JP2013221086A - Polyarylene and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polyarylene or the like having a perfluoroalkyl sulfonic acid as an ion exchange group.SOLUTION: A polyarylene is provided, including a repeating unit having an ion exchange group expressed by formula (1). In the formula, W represents one of a direct bond, -O-, -S-, -SO-, -SO- and -CO-; m represents an integer of 0 to 3; p represents an integer of 1 to 12; q represents an integer of 1 to 12; r represents an integer of 0 to 10; Rrepresents identical or different groups of a fluorine atom, an alkyl group or the like, in which a hydrogen atom included in the alkyl group or the like can be substituted with at least one selected from the group consisting of a fluorine atom or the like, or two of Rwith adjoining bonding positions cay be bonded together with a carbon atom on a benzene ring to which the Ris bonded, to form a ring.

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. As polyarylene having perfluoroalkylsulfonic acid as an ion exchange group, for example, a polymer having an aromatic group in the main chain structure and having perfluoroalkylsulfonic acid in the side chain is known. (For example, refer to Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, etc.).

JP 2005-255789 A (Example) Japanese Patent Laying-Open No. 2005-320523 (Example) Japanese Patent Laying-Open No. 2005-2596 (Example) JP-A-2005-314452 (Example)

  An object of the present invention is to provide a novel polyarylene having perfluoroalkylsulfonic acid as an ion exchange group.

（式中、Ｗは直接結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−のいずれかを表わす。ｍは０〜３の整数を表わす。ｐは１〜１２の整数を表わす。ｑは１〜１２の整数を表わす。ｒは０〜１０の整数を表わす。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。）
で示されるイオン交換基を有する繰り返し単位を含むことを特徴とするポリアリーレン；
２．式（２）

（式中、Ｗは、直接結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−のいずれかを表わす。ｍは０〜３整数を表わす。ｐは１〜１２の整数を表わす。ｑは１〜１２の整数を表わす。ｒは０〜１０の整数を表わす。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。）
で示されるイオン交換基を有する繰り返し単位を含むことを特徴とするポリアリーレン；
３．式（３）

（式中、Ｗは同一又は相異なり、直接結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−のいずれかを表わす。ｍは０〜３整数を表わす。ｐは１〜１２の整数を表わす。ｑは１〜１２の整数を表わす。ｒは０〜１０の整数を表わす。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。）
で示されるイオン交換基を有する繰り返し単位を含むことを特徴とするポリアリーレン；
４．下記式（１１）

（式中、ａ、ｂ及びｃは、同一又は相異なって、０又は１を表わす。ｎは５以上の整数を表わす。Ａｒ^１、Ａｒ^２、Ａｒ^３及びＡｒ^４は、同一又は相異なって、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、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；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炭素数１〜２０のアルコキシ基；フッ素原子、シアノ基、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；フッ素原子、シアノ基、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、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、同一又は相異なって、単結合、カルボニル基、スルホニル基、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、同一又は相異なって、酸素原子又は硫黄原子を表わす。）
で示される繰り返し単位を含むことを特徴とする請求項１〜３のいずれかの請求項記載のポリアリーレン；
５．下記式（１２）

（式中、Ａｒ^０は、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、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；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炭素数１〜２０のアルコキシ基；フッ素原子、シアノ基、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のアリール基；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のアリールオキシ基及び炭素数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；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炭素数２〜２０のアシル基；及び、保護基を有していてもよいスルホ基；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。）
で示される繰り返し単位を含むことを特徴とする請求項１〜３のいずれかの請求項記載のポリアリーレン；
６．式（１４）

（式中、Ｒ^１は同一又は相異なり、水素原子、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^２は同一又は相異なり、０〜４の整数を表わし、ｈは１〜１０の整数を表わす。）
で示される繰り返し単位を含むことを特徴とする請求項１〜３のいずれかの請求項記載のポリアリーレン；
７．式（４）で示されることを特徴とするジハロベンゼン化合物

（式中、Ｗは直接結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−のいずれかを表わす。ｍは０〜３整数を表わす。ｐは１〜１２の整数を表わす。ｑは１〜１２の整数を表わす。ｒは０〜１０の整数を表わす。ｌは１又は２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。Ｘ^１は同一又は相異なり、塩素原子、臭素原子又はヨウ素原子を表わす。ＳＯ_３ＭはＳＯ_３Ｍ_１又はＳＯ_３ ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は水素原子を表わし、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。）；
８．式（５）で示されることを特徴とするジハロビフェニル化合物

（式中、Ｗは同一又は相異なり、直接結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−のいずれかを表わす。ｍは０〜３整数を表わす。ｐは１〜１２の整数を表わす。ｑは１〜１２の整数を表わす。ｒは０〜１０の整数を表わす。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。Ｘ^１は同一又は相異なり、塩素原子、臭素原子又はヨウ素原子を表わす。ＳＯ_３Ｍは同一又は相異なり、ＳＯ_３Ｍ_１又はＳＯ_３ ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は水素原子を表わし、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。）；
９．式（６）で示されることを特徴とするジハロベンゼン化合物

（式中、Ｗは、直接結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−のいずれかを表わす。ｍは０〜３整数を表わす。ｐは１〜１２の整数を表わす。ｑは１〜１２の整数を表わす。ｒは０〜１０の整数を表わす。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。Ｘ^１は、塩素原子、臭素原子又はヨウ素原子を表わし、Ｘ^２は、塩素原子、臭素原子又はヨウ素原子を表わす。ＳＯ_３ＭはＳＯ_３Ｍ_１又はＳＯ_３ ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は水素原子を表わし、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。）；
１０．ニッケル化合物の存在下に、式（４）、式（５）及び式（６）のいずれかで示される化合物を含むモノマー組成物を重合させ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；
１１．式（６）

（式中、Ｗは、直接結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−のいずれかを表わす。ｍは０〜３整数を表わす。ｐは１〜１２の整数を表わす。ｑは１〜１２の整数を表わす。ｒは０〜１０の整数を表わす。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。Ｘ^１は、塩素原子、臭素原子又はヨウ素原子を表わし、Ｘ^２は、塩素原子、臭素原子又はヨウ素原子を表わす。ＳＯ_３ＭはＳＯ_３Ｍ_１又はＳＯ_３ ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は水素原子を表わし、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。）
で示されるジハロベンゼン化合物のＸ^２の脱離によりカップリング反応させる工程を含む式（５）

（式中、Ｗ、ｍ、ｐ、ｑ、ｒ、Ｘ^１、Ｍ、Ｒ^１は前記と同じ意味を表わす。）
で示されるジハロビフェニル化合物の製造方法；
１２．式（７）

（式中、Ｗは直接結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−のいずれかを表わす。ｍは０〜３整数を表わす。ｐは１〜１２の整数を表わす。ｑは１〜１２の整数を表わす。ｒは０〜１０の整数を表わす。
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。Ｘ^１は、塩素原子、臭素原子又はヨウ素原子を表わす。ＳＯ_３ＭはＳＯ_３Ｍ_１又はＳＯ_３ ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は水素原子を表わし、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。ＡはＮＨ_２又はＮＨ_３の酸付加塩を表わす。）
で示されるアニリン化合物におけるＡをジアゾ化し、脱窒素及びハロゲン化させる工程を含むｌが１を表す式（４）

（式中、Ｗ、ｍ、ｐ、ｑ、ｒ、ｌ、Ｘ^１、Ｍ、Ｒ^１は前記と同じ意味を表わす。）
で示されるジハロベンゼン化合物の製造方法；
１３．式（９）

（式中、ｍは０〜３の整数を表わす。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。Ｘ^３は、臭素原子又はヨウ素原子を表わす。ＡはＮＨ_２又はＮＨ_３の酸付加塩を表わす。）
で示される化合物と
式（１０）

（式中、Ｗは、直接結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−のいずれかを表わす。ｐは１〜１２の整数を表わす。ｑは１〜１２の整数を表わす。ｒは０〜１０の整数を表わす。ＳＯ_３ＭはＳＯ_３Ｍ_１又はＳＯ_３ ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は水素原子を表わし、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。）
で示される化合物を金属銅の存在下に、カップリングさせる反応工程を含む式（８）

（式中、Ｗ、ｍ、ｐ、ｑ、ｒ、Ａ、Ｍ、Ｒ^１は前記と同じ意味を表わす。）
で示されるアニリン化合物の製造方法；
等を提供するものである。 Under such circumstances, the present inventors have intensively studied polyarylene having perfluoroalkylsulfonic acid as an ion exchange group, and as a result, have reached the following present invention. That is, the present invention
1. Formula (1)

