフィニル基、またはメチルスルホニル基等の硫黄含有基、ジメチルアミノ基、ピリジル基等の複素環基、エステル基、ニトロ基、シアノ基等を例示することができる。また、Ｒ_３とＲ_７、またはＲ_３と窒素原子は結合して環を形成して、例えば、環状イミド、環状アミド等を形成することができる。
【００２８】
式（Ｉ）で表される繰り返し単位として、具体的には下記式に示す繰り返し単位を例示することができる。
【００２９】
【化１１】

【００３０】
本発明の新規重合体は、式（Ｉ）で表される繰り返し単位に、必要に応じて共重合可能な共役二重結合を有する単量体から誘導される繰り返し単位を含めることができ、そのような単量体としては、スチレン、α−メチルスチレン、α−メチル−ｐ−メチルスチレン、ｐ−メチルスチレン、ｍ−メチルスチレン、ｏ−メチルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、２，５−ジメチルスチレン、ｐ−イソプロピルスチレン、２，４，６−トリイソプロピルスチレン、ｐ−ｔ−ブトキシスチレン、ｐ−ｔ−ブトキシ−α−メチルスチレン、ｍ−ｔ−ブトキシスチレン、１，２，２−トリフルオロビニルベンゼン、４−フルオロスチレン等のビニル芳香族単量体、ビニルピリジン等のヘテロ原子含有芳香族ビニル化合物、メチルビニルケトン、エチルビニルケトン等のビニルケトン化合物、アクリル酸メチル、アクリル酸エチル等のアクリル酸エステル、（メタ）アクリル酸アミド又は（メタ）アクリロニトリル、１，３−ブタジエン、イソプレン、２，３−ジメチルブタジエン、２−エチル−１，３−ブタジエン、１，３−ペンタジエン等の共役ジエン単量体、１，１，１−トリスルオロプロピレン等を例示することができる。これらの化合物は１種又は２種以上の混合物として使用することができ、ブロック共重合、ランダム共重合等させることができる。
【００３１】
本発明の重合体の分子量は特に制限されないが、５，０００以上、さらに１０，０００以上が好ましく、１，０００，０００以下が望ましい。
【００３２】
本発明の重合体は、式（ＩＶ）で表される単量体、または、式（ＩＶ）で表される単量体と必要に応じて共重合体可能な単量体とを、用いる単量体の種類により公知の重合方法を適宜選択して重合することにより製造することができ、そのような重合法としてラジカル重合法、カチオン重合法、アニオン重合法いずれの方法も用いることができ、溶液重合法、バルク重合法、懸濁重合法等、いずれも公知方法を適宜組み合わせて用いることができる。
【００３３】
式（ＩＶ）で表される化合物中、Ｒ_１１及びＲ_１２はそれぞれ独立に、水素原子、ハロゲン原子、またはＣ１〜Ｃ１０炭化水素基を表し、Ｒ_１及びＲ_２で例示した具体例を同様に例示することができ、Ｒ_１１及びＲ_１２は、連結して環を形成してもよく、Ｒ_１３は、水素原子、ハロゲン原子、Ｃ１〜Ｃ１０炭化水素基、またはカルボニル基を含む有機基を表し、Ｒ_３で例示した具体例を同様に例示することができ、Ｒ_１３とＲ_１７、またはＲ_１３と窒素原子は結合して環を形成してもよく、例えば、環状イミド、環状アミド等を形成することができ、Ｒ_１４は、電子吸引基を表し、Ｒ_４で例示した具体例を同様に例示することができ、Ｒ_１７は、水素原子または有機基を表し、Ｒ_７で例示した具体例と同様の具体例を例示することができ、ｎは１以上の整数を表し、ｎが２以上の場合、Ｒ_１４は同一または相異なっていてもよい。
【００３４】
以下本発明を実施例を用いて詳細に説明するが、本発明の範囲は実施例に限定されるものではない。
【００３５】
【実施例】
実施例１（Ｎ−（４−アセチルアミノスルフォニル）フェニルメタクリルアミド（モノマー１）の合成）
微量のＮ−フェニル−β−ナフチルアミンを含むアセトン５０ｍｌにスルファアセトアミド４６ｍｍｏｌを溶解して得た溶液を１０℃で常に撹拌しながら、これにメタクリロイルクロライド４６ｍｍｏｌを一滴ずつ加え、５０℃で２時間加熱した。薄層クロマトグラフィー（ＴＬＣ）で原料がなくなったことを確認し、溶媒を蒸発させ、水１００ｍｌを加えて溶解し、ＮａＨＣＯ_３溶液（６ｇ／２０ｍｌＨ_２０）で中和させ、析出した結晶をろ過し、エーテルで洗浄した。さらに、エタノールで再結晶した目的物を収率は３７％で得た。（融点：１９６℃、分解点：２５１℃）目的物の^１ＨＮＭＲスペクトルを図１に示す。
実施例２（Ｎ−（４−ペンゾイルアミノスルフォニル）フェニルメタクリルアミド（モノマー２）の合成）
（１）スルファニルアミド、Ｋ_２ＣＯ_３（０．５当量）、フェニルベンゾエートを混合し、１８０℃で２０分間加熱した後、室温まで冷却し、１００ｍｌの５重量％のＮａ_２ＣＯ_３溶液を加えて溶解し、不溶物を濾過後、ベンゼンで３回抽出して、フェノールを取り除き、水層に希塩酸（濃塩酸１７ｍｌを水１８０ｍｌで希釈）を一滴ずつ加え、析出した結晶を濾過し、エタノールで再結晶、乾燥し、スルファベンツアミドを収率は４１％で得た。
（２）微量のフェニル−β−ナフチルアミンを含むアセトン５０ｍｌに上記のようにして調製したスルフォベンツアミド４４ｍｏｌを溶解し、１０℃で常に撹伴しながら、メタクリロイルクロライド４４ｍｏｌを一滴ずつ加え、５０℃で２時間加熱した。ＴＬＣで原料消失を確認後、溶媒を留去し、水１００ｍｌを加えて溶解し、ＮａＨＣＯ_３溶液（６ｇ／２０ｍｌＨ_２Ｏ）で中和し、析出した結晶をろ過、エーテルで洗浄し、さらにエタノールで再結晶し、目的物を、収率は４１％で得た。（融点：２３０℃、分解点：２５７℃）目的物の^１ＨＮＭＲを図２に示す。
