JP2013209459A - Polyarylene and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new copolymer using an ion exchange group-free monomer useful as a polymer electrolyte for solid polymer type fuel batteries, and to provide a method for producing the same, and the like.SOLUTION: A copolymer is characterized by containing ion exchange group-free repeating units represented by formula (1) and ion exchange group-having repeating units represented by formula (3), and the like (Aris a divalent aromatic group containing one or more sulfo groups represented by formula (2)).

Description

  The present invention relates to polyarylene and a method for producing the same.

Polyarylene having an ion exchange group is useful as a polymer electrolyte for a polymer electrolyte fuel cell. Examples of the monomer having an ion exchange group include 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), 2,5-dichlorobenzenesulfonic acid (2,2-dimethyl). Propyl), 3- (2,5-dichlorobenzoyl) benzenesulfonic acid (2,2-dimethylpropyl) and the like are known (see, for example, Patent Document 1, Patent Document 2, Patent Document 3, etc.).
In addition, it is known that polyarylene having an ion exchange group is copolymerized with a monomer having no ion exchange group in order to improve mechanical strength. As a monomer having no ion exchange group, for example, 2,5-dichlorobenzophenone is known, but in order to further improve characteristics such as power generation performance and mechanical strength, it does not have an ion exchange group. New copolymers using monomers have been desired (see, for example, Patent Document 3 and Patent Document 4).

JP 2007-270118 A (Example) JP 2007-284653 A (Example) JP 2005-82757 A (Example) JP 2010-272363 A (Example)

  An object of the present invention is to provide a new copolymer using a monomer having no ion exchange group useful as a polymer electrolyte for a polymer electrolyte fuel cell, a method for producing the same, and the like.

（式中、Ａｒ^０は同一又は相異なり、１価の芳香族基を表わす。１価の芳香族基に含まれる水素原子は、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基、炭素数７〜２０のアリールカルボニル基及びシアノ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。Ｒ^１は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基及び炭素数２〜２０のアシル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。また、結合位置が隣接する２つのＲ^１が結合して当該Ｒ^１が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。ｍは１〜４の整数であり、ｎは０〜３の整数であり、ｍ＋ｎは１〜４の整数である。）
で表されるイオン交換基を有さない繰り返し単位と、下記式（３）

（式中、Ａｒ^２は下記式（２）

で表されるスルホ基を１つ以上含む２価の芳香族基を表わす。ここで２価の芳香族基に含まれる水素原子は、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基、炭素数７〜２０のアリールカルボニル基又はシアノ基で置換されていてもよい。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及び炭素数７〜２０のアリールカルボニル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及び炭素数７〜２０のアリールカルボニル基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。）
で表されるイオン交換基を有する繰り返し単位とを含むことを特徴とする共重合体；
２．前記式（１）が下記式（４）

（式中、Ｒ^１、Ｒ^２は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基及び炭素数２〜２０のアシル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。また、結合位置が隣接する２つのＲ^１が結合して当該Ｒ^１が結合するベンゼン環上の炭素原子と共に環を形成していてもよく、また結合位置が隣接する２つのＲ^２が結合して当該Ｒ^２が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。ｎは０〜３の整数であり、ｘは０〜５の整数を表わす。）
で表わされることを特徴とする前項１記載の共重合体；
３．前記式（１）が下記式（５）

（式中、Ｒ^１、Ｒ^２は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基及び炭素数２〜２０のアシル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。ｎは０〜３の整数である。また、結合位置が隣接する２つのＲ^１が結合して当該Ｒ^１が結合するベンゼン環上の炭素原子と共に環を形成していてもよく、また結合位置が隣接する２つのＲ^２が結合して当該Ｒ^２が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。）
で表わされることを特徴とする前項１記載の共重合体；
４． 前記式（１）が下記式（６）

（式中、Ｒ^１、Ｒ^２は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基及び炭素数２〜２０のアシル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。また、結合位置が隣接する２つのＲ^１が結合して当該Ｒ^１が結合するベンゼン環上の炭素原子と共に環を形成していてもよく、また結合位置が隣接する２つのＲ^２が結合して当該Ｒ^２が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。ｎは０〜３の整数であり、ｘは０〜５の整数を表わす。）
で表わされることを特徴とする前項１記載の共重合体；
５．前記式（１）が下記式（７）

（式中、Ｒ^２は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基及び炭素数２〜２０のアシル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。また、結合位置が隣接する２つのＲ^２が結合して当該Ｒ^２が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。）
で表わされることを特徴とする前項１記載の共重合体；
６．式（９）

（式中、Ｘはハロゲン原子を表わす。Ａｒ^２は下記式（８）

（式中、−ＯＭは−ＯＭ_１又は−Ｏ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は炭素数１〜２０のアルキル基を表わし、Ｍ_２ ⁺はアルカリ金属カチオン又はアンモニウム化合物のカチオンを表わす）
で表される基を１つ以上含む２価の芳香族基を表わす。ここで２価の芳香族基に含まれる水素原子は、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基、炭素数７〜２０のアリールカルボニル基又はシアノ基で置換されていてもよい。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及び炭素数７〜２０のアリールカルボニル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及び炭素数７〜２０のアリールカルボニル基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。）
で表されるジハロスルホ化合物と式（１０）

（式中、Ａｒ^０は同一又は相異なり、１価の芳香族基を表わす。１価の芳香族基に含まれる水素原子は、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基、炭素数７〜２０のアリールカルボニル基及びシアノ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。Ｒ^１は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及び炭素数７〜２０のアリールカルボニル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。また、結合位置が隣接する２つのＲ^１が結合して当該Ｒ^１が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。ｍは１〜４の整数であり、ｎは０〜３の整数であり、ｍ＋ｎは１〜４の整数である。）
で表されるジハロスルホニル化合物を含むモノマー組成物をニッケル化合物の存在下、重合する工程、前記重合工程で得られた重合物が有する式（８）で表される基をスルホ基に変換する工程を含むことを特徴とする共重合体の製造方法；
７．ニッケル化合物がハロゲン化ニッケルであり、含窒素二座配位子及び亜鉛の共存下に重合させることを特徴とする前項６記載の共重合体の製造方法；
８．前記式（９）で表されるジハロスルホ化合物が、下記式（１１）

（式中、−ＯＭは−ＯＭ_１又は−Ｏ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は炭素数１〜２０のアルキル基を表わし、Ｍ_２ ⁺はアルカリ金属カチオン又はアンモニウム化合物のカチオンを表わす。Ｘはハロゲン原子を表わす。Ｒ^１は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基、炭素数７〜２０のアリールカルボニル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及び炭素数７〜２０のアリールカルボニル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及び炭素数７〜２０のアリールカルボニル基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。また、結合位置が隣接する２つのＲ^１が結合して当該Ｒ^１が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。ｍは１〜４の整数であり、ｎは０〜３の整数であり、ｍ＋ｎは１〜４の整数を表わす。lは１または２を表わす。）
で表されることを特徴とする前項６又は７記載の共重合体の製造方法；
９．前記式（９）で表されるジハロスルホ化合物が、下記式（１２）

（式中、−ＯＭは−ＯＭ_１又は−Ｏ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は炭素数１〜２０のアルキル基を表わし、Ｍ_２ ⁺はアルカリ金属カチオン又はアンモニウム化合物のカチオンを表わす。Ｘはハロゲン原子を表わす。Ｒ^１は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基及び炭素数２〜２０のアシル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。また、結合位置が隣接する２つのＲ^１が結合して当該Ｒ^１が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。ｍは１〜４の整数を表わし、ｎは０〜３の整数を表わし、ｍ＋ｎは１〜４の整数を表わす。）
で表される化合物であることを特徴とする前項６又は７記載の共重合体の製造方法；
１０．前記式（９）で表されるジハロスルホ化合物が、下記式（１３）

（式中、−ＯＭは−ＯＭ_１又は−Ｏ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は炭素数１〜２０のアルキル基を表わし、Ｍ_２ ⁺はアルカリ金属カチオン又はアンモニウム化合物のカチオンを表わす。Ｘはハロゲン原子を表わす。Ｒ^１は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基、炭素数７〜２０のアリールカルボニル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及び炭素数７〜２０のアリールカルボニル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及び炭素数７〜２０のアリールカルボニル基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。また、結合位置が隣接する２つのＲ^１が結合して当該Ｒ^１が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。ｎは０〜３の整数を表わす。）
で表される化合物であることを特徴とする前項６又は７記載の共重合体の製造方法；
１１．式（９）で表されるジハロスルホ化合物が、下記式（１４）