(Wherein W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—, m represents an integer of 0 to 3, and p represents 1 to 12). Q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Represents an alkoxy 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, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, carbon A hydrogen atom 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 and an acyl group having 2 to 20 carbon atoms is a fluorine atom, a cyano group, or a carbon number. 1-20 alkyl group, C1-C20 alkoxy group, C6 The aryl group may be substituted with at least one selected from the group consisting of an aryl group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms. R ¹ may be bonded to form a ring together with the carbon atom on the benzene ring to which R ¹ is bonded.)
A polyarylene comprising a repeating unit having an ion exchange group represented by:
2. Formula (2)

(In the formula, W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—. M represents an integer of 0 to _3. p represents 1 to 12. Q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Represents an alkoxy 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, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, carbon A hydrogen atom 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 and an acyl group having 2 to 20 carbon atoms is a fluorine atom, a cyano group, or a carbon number. 1-20 alkyl group, C1-C20 alkoxy group, C6 The aryl group may be substituted with at least one selected from the group consisting of an aryl group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms. R ¹ may be bonded to form a ring together with the carbon atom on the benzene ring to which R ¹ is bonded.)
A polyarylene comprising a repeating unit having an ion exchange group represented by:
3. Formula (3)

(Wherein, W is the same or different and represents any of a direct bond, —O—, —S—, —SO—, —SO ₂ —, —CO—. M represents an integer of 0 to _3. p. Represents an integer of 1 to 12. q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, carbon. 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, or a cyano group, where 1 to 20 carbon atoms are represented. The hydrogen atom contained in the alkyl group, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aryloxy group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms is a fluorine atom, cyano Group, an alkyl group having 1 to 20 carbon atoms, an alcohol having 1 to 20 carbon atoms It may be substituted with at least one selected from the group consisting of a Si group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms and an acyl group having 2 to 20 carbon atoms. coupling position may form a ring with the carbon atoms on the benzene ring to which the R ¹ by bonding two of R ¹ adjacent binds.)
A polyarylene comprising a repeating unit having an ion exchange group represented by:
4). Following formula (11)

(In the formula, a, b and c are the same or different and represent 0 or 1. n represents an integer of 5 or more. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the same or different. A divalent aromatic group, wherein the hydrogen atom contained in the divalent aromatic group 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 An alkyl group having 1 to 20 carbon atoms which may be substituted with at least one selected from the group consisting of aryloxy groups having 6 to 20 carbon atoms; a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms which 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; a fluorine atom, a cyano group, 1-20 carbon atoms An aryl group having 6 to 20 carbon atoms which may be substituted with at least one selected from the group consisting of an alkoxy group and an aryloxy group having 6 to 10 carbon atoms; a fluorine atom, a cyano group, and a carbon atom having 1 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 an alkoxy group and an aryloxy group having 6 to 20 carbon atoms; and a fluorine atom, a cyano group, and one carbon atom From an acyl group having 2 to 20 carbon atoms, which may be substituted with at least one selected from the group consisting of an alkoxy group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms Y ¹ and Y ² may be the same or different and each may be substituted with at least one group selected from the group consisting of a single bond, a carbonyl group, and a sulfonyl group. Group, isopropylidene group, hexafluoroisopropylidene group or fluorene-9,9-diyl group, and Z ¹ and Z ² are the same or different and each represents an oxygen atom or a sulfur atom.)
The polyarylene according to any one of claims 1 to 3, comprising a repeating unit represented by:
5. Following formula (12)

(In the formula, Ar ⁰ represents a divalent aromatic group. Here, a hydrogen atom contained in the divalent aromatic group is a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, or a carbon number. An alkyl group having 1 to 20 carbon atoms which 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; fluorine atom, cyano group, carbon number An alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, which 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 A carbon atom 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; Aryl group; 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 aryloxy group having 6 to 20 carbon atoms and an acyl group having 2 to 20 carbon atoms An aryloxy group having 6 to 20 carbon atoms; a 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 Substituted with at least one selected from the group consisting of an acyl group having 2 to 20 carbon atoms which may be substituted with at least one selected; and a sulfo group which may have a protecting group. May be.)
The polyarylene according to any one of claims 1 to 3, comprising a repeating unit represented by:
6). Formula (14)

(In the formula, R ¹ is the same or different and is a hydrogen atom, 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. 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 atom Good .m ² to form a ring are the same or different, represents an integer of 0 to 4, h is an integer of 1 to 10.)
The polyarylene according to any one of claims 1 to 3, comprising a repeating unit represented by:
7. A dihalobenzene compound represented by the formula (4)

(In the formula, W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—. M represents an integer of 0 to _3. p represents an integer of 1 to 12. Q represents an integer, q represents an integer of 1 to 12. r represents an integer of 0 to 10. l represents 1 or 2. R ¹ is the same or different and is a fluorine atom or an alkyl having 1 to 20 carbon atoms. Group, 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, or a cyano group. A hydrogen atom contained in an alkyl group having -20 carbon atoms, an alkoxy group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms, an aryloxy group having 6-20 carbon atoms, and an acyl group having 2-20 carbon atoms is fluorine. An atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an atom having 1 to 20 carbon atoms It may be substituted with at least one selected from the group consisting of a alkoxy group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms and an acyl group having 2 to 20 carbon atoms. 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, and X ¹ is the same or different and is a chlorine atom, bromine atom or iodine. .SO ₃ M representing the atoms _SO 3 _{M 1} or _SO ³ - represents an _{M 2} ^+, where, _{M 1} is a hydrogen atom, _{M 2} ⁺ represents a cation of an alkali metal cation or ammonium compound);..
8). A dihalobiphenyl compound represented by the formula (5)

(Wherein, W is the same or different and represents any of a direct bond, —O—, —S—, —SO—, —SO ₂ —, —CO—. M represents an integer of 0 to _3. p. Represents an integer of 1 to 12. q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, carbon. 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, or a cyano group, where 1 to 20 carbon atoms are represented. The hydrogen atom contained in the alkyl group, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aryloxy group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms is a fluorine atom, cyano Group, an alkyl group having 1 to 20 carbon atoms, an alcohol having 1 to 20 carbon atoms It may be substituted with at least one selected from the group consisting of a Si group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms and an acyl group having 2 to 20 carbon atoms. 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, and X ¹ is the same or different and is a chlorine atom, bromine atom or iodine. SO ₃ M is the same or different and represents SO ₃ M ₁ or SO ₃ ⁻ M ₂ ⁺ , where M ₁ represents a hydrogen atom and M ₂ ⁺ represents a cation of an alkali metal cation or an ammonium compound. Represents);
9. A dihalobenzene compound represented by the formula (6)

(In the formula, W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—. M represents an integer of 0 to _3. p represents 1 to 12. Q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Represents an alkoxy 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, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, carbon A hydrogen atom 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 and an acyl group having 2 to 20 carbon atoms is a fluorine atom, a cyano group, or a carbon number. 1-20 alkyl group, C1-C20 alkoxy group, C6 The aryl group may be substituted with at least one selected from the group consisting of an aryl group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms. R ¹ may be bonded to form a ring together with the carbon atom on the benzene ring to which R ¹ is bonded, X ¹ represents a chlorine atom, a bromine atom or an iodine atom, X ² represents a chlorine atom, .SO ₃ M representing a bromine atom or an iodine atom is _SO 3 _{M 1} or _SO ³ -. represents an _{M 2} ^+, where, _{M 1} is a hydrogen atom, _{M 2} ⁺ is a cation of an alkali metal cation or ammonium compound Represent);
10. A process for producing a polyarylene comprising polymerizing a monomer composition containing a compound represented by any one of formula (4), formula (5) and formula (6) in the presence of a nickel compound;
11. Formula (6)

(In the formula, W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—. M represents an integer of 0 to _3. p represents 1 to 12. Q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Represents an alkoxy 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, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, carbon A hydrogen atom 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 and an acyl group having 2 to 20 carbon atoms is a fluorine atom, a cyano group, or a carbon number. 1-20 alkyl group, C1-C20 alkoxy group, C6 The aryl group may be substituted with at least one selected from the group consisting of an aryl group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms. R ¹ may be bonded to form a ring together with the carbon atom on the benzene ring to which R ¹ is bonded, X ¹ represents a chlorine atom, a bromine atom or an iodine atom, X ² represents a chlorine atom, .SO ₃ M representing a bromine atom or an iodine atom is _SO 3 _{M 1} or _SO ³ -. represents an _{M 2} ^+, where, _{M 1} is a hydrogen atom, _{M 2} ⁺ is a cation of an alkali metal cation or ammonium compound Represents.)
Wherein the coupling reaction is caused by elimination of X ² of the dihalobenzene compound represented by formula (5):

(W, m, p, q, r, X ¹ , M, R ¹ represent the same meaning as described above.)
A process for producing a dihalobiphenyl compound represented by:
12 Formula (7)