実施例３（Ｎ−（４−メチルスルフォニルアミノスルフォニル）フェニルメタクリルアミド（モノマー３）の合成）
（１）スルファニルアミド、Ｋ_２ＣＯ_３（０．５当量）、フェニルメタンスルフォネートを混合し、１８０℃で２０分間加熱した後、室温まで冷却し、１００ｍｌの５重量％のＮａ_２ＣＯ_３溶液を加えて溶解し、不溶物を濾過後、濾液に塩酸加え中和した。析出した結晶を濾過、乾燥し、シリカゲルカラムクロマトグラフィー（展開溶媒：エタノール：ベンゼン＝１：２）で分離し、エタノールで再結晶、乾燥し、スルファメタンスルフォンアミドを収率は２０％で得た。
（２）微量のフェニルーβ−ナフチルアミンを含むアセトン５０ｍｌに上記の予にして調製したスルフォンアミド４４ｍｏｌを溶解し、１０℃で撹拌しながら、メタクリロイルクロライド４４ｍｏｌを一滴ずつ加え、５０℃で３時間加熱した。ＴＬＣで原料の消失を確認後、溶媒を留去し、得られた結晶をエーテルで洗浄し、さらにエタノールで再結晶して、目的物を収率４５％で得た。（融点：２３１℃、分解点：２５０℃）目的物の^１ＨＮＭＲを図３に示す。
実施例４（Ｎ−（４−トリフルオロメチルスルフォニルアミドスルフォニル）フェニルメタクリルアミド（モノマー４）の合成）
（１）スルファニルアミド、Ｋ_２ＣＯ_３（０．５当量）、４−ニトロフエニルトリフルオロメタンスルフオネート（１．０当量）を混合し、１８０℃で２０分間加熱した後、室温まで冷却し、１００ｍｌの５重量％のＮａ_２ＣＯ_３溶液を加えて溶解し、不溶物を濾過後、濾液に塩酸加え中和した。析出した結晶を濾過、乾燥し、シリカゲルカラムクロマトグラフィー（展開溶媒：エタノール：ベンゼン＝１：２）で分離し、エタノールで再結晶、乾燥し、スルファトリフルオロメタンスルフォンアミドを収率は１５％で得た。
（２）微量のフェニル−β−ナフチルアミンを含むアセトン５０ｍｌに上記のようにして調製したスルフォンアミド４４ｍｏｌを溶解し、１０℃で撹拌しながら、メタクリロイルクロライド４４ｍｏｌを一滴ずつ加え、５０℃で３時間加熱した。ＴＬＣで原料の消失を確認後、溶媒を留去し、得られた結晶をエーテルで洗浄し、さらに酢酸エチルで再結晶して、目的物を収率１０％で得た。（融点：２０１℃、分解点：２１５℃）目的物の^１ＨＮＭＲを図４に示す。
実施例５（Ｎ−（４−トリフルオロアセチルアミドスルフォニル）フェニルメタクリルアミド（モノマー５）の合成）
（１）スルファニルアミドとＫ_２ＣＯ_３（０．５当量）を混ぜ、１８０℃で２０分間、加熱した。室温まで冷却し、メタノールを加えて溶解し、撹拌しながら、トリフルオロ酢酸メチルあるいはトリフルオロ酢酸フェニル（１．０当量）を一滴ずつ加え、３時間撹拌した。不溶物をろ過し、溶媒を留去し、５重量％のＮａ_２ＣＯ_３溶液を加えて溶解し、さらに不溶物を濾過後、塩酸を加えて中和し、析出した結晶を濾過した。得られた結晶をシリカゲルクロマトグラフィー（展開溶媒：エタノール：ベンゼン＝１：２）で分離し、アセトン／エタノール（体積比７：３）で再結晶をし、スルファトリフルオロアセトアミドを収率は４１％で得た。
（２）微量のフェニル−β−ナフチルアミンを含むアセトン５０ｍｌに上記のようにして調製したスルフォンアミド４４ｍｏｌを溶解し、１０℃で撹拌しながら、メタクリロイルクロライド４４ｍｏｌを一滴ずつ加え、５０℃で３時間加熱した。ＴＬＣで原料の消失を確認後、冷却し、析出した結晶を濾過し、さらにアセトニトリルで再結晶して、目的物を収率４１％で得た。（融点：２６４℃、分解点：２６９℃）目的物の^１ＨＮＭＲを図５に示す。
実施例６（Ｎ−（４−バーフルオロオクタノイルアミドスルフォニル）フェニルメタクリルアミド（モノマー６）の合成方法
（１）スルファニルアミドとＫ_２ＣＯ_３（０．５当量）を混ぜ、１８０℃で２０分間、加熱した。室温まで冷却し、メタノールを加えて溶解し、撹拌しながら、メチルパーフルオロオクタノエート（１．０当量）を一滴ずつ加え、３時間撹拌した。不溶物をろ過し、溶媒を留去し、５重量％のＮａ_２ＣＯ_３溶液を加えて溶解し、さらに不溶物を濾過後、塩酸を加えて中和し、析出した結晶を濾過し、さらにメタノールを加えて水分を共沸させ、１２時間乾燥させた。得られた結晶をシリカゲルクロマトグラフィー（展開溶媒：エタノール：ベンゼン＝１：２）で分離し、アセトン／エタノール（体積比７：３）で再結晶をし、スルファパーフルオロオクタノイルアミドを収率は２９％で得た。
（２）微量のフェニル−β−ナフチルアミンを含むアセトン５０ｍｌに上記のようにして調製したスルフォンアミド４４ｍｏｌを溶解し、１０℃で撹拌しながら、メタクリロイルクロライド４４ｍｏｌを一滴ずつ加え、５０℃で３時間加熱した。ＴＬＣで原料の消失を確認後、冷却し、析出した結晶を濾過し、さらにアセトン／エタノール（体積比１：１）で再結晶して、目的物を収率４１％で得た。（融点：２３３℃、分解点：２６２℃）目的物の^１ＨＮＭＲを図６に示す。
実施例７
実施例１〜６によって得られたメタクリルアミド化合物のｐＫａを、以下の方法に従って測定した。
【００３６】
モノマー１及び２に関しては、水酸化ナトリウム水溶液にて滴定を行い、当量点を与える滴定量の中間点のｐＨをｐＫａとした。モノマー３〜６には関しては、１ｍｍｏｌ水溶液のｐＨから酸解離定数Ｋａを求め、−ｌｏｇＫａをｐＫａとした。その結果をまとめて表１に示す。
【００３７】
【表１】

