JP2013221085A - Aromatic dihalide compound and method of producing polymer thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a novel copolymer using a monomer containing a no ion exchange group and being useful as a polymer electrolyte for a solid polymer fuel cell, and a method of producing an aromatic dihalide compound serving as the monomer constituting the copolymer.SOLUTION: In an aromatic dihalide compound, a fluorine atom is bonded to an aromatic ring. In a method of producing an aromatic dihalide compound, the aromatic dihalide compound is synthesized from an aromatic hydroxide. A method of producing polyarylene represented by a formula includes a process of polymerizing a monomer composition containing the synthesized aromatic dihalide compound and a dihalo sulfone compound, and a process of converting a sulfonic acid ester group included in the polymer obtained by the polymerization process into a sulfonic acid group.

Description

  The present invention relates to an aromatic dihalide compound and a method for producing a polymer thereof.

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 polyarylenes 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 novel method for producing a copolymer using a monomer having no ion exchange group, which is useful as a polymer electrolyte for a solid polymer fuel cell, and to constitute the copolymer. It is to provide a method for producing an aromatic dihalide compound as a monomer.

（式中、Ａｒ^１はフッ素原子を１つ以上含む２価の芳香族基を表わす。ここで、フッ素原子を１つ以上含む２価の芳香族基に含まれる水素原子は、
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炭素数１〜２０のアルキル基；
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炭素数１〜２０のアルコキシ基；
シアノ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基及び炭素数６〜１０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炭素数６〜２０のアリール基；
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炭素数６〜２０のアリールオキシ基；及び
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炭素数２〜２０のアシル基；
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。Ｘは塩素原子、臭素原子又はヨウ素原子を表わす。）
で示される芳香族ジハライド化合物と、下記式（２）

（式中、Ｒは水素原子、水酸基、炭素数６〜２０のアリール基、塩素原子、臭素原子又はヨウ素原子を表わす。ａ、ｂ及びｃは同一又は相異なり、０又は１を表わし、ｎは５以上の整数を表わす。Ａｒ^２、Ａｒ^３、Ａｒ^４及びＡｒ^５は同一又は相異なり、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、
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炭素数１〜２０のアルキル基；
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炭素数１〜２０のアルコキシ基；
シアノ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基及び炭素数６〜１０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炭素数６〜２０のアリール基；
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炭素数６〜２０のアリールオキシ基；及び
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炭素数２〜２０のアシル基；
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。
Ｙ^１及びＹ^２は同一又は相異なり、単結合、カルボニル基、スルホ基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基又はフルオレン−９，９−ジイル基を表わす。
Ｚ^１及びＺ^２は同一又は相異なり、酸素又は硫黄原子を表わす。）
で示される芳香族水酸化物とを反応させる工程を含むことを特徴とする、下記式（３）

（式中、Ａｒ^１１は、Ａｒ^１が含む１つ以上のフッ素原子が、下記式（４）

（式中、Ｒは水素原子、水酸基、炭素数６〜２０のアリール基、塩素原子、臭素原子又はヨウ素原子を表わす。ａ、ｂ及びｃは同一又は相異なり、０又は１を表わし、ｎは５以上の整数を表わす。Ａｒ^２、Ａｒ^３、Ａｒ^４及びＡｒ^５は同一又は相異なり、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、
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炭素数１〜２０のアルキル基；
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炭素数１〜２０のアルコキシ基；
シアノ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基及び炭素数６〜１０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炭素数６〜２０のアリール基；
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炭素数６〜２０のアリールオキシ基；及び
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炭素数２〜２０のアシル基；
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。
Ｙ^１及びＹ^２は同一又は相異なり、単結合、カルボニル基、スルホ基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基又はフルオレン−９，９−ジイル基を表わす。
Ｚ^１及びＺ^２は同一又は相異なり、酸素又は硫黄原子を表わす。）
で示される基を１つ以上含む２価の芳香族基を表わす。ここで、式（４）で示される基を１つ以上含む２価の芳香族基に含まれる水素原子は、
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炭素数１〜２０のアルキル基；
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炭素数１〜２０のアルコキシ基；
シアノ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基及び炭素数６〜１０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炭素数６〜２０のアリール基；
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炭素数６〜２０のアリールオキシ基；及び
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炭素数２〜２０のアシル基；
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。Ｘは塩素原子、臭素原子又はヨウ素原子を表わす。）
で示される基で置換されてなる２価の芳香族基である。）
で示される芳香族ジハライド化合物の製造方法；

２．前記式（１）におけるＡｒ^１が、下記式（５）

（式中、Ｒ^１は同一又は相異なり、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、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。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０〜３の整数を表わす。）
で示される２価の芳香族基であることを特徴とする前項１記載の芳香族ジハライド化合物の製造方法。

３．前項１又は前項２記載の製造方法により製造され得る芳香族ジハライド化合物を含むモノマー組成物を重合する工程を含むことを特徴とするポリアリーレンの製造方法；

４．前記式（３）で示される芳香族ジハライド化合物又は式（６）

（式中、Ｒは水素原子、水酸基、炭素数６〜２０のアリール基、塩素原子、臭素原子又はヨウ素原子を表わす。Ｘは塩素原子、臭素原子又はヨウ素原子を表わす。
Ｒ^１は同一又は相異なり、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、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。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０〜３の整数を表わす。
ａ、ｂ及びｃは同一又は相異なり、０又は１を表わし、ｎは５以上の整数を表わす。Ａｒ^２、Ａｒ^３、Ａｒ^４及びＡｒ^５は同一又は相異なり、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、
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炭素数１〜２０のアルキル基；
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炭素数１〜２０のアルコキシ基；
シアノ基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基及び炭素数６〜１０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炭素数６〜２０のアリール基；
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炭素数６〜２０のアリールオキシ基；及び
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炭素数２〜２０のアシル基
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。
Ｙ^１及びＹ^２は同一又は相異なり、単結合、カルボニル基、スルホ基、イソプロピリデン基、ヘキサフルオロイソプロピリデン基又はフルオレン−９，９−ジイル基を表わす。
Ｚ^１及びＺ^２は同一又は相異なり、酸素又は硫黄原子を表わす。）
で示される芳香族ジハライド化合物と、式（９）