(In the formula, W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—. M represents an integer of 0 to _3. p represents an integer of 1 to 12. Q represents an integer, q represents an integer of 1 to 12, and r represents an integer of 0 to 10.
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 carbon number. It represents 2 to 20 acyl groups or cyano groups. Here, it is contained in 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, and an acyl group having 2 to 20 carbon atoms. The hydrogen atom 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 and a carbon number. It may be substituted with at least one selected from the group consisting of 2 to 20 acyl 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. X ¹ represents a chlorine atom, a bromine atom or an iodine atom. SO ₃ M represents SO ₃ M ₁ or SO ₃ ⁻ M ₂ ⁺ . Here, M ₁ represents a hydrogen atom, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. A represents an acid addition salt of NH ₂ or NH ₃ . )
In the aniline compound represented by formula (4), l represents 1 including the step of diazotizing, denitrogenating and halogenating A

(W, m, p, q, r, l, X ¹ , M, R ¹ represent the same meaning as described above.)
A process for producing a dihalobenzene compound represented by:
13. Formula (9)

(In the formula, m represents an integer of 0 to 3. 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 having 6 to 20 carbon atoms. Group, 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 carbon atoms. A hydrogen atom contained in an aryl group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms is a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, It may be substituted with at least one 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 and acyl groups having 2 to 20 carbon atoms. Also, the bonding position is adjacent And R ¹ may be bonded to form a ring together with the carbon atom on the benzene ring to which R ¹ is bonded, X ³ represents a bromine atom or an iodine atom, A represents NH ₂ or NH ₃ Represents an acid addition salt of
And a compound of formula (10)

(Wherein, W represents any of a direct bond, —O—, —S—, —SO—, —SO ₂ —, —CO—, p represents an integer of 1 to 12, and q represents 1 to 1. .SO ₃ M .r is an integer of 0 to an integer of 12 _SO 3 _{M 1} or _SO ³ -. represents an _{M 2} ⁺ wherein, _{M 1} is a hydrogen atom, _{M 2} ⁺ represents an alkali Represents a metal cation or a cation of an ammonium compound.)
Comprising a reaction step of coupling the compound represented by formula (8) in the presence of metallic copper

(W, m, p, q, r, A, M and R ¹ in the formula represent the same meaning as described above.)
A process for producing an aniline compound represented by:
Etc. are provided.

  According to the present invention, a novel polyarylene having perfluoroalkylsulfonic acid as an ion exchange group can be provided.

  The present invention will be described in detail below. First, the polyarylene containing a repeating unit having an ion exchange group represented by the formula (1) will be described.

In formula (1), 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 an aryl group having 6 to 20 carbon atoms. An aryloxy group, an acyl group having 2 to 20 carbon atoms, or a cyano group is represented. Here, it is contained in 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, and an acyl group having 2 to 20 carbon atoms. The hydrogen atom 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 and a carbon number. It may be substituted with at least one selected from the group consisting of 2 to 20 acyl 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, 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.

In formula (1), W represents any of a direct bond, —O—, —S—, —SO—, —SO ₂ —, and —CO—. m represents an integer of 0 to 3. p represents an integer of 1 to 12. q represents an integer of 1 to 12. r represents an integer of 0 to 10. Preferably, W represents a direct bond or —O—. Preferably m represents 0. Preferably, p represents 1-3. More preferably, 2 is represented. Preferably q represents 1-3. More preferably, 2 is represented. Preferably, r represents 0-3. More preferably, 1 is represented.

  Specific examples of the compound represented by the formula (1) include repeating units represented by the following formulas (1a-1) to (1a-7).

In formula (2), m, p, q, r, R ¹ and W represent the same meaning as described above. Preferably, W represents a direct bond or —O—. Preferably m represents 0. Preferably, p represents 1-3. More preferably, 2 is represented. Preferably q represents 1-3. More preferably, 2 is represented. Preferably, r represents 0-3. More preferably, 1 is represented.

  Specific examples of the repeating unit having an ion exchange group represented by the formula (2) include repeating units represented by the following formulas (2a) to (2g).

In formula (3), m, p, q, r, R ¹ and W represent the same meaning as described above. Preferably, W represents a direct bond or —O—. Preferably m represents 0. Preferably, p represents 1-3. More preferably, 2 is represented. Preferably q represents 1-3. More preferably, 2 is represented. Preferably, r represents 0-3. More preferably, 1 is represented.

  Specific examples of the compound represented by the formula (3) include repeating units represented by the following formulas (3a) to (3g).

The polymer of the present invention is a polymer containing a repeating unit represented by any one of formula (1), formula (2) and formula (3) having perfluoroalkylsulfonic acid as an ion exchange group. Can be used as a polymer electrolyte because of its ionic conductivity.
As the polymer, for example, a polymer composed only of a repeating unit represented by any one of the formula (1), the formula (2) and the formula (3), for example, the formula (1), the formula (2) and the formula (3) ) A polymer containing a repeating unit represented by any one of the above and other repeating units, for example, a repeating unit represented by any one of formula (1), formula (2) and formula (3) and an aromatic polyether. Examples thereof include polymers.
Here, the “aromatic polyether” means a polymer containing a structural unit composed of a divalent aromatic group which may have a substituent and an ether bond. The ether bond means -O- (ether bond) or -S- (thioether bond).

（式中、ａ、ｂ及びｃは、それぞれ独立に、０又は１を表わし、ｎは５以上の整数を表わす。Ａｒ^１、Ａｒ^２、Ａｒ^３及びＡｒ^４は、それぞれ独立に、２価の芳香族基を表わす。ここで、２価の芳香族基は、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炭素数１〜２０のアルキル基；
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炭素数１〜２０のアルコキシ基；
フッ素原子、シアノ基、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；
フッ素原子、シアノ基、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、
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置換基で置換されていてもよい。
Ｙ^１及びＹ^２は、それぞれ独立に、単結合、カルボニル基、スルホニル基、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、それぞれ独立に、酸素原子又は硫黄原子を表わす。）
で示される繰り返し単位と、式（１）、式（２）及び式（３）のいずれかで示される繰り返し単位とを含む重合体、等を挙げることができる。 Preferred polymers include, for example, formula (11)

(In the formula, a, b and c each independently represent 0 or 1, and n represents an integer of 5 or more. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a divalent group. An aromatic group, wherein the divalent aromatic group 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 an aryloxy group 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:
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 alkoxy group having 1 to 20 carbon atoms;
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 10 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 ;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. It may be substituted with at least one substituent selected from the group consisting of an acyl group having 2 to 20 carbon atoms.
Y ¹ and Y ² each independently represents a single bond, a carbonyl group, a sulfonyl group, an isopropylidene group, a hexafluoroisopropylidene group, or a fluorene-9,9-diyl group. Z ¹ and Z ² each independently represents an oxygen atom or a sulfur atom. )
And a polymer containing the repeating unit represented by formula (1), the formula (2), and the repeating unit represented by any one of the formulas (3).

a, b and c each independently represents 0 or 1; For example, n may be an integer of 5 or more, and preferably an integer in the range of 5 to 200, for example.
Moreover, it is preferable that the number average molecular weight of the structural unit represented by Formula (11) is 3000 or more.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a divalent aromatic group. Examples of the divalent aromatic group include divalent monocyclic aromatic groups such as 1,3-phenylene and 1,4-phenylene, 1,3-naphthalenediyl, 1,4-naphthalenediyl, 1, Divalent condensed aromatic groups such as 5-naphthalenediyl, 1,6-naphthalenediyl, 1,7-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, pyridinediyl, quinoxalinediyl, Heteroaromatic groups such as thiophenediyl can be mentioned. Preferably, a bivalent monocyclic aromatic group etc. can be mentioned, for example.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may be bonded to a fluorine atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or an acyl group, and these further have a substituent. May be.

  Here, examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, 2,2-dimethylpropyl, cyclopentyl, n-hexyl, cyclohexyl, 2 -Alkyl groups having 1 to 10 carbon atoms such as methylpentyl, 2-ethylhexyl, and nonyl, and these groups include fluorine atom, hydroxyl group, cyano group, amino group, methoxy group, ethoxy group, isopropyloxy group, phenyl group, Examples thereof include an alkyl group to which a substituent such as a naphthyl group, a phenoxy group, and a naphthyloxy group is bonded.

  Examples of the alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, n-pentyloxy, 2,2-dimethylpropyloxy, cyclopentyloxy, C1-C10 alkoxy groups such as n-hexyloxy, cyclohexyloxy, 2-methylpentyloxy, 2-ethylhexyloxy, etc., and these groups include fluorine atom, hydroxyl group, cyano group, amino group, methoxy group, ethoxy And an alkoxy group to which a substituent such as a group, isopropyloxy group, phenyl group, naphthyl group, phenoxy group, naphthyloxy group is bonded.

  Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl, and fluorine, hydroxyl, cyano, amino, methoxy, ethoxy, isopropyloxy, and phenyl groups. , Aryl groups to which substituents such as naphthyl group, phenoxy group and naphthyloxy group are bonded.

  Examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms such as phenoxy and naphthyloxy, and fluorine, hydroxyl, cyano, amino, methoxy, ethoxy, and isopropyloxy groups. And an aryloxy group to which substituents such as a phenyl group, a naphthyl group, a phenoxy group, and a naphthyloxy group are bonded.

  Examples of the acyl group include acyl groups having 2 to 20 carbon atoms such as acetyl, propionyl, butyryl, isobutyryl, benzoyl, 1-naphthoyl, and 2-naphthoyl, and these groups include a fluorine atom, a hydroxyl group, a cyano group, and an amino group. And an acyl group substituted by a group, a methoxy group, an ethoxy group, an isopropyloxy group, a phenyl group, a naphthyl group, a phenoxy group, a naphthyloxy group, and the like.

Y ¹ and Y ² each independently represents a single bond, a carbonyl group, a sulfonyl group, an isopropylidene group, a hexafluoroisopropylidene group, or a fluorene-9,9-diyl group. Z ¹ and Z ₂ each independently represent an oxygen atom or a sulfur atom.

Examples of the weight average molecular weight in terms of polystyrene of the structural unit represented by the formula (11) include a range of 1,000 to 2,000,000.
Examples of preferable weight average molecular weight in terms of polystyrene when the polymer of the present invention is used as a polymer electrolyte for a polymer electrolyte fuel cell include a range of 2,000 to 1,000,000. Preferably, the range of 3,000-800,000 etc. can be mentioned, for example.

  Specific examples of the structural unit represented by the formula (11) include structural units represented by the following formulas (11a) to (11z). In the following formula, n represents the same meaning as described above. Specifically, the range of 5-200 etc. can be mentioned, for example. Examples of the weight average molecular weight in terms of polystyrene of the structural unit represented by the formula (11) include 2,000 or more. Preferable examples include 3,000 or more.

Examples of the polymer having a structural unit represented by the formula (11) include those having groups capable of forming a bond by reacting with X ¹ or X ² at both ends of the structural unit represented by the formula (11). be able to. Examples thereof include a polymer having halogen atoms at both ends (hereinafter sometimes referred to as polymer (13)). Examples of the method for producing the polymer (13) include methods described in JP2007-270118A, JP2007-284653A, JP2007-138065A, and the like.
Moreover, a commercially available polymer (13) may be used. Examples of the commercially available polymer (13) include Sumika Excel (registered trademark of Sumitomo Chemical Co., Ltd.) PES 3600P, 4100P, 4800P, Or 5200P etc. can be mentioned.

（式中、Ａｒ^０は、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、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；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炭素数１〜２０のアルコキシ基；フッ素原子、シアノ基、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のアリール基；フッ素原子、シアノ基、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；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炭素数２〜２０のアシル基；及び、保護基を有していてもよいスルホ基；からなる群から選ばれる少なくとも一つの置換基で置換されていてもよい。）を挙げることができる。 As preferred repeating units other than formula (11), for example, formula (12)

(In the formula, Ar ⁰ represents a divalent aromatic group. Here, a hydrogen atom contained in the divalent aromatic group is a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, or a carbon number. An alkyl group having 1 to 20 carbon atoms which 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; fluorine atom, cyano group, carbon number An alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, which 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 A carbon atom 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 aryl group; a carbon atom 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 Aryloxy group; 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 And optionally substituted with at least one substituent selected from the group consisting of an optionally substituted acyl group having 2 to 20 carbon atoms; and a sulfo group optionally having a protecting group. Can do.

  Specific examples of the structural unit represented by the formula (12) 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- Divalent condensed aromatic group such as diyl group; pyridine-2,5-diyl group, pyridine-2,6-diyl group, quinoxaline-2,6-diyl group, thiophene-2,5-diyl group, etc. And a divalent heteroaromatic group. Preferably, a bivalent monocyclic aromatic group, a divalent condensed ring aromatic group, etc. can be mentioned. 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 hydrogen atom contained in 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 6 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 an aryloxy group having 20 to 20 carbon atoms, 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 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 alkoxy group having 1 to 20 carbon atoms;
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 as those described above.

  Specific examples of the repeating unit represented by the formula (12) include repeating units represented by the following formulas (12a) to (12i).

（式中、Ｒ^１は同一又は相異なり、水素原子、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^２は同一又は相異なり、０〜４の整数を表わし、ｈは１〜１０の整数を表わす。）を挙げることができる。 As preferred repeating units other than formula (11) and formula (12), for example, formula (14)

(In the formula, R ¹ is the same or different and is a hydrogen atom, 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. 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 atom Good .m ² to form a ring are the same or different, represents an integer of 0 to 4, h may be mentioned representative.) An integer from 1 to 10.

Specific examples of the repeating unit represented by the formula (14) include the repeating units represented by the following formulas (14a) to (14i).

In the formula (4), m, p, q, r, l, R ¹ and W represent the same meaning as described above. Preferably, W represents a direct bond or —O—. Preferably m represents 0. Preferably, p represents 1-3. More preferably, 2 is represented. Preferably q represents 1-3. More preferably, 2 is represented. Preferably, r represents 0-3. More preferably, 1 is represented. l represents 1 or 2; X ¹ represents a chlorine atom, a bromine atom or an iodine atom. Preferably, it represents a chlorine atom.

In formula (4), SO ₃ M represents SO ₃ M ₁ or SO ₃ ⁻ M ₂ ⁺ . Here, M ₁ represents a hydrogen atom, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound.

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.

Specific examples of the compound represented by the formula (4) include those represented by the following formulas (4a-1) to (4b-7) and those represented by the following formulas (4a-1) to (4b-7). A compound in which a group represented by —SO ₃ H of a compound is replaced with any of —SO ₃ Li, —SO ₃ Na, —SO ₃ K, —SO ₃ Li, —SO ₃ Cs, and —SO ₃ NH ₄ Can be mentioned.

In formula (5), m, p, q, r, R ¹ , W and X ¹ represent the same meaning as described above. Preferably, W represents a direct bond or —O—. Preferably m represents 0. Preferably, p represents 1-3. More preferably, 2 is represented. Preferably q represents 1-3. More preferably, 2 is represented. Preferably, r represents 0-3. More preferably, 1 is represented. Preferably X ¹ represents a chlorine atom.

Specific examples of the compound represented by the formula (5) include those represented by the following formulas (5a-1) to (5b-7) and those represented by the following formulas (5a-1) to (5b-7). -SO ₃ H group is _-SO 3 _Li represented by _{compounds, -SO 3 Na, -SO 3 K} , -SO 3 Li, the compound has been replaced with either _-SO 3 Cs and _-SO 3 NH ₄ is Can be mentioned.

In formula (6), m, p, q, r, R ¹ , W and X ¹ represent the same meaning as described above. Preferably, W represents a direct bond or —O—. Preferably m represents 0. Preferably, p represents 1-3. More preferably, 2 is represented. Preferably q represents 1-3. More preferably, 2 is represented. Preferably, r represents 0-3. More preferably, 1 is represented. Preferably X ¹ represents a chlorine atom. X ² represents a chlorine atom, a bromine atom or an iodine atom. Preferably it represents a chlorine atom.

Specific examples of the compound represented by the formula (6) include compounds represented by the following formulas (6a-1) to (6c-7) and those represented by the following formulas (6a-1) to (6c-7). A compound in which a group represented by —SO ₃ H of a compound is replaced with any of —SO ₃ Li, —SO ₃ Na, —SO ₃ K, —SO ₃ Li, —SO ₃ Cs, and —SO ₃ NH ₄ Can be mentioned.

Examples of the method for producing the polymer of the present invention include a method of polymerizing a monomer composition containing a compound represented by any one of formula (4), formula (5) and formula (6) in the presence of a nickel compound. Can be mentioned.
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), halogen Nickel fluoride (eg, nickel fluoride, nickel chloride, nickel bromide, nickel iodide), nickel carboxylate (eg, nickel formate, nickel acetate), nickel sulfate, nickel carbonate, nickel nitrate, nickel acetylacetonate And 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, 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. As usage-amount in the case of using zinc, the range of 0.5 mol-1.5 mol can be mentioned with respect to a total of 1 mol of a monomer composition, for example.

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-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. 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 of 1 weight times-200 weight times can be mentioned with respect to the total 1 weight part of the monomer composition used, for example. Preferably, the range of 5 weight times-100 weight times 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 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 the completion of the polymerization reaction, the reaction mixture and a solvent in which the produced polymer is difficult to dissolve are mixed to precipitate the polymer, and the precipitated polymer is separated from the reaction mixture using a filtration operation. The polymer of the present invention can be taken out by washing the obtained precipitated polymer with an acid.
After mixing the produced polymer with a solvent that does not dissolve or difficult to dissolve, and the reaction mixture, an acid is added to the resulting mixture to precipitate the polymer, and the precipitated polymer is separated from the reaction mixture by filtration. May be.
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. The amount of acid used can include the amount necessary to acidify the reaction mixture.