【００３８】
表１の結果より、用いる電子吸引基の種類により、ｐＫａ値を制御することができることがわかった。また、これらのモノマーの酸性度は、プロトン伝導性を有するのに十分な値であることが分かった。
実施例８（重合体の合成）
蒸留生成し酸素脱気したアクリロニトリルとモノマー３〜６を表２に示すモル比で混合し、ジメチルスルフォキサイドに溶解し、重合開始剤であるアゾビスイソブチロニトリルを総モノマーに対して１ｍｏｌ％加えて溶解させた。さらにこの重合溶液に窒素ガスを２０分間通気することにより、溶存酸素を取り除いた。密閉容器に封入された重合溶液を振動式恒温槽で６０℃、５〜１２時間加熱撹拌することにより共重合を進行させた。重合物にジメチルスルフォキサイドを加えて溶解することにより粘性溶液を得、これを大量のメタノール中に滴下することにより沈殿物とした。この沈殿物を濾過し、メタノールおよび純水で充分に洗浄後、真空乾燥することにより重合物１〜４を得た。転化率はいずれも５０％前後であった。得られた各重合物について、水酸化ナトリウム標準溶液により滴定し、酸当量を求めた。その値をまとめて表２に示す。
実施例９（重合体膜のプロトン伝導性の評価）
実施例８で得た重合体をジメチルスルフォキサイドに溶解した粘性溶液をガラス基板上に流延し、恒温槽中、常圧下、５０℃で溶媒を蒸発させ、さらに真空下７０℃で乾燥することにより、強靱な高分子膜を得た。
【００３９】
この高分子膜を短冊状に切断し、膜面方向の導電率を白金電極を用いた２端子法を用い評価した。電極を取り付けた高分子膜は恒温恒湿チャンバー（エスペック製ＳＨ−２２１型）中に設置し、インピーダンスアナライザー（ヒューレットパッカード製４１９２Ａ型）を用いて、交流インピーダンス法により膜抵抗を測定し導電率を求めた。尚、チャンバー内の相対湿度は、９９％であった。
【００４０】
導電率の測定結果を表２にまとめて示す。
【００４１】
【表２】

