JP2013209458A - Polyarylene and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polymer having ion exchange groups.SOLUTION: There are provided a polymer and the like, which a polymer is the polymer having ion exchange groups characterized in that (1) a repeating unit having the ion exchange group is composed from a polyarylene; (2) both a fluorine group and a sulfo group are directly bound to an aromatic ring; and (3) the ion exchange capacity is in a range of 3.2-8 meq/g.

Description

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

  Polyarylene having an ion exchange group is useful as a polymer electrolyte for a polymer electrolyte fuel cell. Examples of the monomer having a sulfo group as an ion exchange group include, for example, 4,4′-dichlorobiphenyl-2,2′-disulfonic acid di (2,2-dimethylpropyl), 2,5-dichlorobenzenesulfonic acid (2, 2-dimethylpropyl), 3- (2,5-dichlorobenzoyl) benzenesulfonic acid (2,2-dimethylpropyl) and the like are known (see, for example, Patent Document 1, Patent Document 2, Patent Document 3, etc.). .

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

  An object of the present invention is to provide a polymer having a novel ion exchange group.

（式中、ｗは０〜２の整数を表わし、ｗ’は０〜３の整数を表わす。ｘは０〜２の整数を表わす。ｙは０〜３の整数を表わし、ｙ’は０〜４の整数を表わし、ｙ＋ｙ’は１以上の整数を表わす。ｚは０〜３の整数を表わし、ｚ’は０〜４の整数を表わし、ｚ＋ｚ’は１以上の整数を表わす。また、ｚ’が１以上の整数の場合、ｘは１以上の整数を表わす。Ｒ^１は炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数６〜８のアリール基、炭素数６〜８のアリールオキシ基、炭素数２〜８のアシル基又はシアノ基を表わす。ここで、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数６〜８のアリール基、炭素数６〜８のアリールオキシ基及び炭素数２〜８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１〜８のアルコキシ基、炭素数６〜８のアリール基及び炭素数６〜８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。）
で表されることを特徴とする前項１記載の重合体；
３．前記式（１）中、ｘが０であることを特徴とする前項２記載の重合体；
４．式（１）で表されるイオン交換基を有する繰り返し単位が、式（２）

（式中、ｙ１は同一又は相異なり、１〜３の整数を表わす。）
で表されることを特徴とする前項２記載の重合体；
５．式（１）で表されるイオン交換基を有する繰り返し単位が、式（３）

（式中、ｙ２及びｚ１は、１〜４の整数を表わし、ｙ２＋ｚ１は２〜５の整数を表わす。）
で表されることを特徴とする前項２記載の重合体；
６．式（１）で表されるイオン交換基を有する繰り返し単位が、式（４）

（式中、ｙ２は１〜４の整数を表わす。）
で表されることを特徴とする前項５記載の重合体；
７．イオン交換基を有する重合体であり、イオン交換基を有さない繰り返し単位が式（５）

（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。）
で表されることを特徴とする前項１乃至６のいずれか記載の重合体；
８．イオン交換基を有する重合体であり、イオン交換基を有さない繰り返し単位が式（６）

（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置換基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。）
で表されることを特徴とする前項１乃至６のいずれか記載の重合体；
９．式（７）で表されることを特徴とするジハロスルホ化合物

（式中、ｗは０〜２の整数を表わし、ｗ’は０〜３の整数を表わす。ｘは０〜２の整数を表わす。ｙは０〜２の整数を表わし、ｙ’は０〜４の整数を表わし、ｙ＋ｙ’は１以上の整数を表わす。ｚは０〜３の整数を表わし、ｚ’は０〜４の整数を表わし、ｚ＋ｚ’は１以上の整数を表わす。また、ｚ’が１以上の整数の場合、ｘは１以上の整数を表わす。Ｒ^１は炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数６〜８のアリール基、炭素数６〜８のアリールオキシ基、炭素数２〜８のアシル基又はシアノ基を表わす。ここで、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数６〜８のアリール基、炭素数６〜８のアリールオキシ基及び炭素数２〜８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１〜８のアルコキシ基、炭素数６〜８のアリール基及び炭素数６〜８のアリールオキシ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。また、結合位置が隣接する２つのＲ^１が結合して当該Ｒ^１が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。ｍは１又は２を表わし、Ｍは−ＯＭ_１又は−Ｏ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は炭素数１〜２０のアルキル基を表わし、Ｍ_２ ⁺はアルカリ金属カチオン又はアンモニウム化合物のカチオンを表わし、Ｘは塩素原子、臭素原子又はヨウ素原子を表わす。）；
１０．式（８）で表わされることを特徴とする前項９記載のジハロスルホ化合物；