（式中、−ＯＭは−ＯＭ_１又は−Ｏ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は炭素数１〜２０のアルキル基を表わし、Ｍ_２ ⁺はアルカリ金属カチオン又はアンモニウム化合物のカチオンを表わす。Ｘはハロゲン原子を表わす。Ｒ^１は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基、炭素数７〜２０のアリールカルボニル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及び炭素数７〜２０のアリールカルボニル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基及び炭素数７〜２０のアリールカルボニル基からなる群から選ばれる少なくとも一つの基で置換されていてもよい。ｋは０〜２の整数を表わす。）
で表される化合物であることを特徴とする前項６又は７記載の共重合体の製造方法；
１２．下記式（１５）で表わされるジハロゲン化合物；

（式中、Ｘはハロゲン原子を表わす。Ｒ^２は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基及び炭素数２〜２０のアシル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。また、結合位置が隣接する２つのＲ^２が結合して当該Ｒ^２が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。ｘは０〜５の整数を表わす。）；
１３．Ｘが、塩素原子であることを特徴とする前項１２記載のジハロゲン化合物；
１４．Ｒ^２が、炭素数１〜２０のアルキル基であることを特徴とする前項１２又は１３記載のジハロゲン化合物；
１５．前記式（１５）が、下記式（１６）

（式中、Ｒ^２は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基及び炭素数２〜２０のアシル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つもので置換されていてもよい。）
で表わされることを特徴とする前項１２記載のジハロゲン化合物；
１６．Ｒ^２が、炭素数１〜２０のアルキル基であることを特徴とする前項１５記載のジハロゲン化合物；
１７．下記式（１７）で表わされるジハロゲン化合物

（式中、Ｘはハロゲン原子を表わす。Ｒ^２は同一又は相異なり、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基、炭素数２〜２０のアシル基又はシアノ基を表わす。ここで、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシ基及び炭素数２〜２０のアシル基に含まれる水素原子は、フッ素原子、シアノ基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基及び炭素数６〜２０のアリールオキシ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。）；
１８．Ｘが塩素原子であることを特徴とする前項１７記載のジハロゲン化合物；
１９．Ｒ^２が炭素数１〜２０のアルキル基であることを特徴とする前項１７又は１８記載のジハロゲン化合物；
等を提供するものである。 Under such circumstances, the present inventors have intensively studied a copolymer using a monomer having no ion exchange group, and as a result, have reached the following present invention. That is, the present invention
Following formula (1)

(In the formula, Ar ⁰ is the same or different and represents a monovalent aromatic group. The hydrogen atom contained in the monovalent aromatic group is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. Selected from the group consisting of 20 alkoxy groups, aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, acyl groups having 2 to 20 carbon atoms, arylcarbonyl groups having 7 to 20 carbon atoms and cyano groups R ¹ may be the same or different, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 aryl groups, charcoal The hydrogen atom contained in the aryloxy group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one member selected from the group consisting of 6 to 20 aryloxy groups, and on the benzene ring to which the two R ^{1 s} adjacent to each other are bonded and the R ¹ is bonded. A ring may be formed together with a carbon atom, m is an integer of 1 to 4, n is an integer of 0 to 3, and m + n is an integer of 1 to 4.)
A repeating unit having no ion exchange group represented by formula (3):

(In the formula, Ar ² represents the following formula (2)

A divalent aromatic group containing at least one sulfo group represented by the formula: Here, the hydrogen atom contained in the divalent aromatic group is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. The aryloxy group, an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group. Here, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon The hydrogen atom contained in the arylcarbonyl group having 7 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one selected from the group consisting of an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms. )
And a copolymer having a repeating unit having an ion exchange group represented by:
2. The formula (1) is the following formula (4)

^(Wherein, R 1, ^{R 2} are the same or different, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms An aryloxy group, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon The hydrogen atom contained in the aryloxy group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one member selected from the group consisting of 6 to 20 aryloxy groups, and on the benzene ring to which the two R ^{1 s} adjacent to each other are bonded and the R ¹ is bonded. With carbon atoms May form a, also coupling position may also form a ring with the carbon atoms on the benzene ring to which the R ² by bonding two R ² adjacent to bind .n's 0-3 An integer, and x represents an integer of 0 to 5.)
The copolymer according to item 1 above, which is represented by:
3. Said formula (1) is the following formula (5)

^(Wherein, R 1, ^{R 2} are the same or different, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms An aryloxy group, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon The hydrogen atom contained in the aryloxy group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one selected from the group consisting of 6 to 20 aryloxy groups, n is an integer of 0 to 3. In addition, two R ¹ adjacent to each other in the bonding position are bonded. Ben which the ^{R 1} is attached May together with the carbon atoms on the down ring to form a ring, and also coupled position to form a ring together with the carbon atoms on the two benzene rings to which the R ² and R ² is bonded are bonded to adjacent Good.)
The copolymer according to item 1 above, which is represented by:
4). Said formula (1) is the following formula (6)

^(Wherein, R 1, ^{R 2} are the same or different, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms An aryloxy group, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon The hydrogen atom contained in the aryloxy group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one member selected from the group consisting of 6 to 20 aryloxy groups, and on the benzene ring to which the two R ^{1 s} adjacent to each other are bonded and the R ¹ is bonded. With carbon atoms May form a, also coupling position may also form a ring with the carbon atoms on the benzene ring to which the R ² by bonding two R ² adjacent to bind .n's 0-3 An integer, and x represents an integer of 0 to 5.)
The copolymer according to item 1 above, which is represented by:
5. The formula (1) is the following formula (7)

(In the formula, R ² is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy having 6 to 20 carbon atoms. Group, an acyl group having 2 to 20 carbon atoms or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 6 carbon atoms The hydrogen atom contained in the 20 aryloxy group and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms. And may be substituted with at least one member selected from the group consisting of aryloxy groups, together with the carbon atom on the benzene ring to which the two adjacent R ² atoms are bonded to each other and the R ² atom is bonded thereto. Forming a ring Even if it is.)
The copolymer according to item 1 above, which is represented by:
6). Formula (9)

(In the formula, X represents a halogen atom. Ar ² represents the following formula (8).

(In the formula, -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. Represent)
Represents a divalent aromatic group containing one or more groups represented by the formula: Here, the hydrogen atom contained in the divalent aromatic group is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. The aryloxy group, an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group. Here, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon The hydrogen atom contained in the arylcarbonyl group having 7 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one selected from the group consisting of an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms. )
And a dihalosulfo compound represented by the formula (10)

(In the formula, Ar ⁰ is the same or different and represents a monovalent aromatic group. The hydrogen atom contained in the monovalent aromatic group is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. Selected from the group consisting of 20 alkoxy groups, aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, acyl groups having 2 to 20 carbon atoms, arylcarbonyl groups having 7 to 20 carbon atoms and cyano groups R ¹ may be the same or different, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 aryl groups, charcoal A hydrogen atom contained in an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms is a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, carbon It may be substituted with at least one selected from the group consisting of an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms, and two adjacent R ¹ groups bonded to each other A ring may be formed together with the carbon atom on the benzene ring to which R ¹ is bonded, m is an integer of 1 to 4, n is an integer of 0 to 3, and m + n is an integer of 1 to 4. is there.)
A step of polymerizing a monomer composition containing a dihalosulfonyl compound represented by formula (8) in the presence of a nickel compound, and converting a group represented by the formula (8) of the polymer obtained in the polymerization step to a sulfo group. A process for producing a copolymer, comprising a step;
7). The method for producing a copolymer according to item 6 above, wherein the nickel compound is nickel halide and polymerized in the presence of a nitrogen-containing bidentate ligand and zinc;
8). The dihalosulfo compound represented by the formula (9) is represented by the following formula (11).