【００４２】
【発明の効果】
以上述べたように、本発明の繰り返し単位を有する重合体は、従来にない新規な構造を有しており、工業的に安価に製造が可能であり、成形して得られる膜質は強固であるとともに、十分なプロトン伝導性を有するものである。このような重合体は、燃料電池の固体電解質として有用であり、産業上の利用価値は高いといえる。
【図面の簡単な説明】
【図１】モノマー１の^１ＨＮＭＲスペクトルを示す。
【図２】モノマー２の^１ＨＮＭＲスペクトルを示す。
【図３】モノマー３の^１ＨＮＭＲスペクトルを示す
【図４】モノマー４の^１ＨＮＭＲスペクトルを示す
【図５】モノマー５の^１ＨＮＭＲスペクトルを示す
【図６】モノマー６の^１ＨＮＭＲスペクトルを示す[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel polymer having a strongly acidic proton, and more particularly to a high proton conductive electrolyte which can be used for electrolytes such as fuel cells, water electrolysis, salt electrolysis, oxygen concentrators, humidity sensors, gas sensors, and the like. It is.
[0002]
[Prior art]
As a proton conductive membrane composed of a polymer compound, a perfluorocarbon sulfonic acid membrane represented by Nafion (registered trademark) is known to have practical stability, but has excellent acid resistance and oxidation resistance. On the other hand, it has been pointed out that problems such as difficulty in production, very high cost, and a decrease in water content at high temperatures lower proton conductivity, so that sufficient water management must be performed. Was.
[0003]
In order to solve the above problems, as a polymer that is easy to manufacture, cheaper, has usable proton conductivity, and has practically sufficient handling properties, it has three or more amino groups. A polyimide resin composition containing a recurring unit obtained by polycondensation of a polyfunctional component and a tetracarboxylic dianhydride, comprising a phenolic hydroxyl group, a sulfonic acid group, a carboxylic acid group, or a proton such as a phosphate group. There is known a proton conductive polyimide resin composition containing a conductive substituent. (See Patent Document 1)
There is also known a high proton conductive electrolyte comprising a hydrocarbon polymer and a super strong acid group, wherein the super strong acid group is introduced in an ion exchange capacity of 1.50 meq / g or more. It is known that the super-strong acid group is a fluorine sulfonic acid group or a fluorine-based sulfonimide group, and the hydrocarbon-based polymer is a graft copolymer obtained by grafting polystyrene as a side chain to a main chain containing a CF bond. Have been. (See Patent Document 2)
[0004]
[Patent Document 1]
JP-A-2002-105199 [0005]
[Patent Document 2]
JP 2001-302721 A
[Problems to be solved by the invention]
However, all of them are expensive fluorine-containing polymers and have problems in terms of cost and insufficient proton conductivity under high temperature and low humidity conditions.
[0007]
An object of the present invention is to provide a novel polymer which is easy to produce, is less expensive, has usable proton conductivity, and has sufficient proton conductivity even under high temperature and low humidity. I do.
[0008]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a polymer having a (meth) acrylic acid skeleton as a main chain and a sulfonamide group having an electron-withdrawing group on a nitrogen atom as a pendant has a novel skeleton. Further, the present inventors have found that they have protons having high acidity and are easy to handle, and have completed the present invention.
[0009]
That is, the present invention
(1) Formula (I)
[0010]
Embedded image

[0011]
(Wherein, _{R 1} and _{R 2} each independently represent a hydrogen atom, a halogen atom or C1~C10 hydrocarbon group,, _{R 1} and _{R 2} may be bonded to form a ring, _{R 3} Represents a hydrogen atom, a halogen atom, a C1-C10 hydrocarbon group, or an organic group containing a carbonyl group, and may combine with an atom contained in Y to form a ring, and R ₄ represents an electron-withdrawing group. Y represents a divalent or higher valent linking group, k represents an integer of 1 or more, and when k is 2 or more, R ₄ may be the same or different.) Regarding a novel polymer characterized by having
(2) The novel polymer according to (1), wherein in formula (I), Y is a divalent or higher valent organic linking group having an aromatic hydrocarbon skeleton.
(3) In the formula (I), Y represents the formula (II)
[0012]
Embedded image

[0013]
(Wherein, X represents an oxygen atom, a sulfur atom, or a substituted or unsubstituted nitrogen atom, R ₅ represents an organic group, n represents 0 or any integer of 1-4, and n represents 2 In the above case, R ₅ may be the same or different, and R ₅ may be bonded to each other to form a ring, • represents a bonding point, and m represents an integer of 1 to 5). A novel polymer according to (1) or (2), which is an organic linking group represented by
(4) In the formula (II), X is NR ₆ (R ₆ represents a hydrogen atom or an organic group), wherein the novel polymer according to (3),
(5) The repeating unit represented by the formula (I) is represented by the formula (III)
[0014]
Embedded image

[0015]
(Wherein, R _{1 to} R ₄ and k represent the same meaning as described above, R ₇ represents a hydrogen atom or an organic group, and R ₃ and R ₇ , or R ₃ and a nitrogen atom are bonded to form a ring. May be formed.) The novel polymer according to (1), which is a repeating unit represented by the formula (1):
(6) Formula (IV)
[0016]
Embedded image