（式中、ｗは０〜２の整数を表わし、ｙ１は１〜３の整数を表わし、ｚは１〜３の整数を表わす。Ｒ^１は炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数６〜８のアリール基、炭素数６〜８のアリールオキシ基、炭素数２〜８のアシル基又はシアノ基を表わす。ここで、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数６〜８のアリール基、炭素数６〜８のアリールオキシ基及び炭素数２〜８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１〜８のアルコキシ基、炭素数６〜８のアリール基及び炭素数６〜８のアリールオキシ基からなる群から選ばれる少なくとも一つのもので置換されていてもよい。また、結合位置が隣接する２つのＲ^１が結合して当該Ｒ^１が結合するベンゼン環上の炭素原子と共に環を形成していてもよい。Ｍは−ＯＭ_１又は−Ｏ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は炭素数１〜２０のアルキル基を表わし、Ｍ_２ ⁺はアルカリ金属カチオン又はアンモニウム化合物のカチオンを表わし、Ｘは塩素原子、臭素原子又はヨウ素原子を表わす。）；
１１．式（９）で表わされることを特徴とする前項９又は前項１０記載のジハロスルホ化合物

（式中、ｙ１は同一又は相異なり、１〜３の整数を表わす。Ｍは−ＯＭ_１又は−Ｏ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は炭素数１〜２０のアルキル基、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し、Ｘは塩素原子、臭素原子又はヨウ素原子を表わす。）；
１２．下記式（１０）で表わされることを特徴とする前項９記載ジハロスルホ化合物

（式中、ｙ２は１〜４の整数を表わす。Ｍは−ＯＭ_１又は−Ｏ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は炭素数１〜２０のアルキル基、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し、Ｘは塩素原子、臭素原子又はヨウ素原子を表わす。）；
１３．前項９記載のジハロスルホ化合物を含むモノマー組成物を重合する工程、及び、前記重合工程により得られた重合物が有する式−ＳＯ_２ＯＭで示される基を式−ＳＯ_２ＯＨで示される基に変換する工程を含むことを特徴とする重合体の製造方法；
１４．下記式（１１）で表される繰り返し単位を含むことを特徴とする重合体

（式中、Ｍは−ＯＭ_１又は−Ｏ^-Ｍ_２ ⁺を表わす。ここで、Ｍ_１は炭素数１〜２０のアルキル基を表わし、Ｍ_２ ⁺はアルカリ金属カチオン又はアンモニウム化合物のカチオンを表わす。ｗは０〜２の整数を表わし、ｗ’は０〜３の整数を表わす。ｘは０〜２の整数を表わす。ｙは０〜３の整数を表わし、ｙ’は０〜４の整数を表わし、ｙ＋ｙ’は１以上の整数を表わす。ｚは０〜３の整数を表わし、ｚ’は０〜４の整数を表わし、ｚ＋ｚ’は１以上の整数を表わす。また、ｚ’が１以上の整数の場合、ｘは１以上の整数を表わす。Ｒ^１は炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数６〜８のアリール基、炭素数６〜８のアリールオキシ基、炭素数２〜８のアシル基又はシアノ基を表わす。ここで、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数６〜８のアリール基、炭素数６〜８のアリールオキシ基及び炭素数２〜８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１〜８のアルコキシ基、炭素数６〜８のアリール基及び炭素数６〜８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。）；
等である。 Under such circumstances, the present inventors have intensively studied a polymer having a sulfo group, resulting in the following present invention. That is, the present invention
1. A polymer having an ion exchange group, wherein the repeating unit having the ion exchange group is composed of 1) polyarylene, 2) both a fluorine group and a sulfo group are directly bonded to the aromatic ring, and 3) the ion exchange capacity is increased. A polymer characterized by being in the range of 3.2 meq / g to 8 meq / g;
2. The repeating unit having an ion exchange group has the formula (1)