（式中、Ｘは塩素原子、臭素原子又はヨウ素原子を表わす。Ａｒは下記式（１０）

（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。）
で示される基を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。さらにここで、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つの置換基が結合して当該置換基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。）
で示されるジハロスルホ化合物とを含むモノマー組成物を重合する工程、前記重合工程により得られた重合物が有する式（１０）で示される基を下記式（１１）

で示されるスルホ基に変換する工程を含むことを特徴とする、前記式（４）で示される基を１つ以上含む上記式（５）で示される２価の芳香族基と下記式（１２）

（式中、Ａｒは上記式（９）で示される基に含まれる２価の芳香族基と同じ意味を表わす。）
で示される繰り返し単位とを含むポリアリーレンの製造方法。

５．前記式（９）で示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は塩素原子、臭素原子又はヨウ素原子を表わす。Ｒ^３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^３が結合して当該Ｒ³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。ｋは０〜３の整数を表わす。ｊは１〜４の整数を表わす。ｋ＋ｊは１〜４の整数を表わす。）
で示される化合物であることを特徴とする前項４記載のポリアリーレンの製造方法；

６．前記式（９）で示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は塩素原子、臭素原子又はヨウ素原子を表わす。Ｒ^３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。また、結合位置が隣接する２つのＲ^３が結合して当該Ｒ^３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。ｋは０〜３の整数を表わす。）
で示される化合物であることを特徴とする前項４記載のポリアリーレンの製造方法；

７．前記式（９）で示されるジハロスルホ化合物が、下記式（１５）

（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は塩素原子、臭素原子又はヨウ素原子を表わす。Ｒ^３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。また、結合位置が隣接する２つのＲ^３が結合して当該Ｒ³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。ｉは０〜２の整数を表わす。）
で示される化合物であることを特徴とする前項４記載のポリアリーレンの製造方法；

８．前記芳香族ジハライド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、重合する工程を含むことを特徴とする前項４〜７のいずれか記載のポリアリーレンの製造方法；

等を提供するものである。 Under such circumstances, the present inventors diligently studied a method for producing a copolymer using a monomer having no ion exchange group, resulting in the following present invention. That is, the present invention

1. Following formula (1)

(In the formula, Ar ¹ represents a divalent aromatic group containing one or more fluorine atoms. Here, the hydrogen atom contained in the divalent aromatic group containing one or more fluorine atoms is:
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkyl groups;
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkoxy groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms. ~ 20 aryl groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. And substituted with at least one selected from the group consisting of 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 optionally substituted acyl group having 2 to 20 carbon atoms;
It may be substituted with at least one group selected from the group consisting of X represents a chlorine atom, a bromine atom or an iodine atom. )
An aromatic dihalide compound represented by formula (2):

(In the formula, R represents a hydrogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, a chlorine atom, a bromine atom or an iodine atom. A, b and c are the same or different and represent 0 or 1, and n represents Represents an integer greater than or equal to ^5. Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are the same or different and represent a divalent aromatic group, wherein the hydrogen atom contained in the divalent aromatic group is
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkyl groups;
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkoxy groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms. ~ 20 aryl groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. And substituted with at least one selected from the group consisting of 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 optionally substituted acyl group having 2 to 20 carbon atoms;
It may be substituted with at least one group selected from the group consisting of
Y ¹ and Y ² are the same or different and each represents a single bond, a carbonyl group, a sulfo group, an isopropylidene group, a hexafluoroisopropylidene group, or a fluorene-9,9-diyl group.
Z ¹ and Z ² are the same or different and represent an oxygen or sulfur atom. )
Comprising the step of reacting with an aromatic hydroxide represented by formula (3):

(In the formula, Ar ¹¹ represents one or more fluorine atoms contained in Ar ^{1 in the following} formula (4):

(In the formula, R represents a hydrogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, a chlorine atom, a bromine atom or an iodine atom. A, b and c are the same or different and represent 0 or 1, and n represents Represents an integer greater than or equal to ^5. Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are the same or different and represent a divalent aromatic group, wherein the hydrogen atom contained in the divalent aromatic group is
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkyl groups;
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkoxy groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms. ~ 20 aryl groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. And substituted with at least one selected from the group consisting of 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 optionally substituted acyl group having 2 to 20 carbon atoms;
It may be substituted with at least one group selected from the group consisting of
Y ¹ and Y ² are the same or different and each represents a single bond, a carbonyl group, a sulfo group, an isopropylidene group, a hexafluoroisopropylidene group, or a fluorene-9,9-diyl group.
Z ¹ and Z ² are the same or different and represent an oxygen or sulfur atom. )
Represents a divalent aromatic group containing one or more groups represented by Here, the hydrogen atom contained in the divalent aromatic group containing one or more groups represented by the formula (4) is:
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkyl groups;
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkoxy groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms. ~ 20 aryl groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. And substituted with at least one selected from the group consisting of 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 optionally substituted acyl group having 2 to 20 carbon atoms;
It may be substituted with at least one group selected from the group consisting of X represents a chlorine atom, a bromine atom or an iodine atom. )
It is a divalent aromatic group substituted by the group shown by these. )
A process for producing an aromatic dihalide compound represented by:

2. Ar ¹ in the formula (1) is the following formula (5).

(In the formula, R ¹ is the same or different and is 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, carbon Represents an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group, wherein the alkyl group has 1 to 20 carbon atoms, the alkoxy group has 1 to 20 carbon atoms, or has 6 to 20 carbon atoms. The hydrogen atom contained in the aryl group, the aryloxy group having 6 to 20 carbon atoms, the acyl group having 2 to 20 carbon atoms and the arylcarbonyl group having 7 to 20 carbon atoms is a cyano group, an alkyl group having 1 to 20 carbon atoms, From the group consisting of 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 an arylcarbonyl group having 7 to 20 carbon atoms. To be elected It may be substituted with at least one group, and 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. Represents an integer of 0 to 3.)
2. The method for producing an aromatic dihalide compound according to item 1 above, which is a divalent aromatic group represented by the formula:

3. A method for producing a polyarylene, comprising a step of polymerizing a monomer composition containing an aromatic dihalide compound that can be produced by the production method according to the preceding item 1 or 2.