[0017]
_{(Wherein, R 11} and _{R 12} independently represent a hydrogen atom, a halogen atom or C1~C10 hydrocarbon _{group,, R 11} and _{R 12} may be bonded to form a _{ring, R 13} represents a hydrogen atom, a halogen atom, an organic group containing a C1~C10 hydrocarbon group or a carbonyl _{group,, R 13} and _{R 17} or _{R 13} and the nitrogen atom, may form a ring bond, R ₁₄ represents an electron withdrawing group, R ₁₇ represents a hydrogen atom or an organic group, n represents an integer of 1 or more, and when n is 2 or more, R ₁₄ may be the same or different.) With respect to the compound represented by
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
The novel polymer of the present invention is characterized by having a repeating unit represented by the formula (I). In the formula (I), R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or a C1 to C10 hydrocarbon group, specifically, a halogen atom such as a fluorine atom, a chloro atom, and a bromo atom; Hydrocarbons having 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, phenyl group, naphthyl group and benzyl group Represents a group, and R ₁ and R ₂ may combine to form a ring.
[0019]
R ₃ represents a hydrogen atom, a halogen atom, a C1 to C10 hydrocarbon group, or an organic group containing a carbonyl group, specifically, a halogen atom such as a fluorine atom, a chloro atom, and a bromo atom, a methyl group, and an ethyl group. , N-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, phenyl group, naphthyl group, hydrocarbon group having 1 to 10 carbon atoms such as benzyl group, carboxyl group, Methoxycarbonyl group, represents an organic group containing a carbonyl group such as an ester group such as an ethoxycarbonyl group, an acyl group such as a formyl group, an acetyl group or a benzoyl group, and may form a ring by bonding with an atom included in Y. For example, when a nitrogen atom is contained in Y, a nitrogen atom and a carbonyl group are bonded to form a cyclic imide or an alkylene chain to form a cyclic amide or the like. Can be achieved.
[0020]
R _{1 to} R ₃ may each independently have a substituent on an appropriate carbon atom, and specific examples of such a substituent include a fluorine atom, a chloro atom, and a bromo atom. Halogen atom, hydrocarbon group such as methyl group, ethyl group, n-propyl group, phenyl group, naphthyl group, benzyl group, acyl group such as acetyl group, benzoyl group, nitrile group, nitro group, methoxy group, phenoxy group And the like, such as a hydrocarbonoxy group, a methylthio group, a methylsulfinyl group, a methylsulfonyl group, an amino group, a dimethylamino group, and an anilino group.
[0021]
R ₄ represents an electron-withdrawing group, and is not particularly limited as long as it is a functional group capable of increasing the acidity of a proton on a nitrogen atom or stabilizing an electron on a nitrogen atom by resonance. Group, phenylacetyl group, phenoxyacetyl group, phenylsulfonylacetyl group, pentafluorophenylacetyl group, pentadecanoyl group, nonanoyl group, nonadecanoyl group, hexadecanoyl group, 3-pentenoyl group, 8-octadecenoyl group, acetoacetyl group , 3-acetyl-2-propenoyl, 4-hexenoylacetyl, 11-pentanoylundecanoyl, 9-nonanoylnonanoyl, 6-dodecanoylhexanoyl, 4-tetradecanoylbutanoyl Group, 2-octinoyl group, 2-noninoyl group, benzoyl group, 4-methylbenzoy Group, 4-nitrobenzoyl group, pentafluorobenzoyl group, trifluoroacetyl group, perfluorononanoyl group, perfluoropropanoyl group, perfluorobutanoyl group, perfluorodecanoyl group, methanesulfonyl group, trifluoromethanesulfonyl Group, perfluorononylsulfonyl group, perfluoropropylsulfonyl group, perfluorobutylsulfonyl group, perfluorodecylsulfonyl group, p-toluenesulfonyl group, tetrafluorophenylsulfonyl group, phenyl group, 4-nitrophenyl group, 2,4 -Dinitrophenyl group and the like.
[0022]
Y represents a divalent or higher linking group, and specific examples thereof include an oxygen atom, a sulfur atom, an unsubstituted or substituted nitrogen atom, and an organic group represented by the following formula. Incidentally, the oxygen atom in the following formula can be appropriately replaced with a sulfur atom, a nitrogen atom, a silicon atom, a silicon atom-oxygen atom or the like. Further, the linking group exemplified below may have a substituent on an appropriate carbon atom. As such a substituent, specifically, a halogen atom such as a fluorine atom, a chloro atom, or a bromo atom Hydrocarbon groups such as methyl group, ethyl group, n-propyl group, phenyl group, naphthyl group and benzyl group, acyl groups such as acetyl group and benzoyl group, nitrile group, nitro group, methoxy group and phenoxy group. Examples thereof include a hydrogenoxy group, a methylthio group, a methylsulfinyl group, a methylsulfonyl group, an amino group, a dimethylamino group, and an anilino group.
[0023]
Embedded image

[0024]
Embedded image

[0025]
Y is particularly preferably a divalent or higher valent organic linking group having an aromatic hydrocarbon skeleton, and specific examples thereof include an organic linking group represented by the formula (II).
[0026]
In the formula (II), X represents an oxygen atom, a sulfur atom, or a substituted or unsubstituted nitrogen atom, and R ₅ represents a carbon atom such as a methyl group, an ethyl group, an aryl group, a propargyl group, a benzyl group, or a phenyl group. Hydrogen group, methoxy group, phenoxy group, or alkoxy group such as acetoxy group, methylthio group, methylsulfinyl group, sulfur-containing group such as methylsulfonyl group, dimethylamino group, heterocyclic group such as pyridyl group, ester group, nitro group, an organic group such as a cyano group, n represents an integer of 0 or 1 to 4, when n is 2 or more, may be the same or different, attached at R ₅ together ring And m represents an integer of any of 1 to 5. In addition, * represents a bonding point, and represents that it bonds with a carbonyl group or a sulfonamide group at the bonding point.
[0027]
As the repeating unit represented by the formula (I), a repeating unit represented by the formula (III) can be particularly preferably exemplified. In the formula (III), R _{1 to} R ₄ and k have the same meaning as described above, and similar specific examples can be given. R ₇ represents a hydrogen atom or an organic group. In this case, the organic group refers to a functional group containing a carbon atom and capable of bonding to a nitrogen atom, and specifically, a hydrocarbon such as a methyl group, an ethyl group, an aryl group, a propargyl group, a benzyl group, or a phenyl group. Group, methoxy group, phenoxy group, or acetoxy group or other alkoxy group, methylthio group, methylsulfinyl group, or sulfur-containing group such as methylsulfonyl group, dimethylamino group, heterocyclic group such as pyridyl group, ester group, nitro group , Cyano group and the like. Further, R ₃ and R ₇ , or R ₃ and a nitrogen atom can be bonded to form a ring, for example, to form a cyclic imide, a cyclic amide, or the like.
[0028]
Specific examples of the repeating unit represented by the formula (I) include a repeating unit represented by the following formula.
[0029]
Embedded image