Wherein w represents an integer of 0 to 2, w ′ represents an integer of 0 to 3, x represents an integer of 0 to 2, y represents an integer of 0 to 3, and y ′ represents 0 to 0. 4 represents an integer of 4, y + y ′ represents an integer of 1 or more, z represents an integer of 0 to 3, z ′ represents an integer of 0 to 4, z + z ′ represents an integer of 1 or more, and z When 'is an integer of 1 or more, x represents an integer of 1 or more, R ¹ is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, or the number of carbon atoms Represents an aryloxy group having 6 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a cyano group, where an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl having 6 to 8 carbon atoms Group, an aryloxy group having 6 to 8 carbon atoms and an acyl group having 2 to 8 carbon atoms include a fluorine atom, a cyano group, and a carbon number It may be substituted with at least one selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, and an aryloxy group having 6 to 8 carbon atoms, and the bonding positions are adjacent. two R ¹ is bonded to together with the carbon atoms on the benzene ring to which the R ¹ are bonded may form a ring.)
The polymer according to item 1 above, which is represented by:
3. In the above formula (1), x is 0;
4). The repeating unit having an ion exchange group represented by formula (1) is represented by formula (2).

(Wherein y1 is the same or different and represents an integer of 1 to 3)
The polymer according to item 2 above, which is represented by:
5. The repeating unit having an ion exchange group represented by formula (1) is represented by formula (3).

(Wherein y2 and z1 represent an integer of 1 to 4, and y2 + z1 represents an integer of 2 to 5)
The polymer according to item 2 above, which is represented by:
6). The repeating unit having an ion exchange group represented by formula (1) is represented by formula (4).

(Wherein y2 represents an integer of 1 to 4)
The polymer according to item 5 above, which is represented by:
7). A polymer having an ion exchange group, wherein the repeating unit having no ion exchange group is represented by formula (5)

(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 polymer according to any one of items 1 to 6 above, which is represented by:
8). A polymer having an ion exchange group, wherein the repeating unit having no ion exchange group is represented by formula (6)

(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 substituent 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 And 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 acyl group having 2 to 20 carbon atoms which may be substituted with
The polymer according to any one of items 1 to 6 above, which is represented by:
9. A dihalosulfo compound represented by the formula (7)

(In the formula, w represents an integer of 0 to 2, w ′ represents an integer of 0 to 3. x represents an integer of 0 to 2, y represents an integer of 0 to 2, and y ′ represents 0 to 0. 4 represents an integer of 4, y + y ′ represents an integer of 1 or more, z represents an integer of 0 to 3, z ′ represents an integer of 0 to 4, z + z ′ represents an integer of 1 or more, and z When 'is an integer of 1 or more, x represents an integer of 1 or more, R ¹ is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, or the number of carbon atoms Represents an aryloxy group having 6 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a cyano group, where an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl having 6 to 8 carbon atoms Group, an aryloxy group having 6 to 8 carbon atoms and an acyl group having 2 to 8 carbon atoms include a fluorine atom, a cyano group, and a carbon number It may be substituted with at least one selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, and an aryloxy group having 6 to 8 carbon atoms, and the bonding positions are adjacent. Two R ¹ may combine to form a ring together with the carbon atom on the benzene ring to which the R ¹ is bonded, m represents 1 or 2, and M represents —OM ₁ or —O ⁻ M ₂ ^+. Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound, and X represents a chlorine atom, a bromine atom or an iodine atom);
10. The dihalosulfo compound according to item 9, which is represented by the formula (8):

(In the formula, w represents an integer of 0 to 2, y1 represents an integer of 1 to 3, z represents an integer of ¹ to 3. R ¹ represents an alkyl group having 1 to 8 carbon atoms, 1 to 1 carbon atoms. Represents an alkoxy group having 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aryloxy group having 6 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a cyano group, wherein an alkyl group having 1 to 8 carbon atoms, Hydrogen atoms contained in an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aryloxy group having 6 to 8 carbon atoms, and an acyl group having 2 to 8 carbon atoms are a fluorine atom, a cyano group, and a carbon atom. It may be substituted with at least one selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms and an aryloxy group having 6 to 8 carbon atoms, and the bonding position is adjacent. two R ¹ is bonded to the benzene ring to which the R ¹ is attached to Good .M also form a ring with the carbon atoms -OM ₁ or ^-O -. Represents a ⁺ _{M 2} wherein, _{M 1} is an alkyl group having 1 to 20 carbon atoms, _{M 2} ⁺ is an alkali metal Represents a cation or a cation of an ammonium compound, and X represents a chlorine atom, a bromine atom or an iodine atom);
11. 11. The dihalosulfo compound according to item 9 or 10, wherein the compound is represented by formula (9)