(In the formula, -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. X represents a halogen atom, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. Represents an aryloxy group having 20 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group, where an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms Group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms are a fluorine atom, a Group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon It may be substituted with at least one selected from the group consisting of arylcarbonyl groups of 7 to 20. In addition, on the benzene ring to which the two R ^{1 s} adjacent to each other are bonded and the R ¹ is bonded. And m is an integer of 1 to 4, n is an integer of 0 to 3, m + n is an integer of 1 to 4, and l is 1 or 2. .)
The method for producing a copolymer according to item 6 or 7, wherein the copolymer is represented by:
9. The dihalosulfo compound represented by the formula (9) is represented by the following formula (12):

(In the formula, -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. X represents a halogen atom, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. Represents an aryloxy group having 20 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, where an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms , A hydrogen atom contained in an aryloxy group having 6 to 20 carbon atoms and an acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 carbon atoms At least one may be substituted by one selected from the group consisting of aryloxy groups 20. Furthermore, the carbon atoms on the benzene ring to which the R ¹ are attached two of R ¹ binding position adjacent bond to And m may represent an integer of 1 to 4, n represents an integer of 0 to 3, and m + n represents an integer of 1 to 4.)
The method for producing a copolymer according to item 6 or 7, wherein the copolymer is a compound represented by the formula:
10. The dihalosulfo compound represented by the formula (9) is represented by the following formula (13):

(In the formula, -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. X represents a halogen atom, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. Represents an aryloxy group having 20 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group, where an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms Group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms are a fluorine atom, a Group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon It may be substituted with at least one selected from the group consisting of arylcarbonyl groups of 7 to 20. In addition, on the benzene ring to which the two R ^{1 s} adjacent to each other are bonded and the R ¹ is bonded. And n may represent an integer of 0 to 3.)
The method for producing a copolymer according to item 6 or 7, wherein the copolymer is a compound represented by the formula:
11. The dihalosulfo compound represented by the formula (9) is represented by the following formula (14):

(In the formula, -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. X represents a halogen atom, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. Represents an aryloxy group having 20 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group, where an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms Group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms are a fluorine atom, a Group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon (It may be substituted with at least one group selected from the group consisting of arylcarbonyl groups of 7 to 20. k represents an integer of 0 to 2.)
The method for producing a copolymer according to item 6 or 7, wherein the copolymer is a compound represented by the formula:
12 A dihalogen compound represented by the following formula (15);

(In the formula, X represents a halogen atom. R ² is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon. Represents an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. The hydrogen atom contained in the aryl group, the aryloxy group having 6 to 20 carbon atoms, and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. And may be substituted with at least one selected from the group consisting of a group and an aryloxy group having 6 to 20 carbon atoms, and two R ² adjacent to each other at the bonding position are bonded to each other to bond the R ² Benzene ring The good .x also form a ring with the carbon atom represent an integer of 0-5).;
13. 13. The dihalogen compound as described in 12 above, wherein X is a chlorine atom;
14 14. The dihalogen compound according to item 12 or 13, wherein R ² is an alkyl group having 1 to 20 carbon atoms;
15. The formula (15) is converted into the following formula (16).

(In the formula, R ² is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy having 6 to 20 carbon atoms. Group, an acyl group having 2 to 20 carbon atoms or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 6 carbon atoms The hydrogen atom contained in the 20 aryloxy group and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms. And may be substituted with at least one selected from the group consisting of aryloxy groups of
The dihalogen compound according to item 12 above, which is represented by:
16. 16. The dihalogen compound according to 15 above, wherein R ² is an alkyl group having 1 to 20 carbon atoms;
17. Dihalogen compound represented by the following formula (17)

(In the formula, X represents a halogen atom. R ² is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon. Represents an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. The hydrogen atom contained in the aryl group, the aryloxy group having 6 to 20 carbon atoms, and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. And may be substituted with at least one selected from the group consisting of a group and an aryloxy group having 6 to 20 carbon atoms);
18. 18. The dihalogen compound as described in 17 above, wherein X is a chlorine atom;
19. 19. The dihalogen compound according to item 17 or 18 above, wherein R ² is an alkyl group having 1 to 20 carbon atoms;
Etc. are provided.

  ADVANTAGE OF THE INVENTION According to this invention, the novel copolymer using the monomer which does not have an ion exchange group useful as a polymer electrolyte for solid polymer fuel cells, and its manufacturing method can be provided.

  The present invention will be described in detail below. First, a repeating unit having no ion exchange group represented by formula (1), formula (4), formula (5), formula (6), and formula (7), and an ion exchange group represented by formula (3) A polyarylene containing a repeating unit having the following will be described.

In the formula (1), Ar ⁰ is the same or different and represents a monovalent aromatic group. Ar ⁰ includes, for example, a monovalent monocyclic aromatic group such as 1-phenyl group; a divalent condensed aromatic group such as naphthalen-1-yl group and naphthalen-3-yl group; pyridine- And divalent heteroaromatic groups such as 2-yl group, pyridin-3-yl group, pyridin-4-yl group, quinoxalin-2-yl group, and thiophen-2-yl group. Preferable examples include a monovalent monocyclic aromatic group and a monovalent condensed ring aromatic group. More preferable examples include 1-phenyl group, 1-naphthyl group, 2-naphthyl group and the like.

  The hydrogen atom contained in the monovalent aromatic group includes a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms. It may be substituted with at least one selected from the group consisting of an oxy group, an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms and a cyano group.

R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a cyano group. Represents. Here, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon The arylcarbonyl group having 7 to 20 atoms is a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. It may be substituted with at least one group selected from the group consisting of oxy groups. In addition, two R ^{1 s} adjacent to each other at the bonding position may be bonded to form a ring together with the carbon atom on the benzene ring to which the R ¹ is bonded.

  Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2,2-dimethyl-1-propyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n- Decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n- Examples thereof include linear, branched or cyclic alkyl groups such as an icosyl group.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, and n-pentyloxy. Group, 2,2-dimethylpropoxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, 2-methylpentyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n -Nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, - icosyloxy group of linear, alkoxy group branched or cyclic and the like.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 3-phenanthryl group, and a 2-anthryl group.
Examples of the aryloxy group having 6 to 20 carbon atoms include 6 to 20 carbon atoms such as phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 3-phenanthryloxy group, and 2-anthryloxy group. The thing comprised from 20 aryl groups and an oxygen atom is mentioned.

m represents an integer of 1 to 4. Preferably m represents 1 or 2. n represents an integer of 0 to 3. Preferably 0 is represented.

  Specific examples of the repeating unit having no ion exchange group represented by the formula (1) include repeating units represented by the following formulas (1a) to (1x).

In formula (3), examples of the divalent aromatic group in Ar ² include divalent monocyclic aromatic groups such as 1,3-phenylene group and 1,4-phenylene group; naphthalene-1,3 -Diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl group, naphthalene-2,6-diyl group, naphthalene A divalent condensed aromatic group such as -2,7-diyl group; pyridine-2,5-diyl group, pyridine-2,6-diyl group, quinoxaline-2,6-diyl group, thiophene-2, A divalent heteroaromatic group such as a 5-diyl group; and the like. Preferable examples include a divalent monocyclic aromatic group, a divalent condensed ring aromatic group, and the like. More preferably, for example, 4-phenylene group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, etc. Can do.

The divalent aromatic group includes a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy having 6 to 20 carbon atoms. An alkyl group having 1 to 20 carbon atoms which may be substituted with at least one selected from the group consisting of a group, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms;
It may be substituted with at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A good C1-C20 alkoxy group;
An aryl group having 6 to 20 carbon atoms which may be substituted with at least one selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms;
An aryloxy group having 6 to 20 carbon atoms which may be substituted with at least one selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms ;
An arylcarbonyl group having 7 to 20 carbon atoms which may be substituted with at least one selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms ;as well as,
It may be substituted with at least one selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. An acyl group having 2 to 20 carbon atoms;
It may be substituted with at least one substituent selected from the group consisting of

  Such an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and 7 carbon atoms. Examples of the arylcarbonyl group of ˜20 include the same ones as described above.

Specific examples of the repeating unit having an ion exchange group represented by the formula (3) include repeating units represented by the following formulas (3a) to (3t).

In formula (4), R ¹ and n represent the same meaning as described above. R ² is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a carbon number. A 2-20 acyl group, a C7-20 arylcarbonyl group, or a cyano group is represented. Here, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon The arylcarbonyl group having 7 to 20 atoms is a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. It may be substituted with at least one group selected from the group consisting of an oxy group, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms. Further, two R ² adjacent to each other at the bonding position may be bonded to form a ring together with the carbon atom on the benzene ring to which the R ² is bonded.

  x represents an integer of 0 to 5. Preferably, x represents an integer of 0-2.

  Specific examples of the repeating unit having an ion exchange group represented by the formula (4) include repeating units represented by the following formulas (4a) to (4j).

In formula (5), R ¹ , R ² and n represent the same meaning as described above.

  Specific examples of the repeating unit having no ion exchange group represented by the formula (5) include the repeating units represented by the following formulas (5a) to (5j).

In formula (6), R ¹ , R ² , x, n represent the same meaning as described above.

  Specific examples of the repeating unit having no ion exchange group represented by the formula (6) include repeating units represented by the following formulas (6a) to (6h).

In formula (7), R ² represents the same meaning as described above.

  Specific examples of the repeating unit having no ion exchange group represented by the formula (7) include the repeating units represented by the following formulas (7a) to (7f).

  The polystyrene-converted weight average molecular weight of the polymer containing the repeating unit having no ion exchange group represented by formula (1) and the repeating unit having an ion exchange group represented by formula (3) is, for example, at least 1,000 etc. can be mentioned. Preferable examples include at least 10,000. More preferable examples include at least 100,000.

  Next, a method for producing polyarylene comprising a repeating unit having no ion exchange group represented by formula (1) and a repeating unit having an ion exchange group represented by formula (3) will be described.

In formula (8), M represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound.