4). The aromatic dihalide compound represented by the formula (3) or the formula (6)

(In the formula, R represents a hydrogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, a chlorine atom, a bromine atom or an iodine atom. X represents a chlorine atom, a bromine atom or an iodine atom.
R ¹ is the same or different and is 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 2 to 20 carbon atoms. An acyl group, 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 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 6 to 20 carbon atoms. The aryloxy group may be substituted with at least one group selected from the group consisting of an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms. 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. m represents an integer of 0 to 3.
a, b and c are the same or different and represent 0 or 1, and n represents an integer of 5 or more. Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are the same or different and represent a divalent aromatic group. Here, the hydrogen atom contained in the divalent aromatic group is
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkyl groups;
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkoxy groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms. ~ 20 aryl groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. And substituted with at least one selected from the group consisting of 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 group selected from the group consisting of acyl groups having 2 to 20 carbon atoms.
Y ¹ and Y ² are the same or different and each represents a single bond, a carbonyl group, a sulfo group, an isopropylidene group, a hexafluoroisopropylidene group, or a fluorene-9,9-diyl group.
Z ¹ and Z ² are the same or different and represent an oxygen or sulfur atom. )
An aromatic dihalide compound represented by formula (9):

(In the formula, X represents a chlorine atom, a bromine atom or an iodine atom. Ar represents the following formula (10):

(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. Represents.)
Represents a divalent aromatic group containing one or more groups represented by 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. Further, 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 The hydrogen atom contained in the arylcarbonyl group having 7 to 20 carbon 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, carbon 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. Further, two substituents 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 substituent is bonded. )
A step of polymerizing a monomer composition containing a dihalosulfo compound represented by formula (11), a group represented by formula (10) of the polymer obtained by the polymerization step is represented by the following formula (11)

A divalent aromatic group represented by the above formula (5) containing one or more groups represented by the above formula (4), and a step of converting to a sulfo group represented by the following formula (12): )

(In the formula, Ar represents the same meaning as the divalent aromatic group contained in the group represented by the formula (9)).
The manufacturing method of the polyarylene containing the repeating unit shown by these.

5. 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 chlorine atom, a bromine atom or an iodine atom, and R ³ 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 alkyl group having 6 to 20 carbon atoms. An aryl group, an aryloxy group having 6 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, wherein the alkyl group having 1 to 20 carbon atoms, carbon Hydrogen sources contained in 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 an arylcarbonyl group having 7 to 20 carbon 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, an aryloxy group having 6 to 20 carbon atoms, or 2 to 20 carbon atoms. at least one may be substituted by one selected from the group consisting of acyl and aryl carbonyl group having 7 to 20 carbon atoms. Further, the said R ³ bond positions are bonded two R ³ adjacent A ring may be formed together with carbon atoms on the benzene ring to be bonded, k represents an integer of 0 to 3, j represents an integer of 1 to 4, and k + j represents an integer of 1 to 4.)
The method for producing polyarylene according to item 4 above, which is a compound represented by the formula:

6). 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 chlorine atom, a bromine atom or an iodine atom, and R ³ 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 alkyl group having 6 to 20 carbon atoms. An aryl group, an aryloxy group having 6 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, wherein the alkyl group having 1 to 20 carbon atoms, carbon Hydrogen sources contained in 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 an arylcarbonyl group having 7 to 20 carbon 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, an aryloxy group having 6 to 20 carbon atoms, or 2 to 20 carbon atoms. at least one may be substituted with a group selected from the group consisting of acyl and aryl carbonyl group having 7 to 20 carbon atoms. Further, the said R ³ bond positions are bonded two R ³ adjacent A ring may be formed together with carbon atoms on the benzene ring to be bonded. K represents an integer of 0 to 3.)
The method for producing polyarylene according to item 4 above, which is a compound represented by the formula:

7. The dihalosulfo compound represented by the formula (9) is represented by the following formula (15):

(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 chlorine atom, a bromine atom or an iodine atom, and R ³ 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 alkyl group having 6 to 20 carbon atoms. An aryl group, an aryloxy group having 6 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, wherein the alkyl group having 1 to 20 carbon atoms, carbon Hydrogen sources contained in 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 an arylcarbonyl group having 7 to 20 carbon 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, an aryloxy group having 6 to 20 carbon atoms, or 2 to 20 carbon atoms. at least one may be substituted with a group selected from the group consisting of acyl and aryl carbonyl group having 7 to 20 carbon atoms. Further, the said R ³ bond positions are bonded two R ³ adjacent A ring may be formed together with carbon atoms on the benzene ring to which i is bonded, and i represents an integer of 0 to 2.)
The method for producing polyarylene according to item 4 above, which is a compound represented by the formula:

8). The method for producing polyarylene according to any one of the preceding items 4 to 7, further comprising a step of polymerizing the monomer composition containing the aromatic dihalide compound in the presence of a nickel compound;

Etc. are provided.

  According to the present invention, a novel method for producing a copolymer using a monomer having no ion exchange group, which is useful as a polymer electrolyte for a polymer electrolyte fuel cell, and the copolymer are constituted. A method for producing an aromatic dihalide compound as a monomer can be provided.