(Wherein y1 is the same or different and represents an integer of _{1 to 3.} M represents —OM ₁ or —O ⁻ M ₂ ⁺ , where M ₁ represents an alkyl group having 1 to 20 carbon atoms, M ₂ ⁺ represents a cation of an alkali metal cation or ammonium compound, X represents a chlorine atom, a bromine atom or an iodine atom).;
12 9. The dihalosulfo compound according to item 9, which is represented by the following formula (10):

(Wherein y2 represents an integer of 1 to 4, M represents —OM ₁ or —O ⁻ M ₂ ⁺ , where M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal. Represents a cation or a cation of an ammonium compound, and X represents a chlorine atom, a bromine atom or an iodine atom);
13. The step of polymerizing the monomer composition containing the dihalosulfo compound according to item 9 above, and the group represented by the formula —SO ₂ OM of the polymer obtained by the polymerization step is converted into a group represented by the formula —SO ₂ OH A process for producing a polymer comprising the step of:
14 A polymer comprising a repeating unit represented by the following formula (11)

(In the formula, M represents —OM ₁ or —O ⁻ M ₂ ⁺ , where M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. W represents an integer of 0 to 2, w ′ represents an integer of 0 to 3, x represents an integer of 0 to 2, y represents an integer of 0 to 3, and y ′ represents an integer of 0 to 4. Y + y ′ represents an integer of 1 or more, z represents an integer of 0 to 3, z ′ represents an integer of 0 to 4, z + z ′ represents an integer of 1 or more, and z ′ is 1 In the case of the above integers, x represents an integer greater than or equal to ^1. R1 is a C1-C8 alkyl group, a C1-C8 alkoxy group, a C6-C8 aryl group, C6-C8. An aryloxy group, an acyl group having 2 to 8 carbon atoms or a cyano group, wherein an alkyl group having 1 to 8 carbon atoms, A hydrogen atom contained in an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aryloxy group having 6 to 8 carbon atoms and an acyl group having 2 to 8 carbon atoms includes a fluorine atom, a cyano group, and a carbon number It may be substituted with at least one selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, and an aryloxy group having 6 to 8 carbon atoms, and the bonding positions are adjacent. And two R ¹ may be bonded to form a ring together with the carbon atom on the benzene ring to which the R ¹ is bonded.);
Etc.

  According to the present invention, a polymer having a novel ion exchange group can be provided.

Hereinafter, the present invention will be described in detail.
The compound of the present invention is a polymer having an ion exchange group, and the repeating unit having the ion exchange group is composed of 1) polyarylene, and 2) both a fluorine group and a sulfo group are directly bonded to the aromatic ring. ) A polymer characterized by having an ion exchange capacity in the range of 3.2 meq / g to 8 meq / g.

繰り返し単位あたりの分子量は１８８．１８である。つまり１８８．１８ｇあたり１つのスルホン酸、すなわちイオン交換基があることになり、この重合体１ｇあたりのイオン交換容量は１÷１８８．１８×１０００＝５．３１（ｍｅｑ／ｇ）となる。 The ion exchange capacity is milliequivalents of ion exchange groups per 1 g of compound and can be calculated from the molecular weight. For example, in the case of a polymer having the following repeating unit (A):

The molecular weight per repeating unit is 188.18. That is, there is one sulfonic acid, that is, an ion exchange group per 188.18 g, and the ion exchange capacity per 1 g of the polymer is 1 / 188.18 × 1000 = 5.31 (meq / g).

  The ion exchange capacity of the compound of the present invention is preferably 3.2 meq to 8 meq, more preferably 3.6 meq to 6 meq.