Examples of the ion exchange capacity (measured by a titration method) of the polymer thus obtained include a range of 0.2 meq / g to 4.9 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.

  The polymer thus obtained is useful as a polymer electrolyte used as a constituent material of a solid polymer fuel cell. The polymer electrolyte is excellent in ionic conductivity.

（式中、ｍ、ｐ、ｑ、ｒ、Ｒ^１、Ｗ、Ｘ^１及びＸ^２は前記と同じ意味を表わす。）
で表わされるジハロベンゼン化合物のＸ^２の脱離によりカップリング反応させる工程を含む方法等を挙げることができる。例えば、ＷＯ２０１１／０３９２１Ａ１の実施例２に記載される方法に準じて合成することができる。
ここで、好ましくは、Ｘ^２は臭素原子、ヨウ素原子である。より好ましくは、Ｘ^１が塩素原子の場合には、Ｘ^２は臭素原子、ヨウ素原子が好ましい。Ｘ^１が臭素原子の場合には、Ｘ^２はヨウ素原子が好ましい。 As a manufacturing method of the dihalobiphenyl compound represented by Formula (5), for example, Formula (6)

(In the formula, m, p, q, r, R ¹ , W, X ¹ and X ² represent the same meaning as described above.)
And a method including a step of coupling reaction by elimination of X ² of the dihalobenzene compound represented by the formula: For example, it can be synthesized according to the method described in Example 2 of WO2011 / 03921A1.
Here, preferably, X ² is a bromine atom, an iodine atom. More preferably, when X ¹ is a chlorine atom, X ² is preferably a bromine atom or an iodine atom. When X ¹ is a bromine atom, X ² is preferably an iodine atom.

（式中、ｍ、ｐ、ｑ、ｒ、Ｒ^１、Ｘ^１は及びＷは前記と同じ意味を表わし、ＡはＮＨ_２又はＮＨ_３の酸付加塩を表わす。）
で表わされる化合物を用い、当該化合物におけるＡのアミノ基を亜硝酸ナトリウム及びハロゲン化水素でジアゾ基に変換した後、１価のハロゲン化銅を用いて脱窒素及びハロゲン化させる反応、いわゆる、Ｓａｎｄｍｅｙｅｒ反応によって製造する方法等を挙げることができる。式（７）で示される化合物の具体例としては、下記式（７ａ−１）〜式（７ｂ−７）で示される化合物および下記式（７ａ−１）〜式（７ｂ−７）で示される化合物の−ＳＯ_３Ｈで示される基が−ＳＯ_３Ｌｉ、−ＳＯ_３Ｎａ、−ＳＯ_３Ｋ、−ＳＯ_３Ｌｉ、−ＳＯ_３Ｃｓおよび−ＳＯ_３ＮＨ_４のいずれかで置き換えられた化合物等を挙げることができる。 Examples of the method for producing a dihalobenzene compound represented by formula (4) or a dihalobenzene compound represented by formula (6) when l represents 1 include, for example, formula (7)

(In the formula, m, p, q, r, R ¹ , X ¹ and W represent the same meaning as described above, and A represents an acid addition salt of NH ₂ or NH ₃ ).
A reaction in which the amino group of A in the compound is converted to a diazo group with sodium nitrite and hydrogen halide, followed by denitrogenation and halogenation using monovalent copper halide, so-called Sandmeyer Examples include a method of producing by reaction. Specific examples of the compound represented by the formula (7) include compounds represented by the following formulas (7a-1) to (7b-7) and those represented by the following formulas (7a-1) to (7b-7). A compound in which a group represented by —SO ₃ H of a compound is replaced with any of —SO ₃ Li, —SO ₃ Na, —SO ₃ K, —SO ₃ Li, —SO ₃ Cs, and —SO ₃ NH ₄ Can be mentioned.

  Next, the manufacturing method of the aniline compound shown by Formula (8) is demonstrated.

In formula (9), m, R ¹ and A represent the same meaning as described above. X ³ represents a bromine atom or an iodine atom. Specific examples of the compound represented by the formula (9) include compounds represented by the following formulas (9a) to (9d).

In formula (10), W, p, q, r, M, and R ¹ have the same meaning as described above. Specific examples of the compound represented by the formula (10) include compounds represented by the following formulas (10a-1) to (10a-7) and those represented by the following formulas (10a-1) to (10a-7). A compound in which a group represented by —SO ₃ H of a compound is replaced with any of —SO ₃ Li, —SO ₃ Na, —SO ₃ K, —SO ₃ Li, —SO ₃ Cs, and —SO ₃ NH ₄ Can be mentioned.

  As a method of obtaining a aniline compound represented by the formula (8) by coupling a compound represented by the formula (9) and a compound represented by the formula (10) in the presence of metallic copper, for example, J. Org. Org. Chem. It can be synthesized according to the method described in 2010, 75, 6814.

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

Molecular weight measurement:
When the conjugated aromatic compound obtained is a polymer, it is analyzed by gel permeation chromatography (hereinafter abbreviated as GPC). The 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 analysis results.
<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 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.

１−ブロモ−４−クロロ−２−（トリフルオロメチル）ベンゼン１３０．０ｇと銅粉末６４．０ｇと１価のヨウ化銅４．８ｇと２，２’-ビピリジル３．９gとＮ−メチル−２−ピロリドン５２０．０ｇとを混合し、得られた混合物を窒素雰囲気下において１２０℃で７時間保温した。得られた反応混合物を２５℃まで冷却し、これを１９％塩酸７２０．８ｇとトルエン７２０．０ｇとからなる混合液に滴下した。得られた混合物を分液して回収されたトルエン層を５％水酸化ナトリウム水溶液で洗浄した後、更に水で洗浄して硫酸ナトリウムで乾燥させた。このようにして得られたトルエン層から硫酸ナトリウムを濾別して、得られた濾液を濃縮乾固することにより、粗生成物７９．７ｇを得た。得られた粗生成物をシリカゲルクロマトグラフィ（溶媒；ヘキサン）により精製し、得られた精製物を濃縮乾固することにより、４，４’−ジクロロ−２，２’−ビス（トリフルオロメチル）ビフェニル７０．０ｇ（収率７７．８％）を得た。
^１Ｈ−ＮＭＲ（重クロロホルム、δ（ｐｐｍ））：７．２１（ｄ，２Ｈ）、７．５３（ｄｄ、２Ｈ）、７．７４（ｄ、２Ｈ）
^１９Ｆ−ＮＭＲ（重クロロホルム、δ（ｐｐｍ））：５８．６（ｓ，６Ｆ）
マススペクトル（ＥＩ、ｍ／ｚ）：３５８（Ｍ^−１） [Production Example 1]
Synthesis of 4,4'-dichloro-2,2'-bis (trifluoromethyl) biphenyl

130.0 g of 1-bromo-4-chloro-2- (trifluoromethyl) benzene, 64.0 g of copper powder, 4.8 g of monovalent copper iodide, 3.9 g of 2,2′-bipyridyl and N-methyl- 2-Pyrrolidone (520.0 g) was mixed, and the resulting mixture was kept at 120 ° C. for 7 hours under a nitrogen atmosphere. The resulting reaction mixture was cooled to 25 ° C., and this was added dropwise to a mixed solution consisting of 720.8 g of 19% hydrochloric acid and 720.0 g of toluene. The toluene layer recovered by separating the obtained mixture was washed with a 5% aqueous sodium hydroxide solution, then further washed with water and dried over sodium sulfate. Sodium sulfate was filtered off from the toluene layer thus obtained, and the obtained filtrate was concentrated to dryness to obtain 79.7 g of a crude product. The obtained crude product was purified by silica gel chromatography (solvent; hexane), and the purified product obtained was concentrated to dryness to give 4,4′-dichloro-2,2′-bis (trifluoromethyl) biphenyl. 70.0 g (yield 77.8%) was obtained.
¹ H-NMR (deuterated chloroform, δ (ppm)): 7.21 (d, 2H), 7.53 (dd, 2H), 7.74 (d, 2H)
¹⁹ F-NMR (deuterated chloroform, δ (ppm)): 58.6 (s, 6F)
Mass spectrum (EI, m / z): 358 (M ⁻¹ )