Hereinafter, the present invention will be described in detail.
First, any compound of an aromatic dihalide compound represented by the formula (1), an aromatic dihalide compound containing a divalent aromatic group represented by the formula (5), and an aromatic represented by the formula (2) The group hydroxide will be described.

  In the aromatic dihalide compound represented by the formula (1), X represents a chlorine atom, a bromine atom or an iodine atom. Preferably it represents a chlorine atom.

Examples of the “divalent aromatic group” in the “divalent aromatic group containing one or more fluorine atoms” in Ar ¹ include 2 such as 1,3-phenylene group, 1,4-phenylene group and the like. Monovalent aromatic group; naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7 A divalent condensed ring aromatic group such as a diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group; pyridine-2,5-diyl group, pyridine-2,6-diyl group And divalent heteroaromatic groups such as quinoxaline-2,6-diyl group and thiophene-2,5-diyl group. Preferable examples include a divalent monocyclic aromatic group, a divalent condensed ring aromatic group, and the like. More preferably, for example, 1,4-phenylene group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, etc. Can be mentioned.
The “divalent aromatic group containing one or more fluorine atoms” means that a hydrogen atom contained in these “divalent aromatic groups” is substituted with one or more fluorine atoms, Substituted with one fluorine atom.

  The hydrogen atom contained in the “divalent aromatic group” includes 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 an oxy 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 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 6 to 20 carbon atoms. The aryloxy group may be substituted with at least one group selected from the group consisting of an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms.

  Specific examples of the alkyl group having 1 to 20 carbon atoms include, for example, 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 a linear, branched or cyclic alkyl group such as a group and n-icosyl group.

  Specific 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, n-pentyloxy group, 2,2-dimethylpropoxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, 2-methylpentyloxy group, n-octyloxy group, 2-ethylhexyl Oxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexa Decyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyl Alkoxy group, n- icosyloxy group of linear, mention may be made of branched or cyclic alkoxy group.

  Specific 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.

  Specific examples of the aryloxy group having 6 to 20 carbon atoms include the phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 3-phenanthryloxy group, 2-anthryloxy group and the like. Examples thereof include those composed of an aryl group having 6 to 20 carbon atoms and an oxygen atom.

  Specific examples of the acyl group having 2 to 20 carbon atoms include aliphatic acyl groups having 2 to 20 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, and an isobutyryl group.

In the aromatic dihalide compound containing a divalent aromatic group represented by the formula (5), R ¹ is the same or different and is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 6 carbon atoms. Represents an aryl group having -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. 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 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 6 to 20 carbon atoms. The aryloxy group may be substituted with at least one selected from the group consisting of an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms. Further, two Rs 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 is bonded. m represents an integer of 0 to 3, and 0 or 1 is preferable.

  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. Specific examples of the arylcarbonyl group of ˜20 include the same as those described above.

R represents a hydrogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, a chlorine atom, a bromine atom or an iodine atom. a, b and c are the same or different and represent 0 or 1, and n represents an integer of 5 or more.
Y ¹ and Y ² are the same or different and each represents a single bond, a carbonyl group, a sulfo group, an isopropylidene group, a hexafluoroisopropylidene group, or a fluorene-9,9-diyl group.
Z ¹ and Z ² are the same or different and represent an oxygen or sulfur atom.

Specific examples of the aromatic dihalide compound represented by the formula (1) and the aromatic dihalide compound containing a divalent aromatic group represented by the formula (5) include the following formulas (1a) to (1n). The repeating unit shown etc. can be mentioned.

In the aromatic hydroxide represented by the formula (2), Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are the same or different and represent a divalent aromatic group. Here, the “divalent aromatic group” is a divalent aromatic group having neither an ion exchange group nor a protected ion exchange group. As the “divalent aromatic group”, for example, a heteroaromatic group in which the carbon atoms of the exemplified hydrocarbon-based aromatic group or a hydrocarbon aromatic group having 6 to 20 carbon atoms as the Ar ¹ is replaced with a heteroatom.
Examples of the group in which the hydrogen atom contained in the “divalent aromatic group” may be substituted include those exemplified as the substituent for Ar ¹ (excluding the fluorine atom). . Preferred examples of the divalent aromatic group include k that includes a divalent aromatic group having no substituent.

  Examples of the weight average molecular weight in terms of polystyrene of the aromatic hydroxide represented by the formula (2) include 2,000 to 200,000. Preferably, the thing of 3,000-100,000 can be mentioned, for example.

Specific examples of the aromatic hydroxide represented by the formula (2) include the following compounds. Here, examples of n include 5 to 200. Preferably, for example, 10-150 can be mentioned. More preferably, for example, 20-100 can be mentioned.

  As a manufacturing method of the aromatic hydroxide shown by Formula (2), what was manufactured according to well-known methods, such as Japan patent 2745727, for example, may be used, and what is marketed May be used. As what is marketed, Sumitomo Chemical Co., Ltd. Sumika Excel PES (trademark) etc. can be mentioned, for example.

  Next, the manufacturing method of the aromatic dihalide compound shown by Formula (3) and the manufacturing method of the aromatic dihalide compound shown by Formula (6) are demonstrated.

  Any one of the aromatic dihalide compound represented by the formula (1) and the aromatic dihalide compound containing a divalent aromatic group represented by the formula (5), and the aromatic water represented by the formula (2) Examples of the method of reacting with an oxide include a method of condensing in the presence of an alkali such as potassium carbonate, such as the method described in Reference Example 4 in JP-A-2004-190002. At this time, it is preferable to control the reaction temperature to 150 ° C. or lower so that the chlorine atom, bromine atom or iodine atom represented by X does not react.