In formula (1), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or 2 to 2 carbon atoms. 20 represents an acyl group, an arylcarbonyl group having 7 to 20 carbon atoms, or a cyano group. Here, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and carbon The hydrogen atom contained in the arylcarbonyl group having 7 to 20 carbon atoms includes a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number. It may be substituted with at least one group selected from the group consisting of an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms and an arylcarbonyl group having 7 to 20 carbon atoms. When R ¹ is plural, R ¹ may be the same group or different groups. Moreover, two adjacent R ^1s may be bonded to form a ring.

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

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

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

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

  In formula (1), w represents an integer of 0 to 2, and w ′ represents an integer of 0 to 3. x represents an integer of 0-2. y represents an integer of 0 to 3, y 'represents an integer of 0 to 4, and y + y' represents an integer of 1 or more. z represents an integer of 0 to 3, z 'represents an integer of 0 to 4, and z + z' represents an integer of 1 or more. When z 'is an integer of 1 or more, x represents an integer of 1 or more.

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

  In the formula (1), x is preferably 0 from the viewpoint of ease of synthesis.

  In formula (2), y1 is the same or different and represents an integer of 1 to 3, and preferably, y1 is 1 or 2.

  Specific examples of the compound represented by the formula (2) include repeating units represented by the following formulas (2a) to (2f).

  In formula (3), y2 and z1 represent an integer of 1 to 4, and y2 + z1 represents an integer of 2 to 5. y2 is preferably 2 to 4 from the viewpoint of synthesis, and z1 is preferably 1 or 2 from the viewpoint of synthesis.

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

  In formula (4), y2 represents an integer of 1 to 4, and y2 is preferably 2 to 4 from the viewpoint of synthesis.

  Specific examples of the compound represented by the formula (4) include repeating units represented by the following formulas (4a) to (4c).

The polymer of the present invention is a polymer containing a structural unit derived from the phenylsulfonic acid compound represented by the formula (1), and since the polymer has ion conductivity, it can be used as a polymer electrolyte. .
Examples of the polymer include a homopolymer of a phenylsulfonic acid compound represented by the formula (1), for example, a polymer of the phenylsulfonic acid compound represented by the formula (1) and another monomer, for example, an aromatic polyether. And a polymer of a phenylsulfonic acid compound represented by the formula (1).
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, and the ether bond is represented by —O— ( Ether bond) and -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。）
で表わされる構造単位と、式（１）で表わされるフェニルスルホン酸化合物に由来する構造単位とを含む重合体、等が挙げられる。 Preferred polymers include, for example, formula (5)

(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. The hydrogen atom contained in the divalent aromatic group is a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 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 20 aryloxy groups;
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 a structural unit derived from a phenylsulfonic acid compound represented by the formula (1), and the like.

a, b and c each independently represent 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 (5) 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, Examples include heteroaromatic groups such as thiophenediyl. A divalent monocyclic aromatic group is preferred.

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 groups further have a substituent. You may do it.

  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, or 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 substituents such as an isopropyloxy group, a phenyl group, a naphthyl group, a phenoxy group, and a naphthyloxy group are 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. 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 with a group, methoxy group, ethoxy group, isopropyloxy group, phenyl group, naphthyl group, phenoxy group, 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 (5) 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. are mentioned, for example.

Specific examples of the structural unit represented by the formula (5) include structural units represented by the following formulas (5a) to (5y). In the following formulae, n represents the same meaning as described above, and specifically, for example, a range of 5 to 200 is exemplified. Examples of the weight average molecular weight in terms of polystyrene of the structural unit represented by the formula (5) include 2,000 or more, and preferably 3,000 or more.

Examples of the polymer having the structural unit represented by the formula (5) include groups having a group capable of reacting with X1 to form a bond at both ends of the structural unit represented by the formula (5). And a polymer having a halogen atom (hereinafter abbreviated as polymer (12)). Examples of the method for producing the polymer (12) include methods described in JP2007-270118A, JP2007-284653A, JP2007-138065A, and the like.
Further, a commercially available polymer (12) may be used, and examples of the commercially available polymer (12) include Sumika Excel (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置換基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。）が挙げられる。 As preferred repeating units other than formula (5), for example, formula (6)

(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 substituent 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 And 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 may be substituted with at least one substituent selected from the group consisting of an acyl group having 2 to 20 carbon atoms which may be substituted with

  Specific examples of the structural unit represented by the formula (6) include, for example, 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, A divalent condensed aromatic group such as 7-diyl group; pyridine-2,5-diyl group, pyridine-2,6-diyl group, quinoxaline-2,6-diyl group, thiophene-2,5-diyl A divalent heteroaromatic group such as a group; and the like. Among these, a divalent monocyclic aromatic group and a divalent condensed ring aromatic group are preferable, and a 1,4-phenylene group, a naphthalene-1,4-diyl group, a naphthalene-1,5-diyl group, Naphthalene-2,6-diyl group and naphthalene-2,7-diyl group are more preferred.