銅２９３．２ｇ、ジメチルスルホキシド４４０ｇ及びクロロヨードベンゼン１１０ｇを混合して、得られた混合物を１２０℃で２時間加熱撹拌した。その後系内にドデカフルオロジヨードヘキサン５０．３ｇを加えて１２０℃で４時間加熱撹拌した。次いで、系内に水１７８４ｇ及びトルエン１７８４ｇを加えて分液した。分液後、得られた有機層を6ｍｏｌ／Ｌ塩酸で２回洗浄した後、得られた混合物を水洗（４回繰り返し）して、得られた有機層をシリカゲルカラムを通して濃縮することにより、粗生成物を６８ｇ得た。
得られた粗生成物にメタノール５９２ｇ及びエタノール１６ｇを加えて加熱し溶解した後、得られた混合物を冷却して精製した固体をろ別し、乾燥させることにより、１，６−ジ（ｐ−クロロベンジル）ドデカフルオロヘキサンを１７．３ｇ（収率３５％）得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δ（ｐｐｍ））：７．４６−７．５４（ｄｄ、８Ｈ） [Production Example 2]
Synthesis of 1,6-di (p-chlorobenzyl) dodecafluorohexane

293.2 g of copper, 440 g of dimethyl sulfoxide and 110 g of chloroiodobenzene were mixed, and the resulting mixture was heated and stirred at 120 ° C. for 2 hours. Thereafter, 50.3 g of dodecafluorodiiodohexane was added to the system, and the mixture was heated and stirred at 120 ° C. for 4 hours. Next, 1784 g of water and 1784 g of toluene were added to the system to separate the layers. After separation, the obtained organic layer was washed twice with 6 mol / L hydrochloric acid, and then the resulting mixture was washed with water (repeated four times). 68 g of product was obtained.
After adding 592 g of methanol and 16 g of ethanol to the obtained crude product and heating to dissolve it, the obtained mixture was cooled and the purified solid was filtered off and dried to obtain 1,6-di (p- 17.3 g (yield 35%) of chlorobenzyl) dodecafluorohexane was obtained.
¹ H-NMR (CDCl ₃ , δ (ppm)): 7.46-7.54 (dd, 8H)

冷却装置を備えたガラス製反応容器に、窒素雰囲気下、室温で、４−クロロー２−ヨードアニリン１７０ｇ、銅粉末１０２ｇをジメチルスルホキシド６８０ｇに溶解させて１２０℃に昇温した。得られた混合物を２時間保温した後、これに５−ヨードーオクタフルオロー３−オキサペンタンスルホン酸カリウム１０２ｇを加え、さらに、２時間保温した。反応混合物を水２７２０ｇとトルエン１３６０ｇとの混合液に注ぎ込み、生成した不溶物を濾別した後、分液を行った。分液後の水層をトルエン１３６０ｇで２回洗浄した後、得られた水層を濃縮乾固した。これに５０％硫酸９２４ｇを加え、生じた析出物を濾過操作により回収した。得られた析出物を１０％硫酸４１５ｇで洗浄した後、濾過することにより、中間体Ａを５９．１ｇ（収率４１％）得た。
中間体Ａ５２．１ｇを水２８７ｇと濃硫酸１４ｇとの混合溶液に溶解した。得られた溶解液に、０℃で３６％亜硝酸ナトリウム水溶液２６．４ｇを徐々に滴下し、１時間保温した（以下、「ジアゾマス１」と記す）。一方で、１価の臭化銅２０．８ｇを４８％臭化水素酸２５１ｇに溶解した。得られた溶解液を５０℃に昇温した。これに前記「ジアゾマス１」全量を滴下し、２時間保温した。得られた反応混合物を室温に冷却した後、これにジエチルエーテル５５５ｇと水２０８ｇとを加えた。分液後の油層を水５５５ｇで２回洗浄し、更に硫酸ナトリウムで乾燥した。このようにして得られた油層から硫酸ナトリウムを濾別して、得られた濾液を濃縮乾固した。得られた固体を水１８ｇに溶解した後、得られた溶解液を５％水酸化ナトリウム水溶液でｐＨ６に調整した後、濃縮・乾燥することにより、茶色固体の化合物Ｂ ２９．２ｇ（収率３４．１％）を得た。
^１Ｈ−ＮＭＲ（重ジメチルスルホキシド、δ（ｐｐｍ））：７．８９（ｄ、１Ｈ）、７．６７（ｄ、１Ｈ）、７．６７（ｄｄ、１Ｈ）
^１９Ｆ−ＮＭＲ（重ジメチルスルホキシド、δ（ｐｐｍ））：―８２．２、―８５．４、―１０９．３、−１１８．０
マススペクトル（ＥＳＩ、ｍ／ｚ）：４８５（Ｍ―Ｎａ） [Example 1]
Synthesis of Compound B

In a glass reaction vessel equipped with a cooling device, 170 g of 4-chloro-2-iodoaniline and 102 g of copper powder were dissolved in 680 g of dimethyl sulfoxide at room temperature under a nitrogen atmosphere, and the temperature was raised to 120 ° C. After the resulting mixture was kept warm for 2 hours, 102 g of potassium 5-iodooctafluoro-3-oxapentanesulfonate was added thereto, and further kept warm for 2 hours. The reaction mixture was poured into a mixture of 2720 g of water and 1360 g of toluene, and the insoluble matter produced was filtered off, followed by liquid separation. The aqueous layer after separation was washed twice with 1360 g of toluene, and then the obtained aqueous layer was concentrated to dryness. To this was added 924 g of 50% sulfuric acid, and the resulting precipitate was recovered by filtration. The obtained precipitate was washed with 415 g of 10% sulfuric acid and filtered to obtain 59.1 g of intermediate A (yield 41%).
Intermediate A 52.1 g was dissolved in a mixed solution of 287 g of water and 14 g of concentrated sulfuric acid. To the resulting solution, 26.4 g of a 36% aqueous sodium nitrite solution was gradually added dropwise at 0 ° C. and kept warm for 1 hour (hereinafter referred to as “diazomas 1”). On the other hand, 20.8 g of monovalent copper bromide was dissolved in 251 g of 48% hydrobromic acid. The resulting solution was heated to 50 ° C. The whole amount of the “diazomas 1” was added dropwise thereto and kept warm for 2 hours. After the resulting reaction mixture was cooled to room temperature, 555 g of diethyl ether and 208 g of water were added thereto. The separated oil layer was washed twice with 555 g of water and further dried over sodium sulfate. Sodium sulfate was filtered off from the oil layer thus obtained, and the resulting filtrate was concentrated to dryness. After the obtained solid was dissolved in 18 g of water, the obtained solution was adjusted to pH 6 with a 5% aqueous sodium hydroxide solution and then concentrated and dried to obtain 29.2 g of Compound B as a brown solid (yield 34). 0.1%).
¹ H-NMR (heavy dimethyl sulfoxide, δ (ppm)): 7.89 (d, 1H), 7.67 (d, 1H), 7.67 (dd, 1H)
¹⁹ F-NMR (heavy dimethyl sulfoxide, δ (ppm)): −82.2, −85.4, −109.3, −118.0
Mass spectrum (ESI, m / z): 485 (M-Na)

実施例１で合成した化合物Ｂ２．６ｇにＮ−メチル−２−ピロリドン２３．５ｇを加え、得られた混合物を１００℃に加熱して溶解した。得られた溶解液を減圧濃縮して、Ｎ−メチル−２−ピロリドンを１０．４ｇ留去した。濃縮マス水分値は６３ｐｐｍであった。得られた濃縮物を２５℃に冷却した後、これに銅粉末６５０ｍｇと１価のヨウ化銅４９．６ｍｇとビピリジン４０．３ｍｇとを加え、得られた混合物を１５０℃に昇温し、３時間保温した。得られた反応混合物を水２１．９ｇに注ぎ込み、生成した不溶物を濾別した後、濾液を濃縮乾固することにより、粗成生物３．７５ｇを得た。粗成生物２．４５ｇをシリカゲルカラムクロマトグラフィ（溶媒；２−プロパノール）により精製し、得られた精製物を濃縮乾固することにより、化合物Ｃ１．５４ｇ（収率９２．９％）を得た。
マススペクトル（ＥＳＩ、ｍ／ｚ）：８１４（Ｍ−２Ｎａ＋２Ｈ） [Example 2]
Synthesis of Compound C

N-methyl-2-pyrrolidone (23.5 g) was added to 2.6 g of the compound B synthesized in Example 1, and the resulting mixture was heated to 100 ° C. and dissolved. The resulting solution was concentrated under reduced pressure to distill off 10.4 g of N-methyl-2-pyrrolidone. The concentrated mass moisture value was 63 ppm. After cooling the obtained concentrate to 25 ° C., 650 mg of copper powder, 49.6 mg of monovalent copper iodide and 40.3 mg of bipyridine were added thereto, and the resulting mixture was heated to 150 ° C. and heated to 3 ° C. Keep warm for hours. The obtained reaction mixture was poured into 21.9 g of water, the insoluble matter produced was filtered off, and the filtrate was concentrated to dryness to obtain 3.75 g of a crude product. 2.45 g of the crude product was purified by silica gel column chromatography (solvent; 2-propanol), and the purified product obtained was concentrated to dryness to obtain 1.54 g of Compound C (yield 92.9%).
Mass spectrum (ESI, m / z): 814 (M-2Na + 2H)

で示される繰り返し単位からなるポリアリーレンを得た。収量は２０９ｍｇであった。
Ｍｗは９．７×１０^３、Ｍｎは８．３×１０^３であった。 [Example 3]
In a glass reaction vessel equipped with a cooling device, 528 mg of bipyridine and 446 mg of compound B were dissolved in 3.6 g of dimethyl sulfoxide in a nitrogen atmosphere at room temperature, and the temperature was raised to 50 ° C. Next, 856 mg of nickel (0) bis (cyclooctadiene) was added thereto, and the resulting mixture was heated to 70 ° C. and stirred at the same temperature for 5 hours.
The resulting reaction mixture was poured into 16 g of 20% nitric acid, and the produced precipitate was collected by filtration. The obtained precipitate was washed with 13% hydrochloric acid three times, and then washed with water until the pH of the filtrate exceeded 3.5. By drying the obtained precipitate after washing with water, the following formula (2e)

A polyarylene composed of repeating units represented by The yield was 209 mg.
Mw was 9.7 × 10 ³ and Mn was 8.3 × 10 ³ .