[0030]
The novel polymer of the present invention can contain a repeating unit derived from a monomer having a conjugated double bond that can be copolymerized, if necessary, in the repeating unit represented by the formula (I). Examples of such a monomer include styrene, α-methylstyrene, α-methyl-p-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, and 2,4-dimethylstyrene. , 2,5-dimethylstyrene, p-isopropylstyrene, 2,4,6-triisopropylstyrene, pt-butoxystyrene, pt-butoxy-α-methylstyrene, mt-butoxystyrene, 1, Vinyl aromatic monomers such as 2,2-trifluorovinylbenzene and 4-fluorostyrene; heteroatom-containing aromatic vinyl compounds such as vinylpyridine; methyl Vinyl ketone compounds such as nyl ketone and ethyl vinyl ketone, acrylates such as methyl acrylate and ethyl acrylate, (meth) acrylamide or (meth) acrylonitrile, 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, Examples thereof include conjugated diene monomers such as 2-ethyl-1,3-butadiene and 1,3-pentadiene, and 1,1,1-trisulfuropropylene. These compounds can be used alone or as a mixture of two or more, and can be subjected to block copolymerization, random copolymerization, or the like.
[0031]
Although the molecular weight of the polymer of the present invention is not particularly limited, it is preferably 5,000 or more, more preferably 10,000 or more, and preferably 1,000,000 or less.
[0032]
The polymer of the present invention comprises a monomer comprising the monomer represented by the formula (IV) or a monomer represented by the formula (IV) and a monomer capable of being copolymerized if necessary. It can be produced by appropriately selecting a known polymerization method depending on the type of the monomer and polymerizing, and any of such radical polymerization methods, cationic polymerization methods, and anion polymerization methods can be used, Any of known methods such as solution polymerization, bulk polymerization, and suspension polymerization can be used in appropriate combination.
[0033]
In the compound represented by the formula (IV), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a halogen atom, or a C1 to C10 hydrocarbon group, and the specific examples exemplified for R ₁ and R ₂ are the same. R ₁₁ and R ₁₂ may combine to form a ring, and R ₁₃ represents a hydrogen atom, a halogen atom, a C1-C10 hydrocarbon group, or an organic group containing a carbonyl group. , R ₃ may be exemplified in the same manner, and R ₁₃ and R ₁₇ , or R ₁₃ and a nitrogen atom may be bonded to form a ring. For example, cyclic imide, cyclic amide and the like R ₁₄ represents an electron-withdrawing group, the specific examples exemplified for R ₄ can be similarly exemplified, and R ₁₇ represents a hydrogen atom or an organic group, and the specific examples exemplified for R ₇ can be formed. Illustrating a specific example similar to the example Wherein n represents an integer of 1 or more, and when n is 2 or more, R ₁₄ may be the same or different.
[0034]
Hereinafter, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the examples.
[0035]
【Example】
Example 1 (Synthesis of N- (4-acetylaminosulfonyl) phenyl methacrylamide (monomer 1))
While constantly stirring a solution obtained by dissolving 46 mmol of sulfaacetamide in 50 ml of acetone containing a trace amount of N-phenyl-β-naphthylamine at 10 ° C, 46 mmol of methacryloyl chloride was added dropwise thereto, and heated at 50 ° C for 2 hours. did. After confirming the disappearance of the starting materials by thin layer chromatography (TLC), the solvent was evaporated, 100 ml of water was added to dissolve the solution, neutralized with a NaHCO ₃ solution (6 g / 20 ml H ₂₀ ), and the precipitated crystals were filtered. And washed with ether. Further, the target product recrystallized with ethanol was obtained in a yield of 37%. (Melting point: 196 ° C., decomposition point: 251 ° C.) The ¹ HNMR spectrum of the target product is shown in FIG.
Example 2 (Synthesis of N- (4-Penzoylaminosulfonyl) phenyl methacrylamide (monomer 2))
(1) Sulfanilamide, K ₂ CO ₃ (0.5 equivalent), and phenylbenzoate were mixed, heated at 180 ° C. for 20 minutes, cooled to room temperature, and 100 ml of a 5% by weight Na ₂ CO ₃ solution was added. After filtering off the insoluble matter and extracting with benzene three times to remove the phenol, dilute hydrochloric acid (17 ml of concentrated hydrochloric acid diluted with 180 ml of water) was added dropwise to the aqueous layer, and the precipitated crystals were filtered and filtered with ethanol. The crystals were recrystallized and dried to obtain sulfabenzamide in a yield of 41%.
(2) Dissolve 44 mol of the sulfobenzamide prepared as described above in 50 ml of acetone containing a trace amount of phenyl-β-naphthylamine, and add 44 mol of methacryloyl chloride dropwise at 10 ° C. while constantly stirring at 50 ° C. For 2 hours. After confirming the disappearance of the raw materials by TLC, the solvent was distilled off, 100 ml of water was added for dissolution, the solution was neutralized with a NaHCO ₃ solution (6 g / 20 ml H ₂ O), and the precipitated crystals were filtered, washed with ether, and further ethanol. To give the desired product in a yield of 41%. (Melting point: 230 ° C., decomposition point: 257 ° C.) ¹ HNMR of the target product is shown in FIG.
Example 3 (Synthesis of N- (4-methylsulfonylaminosulfonyl) phenyl methacrylamide (monomer 3))
(1) Sulfanilamide, K ₂ CO ₃ (0.5 equivalent), and phenylmethanesulfonate were mixed, heated at 180 ° C. for 20 minutes, cooled to room temperature, and 100 ml of 5 wt% Na ₂ CO ₃ The solution was added and dissolved, and the insoluble material was filtered. The filtrate was neutralized by adding hydrochloric acid. The precipitated crystals were filtered, dried, separated by silica gel column chromatography (developing solvent: ethanol: benzene = 1: 2), recrystallized with ethanol, and dried to obtain sulfamethanesulfonamide at a yield of 20%. Was.
(2) 44 mol of the sulfonamide prepared above was dissolved in 50 ml of acetone containing a trace amount of phenyl-β-naphthylamine, and 44 mol of methacryloyl chloride was added dropwise with stirring at 10 ° C., followed by heating at 50 ° C. for 3 hours. . After confirming the disappearance of the starting materials by TLC, the solvent was distilled off, and the obtained crystals were washed with ether and further recrystallized with ethanol to obtain the desired product in a yield of 45%. (Melting point: 231 ° C., decomposition point: 250 ° C.) ¹ HNMR of the target product is shown in FIG.
Example 4 (Synthesis of N- (4-trifluoromethylsulfonylamidosulfonyl) phenyl methacrylamide (monomer 4))
(1) A mixture of sulfanilamide, K ₂ CO ₃ (0.5 equivalent) and 4-nitrophenyltrifluoromethanesulfonate (1.0 equivalent), heated at 180 ° C. for 20 minutes, and then cooled to room temperature , 100 ml of a 5% by weight Na ₂ CO ₃ solution was added to dissolve the mixture, and the insoluble matter was filtered. The filtrate was neutralized with hydrochloric acid. The precipitated crystals were filtered, dried, separated by silica gel column chromatography (developing solvent: ethanol: benzene = 1: 2), recrystallized with ethanol, and dried to obtain sulfatrifluoromethanesulfonamide at a yield of 15%. Obtained.
(2) Dissolve 44 mol of the sulfonamide prepared as described above in 50 ml of acetone containing a trace amount of phenyl-β-naphthylamine, add 44 mol of methacryloyl chloride dropwise while stirring at 10 ° C., and heat at 50 ° C. for 3 hours. did. After confirming disappearance of the starting materials by TLC, the solvent was distilled off, and the obtained crystals were washed with ether and further recrystallized from ethyl acetate to obtain the desired product in a yield of 10%. (Melting point: 201 ° C., decomposition point: 215 ° C.) ¹ HNMR of the target product is shown in FIG.
Example 5 (Synthesis of N- (4-trifluoroacetylamidosulfonyl) phenyl methacrylamide (monomer 5))
(1) Sulfanilamide and K ₂ CO ₃ (0.5 equivalent) were mixed and heated at 180 ° C. for 20 minutes. After cooling to room temperature, methanol was added for dissolution, and while stirring, methyl trifluoroacetate or phenyl trifluoroacetate (1.0 equivalent) was added dropwise, followed by stirring for 3 hours. The insolubles were filtered, the solvent was distilled off, and a 5% by weight Na ₂ CO ₃ solution was added to dissolve. The insolubles were filtered, neutralized with hydrochloric acid, and the precipitated crystals were filtered. The obtained crystals were separated by silica gel chromatography (developing solvent: ethanol: benzene = 1: 2), recrystallized with acetone / ethanol (volume ratio: 7: 3), and sulfatrifluoroacetamide was obtained in a yield of 41. %.
(2) Dissolve 44 mol of the sulfonamide prepared as described above in 50 ml of acetone containing a trace amount of phenyl-β-naphthylamine, add 44 mol of methacryloyl chloride dropwise while stirring at 10 ° C., and heat at 50 ° C. for 3 hours. did. After confirming the disappearance of the raw materials by TLC, the mixture was cooled, the precipitated crystals were filtered, and further recrystallized from acetonitrile to obtain the desired product in a yield of 41%. (Melting point: 264 ° C., decomposition point: 269 ° C.) ¹ HNMR of the target product is shown in FIG.
Example Mix 6 (N-(4-bar-fluoro-octanoyl amide sulfonyl) phenyl methacrylamide (Synthesis method (1) sulfanilamide and _K 2 _CO 3 (0.5 equivalents of monomers 6)), 20 minutes at 180 ° C. After cooling to room temperature, methanol was added for dissolution, and while stirring, methyl perfluorooctanoate (1.0 equivalent) was added dropwise, followed by stirring for 3 hours. The solution was distilled off, and dissolved by adding a 5% by weight Na ₂ CO ₃ solution. The insolubles were filtered, neutralized by adding hydrochloric acid, and the precipitated crystals were filtered. Further, methanol was added to azeotropically remove water. The resulting crystals were separated by silica gel chromatography (developing solvent: ethanol: benzene = 1: 2), and then separated with acetone / ethanol (volume ratio: 7: 3). After recrystallization, sulfaperfluorooctanoylamide was obtained in a yield of 29%.
(2) Dissolve 44 mol of the sulfonamide prepared as described above in 50 ml of acetone containing a trace amount of phenyl-β-naphthylamine, add 44 mol of methacryloyl chloride dropwise while stirring at 10 ° C., and heat at 50 ° C. for 3 hours. did. After confirming the disappearance of the raw materials by TLC, the mixture was cooled, and the precipitated crystals were filtered and further recrystallized from acetone / ethanol (volume ratio: 1: 1) to obtain the desired product in a yield of 41%. (Melting point: 233 ° C., decomposition point: 262 ° C.) ¹ HNMR of the target product is shown in FIG.
Example 7
The pKa of the methacrylamide compounds obtained in Examples 1 to 6 was measured according to the following method.
[0036]
For the monomers 1 and 2, titration was carried out with an aqueous sodium hydroxide solution, and the pH at the midpoint of the titer giving the equivalent point was defined as pKa. For the monomers 3 to 6, the acid dissociation constant Ka was determined from the pH of the 1 mmol aqueous solution, and -logKa was defined as pKa. Table 1 summarizes the results.
[0037]
[Table 1]