Here, examples of the alkali metal cation include lithium ion (Li ⁺ ), sodium ion (Na ⁺ ), potassium ion (K ⁺ ), and cesium ion (Cs ⁺ ). Examples of the cation of the ammonium compound include ammonium ion, methylammonium, diethylammonium, tri (n-propyl) ammonium, tetra (n-butyl) ammonium, diisopropyldiethylammonium, tetra (n-octyl) ammonium, tetra (n -Ammonium ions such as -decyl) ammonium and triphenylammonium.

M ₁ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2,2-dimethyl-1-propyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 2-methylpentyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n- Decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n- Examples thereof include linear, branched or cyclic alkyl groups such as an icosyl group.

In formula (9), Ar ² represents the same meaning as described above. X represents a halogen atom. Preferably, for example, it represents a chlorine atom, a bromine atom, or an iodine atom.

In formula (10), R ¹ , n, Ar ⁰ , m, and X represent the same meaning as described above.

  Specific examples of the repeating unit having an ion exchange group represented by the formula (10) include repeating units represented by the following formulas (10a) to (10O).

In formula (11), X and R ¹ represent the same meaning as described above. M represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. m represents an integer of 1 to 4. Preferably m represents 1 or 2. n represents an integer of 0 to 3. Preferably n represents 0. m + n represents an integer of 1 to 4. l represents 1 or 2; Preferably l represents 1.

In formula (12), R ¹ , M, X, m and n represent the same meaning as described above.

  Specific examples of the compound represented by the formula (12) include isopropyl 2,5-dichlorobenzenesulfonate, 2,5-dichlorobenzenesulfonate (2,2-dimethylpropyl), cyclohexyl 2,5-dichlorobenzenesulfonate. N-octyl 2,5-dichlorobenzenesulfonate, sodium 2,5-dichlorobenzenesulfonate, ammonium 2,5-dichlorobenzenesulfonate, diisopropyl 2,5-dichloro-1,4-benzenedisulfonate, 2, 5-Dichloro-1,4-benzenedisulfonic acid bis (2,2-dimethylpropyl), 2,5-dichloro-1,4-benzenedisulfonic acid dicyclohexyl, 2,5-dichloro-1,4-benzenedisulfonic acid dicarboxylic acid n-octyl, 2,5-dichloro-1,4-benzenedisulfonic acid dina Lithium, 2,5-dichloro-1,4-benzenedisulfonic acid diammonium, isopropyl 3,5-dichlorobenzenesulfonic acid, 3,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), 3,5-dichloro Cyclohexyl chlorobenzenesulfonate, n-octyl 3,5-dichlorobenzenesulfonate, sodium 3,5-dichlorobenzenesulfonate, ammonium 3,5-dichlorobenzenesulfonate,

Isopropyl 2,5-dibromobenzenesulfonate, 2,5-dibromobenzenesulfonate (2,2-dimethylpropyl), cyclohexyl 2,5-dibromobenzenesulfonate, n-octyl 2,5-dibromobenzenesulfonate, 2 , 5-Dibromobenzenesulfonate sodium, 2,5-dibromobenzenesulfonate ammonium, 2,5-dibromo-1,4-benzenedisulfonate diisopropyl, 2,5-dibromo-1,4-benzenedisulfonate bis (2 , 2-dimethylpropyl), dicyclohexyl 2,5-dibromo-1,4-benzenedisulfonate, di-n-octyl 2,5-dibromo-1,4-benzenedisulfonate, 2,5-dibromo-1,4- Disodium benzenedisulfonate, 2,5-dibromo-1,4-benzene Diammonium sulfonate, isopropyl 3,5-dibromobenzenesulfonate, 3,5-dibromobenzenesulfonate (2,2-dimethylpropyl), cyclohexyl 3,5-dibromobenzenesulfonate, 3,5-dibromobenzenesulfonate Examples include n-octyl, sodium 3,5-dibromobenzenesulfonate, ammonium 3,5-dibromobenzenesulfonate, and the like.

  More preferably, for example, 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), sodium 2,5-dichlorobenzenesulfonic acid, 2,5-dichloro-1,4-benzenedisulfonic acid bis (2, 2-dimethylpropyl), 2,5-dichloro-1,4-benzenedisulfonic acid disodium, 3,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), 2,5-dibromobenzenesulfonic acid (2, 2-dimethylpropyl), sodium 2,5-dibromobenzenesulfonate, and the like.

In formula (13), X, R ¹ , M, and n represent the same meaning as described above.

  Specific examples of the compound represented by the formula (13) include dimethyl 4,4′-dichlorobiphenyl-2,2′-disulfonate, diethyl 4,4′-dichlorobiphenyl-2,2′-disulfonate, 4'-dichlorobiphenyl-2,2'-disulfonic acid di (n-propyl), 4,4'-dichlorobiphenyl-2,2'-disulfonic acid diisopropyl, 4,4'-dichlorobiphenyl-2,2'- Di (n-butyl) disulfonate, diisobutyl 4,4′-dichlorobiphenyl-2,2′-disulfonate, di (2,2-dimethylpropyl) 4,4′-dichlorobiphenyl-2,2′-disulfonate 4,4′-dichlorobiphenyl-2,2′-disulfonic acid dicyclohexyl, 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (n-octyl) , 4,4'-dichloro-2,2'-disulfonate, di (n- pentadecyl), 4,4'-dichloro-2,2'-disulfonate, di (n- eicosyl),

3,3′-dimethyl-4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), 5,5′-dimethyl-4,4′-dichlorobiphenyl-2,2 '-Disulfonic acid di (2,2-dimethylpropyl), 6,6'-dimethyl-4,4'-dichlorobiphenyl-2,2'-disulfonic acid di (2,2-dimethylpropyl), 3,3' -Dimethoxy-4,4'-dichlorobiphenyl-2,2'-disulfonic acid di (2,2-dimethylpropyl), 5,5'-dimethoxy-4,4'-dichlorobiphenyl-2,2'-disulfonic acid Di (2,2-dimethylpropyl), 6,6′-dimethoxy-4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), 3,3′-diphenyl-4 , 4'-jiku Robiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), 3,3′-diacetyl-4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl) ), 5,5′-diacetyl-4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl),

4,4'-dibromobiphenyl-2,2'-disulfonic acid dimethyl, 4,4'-dibromobiphenyl-2,2'-disulfonic acid diethyl, 4,4'-dibromobiphenyl-2,2'-disulfonic acid dicarboxylic acid (N-propyl), 4,4′-dibromobiphenyl-2,2′-disulfonic acid diisopropyl, 4,4′-dibromobiphenyl-2,2′-disulfonic acid di (n-butyl), 4,4′- Dibromobiphenyl-2,2′-disulfonic acid diisobutyl, 4,4′-dibromobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), 4,4′-dibromobiphenyl-2,2′- Dicyclohexyl disulfonate, 4,4′-dibromobiphenyl-2,2′-disulfonic acid di (n-octyl), 4,4′-dibromobiphenyl-2,2′- Sulfone, di (n- pentadecyl), 4,4'-dibromo-2,2'-disulfonate, di (n- eicosyl), and the like.

  More preferably, for example, diisopropyl 4,4′-dichlorobiphenyl-2,2′-disulfonate, di (2,2-dimethylpropyl) 4,4′-dichlorobiphenyl-2,2′-disulfonate, 4, Examples include 4'-dibromobiphenyl-2,2'-disulfonic acid diisopropyl and 4,4'-dibromobiphenyl-2,2'-disulfonic acid di (2,2-dimethylpropyl).

In formula (14), X, R ¹ and M represent the same meaning as described above. k represents an integer of 0-2. Preferably 0 is represented.
Specific examples of the compound represented by the formula (14) include tetrasodium 4,4′-dichloro-2,2 ′, 6,6′-biphenyltetrasulfonate, 4,4′-dibromo-2,2 ′, 6,6′-biphenyltetrasulfonic acid tetrasodium, 4,4′-diiodo-2,2 ′, 6,6′-biphenyltetrasulfonic acid tetrasodium, 4,4′-dichloro-2,2 ′, 6 6'-biphenyltetrasulfonic acid tetramethyl, 4,4'-dichloro-2,2 ', 6,6'-biphenyltetrasulfonic acid tetraethyl, 4,4'-dichloro-2,2', 6,6'- Tetrakis (2,2-dimethyl-1-propyl) biphenyltetrasulfonate, 4,4'-dichloro-2,2 ', 6,6'-biphenyltetrasulfonate tetraammonium, 4,4'-dichloro-2, 2 ', 6,6'-Biff Tris (2,2-dimethyl-1-propyl) sodium nyltetrasulfonate, tetrakis (2,2-dimethyl-1-propyl) 4,4′-dichloro-2,2 ′, 6,6′-biphenyltetrasulfonate ), Etc.