で示される繰り返し単位からなるポリアリーレンを得た。収量は３１２ｍｇであった。
Ｍｗは１３．４×１０^３、Ｍｎは１１．８×１０^３であった。 [Example 4]
In a glass reaction vessel equipped with a cooling device, 450 mg of bipyridine and 500 mg of compound C were dissolved in 5.0 g of dimethyl sulfoxide at room temperature under a nitrogen atmosphere, and the temperature was raised to 55 ° C. Next, 720 mg of nickel (0) bis (cyclooctadiene) was added thereto, and the resulting mixture was heated to 70 ° C. and stirred at the same temperature for 5 hours.
The obtained reaction mixture was poured into 20 g of 20% nitric acid, and the produced precipitate was recovered by filtration. The obtained precipitate was washed with 13% hydrochloric acid three times, and then washed with water until the pH of the filtrate exceeded 3.5. By drying the obtained precipitate after washing with water, the following formula (3e)

A polyarylene composed of repeating units represented by The yield was 312 mg.
Mw was 13.4 × 10 ³ and Mn was 11.8 × 10 ³ .

で示される繰り返し単位と下記式（１２ｉ）

で示される繰り返し単位とからなるポリアリーレン共重合体１．０５ｇを得た。得られた重合体のＭｗは１６．２×１０^３、Ｍｎは１１．７×１０^３であった。
得られた重合体のイオン交換容量は０．６４ｍｅｑ／ｇであった。 [Example 5]
In a glass reaction vessel equipped with a cooling device, under nitrogen atmosphere, at room temperature, 1.34 g of bipyridine, 500 mg of compound B and 4,4′-dichloro-2,2′-bis (trifluoromethyl) obtained in Production Example 1 ) 769 mg of biphenyl was dissolved in 10 g of dimethyl sulfoxide and heated to 50 ° C. Next, 2.17 g of nickel (0) bis (cyclooctadiene) was added thereto, and the resulting mixture was heated to 70 ° C. and stirred at the same temperature for 2 hours.
The obtained reaction mixture was poured into 45 g of water, and the produced precipitate was collected by filtration. The obtained precipitate was washed with water three times and then stirred in 20 g of 20% nitric acid to which 20 m of sodium nitrite was added for 1 hour. The precipitate was collected by a filtration operation. The obtained precipitate was washed once with 19% hydrochloric acid, and then washed with water until the pH of the filtrate exceeded 3.5. By drying the obtained precipitate, the following formula (2e)

And a repeating unit represented by the following formula (12i)

Thus, 1.05 g of a polyarylene copolymer composed of the repeating unit represented by Mw of the obtained polymer was 16.2 × 10 ³ and Mn was 11.7 × 10 ³ .
The obtained polymer had an ion exchange capacity of 0.64 meq / g.

［実施例７］
冷却装置を備えたガラス製反応容器に、窒素雰囲気下、室温で、ビピリジン７．００ｇ及び化合物Ｂ２．８０ｇをＮ−メチル−２−ピロリドン３３．６ｇとテトラヒドロフラン５０．４ｇとの混合溶液に溶解させて５０℃に昇温した。次いで、これに４，４’−ジクロロビフェニル−２，２’−ジスルホン酸ビス（２，２−ジメチルプロピル）５．６５ｇとニッケル（０）ビス（シクロオクタジエン）１１．３ｇを加え、得られた混合物を７０℃に加熱し、同温度で２時間攪拌することにより、下記式（２ｅ）で表される繰り返し単位と下記式（１２ｊ）で表される構造とを含む重合体を得た。得られた重合体のＭｗは１９．２×１０^３、Ｍｎは１３．５×１０^３であった。

[Example 6]
In a glass reaction vessel equipped with a cooling apparatus, 750 mg of bipyridine, 350 mg of compound B and 499 mg of 1,6-di (p-chlorobenzyl) dodecafluorohexane obtained in Production Example 2 were added to N-methyl at room temperature under a nitrogen atmosphere. The mixture was dissolved in a mixed solution of 2.8 g of 2-pyrrolidone and 4.2 g of tetrahydrofuran, and the temperature was raised to 50 ° C. Next, 1.18 g of nickel (0) bis (cyclooctadiene) is added thereto, and the resulting mixture is heated to 70 ° C. and stirred at the same temperature for 2 hours, thereby being represented by the following formula (2e). A polymer containing a repeating unit and a structure represented by the following formula (14e) was obtained. Mw of the obtained polymer was 9.3 × 10 ³ and Mn was 8.4 × 10 ³ .

[Example 7]
In a glass reaction vessel equipped with a cooling device, 7.00 g of bipyridine and 2.80 g of compound B were dissolved in a mixed solution of 33.6 g of N-methyl-2-pyrrolidone and 50.4 g of tetrahydrofuran at room temperature in a nitrogen atmosphere. The temperature was raised to 50 ° C. Then, 4.65 g of 4,4′-dichlorobiphenyl-2,2′-disulfonic acid bis (2,2-dimethylpropyl) and 11.3 g of nickel (0) bis (cyclooctadiene) were added thereto. The obtained mixture was heated to 70 ° C. and stirred at the same temperature for 2 hours to obtain a polymer containing a repeating unit represented by the following formula (2e) and a structure represented by the following formula (12j). Mw of the obtained polymer was 19.2 × 10 ³ and Mn was 13.5 × 10 ³ .

Claims (13)

Formula (1)

(Wherein W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—, m represents an integer of 0 to 3, and p represents 1 to 12). Q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Represents an alkoxy 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, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, carbon A hydrogen atom 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 and an acyl group having 2 to 20 carbon atoms is a fluorine atom, a cyano group, or a carbon number. 1-20 alkyl group, C1-C20 alkoxy group, C6 The aryl group may be substituted with at least one selected from the group consisting of an aryl group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms. R ¹ may be bonded to form a ring together with the carbon atom on the benzene ring to which R ¹ is bonded.)
A polyarylene comprising a repeating unit having an ion exchange group represented by the formula: Formula (2)

(In the formula, W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—. M represents an integer of 0 to _3. p represents 1 to 12. Q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Represents an alkoxy 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, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, carbon A hydrogen atom 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 and an acyl group having 2 to 20 carbon atoms is a fluorine atom, a cyano group, or a carbon number. 1-20 alkyl group, C1-C20 alkoxy group, C6 The aryl group may be substituted with at least one selected from the group consisting of an aryl group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms. R ¹ may be bonded to form a ring together with the carbon atom on the benzene ring to which R ¹ is bonded.)
A polyarylene comprising a repeating unit having an ion exchange group represented by the formula: Formula (3)

(Wherein, W is the same or different and represents any of a direct bond, —O—, —S—, —SO—, —SO ₂ —, —CO—. M represents an integer of 0 to _3. p. Represents an integer of 1 to 12. q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, carbon. 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, or a cyano group, where 1 to 20 carbon atoms are represented. The hydrogen atom contained in the alkyl group, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aryloxy group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms is a fluorine atom, cyano Group, an alkyl group having 1 to 20 carbon atoms, an alcohol having 1 to 20 carbon atoms It may be substituted with at least one selected from the group consisting of a Si group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms and an acyl group having 2 to 20 carbon atoms. coupling position may form a ring with the carbon atoms on the benzene ring to which the R ¹ by bonding two of R ¹ adjacent binds.)
A polyarylene comprising a repeating unit having an ion exchange group represented by the formula: Following formula (11)