Specific examples of the method for producing the aromatic dihalide compound represented by the formula (3) produced by such a production method and the aromatic dihalide compound represented by the formula (6) include the following. A compound etc. can be mentioned. Here, examples of n include 5 to 200. Preferably, for example, 10-150 can be mentioned. More preferably, for example, 20-100 can be mentioned.

  Next, a method for producing polyarylene including a step of polymerizing a monomer composition containing an aromatic dihalide compound that can be produced by the above production method will be described.

  The repeating unit in the polyarylene obtained by polymerizing the monomer composition containing the aromatic dihalide compound represented by the formula (3) is chlorine represented by X by the condensation reaction of the aromatic dihalide compound represented by the formula (3). It includes a divalent aromatic group that can be obtained by elimination of an atom, bromine atom or iodine atom. The repeating unit in the polyarylene obtained by polymerizing the monomer composition containing the aromatic dihalide compound represented by the formula (6) is represented by X by the condensation polymerization reaction of the aromatic dihalide compound represented by the formula (6). It includes a divalent aromatic group that can be obtained by elimination of a chlorine atom, bromine atom or iodine atom.

Specific examples of such repeating units include the following divalent aromatic groups. Here, examples of n include 5 to 200. Preferably, for example, 10-150 can be mentioned. More preferably, for example, 20-100 can be mentioned.

  The monomer composition containing the aromatic dihalide compound represented by the formula (3) or the aromatic dihalide compound represented by the formula (6) includes a dihalosulfo compound represented by the formula (9) and a formula (13). A dihalosulfo compound, a dihalosulfo compound represented by formula (14), and a dihalosulfo compound represented by formula (15) may be included.

  In the dihalosulfo compound represented by the formula (9), X represents a chlorine atom, a bromine atom or an iodine atom. Ar represents a divalent aromatic group containing one or more groups represented by the formula (10).

  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 an aryl group having 6 to 20 carbon atoms. It may be substituted with an aryloxy group, an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group. Further, 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 The hydrogen atom contained in the arylcarbonyl group having 7 to 20 carbon 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, carbon 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. Further, two substituents 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 substituent 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, mention may be made of branched or cyclic alkoxy group.

  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. Examples include those composed of 20 aryl groups and oxygen atoms.

  As a C2-C20 acyl group, C2-C20 aliphatic acyl groups, such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, etc. can be mentioned, for example.

  Examples of the arylcarbonyl group having 7 to 20 carbon atoms include a benzoyl group, a 1-naphthoyl group, and a 2-naphthoyl group.

  Examples of the divalent aromatic group 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-2,7-diyl group, etc. A divalent condensed aromatic group such as pyridine-2,5-diyl group, pyridine-2,6-diyl group, quinoxaline-2,6-diyl group, thiophene-2,5-diyl group, etc. A heteroaromatic 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, 1,4-phenylene group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, etc. Can be mentioned.

In formula (10), M represents a cation or an alkyl group having 1 to 20 carbon atoms which may have a substituent. When M is a cation, this M is bonded to a group represented by —SO ₃ by an ionic bond. When M is the alkyl group, this M is bonded to a group represented by —SO ₃ by a covalent bond. doing.

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

In the case where the dihalosulfo compound represented by the formula (9) is a compound represented by the formula (13), X and M represent the same meaning as described above (that is, in the case of the dihalosulfo compound represented by the formula (9)). k represents an integer of 0 to 3. Preferably k represents 0. j represents an integer of 1 to 4; Preferably, j represents 1 or 2. k + j represents an integer of 1 to 4.
R ³ 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 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. Further, two R ³ 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 ³ is bonded.

  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 compound represented by formula (13) include isopropyl 2,5-dichlorobenzenesulfonate, 2,5-dichlorobenzenesulfonate (2,2-dimethylpropyl), and 2,5-dichlorobenzene. Cyclohexyl sulfonate, 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-benzene Di-n-octyl disulfonate, 2,5-dichloro-1,4-benzenedisulfate Disodium acid, diammonium 2,5-dichloro-1,4-benzenedisulfonate, isopropyl 3,5-dichlorobenzenesulfonate, 3,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), 3, Cyclohexyl 5-dichlorobenzenesulfonate, 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, and ammonium 3,5-dibromobenzenesulfonate.

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

In the case where the dihalosulfo compound represented by the formula (9) is a compound represented by the formula (14), X, M, R ³ and k are the same as those described above (that is, in the case of the dihalosulfo compound represented by the formula (9)). Represents meaning.

  Specific examples of the compound represented by the formula (14) include, for example, dimethyl 4,4′-dichlorobiphenyl-2,2′-disulfonate, diethyl 4,4′-dichlorobiphenyl-2,2′-disulfonate. 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (n-propyl), 4,4′-dichlorobiphenyl-2,2′-disulfonic acid diisopropyl, 4,4′-dichlorobiphenyl-2, 2'-disulfonic acid di (n-butyl), 4,4'-dichlorobiphenyl-2,2'-disulfonic acid diisobutyl, 4,4'-dichlorobiphenyl-2,2'-disulfonic acid di (2,2- Dimethylpropyl), 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.

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

In the case where the dihalosulfo compound represented by the formula (9) is a compound represented by the formula (15), X, M, and R ³ have the same meaning as described above (that is, in the case of the dihalosulfo compound represented by the formula (9)). Represent. i represents an integer of 0-2. Preferably it is 0.

Specific examples of the compound represented by the formula (15) 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'-biphenyltetrasulfonic acid tetrakis (2,2-dimethyl-1-propyl), 4,4'-dichloro-2,2 ', 6,6'-biphenyltetrasulfonic acid tetraammonium, 4,4'-dichloro -2, 2 ', 6 Tris (2,2-dimethyl-1-propyl) sodium 6′-biphenyltetrasulfonate, tetrakis (2,2-dimethyl-), 4,4′-dichloro-2,2 ′, 6,6′-biphenyltetrasulfonate 1-propyl) and the like.