[0038]
From the results in Table 1, it was found that the pKa value can be controlled by the type of the electron-withdrawing group used. It was also found that the acidity of these monomers was a value sufficient to have proton conductivity.
Example 8 (Synthesis of polymer)
Acrylonitrile, which is formed by distillation and degassed with oxygen, is mixed with monomers 3 to 6 in the molar ratio shown in Table 2, dissolved in dimethyl sulfoxide, and azobisisobutyronitrile as a polymerization initiator is added to the total monomers. 1 mol% was added and dissolved. Further, dissolved oxygen was removed by bubbling nitrogen gas through this polymerization solution for 20 minutes. The copolymerization was advanced by heating and stirring the polymerization solution sealed in the closed container at 60 ° C. for 5 to 12 hours in a vibration-type constant temperature bath. Dimethyl sulfoxide was added to and dissolved in the polymer to obtain a viscous solution, which was dropped into a large amount of methanol to obtain a precipitate. The precipitate was filtered, sufficiently washed with methanol and pure water, and dried under vacuum to obtain Polymers 1 to 4. The conversions were all around 50%. Each obtained polymer was titrated with a sodium hydroxide standard solution to determine an acid equivalent. Table 2 summarizes the values.
Example 9 (Evaluation of proton conductivity of polymer membrane)
A viscous solution obtained by dissolving the polymer obtained in Example 8 in dimethyl sulfoxide is cast on a glass substrate, the solvent is evaporated at 50 ° C. under normal pressure in a thermostatic oven, and further dried at 70 ° C. under vacuum. As a result, a tough polymer film was obtained.
[0039]
This polymer film was cut into strips, and the conductivity in the film surface direction was evaluated using a two-terminal method using a platinum electrode. The polymer film to which the electrodes were attached was placed in a constant temperature and humidity chamber (SH-221 manufactured by Espec), and the film resistance was measured by an AC impedance method using an impedance analyzer (model 4192A manufactured by Hewlett-Packard) to determine the conductivity. I asked. The relative humidity in the chamber was 99%.
[0040]
Table 2 shows the measurement results of the conductivity.
[0041]
[Table 2]