In formula (15), R ² , x and X have the same meaning as described above.

Specific examples of the repeating unit having no ion exchange group represented by the formula (15) include the repeating units represented by the following formulas (15a) to (15f).

In formula (16), R ² represents the same meaning as described above.

  Specific examples of the compound represented by the formula (16) include repeating units represented by the following formulas (16a) to (16i).

  Next, a method for polymerizing a monomer composition containing a dihalosulfo compound represented by the formula (9) and a dihalosulfonyl compound represented by the formula (10) will be described.

As a method for polymerizing a monomer composition containing a dihalosulfo compound represented by formula (9) and a dihalosulfonyl compound represented by formula (10), for example, the monomer composition is polymerized in the presence of a nickel compound. The method etc. can be mentioned.
Here, examples of the “nickel compound” include zero valence such as nickel (0) bis (cyclooctadiene), nickel (0) (ethylene) bis (triphenylphosphine), nickel (0) tetrakis (triphenylphosphine), and the like. Nickel compounds, nickel halides (eg, nickel fluoride, nickel chloride, nickel bromide, nickel iodide, etc.), nickel carboxylates (eg, nickel formate, nickel acetate, etc.), nickel sulfate, nickel carbonate, nickel nitrate, Examples thereof include divalent nickel compounds such as nickel acetylacetonate and (dimethoxyethane) nickel chloride. Preferable examples include nickel (0) bis (cyclooctadiene) and nickel halide. More preferably, nickel halide etc. can be mentioned, for example.
The amount of the nickel compound used is, for example, 0.01 mol to a total of 1 mol of the monomer composition containing the dihalosulfo compound represented by the formula (9) and the dihalosulfonyl compound represented by the formula (10). The range of 5 mol can be mentioned.

  When polymerizing using a divalent nickel compound as a catalyst, it is preferably carried out in the presence of a nitrogen-containing bidentate ligand. Examples of the nitrogen-containing bidentate ligand include 2,2'-bipyridine, 1,10-phenanthroline, methylenebisoxazoline, N, N'-tetramethylethylenediamine, and the like. Preferable examples include 2,2'-bipyridine. As the usage-amount in the case of using a nitrogen-containing bidentate ligand, the range of 0.2 mol-2 mol etc. can be mentioned with respect to 1 mol of nickel compounds. Preferably, the range of 1 mol-1.5 mol etc. can be mentioned, for example.

  When polymerizing using a divalent nickel compound as a catalyst, it is preferable to use zinc together. Zinc is usually used in powder form. The amount used when using zinc is, for example, 0.5 mol with respect to a total of 1 mol of the monomer composition containing the dihalosulfo compound represented by formula (9) and the dihalosulfonyl compound represented by formula (10) The range of mol-1.5 mol can be mentioned.

The polymerization reaction is preferably performed in the presence of a solvent. The solvent may be any solvent that can dissolve the monomer composition containing the dihalosulfo compound represented by formula (9) and the dihalosulfonyl compound represented by formula (10) and the resulting polymer. Specific examples of such solvents include aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as tetrahydrofuran and 1,4-dioxane; dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N And aprotic polar solvents such as N, dimethylacetamide and hexamethylphosphoric triamide; halogenated hydrocarbon solvents such as dichloromethane and dichloroethane. Such a solvent may be used independently and may be used in mixture of 2 or more types. Of these, ether solvents and aprotic polar solvents are preferable, and tetrahydrofuran, dimethyl sulfoxide, N-methyl-2-pyrrolidone and N, N-dimethylacetamide are more preferable.
The amount of the solvent used is, for example, 1 for a total of 1 part by weight of the monomer composition containing the dihalosulfo compound represented by formula (9) and the dihalosulfonyl compound represented by formula (10). A weight-weight to 200-fold weight can be mentioned. Preferable examples include 5 to 100 times by weight.

The polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen gas.
Examples of the polymerization reaction temperature include a range of 0 ° C to 250 ° C. Preferably, the range of 30 to 100 degreeC can be mentioned, for example. As polymerization time, the range of 0.5 hour-48 hours can be mentioned, for example.

After completion of the polymerization reaction, the polymer of the present invention is prepared by mixing the reaction mixture and a solvent that hardly dissolves the produced polymer to precipitate the polymer, and separating the precipitated polymer from the reaction mixture by filtration. Can be taken out.
After mixing the solvent which does not dissolve | melt the produced | generated polymer or the solvent which is hard to melt | dissolve, and a reaction mixture, an acid may be added and the precipitated polymer may be isolate | separated from a reaction mixture by filtration operation.
Examples of the solvent that does not dissolve or hardly dissolve the produced polymer include water, methanol, ethanol, and acetonitrile. Preferably, water, methanol, etc. can be mentioned, for example.
Examples of the acid include hydrochloric acid and sulfuric acid. Examples of the amount of acid used include the amount necessary to acidify the reaction mixture.

The structural unit derived from the dihalosulfo compound represented by the formula (9) of the obtained polymer contains a group represented by the formula (8), and the group represented by the formula (8) is represented by the formula (2). The method for converting to a sulfo group is carried out according to the methods described in JP 2007-270118 A, JP 2007-177197 A and the like.
Examples of the ion exchange capacity (measured by a titration method) of the polymer thus obtained include a range of 0.5 meq / g to 8.0 meq / g.
The molecular weight and structure of the obtained polymer can be analyzed by ordinary analysis means such as gel permeation chromatography and NMR.

  Any of the polymers thus obtained can be suitably used as a member for a fuel cell. The polymer of the present invention is preferably used as a polymer electrolyte of an electrochemical device such as a fuel cell, and particularly preferably used as a polymer electrolyte membrane.

  Hereinafter, the present invention will be described in more detail with reference to examples.

The polymer described in Example 4 or 5 was analyzed by gel permeation chromatography (hereinafter abbreviated as GPC) (analysis conditions are as follows), and from the analysis results, the weight average molecular weight (Mw) in terms of polystyrene and Number average molecular weight (Mn) was calculated.
<Analysis conditions>
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSK-GEL (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Mobile phase: N, N-dimethylformamide containing lithium bromide (lithium bromide concentration: 10 mmol / dm ³ )
Flow rate: 0.5 mL / min Detection wavelength: 300 nm

Measurement of ion exchange capacity (IEC):
A polymer (polymer electrolyte) to be used for measurement was formed by a solution casting method to obtain a polymer electrolyte membrane, and the obtained polymer electrolyte membrane was cut to an appropriate weight. The dry weight of the cut polymer electrolyte membrane was measured using a halogen moisture meter set at a heating temperature of 105 ° C. Next, the polymer electrolyte membrane dried in this manner was immersed in 5 mL of a 0.1 mol / L sodium hydroxide aqueous solution, 50 mL of ion-exchanged water was further added, and the mixture was allowed to stand for 2 hours. Thereafter, titration was performed by gradually adding 0.1 mol / L hydrochloric acid to the solution in which the polymer electrolyte membrane was immersed, and the neutralization point was determined. Then, the ion exchange capacity (unit: meq / g) of the polymer electrolyte was calculated from the dry weight of the cut polymer electrolyte membrane and the amount of hydrochloric acid required for neutralization.

２，５−ジクロロベンゼンスルホン酸フェニル（Ｊｏｕｎａｌ ｏｆ Ｆｌｕｏｒｉｎｅ Ｃｈｅｍｉｓｔｒｙ，１２７（２００６）３３０−３３６記載される方法に準じて合成）、２０．０ｇ及び脱水テトラヒドロフラン９３ｇを加えて撹拌した後、これにフェニルマグネシウムブロミドの１ｍｏｌ／Ｌテトラヒドロフラン溶液１３６．４ｇを滴下した後６０℃で５時間撹拌した。これに、水を２０ｇ入れて濃縮した後、得られた混合物をトルエン１８９ｇ及び２重量％塩酸２８０ｇを加えて有機層を水層に分離させた。得られた有機層を炭酸ナトリウム水溶液及び食塩水で洗浄した後、硫酸ナトリウムで乾燥し、濃縮することにより、２３．８ｇの粗生成物を得た。粗生成物をヘキサン２７０ｇに加熱溶解させ、冷却して析出した固体を濾別した。得られた固体をヘキサン２４０ｇとトルエン６０ｇとに加熱溶解させて冷却後析出した固体を濾別し、更にトルエン１００ｇで過熱溶解することにより、冷却後析出した固体を濾別し、（２，５−ジクロロフェニル）−フェニルスルホンを２．３６ｇ得た（収率１２．４％）。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δ（ｐｐｍ））：７．６３−７．９０（ｍ、５Ｈ）、８．００（ｄ、２Ｈ）、８．２７（ｄ、１Ｈ）
マススペクトル（ＥＩ、ｍ／ｚ）：２８６（Ｍ^−１）
［実施例２］
２，５−ジクロロフェニル−３’，５’−ジヘキシルスルホンの合成