The repeating unit represented by the formula (12) is a divalent aromatic group which can be obtained by elimination of the chlorine atom, bromine atom or iodine atom represented by X from the dihalosulfo compound represented by the formula (9) by a condensation polymerization reaction. including.
Specific examples of such repeating units include repeating units represented by the following formulas (12a) to (12t).

Examples of the method for polymerizing the monomer composition containing the aromatic halide compound include a method for polymerizing the monomer composition in the presence of a nickel compound.
Examples of the nickel compound include zero-valent nickel compounds such as nickel (0) bis (cyclooctadiene), nickel (0) (ethylene) bis (triphenylphosphine), nickel (0) tetrakis (triphenylphosphine), and nickel halides. (E.g., nickel fluoride, nickel chloride, nickel bromide, nickel iodide, etc.), nickel carboxylate (e.g., nickel formate, nickel acetate, etc.), nickel sulfate, nickel carbonate, nickel nitrate, nickel acetylacetonate, ( Examples thereof include divalent nickel compounds such as dimethoxyethane) nickel chloride. Preferable examples include nickel (0) bis (cyclooctadiene) and nickel halide.
As the usage-amount of a nickel compound, the range etc. of 0.01 mol-5 mol etc. can be mentioned with respect to the total 1 mol of a monomer composition.

  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. When using a nitrogen-containing bidentate ligand, the amount of use can mention the range of 0.2 mol-2 mol etc. 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. As usage-amount in the case of using zinc, the range of 0.5 mol-1.5 mol etc. can be mentioned with respect to a total of 1 mol of a monomer composition.

The polymerization reaction is preferably performed in the presence of a solvent. The solvent may be any solvent that can dissolve the monomer composition 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-dimethyl. Examples include aprotic polar solvents such as formamide, N, 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. Preferable examples include ether solvents and aprotic polar solvents. More preferred examples include tetrahydrofuran, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide and the like.
As a usage-amount of a solvent, the range etc. of 1 weight times-200 weight times etc. can be mentioned with respect to the total 1 weight part of monomer composition used, for example. Preferably, the range of 5 weight times-100 weight times etc. can be mentioned, for example.

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 degreeC-100 degreeC etc. can be mentioned, for example. Examples of the polymerization time include a range of 0.5 hours to 48 hours.

After the completion of the polymerization reaction, the desired polymer is obtained by mixing the reaction mixture and a solvent in which the produced polymer is difficult to dissolve to precipitate the polymer, and separating the precipitated polymer from the reaction mixture using a filtration operation. Can be taken out.
Further, after mixing a solvent that does not dissolve the polymer that is formed or a solvent that is difficult to dissolve with the reaction mixture, an acid is added to the resulting mixture, and the precipitated polymer may be separated from the reaction mixture using a filtration operation. Good.
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. In addition, the usage-amount of an acid should just be an amount required in order to acidify a reaction mixture, for example.

The structural unit derived from the dihalosulfo compound represented by the formula (9) of the obtained polymer contains a group represented by the formula (10). Examples of a method for converting such a group represented by the formula (10) into a sulfo group represented by the formula (11) are described in JP 2007-270118 A, JP 2007-177197 A, and the like. The method etc. can be mentioned.
The ion exchange capacity (measured by titration method) of the polymer thus obtained is, for example, in the 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 obtained polymers can be suitably used as a member for a fuel cell. The polymer 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.

1. Molecular weight measurement:
The polymer described in Example 2 was analyzed by gel permeation chromatography (hereinafter sometimes referred to as GPC) (analysis conditions are as follows). The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were calculated from the results obtained by the analysis.
<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

2. Measurement of ion exchange capacity (IEC):
A polymer electrolyte membrane was obtained by forming a polymer (polymer electrolyte) to be used for measurement by a solution casting method. 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.

スミカエクセル４００３Ｐ（住友化学製、水酸基末端ポリエーテルスルホン）１７．０ｇと炭酸カリウム３．７ｇとジメチルスルホキシド１０２．３ｇとトルエン２０．６ｇとを混合し、８０℃に昇温してから減圧濃縮し、３２．０ｇの留分を取り除いた。得られた濃縮物を２５℃まで冷却し、これに１，４−ジクロロ−２−フルオロベンゼン４．０ｇを滴下した後、得られた混合物を１４０℃で３時間保温した。得られた反応混合物を水３３１．７ｇに注ぎ込み、析出した固体を２Ｎ塩酸、水、メタノールで洗浄した。得られた固体を乾燥することにより、１，４−ジクロロ−２−フルオロベンゼンとポリエーテルスルホンとの縮合物１６．８ｇ（収率９８．５％）を得た。 Example 1 (Condensate of 1,4-dichloro-2-fluorobenzene and polyethersulfone)

Sumika Excel 4003P (manufactured by Sumitomo Chemical Co., Ltd., hydroxyl-terminated polyethersulfone) 17.0 g, potassium carbonate 3.7 g, dimethyl sulfoxide 102.3 g and toluene 20.6 g were mixed, heated to 80 ° C. and concentrated under reduced pressure. A 32.0 g fraction was removed. The obtained concentrate was cooled to 25 ° C., and 4.0 g of 1,4-dichloro-2-fluorobenzene was added dropwise thereto, and then the resulting mixture was kept at 140 ° C. for 3 hours. The obtained reaction mixture was poured into 331.7 g of water, and the precipitated solid was washed with 2N hydrochloric acid, water and methanol. The obtained solid was dried to obtain 16.8 g (yield 98.5%) of a condensate of 1,4-dichloro-2-fluorobenzene and polyethersulfone.