[0042]
【The invention's effect】
As described above, the polymer having a repeating unit of the present invention has an unprecedented novel structure, can be industrially manufactured at low cost, and the film quality obtained by molding is strong. In addition, it has sufficient proton conductivity. Such a polymer is useful as a solid electrolyte for a fuel cell, and can be said to have high industrial utility value.
[Brief description of the drawings]
FIG. 1 shows the ¹ H NMR spectrum of Monomer 1.
FIG. 2 shows the ¹ H NMR spectrum of Monomer 2.
Shows The ¹ HNMR spectrum of 6 Monomer 6 showing The ¹ HNMR spectrum of FIG. 3 Monomer 3 ¹ HNMR shows the spectrum shows The ¹ HNMR spectrum of FIG. 4 Monomer 4 [5] Monomer 5

Claims (6)

Formula (I)

(Wherein, _{R 1} and _{R 2} each independently represent a hydrogen atom, a halogen atom or C1~C10 hydrocarbon group,, _{R 1} and _{R 2} may be bonded to form a ring, _{R 3} Represents a hydrogen atom, a halogen atom, a C1 to C10 hydrocarbon group, or an organic group containing a carbonyl group, and may combine with an atom contained in Y to form a ring, and R ₄ represents an electron withdrawing group. Y represents a divalent or higher valent linking group, k represents an integer of 1 or more, and when k is 2 or more, R ₄ may be the same or different.) A novel polymer characterized by having: The novel polymer according to claim 1, wherein in the formula (I), Y is a divalent or higher valent organic linking group having an aromatic hydrocarbon skeleton. In the formula (I), Y is a group represented by the formula (II)

(Wherein, X represents an oxygen atom, a sulfur atom, or a substituted or unsubstituted nitrogen atom, R ₅ represents an organic group, n represents 0 or any integer of 1-4, and n represents 2 In the above case, R ₅ may be the same or different, and R ₅ may be bonded to each other to form a ring, • represents a bonding point, and m represents an integer of 1 to 5). The novel polymer according to claim 1, wherein the polymer is an organic linking group represented by the formula (I). 4. The novel polymer according to claim 3, wherein in the formula (II), X is NR ₆ (R ₆ represents a hydrogen atom or an organic group). The repeating unit represented by the formula (I) is represented by the formula (III)

(Wherein, R _{1 to} R ₄ and k represent the same meaning as described above, R ₇ represents a hydrogen atom or an organic group, and R ₃ and R ₇ , or R ₃ and a nitrogen atom are bonded to form a ring. The novel polymer according to claim 1, which is a repeating unit represented by the following formula: Formula (IV)

_{(Wherein, R 11} and _{R 12} independently represent a hydrogen atom, a halogen atom or C1~C10 hydrocarbon _{group,, R 11} and _{R 12} may be bonded to form a _{ring, R 13} represents a hydrogen atom, a halogen atom, an organic group containing a C1~C10 hydrocarbon group or a carbonyl _{group,, R 13} and _{R 17} or _{R 13} and the nitrogen atom, may form a ring bond, R ₁₄ represents an electron withdrawing group, R ₁₇ represents a hydrogen atom or an organic group, n represents an integer of 1 or more, and when n is 2 or more, R ₁₄ may be the same or different.) A compound represented by the formula:

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