テトラヒドロフラン１００．０ｇと削状マグネシウム２．４ｇとからなる混合物を６０℃まで昇温し、得られた混合物に３，５−ジヘキシルブロモベンゼン３２．２ｇとテトラヒドロフラン１００．０ｇとからなる溶液を徐々に滴下し、これに窒素雰囲気下において６０℃で１時間保温した。得られた反応混合物を２５℃まで冷却し、これに２，５−ジクロロベンゼンスルホン酸フェニル２０．０ｇを加え、再び６０℃まで昇温して６時間保温した。得られた反応混合物を２５℃まで冷却し、これに水２０．０ｇを加えてから減圧濃縮することにより、テトラヒドロフラン１４０．０ｇを留去した。このようにして得られた濃縮溶液に酢酸エチル３００．５ｇと水３００．５ｇとを加え、分液後の油層を飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥した。硫酸ナトリウムを濾別し、得られた濾液を濃縮乾固することにより、粗生成物４５．３ｇを得た。粗生成物をシリカゲルクロマトグラフィ（溶媒；トルエン／ヘキサン＝１ｗｔ／１ｗｔ）により精製し、得られた溶出液を濃縮乾固して２，５−ジクロロフェニル−３’，５’−ジヘキシルスルホン２２．３ｇ（収率７４％）を得た。
^１Ｈ−ＮＭＲ（重ＤＭＳＯ、δ（ｐｐｍ））：０．８８（ｔ，６Ｈ）、１．２２（ｃ、１２Ｈ）、１．５７（ｃ、４Ｈ）、２．６５（ｔ，４Ｈ）、７．３６−８．２８（ｃ、６Ｈ）
マススペクトル（ＥＩ、ｍ／ｚ）：４５４（Ｍ^−１） [Example 1]
Synthesis of (2,5-dichlorophenyl) -phenylsulfone

2,5-dichlorobenzenesulfonic acid phenyl (synthesized according to the method described in Journal of Fluorine Chemistry, 127 (2006) 330-336), 20.0 g and dehydrated tetrahydrofuran 93 g were added and stirred, and then phenylmagnesium was added. After dropping 136.4 g of a 1 mol / L tetrahydrofuran solution of bromide, the mixture was stirred at 60 ° C. for 5 hours. After adding 20 g of water to this and concentrating, 189 g of toluene and 280 g of 2 wt% hydrochloric acid were added to the resulting mixture to separate the organic layer into an aqueous layer. The obtained organic layer was washed with an aqueous sodium carbonate solution and brine, dried over sodium sulfate, and concentrated to obtain 23.8 g of a crude product. The crude product was dissolved by heating in 270 g of hexane, cooled, and the precipitated solid was separated by filtration. The obtained solid was heated and dissolved in 240 g of hexane and 60 g of toluene, and the solid precipitated after cooling was separated by filtration, and further dissolved by heating with 100 g of toluene, and the solid precipitated after cooling was separated by filtration (2,5 -Dichlorophenyl) -phenylsulfone 2.36 g was obtained (yield 12.4%).
¹ H-NMR (CDCl ₃ , δ (ppm)): 7.63-7.90 (m, 5H), 8.00 (d, 2H), 8.27 (d, 1H)
Mass spectrum (EI, m / z): 286 (M ⁻¹ )
[Example 2]
Synthesis of 2,5-dichlorophenyl-3 ′, 5′-dihexylsulfone

A mixture of 100.0 g of tetrahydrofuran and 2.4 g of ground magnesium was heated to 60 ° C., and a solution of 32.2 g of 3,5-dihexylbromobenzene and 100.0 g of tetrahydrofuran was gradually added to the resulting mixture. The solution was added dropwise, and kept at 60 ° C. for 1 hour in a nitrogen atmosphere. The obtained reaction mixture was cooled to 25 ° C., 20.0 g of phenyl 2,5-dichlorobenzenesulfonate was added thereto, and the temperature was raised again to 60 ° C. and kept for 6 hours. The obtained reaction mixture was cooled to 25 ° C., and 20.0 g of water was added thereto, followed by concentration under reduced pressure, thereby distilling off 140.0 g of tetrahydrofuran. 300.5 g of ethyl acetate and 300.5 g of water were added to the concentrated solution thus obtained, and the oil layer after the separation was washed with saturated brine, and then dried over sodium sulfate. Sodium sulfate was filtered off, and the obtained filtrate was concentrated to dryness to obtain 45.3 g of a crude product. The crude product was purified by silica gel chromatography (solvent; toluene / hexane = 1 wt / 1 wt), and the resulting eluate was concentrated to dryness to give 22.3 g of 2,5-dichlorophenyl-3 ′, 5′-dihexylsulfone ( Yield 74%) was obtained.
¹ H-NMR (deuterated DMSO, δ (ppm)): 0.88 (t, 6H), 1.22 (c, 12H), 1.57 (c, 4H), 2.65 (t, 4H), 7.36-8.28 (c, 6H)
Mass spectrum (EI, m / z): 454 (M ⁻¹ )

テトラヒドロフラン２０．０ｇと削状マグネシウム０．２７ｇとからなる混合物を６０℃まで昇温し、得られた混合物に３，５−ジヘキシルブロモベンゼン３．６ｇとテトラヒドロフラン１０．０ｇとからなる溶液を徐々に滴下し、これを窒素雰囲気下において６０℃で１時間保温した。得られた反応混合物を２５℃まで冷却し、これに４，４’−ジクロロ−２，２’−ビフェニルジスルホン酸ジフェニル（特開２００９−１６１４９３記載の方法に準じて合成）２．０ｇを加え、再び６０℃まで昇温して３０時間保温した。得られた反応混合物を２５℃まで冷却し、水２．０ｇを加えてから減圧濃縮することにより、テトラヒドロフラン２０．０ｇを留去した。このようにして得られた濃縮溶液にトルエン３１．４ｇと水３１．４ｇとを加え、分液後のトルエン層を飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥した。硫酸ナトリウムを濾別し、得られた濾液を濃縮乾固することにより、粗生成物４．２ｇを得た。粗生成物をシリカゲルクロマトグラフィ（溶媒；トルエン／ヘキサン＝１ｗｔ／１ｗｔ）により精製し、得られた溶出液を濃縮乾固して４，４’−ジクロロ−２，２’−ビス（３，５−ジヘキシルフェニルスルホニル）ビフェニル１．５ｇ（収率４８％）を得た。
^１Ｈ−ＮＭＲ（重ＤＭＳＯ、δ（ｐｐｍ））：０．８８（ｔ，１２Ｈ）、１．２２（ｃ、２４Ｈ）、１．５７（ｃ、８Ｈ）、２．６５（ｔ，８Ｈ）、６．８６−８．２４（ｃ、１２Ｈ）
マススペクトル（ＦＤ、ｍ／ｚ）：８３９（Ｍ^−１） [Example 3]
Synthesis of 4,4′-dichloro-2,2′-bis (3,5-dihexylphenylsulfonyl) biphenyl

A mixture of 20.0 g of tetrahydrofuran and 0.27 g of ground magnesium was heated to 60 ° C., and a solution of 3.6 g of 3,5-dihexylbromobenzene and 10.0 g of tetrahydrofuran was gradually added to the resulting mixture. The solution was added dropwise and kept at 60 ° C. for 1 hour in a nitrogen atmosphere. The obtained reaction mixture was cooled to 25 ° C., and 2.0 g of 4,4′-dichloro-2,2′-biphenyldisulfonic acid diphenyl (synthesized according to the method described in JP2009-161493) was added thereto, The temperature was raised again to 60 ° C. and kept for 30 hours. The obtained reaction mixture was cooled to 25 ° C., 2.0 g of water was added, and the mixture was concentrated under reduced pressure to distill away 20.0 g of tetrahydrofuran. To the concentrated solution thus obtained, 31.4 g of toluene and 31.4 g of water were added, and the separated toluene layer was washed with saturated brine and then dried over sodium sulfate. Sodium sulfate was filtered off, and the resulting filtrate was concentrated to dryness to obtain 4.2 g of a crude product. The crude product was purified by silica gel chromatography (solvent; toluene / hexane = 1 wt / 1 wt), and the resulting eluate was concentrated to dryness to give 4,4′-dichloro-2,2′-bis (3,5- 1.5 g (yield 48%) of dihexylphenylsulfonyl) biphenyl was obtained.
¹ H-NMR (heavy DMSO, δ (ppm)): 0.88 (t, 12H), 1.22 (c, 24H), 1.57 (c, 8H), 2.65 (t, 8H), 6.86-8.24 (c, 12H)
Mass spectrum (FD, m / z): 839 (M ⁻¹ )