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１５．６ｇを得た。得られた重合体のＭｗは６．１×１０^５、Ｍｎは１．４×１０^５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２９４ｇと３５％塩酸８．６ｇとを加え、得られた混合物を１２０℃で１８時間攪拌した。
次いで、得られた反応混合物をアセトン９５８ｇ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９５８ｇで３回洗浄した後、これを水９５８ｇ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回洗浄した後、これを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からなるポリアリーレンブロック共重合体１０．２ｇを得た（収率７７％）。得られた重合体のイオン交換容量は３．０５ｍｅｑ／ｇであった。 Example 2 (Synthesis of polymer)
(1) First step:
Under a nitrogen atmosphere, 0.92 g of anhydrous nickel bromide, 0.67 g of 2,2′-bipyridine and 55.3 g of N-methyl-2-pyrrolidone were mixed, and the resulting mixture was stirred at 65 ° C. for 2 hours ( Solution A).
(2) Second step:
6.8 g of the condensate of 1,4-dichloro-2-fluorobenzene and polyethersulfone obtained in Example 1, 2.1 g of zinc powder, 4,4′-dichlorobiphenyl-2,2′- 12.0 g of di (2,2-dimethylpropyl) disulfonate and 101.8 g of N-methyl-2-pyrrolidone were mixed and adjusted to 40 ° C. A solution consisting of 24 mg of methanesulfonic acid and 1.6 g of N-methyl-2-pyrrolidone was added thereto, followed by stirring at 40 ° C. for 3 hours (referred to as Solution B). After the obtained solution B was cooled to 20 ° C., the solution A obtained in the first step was mixed therewith, and the resulting mixture was stirred at 20 ° C. for 9 hours.
Next, the obtained reaction mixture was poured into 469.1 g of 2N hydrochloric acid, and the precipitated solid was washed with water and methanol, and then dried under reduced pressure to obtain the following formula.

As a result, 15.6 g of a polyarylene copolymer having a repeating unit represented by the formula (1) was obtained. Mw of the obtained polymer was 6.1 × 10 ⁵ and Mn was 1.4 × 10 ⁵ .
To the polymer obtained above, 294 g of N-methyl-2-pyrrolidone and 8.6 g of 35% hydrochloric acid were added, and the resulting mixture was stirred at 120 ° C. for 18 hours.
Next, the obtained reaction mixture was poured into 958 g of acetone, and the precipitated solid was washed with acetone. The obtained solid was washed 3 times with 958 g of 13% hydrochloric acid, 958 g of water was added thereto, and the mixture was stirred at 90 ° C. for 15 hours. The cake obtained by filtration was washed 6 times with water, and then dried under reduced pressure to obtain the following formula.

10.2 g of a polyarylene block copolymer consisting of repeating units represented by the formula (yield 77%) was obtained. The resulting polymer had an ion exchange capacity of 3.05 meq / g.

Claims (8)

Following formula (1)

(In the formula, Ar ¹ represents a divalent aromatic group containing one or more fluorine atoms. Here, the hydrogen atom contained in the divalent aromatic group containing one or more fluorine atoms is:
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkyl groups;
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkoxy groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms. ~ 20 aryl groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. And substituted with at least one selected from the group consisting of 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 optionally substituted acyl group having 2 to 20 carbon atoms;
It may be substituted with at least one group selected from the group consisting of X represents a chlorine atom, a bromine atom or an iodine atom. )
An aromatic dihalide compound represented by formula (2):

(In the formula, R represents a hydrogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, a chlorine atom, a bromine atom or an iodine atom. A, b and c are the same or different and represent 0 or 1, and n represents Represents an integer greater than or equal to ^5. Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are the same or different and represent a divalent aromatic group, wherein the hydrogen atom contained in the divalent aromatic group is
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkyl groups;
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkoxy groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms. ~ 20 aryl groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. And substituted with at least one selected from the group consisting of 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 optionally substituted acyl group having 2 to 20 carbon atoms;
It may be substituted with at least one group selected from the group consisting of
Y ¹ and Y ² are the same or different and each represents a single bond, a carbonyl group, a sulfo group, an isopropylidene group, a hexafluoroisopropylidene group, or a fluorene-9,9-diyl group.
Z ¹ and Z ² are the same or different and represent an oxygen or sulfur atom. )
Comprising the step of reacting with an aromatic hydroxide represented by formula (3):

(In the formula, Ar ¹¹ represents one or more fluorine atoms contained in Ar ^{1 in the following} formula (4):

(In the formula, R represents a hydrogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, a chlorine atom, a bromine atom or an iodine atom. A, b and c are the same or different and represent 0 or 1, and n represents Represents an integer greater than or equal to ^5. Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are the same or different and represent a divalent aromatic group, wherein the hydrogen atom contained in the divalent aromatic group is
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkyl groups;
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkoxy groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms. ~ 20 aryl groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. And substituted with at least one selected from the group consisting of 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 optionally substituted acyl group having 2 to 20 carbon atoms;
It may be substituted with at least one group selected from the group consisting of
Y ¹ and Y ² are the same or different and each represents a single bond, a carbonyl group, a sulfo group, an isopropylidene group, a hexafluoroisopropylidene group, or a fluorene-9,9-diyl group.
Z ¹ and Z ² are the same or different and represent an oxygen or sulfur atom. )
Represents a divalent aromatic group containing one or more groups represented by Here, the hydrogen atom contained in the divalent aromatic group containing one or more groups represented by the formula (4) is:
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkyl groups;
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkoxy groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms. ~ 20 aryl groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. And substituted with at least one selected from the group consisting of 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 optionally substituted acyl group having 2 to 20 carbon atoms;
It may be substituted with at least one group selected from the group consisting of X represents a chlorine atom, a bromine atom or an iodine atom. )
It is a divalent aromatic group substituted by the group shown by these. )
The manufacturing method of the aromatic dihalide compound shown by these. Ar ¹ in the formula (1) is the following formula (5).