(In the formula, a, b and c are the same or different and represent 0 or 1. n represents an integer of 5 or more. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the same or different. A divalent aromatic group, wherein the hydrogen atom contained in the divalent aromatic group 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 An alkyl group having 1 to 20 carbon atoms which may be substituted with at least one selected from the group consisting of aryloxy groups having 6 to 20 carbon atoms;
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 alkoxy group having 1 to 20 carbon atoms; 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 10 carbon atoms. An aryl group having 6 to 20 carbon atoms; 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; and 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 6 With at least one group selected from the group consisting of at least one acyl group which may C2-20 optionally substituted with one selected from the group consisting of aryloxy groups 20 may be substituted. Y ¹ and Y ² are the same or different and each represents a single bond, a carbonyl group, a sulfonyl 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 atom or a sulfur atom. )
The polyarylene according to any one of claims 1 to 3, which comprises a repeating unit represented by formula (1). Following formula (12)

(In the formula, Ar ⁰ represents a divalent aromatic group. Here, a hydrogen atom contained in the divalent aromatic group is a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, or a carbon number. An alkyl group having 1 to 20 carbon atoms which 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; fluorine atom, cyano group, carbon number An alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, which 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 A carbon atom 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; Aryl group; 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 aryloxy group having 6 to 20 carbon atoms and an acyl group having 2 to 20 carbon atoms An aryloxy group having 6 to 20 carbon atoms; a 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 Substituted with at least one selected from the group consisting of an acyl group having 2 to 20 carbon atoms which may be substituted with at least one selected; and a sulfo group which may have a protecting group. May be.)
The polyarylene according to any one of claims 1 to 3, which comprises a repeating unit represented by formula (1). Formula (14)

(In the formula, R ¹ is the same or different and is a hydrogen atom, 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. 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 atom Good .m ² to form a ring are the same or different, represents an integer of 0 to 4, h is an integer of 1 to 10.)
The polyarylene according to any one of claims 1 to 3, which comprises a repeating unit represented by formula (1). A dihalobenzene compound represented by the formula (4):

(In the formula, W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—. M represents an integer of 0 to _3. p represents an integer of 1 to 12. Q represents an integer, q represents an integer of 1 to 12. r represents an integer of 0 to 10. l represents 1 or 2. R ¹ is the same or different and is a fluorine atom or an alkyl having 1 to 20 carbon atoms. Group, 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, or a cyano group. A hydrogen atom contained in an alkyl group having -20 carbon atoms, an alkoxy group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms, an aryloxy group having 6-20 carbon atoms, and an acyl group having 2-20 carbon atoms is fluorine. An atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an atom having 1 to 20 carbon atoms It may be substituted with at least one selected from the group consisting of a alkoxy group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms and an acyl group having 2 to 20 carbon atoms. 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, and X ¹ is the same or different and is a chlorine atom, bromine atom or iodine. .SO ₃ M representing the atoms _SO 3 _{M 1} or _SO ³ - represents an _{M 2} ^+, where, _{M 1} is a hydrogen atom, _{M 2} ⁺ represents a cation of an alkali metal cation or ammonium compound).. A dihalobiphenyl compound represented by the formula (5):

(Wherein, W is the same or different and represents any of a direct bond, —O—, —S—, —SO—, —SO ₂ —, —CO—. M represents an integer of 0 to _3. p. Represents an integer of 1 to 12. q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, carbon. 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, or a cyano group, where 1 to 20 carbon atoms are represented. The hydrogen atom contained in the alkyl group, the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aryloxy group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms is a fluorine atom, cyano Group, an alkyl group having 1 to 20 carbon atoms, an alcohol having 1 to 20 carbon atoms It may be substituted with at least one selected from the group consisting of a Si group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms and an acyl group having 2 to 20 carbon atoms. 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, and X ¹ is the same or different and is a chlorine atom, bromine atom or iodine. SO ₃ M is the same or different and represents SO ₃ M ₁ or SO ₃ ⁻ M ₂ ⁺ , where M ₁ represents a hydrogen atom and M ₂ ⁺ represents a cation of an alkali metal cation or an ammonium compound. Represents.) A dihalobenzene compound represented by the formula (6):

(In the formula, W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—. M represents an integer of 0 to _3. p represents 1 to 12. Q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Represents an alkoxy 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, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, carbon A hydrogen atom 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 and an acyl group having 2 to 20 carbon atoms is a fluorine atom, a cyano group, or a carbon number. 1-20 alkyl group, C1-C20 alkoxy group, C6 The aryl group may be substituted with at least one selected from the group consisting of an aryl group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms. R ¹ may be bonded to form a ring together with the carbon atom on the benzene ring to which R ¹ is bonded, X ¹ represents a chlorine atom, a bromine atom or an iodine atom, X ² represents a chlorine atom, .SO ₃ M representing a bromine atom or an iodine atom is _SO 3 _{M 1} or _SO ³ -. represents an _{M 2} ^+, where, _{M 1} is a hydrogen atom, _{M 2} ⁺ is a cation of an alkali metal cation or ammonium compound Represents.) A method for producing polyarylene, comprising a step of polymerizing a monomer composition containing a compound represented by any one of formula (4), formula (5) and formula (6) in the presence of a nickel compound. Formula (6)

(In the formula, W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—. M represents an integer of 0 to _3. p represents 1 to 12. Q represents an integer of 1 to 12. r represents an integer of 0 to 10. R ¹ is the same or different and is a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Represents an alkoxy 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, or a cyano group, wherein an alkyl group having 1 to 20 carbon atoms, carbon A hydrogen atom 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 and an acyl group having 2 to 20 carbon atoms is a fluorine atom, a cyano group, or a carbon number. 1-20 alkyl group, C1-C20 alkoxy group, C6 The aryl group may be substituted with at least one selected from the group consisting of an aryl group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms. R ¹ may be bonded to form a ring together with the carbon atom on the benzene ring to which R ¹ is bonded, X ¹ represents a chlorine atom, a bromine atom or an iodine atom, X ² represents a chlorine atom, .SO ₃ M representing a bromine atom or an iodine atom is _SO 3 _{M 1} or _SO ³ -. represents an _{M 2} ^+, where, _{M 1} is a hydrogen atom, _{M 2} ⁺ is a cation of an alkali metal cation or ammonium compound Represents.)
Wherein the coupling reaction is caused by elimination of X ² of the dihalobenzene compound represented by formula (5):

(W, m, p, q, r, X ¹ , M, R ¹ represent the same meaning as described above.)
The manufacturing method of the dihalobiphenyl compound shown by these. Formula (7)

(In the formula, W represents a direct bond, —O—, —S—, —SO—, —SO ₂ — or —CO—. M represents an integer of 0 to _3. p represents an integer of 1 to 12. Q represents an integer, q represents an integer of 1 to 12, and r represents an integer of 0 to 10.
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 carbon number. It represents 2 to 20 acyl groups or cyano groups. Here, it is contained in 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, and an acyl group having 2 to 20 carbon atoms. The hydrogen atom 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 and a carbon number. It may be substituted with at least one selected from the group consisting of 2 to 20 acyl 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. X ¹ represents a chlorine atom, a bromine atom or an iodine atom. SO ₃ M represents SO ₃ M ₁ or SO ₃ ⁻ M ₂ ⁺ . Here, M ₁ represents a hydrogen atom, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. A represents an acid addition salt of NH ₂ or NH ₃ . )
In the aniline compound represented by formula (4), l represents 1 including the step of diazotizing, denitrogenating and halogenating A

(W, m, p, q, r, l, X ¹ , M, R ¹ represent the same meaning as described above.)
The manufacturing method of the dihalobenzene compound shown by these. Formula (9)

(In the formula, m represents an integer of 0 to 3. 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 having 6 to 20 carbon atoms. Group, 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 carbon atoms. A hydrogen atom contained in an aryl group having 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms is a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, It may be substituted with at least one 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 and acyl groups having 2 to 20 carbon atoms. Also, the bonding position is adjacent And R ¹ may be bonded to form a ring together with the carbon atom on the benzene ring to which R ¹ is bonded, X ³ represents a bromine atom or an iodine atom, A represents NH ₂ or NH ₃ Represents an acid addition salt of
And a compound of formula (10)

(Wherein, W represents any of a direct bond, —O—, —S—, —SO—, —SO ₂ —, —CO—, p represents an integer of 1 to 12, and q represents 1 to 1. .SO ₃ M .r is an integer of 0 to an integer of 12 _SO 3 _{M 1} or _SO ³ -. represents an _{M 2} ⁺ wherein, _{M 1} is a hydrogen atom, _{M 2} ⁺ represents an alkali Represents a metal cation or a cation of an ammonium compound.)
Comprising a reaction step of coupling the compound represented by formula (8) in the presence of metallic copper

(W, m, p, q, r, A, M and R ¹ in the formula represent the same meaning as described above.)
The manufacturing method of the aniline compound shown by these.