で示される４，４’−ジクロロ−２，２’，６，６’−ビフェニルテトラスルホン酸テトラキス（２，２−ジメチル−１−プロピル）２５ｇとニッケル（０）ビス（シクロオクタジエン）５２．８ｇとを加えてから４時間攪拌した。得られた反応混合物をメタノール１２５０ｇに注ぎ込み、析出した固体をメタノール及び水で洗浄した。得られた固体を２０重量％硝酸６５６ｇと混合して２５℃で１時間攪拌し、濾過後の固体にメタノール６５６ｇと水４６０ｇとを加えて７０℃で１時間攪拌した。濾過して得られたケーキをメタノールで２回洗浄し、減圧乾燥することにより下記式

で示される繰り返し単位と下記式

で示される繰り返し単位からなるポリアリーレン共重合体２７．０ｇを得た。
上記で得られた重合体にＮ−メチル−２−ピロリドン３８８ｇと３５重量％塩酸２５．３ｇとを加え、得られた混合物を１２０℃で１５時間攪拌した。得られた反応混合物をアセトン１３３５ｇに注ぎ込み、析出した固体をアセトンで洗浄した。得られた固体を１３重量％塩酸１３３５ｇで３回洗浄した後、水１３３５ｇを加えて９０℃で攪拌した。濾過して得られたケーキを水で６回洗浄し、減圧乾燥することにより下記式

で示される繰り返し単位と下記式

で示される繰り返し単位からなるポリアリーレン共重合体２３．１ｇを得た（収率８４％）。得られた重合体のイオン交換容量は４．８８ｍｅｑ／ｇであった。 [Example 4]
Synthesis of polymer Including 13.2 g of (2,5-dichlorophenyl) -phenylsulfone obtained in Example 1, 32.7 g of 2,2′-bipyridine, 188 g of N-methyl-2-pyrrolidone and 188 g of tetrahydrofuran After heating the solution to 50 ° C., the following formula synthesized according to the method described in JP-A-2011-190237

25 g of 4,4′-dichloro-2,2 ′, 6,6′-biphenyltetrasulfonic acid tetrakis (2,2-dimethyl-1-propyl) and nickel (0) bis (cyclooctadiene) 52. After adding 8 g, the mixture was stirred for 4 hours. The obtained reaction mixture was poured into 1250 g of methanol, and the precipitated solid was washed with methanol and water. The obtained solid was mixed with 656 g of 20 wt% nitric acid and stirred at 25 ° C. for 1 hour, 656 g of methanol and 460 g of water were added to the solid after filtration, and stirred at 70 ° C. for 1 hour. The cake obtained by filtration was washed twice with methanol and dried under reduced pressure to obtain the following formula.

The repeating unit represented by

As a result, 27.0 g of a polyarylene copolymer composed of the repeating unit represented by
To the polymer obtained above, 388 g of N-methyl-2-pyrrolidone and 25.3 g of 35 wt% hydrochloric acid were added, and the resulting mixture was stirred at 120 ° C. for 15 hours. The obtained reaction mixture was poured into 1335 g of acetone, and the precipitated solid was washed with acetone. The obtained solid was washed 3 times with 1335 g of 13 wt% hydrochloric acid, 1335 g of water was added, and the mixture was stirred at 90 ° C. The cake obtained by filtration was washed 6 times with water and dried under reduced pressure to obtain the following formula:

The repeating unit represented by

As a result, 23.1 g of a polyarylene copolymer having a repeating unit represented by the formula (84%) was obtained. The obtained polymer had an ion exchange capacity of 4.88 meq / g.

で示される４，４’−ジクロロ−２，２’，６，６’−ビフェニルテトラスルホン酸テトラキス（２，２−ジメチル−１−プロピル）２６．０ｇと、２，２’−ビピリジン２５．１ｇとＮ−メチル−２−ピロリドン１９５．０ｇとテトラヒドロフラン１９５．０ｇとを含む溶液を６０℃に昇温し、ニッケル（０）ビス（シクロオクタジエン）４０．２ｇを加えてから４時間攪拌した。得られた反応混合物をメタノール１２３３ｇに注ぎ込み、析出した固体をメタノール及び水で洗浄した。得られた固体を２０％硝酸６８２．０ｇと混合して亜硝酸ナトリウム０．５ｇを加えた後、これを２５℃で１時間攪拌し、濾過後の固体にメタノール６８２．０ｇと水６８２．０ｇとを加えて７０℃で１時間攪拌した。濾過して得られたケーキをメタノールで２回洗浄し、減圧乾燥することにより下記式

で示される繰り返し単位と下記式

で示される繰り返し単位から成る含むポリアリーレン共重合体２７．４ｇを得た。得られた重合体のＭｗは３．０×１０^５、Ｍｎは９．８×１０^４であった。
上記で得られた重合体にＮ−メチル−２−ピロリドン４０３．１ｇと３５％塩酸２６．３ｇとを加え、得られた混合物を１２０℃で１８時間攪拌した。得られた反応混合物をアセトン１３８９ｇに注ぎ込み、析出した固体をアセトンで洗浄した。得られた固体を１３％塩酸１３８９ｇで３回洗浄した後、水１３８９ｇを加えて９０℃で１５時間攪拌した。濾過して得られたケーキを水で６回洗浄し、減圧乾燥することにより下記式

で示される繰り返し単位と下記式

で示される繰り返し単位からなるポリアリーレン共重合体２３．９ｇを得た（収率９６％）。得られた重合体のイオン交換容量は４．８８ｍｅｑ／ｇであった。 [Example 5]
Synthesis of polymer 12.2 g of 2,5-dichlorophenyl-3 ′, 5′-dihexylsulfone obtained in Example 2 and the following formula

2,4′-dichloro-2,2 ′, 6,6′-biphenyltetrasulfonic acid tetrakis (2,2-dimethyl-1-propyl) 26.0 g and 2,2′-bipyridine 25.1 g And a solution containing 195.0 g of N-methyl-2-pyrrolidone and 195.0 g of tetrahydrofuran were heated to 60 ° C., 40.2 g of nickel (0) bis (cyclooctadiene) was added, and the mixture was stirred for 4 hours. The obtained reaction mixture was poured into 1233 g of methanol, and the precipitated solid was washed with methanol and water. The obtained solid was mixed with 682.0 g of 20% nitric acid and 0.5 g of sodium nitrite was added. The mixture was stirred at 25 ° C. for 1 hour, and 682.0 g of methanol and 682.0 g of water were added to the filtered solid. And stirred at 70 ° C. for 1 hour. The cake obtained by filtration was washed twice with methanol and dried under reduced pressure to obtain the following formula.

The repeating unit represented by

27.4 g of a polyarylene copolymer containing a repeating unit represented by the formula (1) was obtained. Mw of the obtained polymer was 3.0 × 10 ⁵ and Mn was 9.8 × 10 ⁴ .
To the polymer obtained above, 403.1 g of N-methyl-2-pyrrolidone and 26.3 g of 35% hydrochloric acid were added, and the resulting mixture was stirred at 120 ° C. for 18 hours. The obtained reaction mixture was poured into 1389 g of acetone, and the precipitated solid was washed with acetone. The obtained solid was washed 3 times with 1389 g of 13% hydrochloric acid, 1389 g of water was added, and the mixture was stirred at 90 ° C. for 15 hours. The cake obtained by filtration was washed 6 times with water and dried under reduced pressure to obtain the following formula:

The repeating unit represented by

As a result, 23.9 g of a polyarylene copolymer having a repeating unit represented by the formula (yield 96%) was obtained. The obtained polymer had an ion exchange capacity of 4.88 meq / g.

  ADVANTAGE OF THE INVENTION According to this invention, the novel copolymer using the monomer which does not have an ion exchange group useful as a polymer electrolyte for solid polymer fuel cells, and its manufacturing method can be provided.