(In the formula, R ¹ is the same or different and is 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, carbon Represents an acyl group having 2 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group, wherein the alkyl group has 1 to 20 carbon atoms, the alkoxy group has 1 to 20 carbon atoms, or has 6 to 20 carbon atoms. The hydrogen atom contained in the aryl group, the aryloxy group having 6 to 20 carbon atoms, the acyl group having 2 to 20 carbon atoms and the arylcarbonyl group having 7 to 20 carbon atoms is a cyano group, an alkyl group having 1 to 20 carbon atoms, From the group consisting of 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 an arylcarbonyl group having 7 to 20 carbon atoms. To be elected It may be substituted with at least one group, and 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. Represents an integer of 0 to 3.)
The method for producing an aromatic dihalide compound according to claim 1, wherein the aromatic dihalide compound is a divalent aromatic group represented by the formula: A method for producing a polyarylene, comprising a step of polymerizing a monomer composition containing an aromatic dihalide compound that can be produced by the production method according to claim 1. The aromatic dihalide compound represented by the formula (3) or the formula (6)

(In the formula, R represents a hydrogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, a chlorine atom, a bromine atom or an iodine atom. X represents a chlorine atom, a bromine atom or an iodine atom.
R ¹ is the same or different and is 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 2 to 20 carbon atoms. An acyl group, 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 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 6 to 20 carbon atoms. The aryloxy group may be substituted with at least one group selected from the group consisting of an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms. 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. m represents an integer of 0 to 3.
a, b and c are the same or different and represent 0 or 1, and n represents an integer of 5 or more. Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are the same or different and represent a divalent aromatic group. Here, the hydrogen atom contained in the divalent aromatic group is
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkyl groups;
1 carbon atom which may be substituted with at least one selected from the group consisting of 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 ~ 20 alkoxy groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 10 carbon atoms. ~ 20 aryl groups;
6 carbon atoms which may be substituted with at least one selected from the group consisting of a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. And substituted with at least one selected from the group consisting of 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 group selected from the group consisting of acyl groups having 2 to 20 carbon atoms.
Y ¹ and Y ² are the same or different and each represents a single bond, a carbonyl group, a sulfo group, an isopropylidene group, a hexafluoroisopropylidene group, or a fluorene-9,9-diyl group.
Z ¹ and Z ² are the same or different and represent an oxygen or sulfur atom. )
An aromatic dihalide compound represented by formula (9):

(In the formula, X represents a chlorine atom, a bromine atom or an iodine atom. Ar represents the following formula (10):

(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. Represents.)
Represents a divalent aromatic group containing one or more groups represented by 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. Further, 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 The hydrogen atom contained in the arylcarbonyl group having 7 to 20 carbon 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, carbon 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. Further, two substituents 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 substituent is bonded. )
A step of polymerizing a monomer composition containing a dihalosulfo compound represented by formula (11), a group represented by formula (10) of the polymer obtained by the polymerization step is represented by the following formula (11)

A divalent aromatic group represented by the above formula (5) containing one or more groups represented by the above formula (4), and a step of converting to a sulfo group represented by the following formula (12): )

(In the formula, Ar represents the same meaning as the divalent aromatic group contained in the group represented by the formula (9)).
The manufacturing method of the polyarylene containing the repeating unit shown by these. 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 chlorine atom, a bromine atom or an iodine atom, and R ³ 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 alkyl group having 6 to 20 carbon atoms. An aryl group, an aryloxy group having 6 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, wherein the alkyl group having 1 to 20 carbon atoms, carbon Hydrogen sources contained in 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 an arylcarbonyl group having 7 to 20 carbon 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, an aryloxy group having 6 to 20 carbon atoms, or 2 to 20 carbon atoms. at least one may be substituted by one selected from the group consisting of acyl and aryl carbonyl group having 7 to 20 carbon atoms. Further, the said R ³ bond positions are bonded two R ³ adjacent A ring may be formed together with carbon atoms on the benzene ring to be bonded, k represents an integer of 0 to 3, j represents an integer of 1 to 4, and k + j represents an integer of 1 to 4.)
The method for producing polyarylene according to claim 4, 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 chlorine atom, a bromine atom or an iodine atom, and R ³ 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 alkyl group having 6 to 20 carbon atoms. An aryl group, an aryloxy group having 6 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, wherein the alkyl group having 1 to 20 carbon atoms, carbon Hydrogen sources contained in 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 an arylcarbonyl group having 7 to 20 carbon 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, an aryloxy group having 6 to 20 carbon atoms, or 2 to 20 carbon atoms. at least one may be substituted with a group selected from the group consisting of acyl and aryl carbonyl group having 7 to 20 carbon atoms. Further, the said R ³ bond positions are bonded two R ³ adjacent A ring may be formed together with carbon atoms on the benzene ring to be bonded. K represents an integer of 0 to 3.)
The method for producing polyarylene according to claim 4, wherein the compound is represented by the formula: The dihalosulfo compound represented by the formula (9) is represented by the following formula (15):

(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 chlorine atom, a bromine atom or an iodine atom, and R ³ 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 alkyl group having 6 to 20 carbon atoms. An aryl group, an aryloxy group having 6 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, wherein the alkyl group having 1 to 20 carbon atoms, carbon Hydrogen sources contained in 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 an arylcarbonyl group having 7 to 20 carbon 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, an aryloxy group having 6 to 20 carbon atoms, or 2 to 20 carbon atoms. at least one may be substituted with a group selected from the group consisting of acyl and aryl carbonyl group having 7 to 20 carbon atoms. Further, the said R ³ bond positions are bonded two R ³ adjacent A ring may be formed together with carbon atoms on the benzene ring to which i is bonded, and i represents an integer of 0 to 2.)
The method for producing polyarylene according to claim 4, wherein the compound is represented by the formula: The method for producing polyarylene according to any one of claims 4 to 7, comprising a step of polymerizing a monomer composition containing the aromatic dihalide compound in the presence of a nickel compound.