Claims (19)

Formula (1)

(In the formula, Ar ⁰ is the same or different and represents a monovalent aromatic group. The hydrogen atom contained in the monovalent aromatic group is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. Selected from the group consisting of 20 alkoxy groups, aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, acyl groups having 2 to 20 carbon atoms, arylcarbonyl groups having 7 to 20 carbon atoms and cyano groups R ¹ may be the same or different, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 aryl groups, charcoal The hydrogen atom contained in the aryloxy group having 6 to 20 carbon atoms consists of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. It may be substituted with at least one member selected from the group, and two adjacent R ¹ groups may be bonded to form a ring with the carbon atom on the benzene ring to which the R ¹ unites. M is an integer of 1 to 4, n is an integer of 0 to 3, and m + n is an integer of 1 to 4.)
A repeating unit having no ion exchange group represented by formula (3):

(In the formula, Ar ² represents the following formula (2)

In which the hydrogen atom contained in the divalent aromatic group is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Substituted with an alkoxy group having -20 carbon atoms, an aryl group having 6-20 carbon atoms, an aryloxy group having 6-20 carbon atoms, an acyl group having 2-20 carbon atoms, an arylcarbonyl group having 7-20 carbon atoms, or a cyano group. May be. Here, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon The hydrogen atom contained in the arylcarbonyl group having 7 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one selected from the group consisting of an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms. )
And a repeating unit having an ion exchange group represented by the formula: The formula (1) is the following formula (4)

^(Wherein, R 1, ^{R 2} are the same or different, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms An aryloxy group, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon The hydrogen atom contained in the aryloxy group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one member selected from the group consisting of 6 to 20 aryloxy groups, and on the benzene ring to which the two R ^{1 s} adjacent to each other are bonded and the R ¹ is bonded. With carbon atoms May form a, also coupling position may also form a ring with the carbon atoms on the benzene ring to which the R ² by bonding two R ² adjacent to bind .n's 0-3 An integer, and x represents an integer of 0 to 5.)
The copolymer according to claim 1, which is represented by: Said formula (1) is the following formula (5)

^(Wherein, R 1, ^{R 2} are the same or different, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms An aryloxy group, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon The hydrogen atom contained in the aryloxy group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one selected from the group consisting of 6 to 20 aryloxy groups, n is an integer of 0 to 3. In addition, two R ¹ adjacent to each other in the bonding position are bonded. Ben which the ^{R 1} is attached May together with the carbon atoms on the down ring to form a ring, and also coupled position to form a ring together with the carbon atoms on the two benzene rings to which the R ² and R ² is bonded are bonded to adjacent Good.)
The copolymer according to claim 1, which is represented by: Said formula (1) is the following formula (6)

^(Wherein, R 1, ^{R 2} are the same or different, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms An aryloxy group, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon The hydrogen atom contained in the aryloxy group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one member selected from the group consisting of 6 to 20 aryloxy groups, and on the benzene ring to which the two R ^{1 s} adjacent to each other are bonded and the R ¹ is bonded. With carbon atoms May form a, also coupling position may also form a ring with the carbon atoms on the benzene ring to which the R ² by bonding two R ² adjacent to bind .n's 0-3 An integer, and x represents an integer of 0 to 5.)
The copolymer according to claim 1, which is represented by: The formula (1) is the following formula (7)

(In the formula, R ² is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy having 6 to 20 carbon atoms. Group, an acyl group having 2 to 20 carbon atoms or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 6 carbon atoms The hydrogen atom contained in the 20 aryloxy group and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms. And may be substituted with at least one member selected from the group consisting of aryloxy groups, together with the carbon atom on the benzene ring to which the two adjacent R ² atoms are bonded to each other and the R ² atom is bonded thereto. Forming a ring Even if it is.)
The copolymer according to claim 1, which is represented by: Formula (9)

(In the formula, X represents a halogen atom. Ar ² represents the following formula (8).

(In the formula, -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. Represent)
A hydrogen atom contained in the divalent aromatic group is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or a carbon atom having 1 to 2 carbon atoms. Substituted with 20 alkoxy groups, 6 to 20 aryl groups, 6 to 20 aryloxy groups, 2 to 20 acyl groups, 7 to 20 arylcarbonyl groups, or a cyano group. Also good. Here, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon The hydrogen atom contained in the arylcarbonyl group having 7 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one selected from the group consisting of an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms. )
And a dihalosulfo compound represented by the formula (10)

(In the formula, Ar ⁰ is the same or different and represents a monovalent aromatic group. The hydrogen atom contained in the monovalent aromatic group is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. Selected from the group consisting of 20 alkoxy groups, aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, acyl groups having 2 to 20 carbon atoms, arylcarbonyl groups having 7 to 20 carbon atoms and cyano groups R ¹ may be the same or different, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 aryl groups, charcoal A hydrogen atom contained in an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms is a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, carbon It may be substituted with at least one selected from the group consisting of an aryl group having 6 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms, and two adjacent R ¹ groups bonded to each other A ring may be formed together with the carbon atom on the benzene ring to which R ¹ is bonded, m is an integer of 1 to 4, n is an integer of 0 to 3, and m + n is an integer of 1 to 4. X represents a halogen atom.)
A step of polymerizing a monomer composition containing a dihalosulfonyl compound represented by formula (8) in the presence of a nickel compound, and converting a group represented by the formula (8) of the polymer obtained in the polymerization step to a sulfo group. The manufacturing method of the copolymer characterized by including a process.   The method for producing a copolymer according to claim 6, wherein the nickel compound is nickel halide, and polymerization is performed in the presence of a nitrogen-containing bidentate ligand and zinc. The dihalosulfo compound represented by the formula (9) is represented by the following formula (11).

(In the formula, -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. X represents a halogen atom, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. Represents an aryloxy group having 20 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group, where an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms Group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms are a fluorine atom, a Group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon It may be substituted with at least one selected from the group consisting of arylcarbonyl groups of 7 to 20. In addition, on the benzene ring to which the two R ^{1 s} adjacent to each other are bonded and the R ¹ is bonded. And m is an integer of 1 to 4, n is an integer of 0 to 3, m + n is an integer of 1 to 4, and l is 1 or 2. .)
It is represented by these. The manufacturing method of the copolymer of Claim 6 or 7 characterized by the above-mentioned. The dihalosulfo compound represented by the formula (9) is represented by the following formula (12):

(In the formula, -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. X represents a halogen atom, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. Represents an aryloxy group having 20 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, where an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms , A hydrogen atom contained in an aryloxy group having 6 to 20 carbon atoms and an acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 carbon atoms At least one may be substituted by one selected from the group consisting of aryloxy groups 20. Furthermore, the carbon atoms on the benzene ring to which the R ¹ are attached two of R ¹ binding position adjacent bond to And m may represent an integer of 1 to 4, n represents an integer of 0 to 3, and m + n represents an integer of 1 to 4.)
The method for producing a copolymer according to claim 6 or 7, wherein the compound is represented by the formula: The dihalosulfo compound represented by the formula (9) is represented by the following formula (13):

(In the formula, -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. X represents a halogen atom, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. Represents an aryloxy group having 20 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group, where an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms Group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms are a fluorine atom, a Group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon It may be substituted with at least one selected from the group consisting of arylcarbonyl groups of 7 to 20. In addition, on the benzene ring to which the two R ^{1 s} adjacent to each other are bonded and the R ¹ is bonded. And n may represent an integer of 0 to 3.)
The method for producing a copolymer according to claim 6 or 7, wherein the compound is represented by the formula: The dihalosulfo compound represented by the formula (9) is represented by the following formula (14):

(In the formula, -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. X represents a halogen atom, and R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. Represents an aryloxy group having 20 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group, where an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms Group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms are a fluorine atom, a Group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon (It may be substituted with at least one group selected from the group consisting of arylcarbonyl groups of 7 to 20. k represents an integer of 0 to 2.)
The method for producing a copolymer according to claim 6 or 7, wherein the compound is represented by the formula: A dihalogen compound represented by the following formula (15).

(In the formula, X represents a halogen atom. R ² is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon. Represents an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. The hydrogen atom contained in the aryl group, the aryloxy group having 6 to 20 carbon atoms, and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. And may be substituted with at least one selected from the group consisting of a group and an aryloxy group having 6 to 20 carbon atoms, and two R ² adjacent to each other at the bonding position are bonded to each other to bond the R ² Benzene ring The good .x also form a ring with the carbon atom represent an integer of 0-5.) The dihalogen compound according to claim 12, wherein X is a chlorine atom. The dihalogen compound according to claim 12 or 13, wherein R ² is an alkyl group having 1 to 20 carbon atoms. The formula (15) is converted into the following formula (16).

(In the formula, R ² is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy having 6 to 20 carbon atoms. Group, an acyl group having 2 to 20 carbon atoms or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 6 carbon atoms The hydrogen atom contained in the 20 aryloxy group and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms. And may be substituted with at least one selected from the group consisting of aryloxy groups of
The dihalogen compound according to claim 12, which is represented by: The dihalogen compound according to claim 15, wherein R ² is an alkyl group having 1 to 20 carbon atoms. A dihalogen compound represented by the following formula (17).

(In the formula, X represents a halogen atom. R ² is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon. Represents an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. The hydrogen atom contained in the aryl group, the aryloxy group having 6 to 20 carbon atoms, and the acyl group having 2 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. And may be substituted with at least one selected from the group consisting of a group and an aryloxy group having 6 to 20 carbon atoms.) 18. The dihalogen compound according to claim 17, wherein X is a chlorine atom. The dihalogen compound according to claim 17 or 18, wherein R ² is an alkyl group having 1 to 20 carbon atoms.