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 ones as described above.

  Specific examples of the repeating unit represented by the formula (6) include repeating units represented by the following formulas (6a) to (6g).

In formula (7), R ¹ , w, w ′, x, x ′, y, z, z ′ represent the same meaning as described above. m represents 1 or 2. X represents a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom.

In formula (7), M represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. When M is —OM ₁ , this M is covalently bonded to the group represented by —SO ₃ , and when M is —O ⁻ M ₂ ^+, it is represented by M ₂ ⁺ and —SO _3. It is bonded to the group with an ionic bond.

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 (7) include compounds represented by the following formulas (7a) to (7af).

In formula (8), R ¹ , w, z, X and M represent the same meaning as described above. y1 represents an integer of 1 to 3.

  Specific examples of the compound represented by the formula (8) include compounds represented by the following formulas (8a) to (8g).

  In formula (9), M, X, and y1 have the same meaning as described above.

  Specific examples of the compound represented by the formula (9) include compounds represented by the following formulas (9a) to (9m).

  In formula (10), M, X, and y1 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) to (10j).

In formula (11), R ¹ , M, w, w ′, x, y, y ′, z, and z ′ represent the same meaning as described above.

  Specific examples of the compound represented by the formula (11) include repeating units represented by the following formulas (11a) to (11l).

As a method for polymerizing the phenylsulfonic acid compound represented by the formula (7) on the polymer (12), for example, a composition containing the phenylsulfonic acid compound represented by the polymer (12) and the formula (7) is nickel. Examples include a method of polymerizing in the presence of a compound, for example, a method of polymerizing a phenylsulfonic acid compound represented by the formula (7) in the presence of a nickel compound, and then adding a polymer (12) to further polymerize. Can do.
Examples of the nickel compound include the same nickel compounds as those described above.
As a usage-amount of a nickel compound, the range etc. of 0.01 mol-5 mol etc. are mentioned with respect to 1 mol of nickel compounds about the phenylsulfonic acid compound represented by Formula (7).

  When polymerizing using a divalent nickel compound as a catalyst, it is preferably carried out in the presence of a nitrogen-containing bidentate ligand. Examples of the nitrogen-containing bidentate ligand include 2,2′-bipyridine, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine, and 2,2′-bipyridine is preferable. . When the nitrogen-containing bidentate ligand is used, the amount used thereof can be, for example, in the range of 0.2 mol to 2 mol with respect to 1 mol of the nickel compound, and preferably 1 mol to 2 mol, for example. The range of 1.5 mol is mentioned.

  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 1 mol of phenylsulfonic acid compounds represented by Formula (7), for example.

The polymerization reaction is preferably performed in the presence of a solvent. The solvent may be any solvent that can dissolve the phenylsulfonic acid compound represented by formula (7), the polymer (12), and the resulting polymer. Specific examples of such solvents include aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as tetrahydrofuran and 1,4-dioxane; dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N And aprotic polar solvents such as N, dimethylacetamide and hexamethylphosphoric triamide; halogenated hydrocarbon solvents such as dichloromethane and dichloroethane. Such a solvent may be used independently and may be used in mixture of 2 or more types. Of these, ether solvents and aprotic polar solvents are preferable, and tetrahydrofuran, dimethyl sulfoxide, N-methyl-2-pyrrolidone and N, N-dimethylacetamide are more preferable.
The amount of the solvent used is usually 1 to 200 times by weight, preferably 5 to 100 times by weight, with respect to the phenylsulfonic acid compound represented by the formula (7) used. When the amount is 1 part by weight or more, a polymer having a large molecular weight tends to be easily obtained. ,

The polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen gas.
The polymerization reaction temperature is usually 0 ° C to 250 ° C, preferably 30 ° C to 100 ° C. The polymerization time is usually 0.5 hours to 48 hours.

After the completion of the polymerization reaction, the polymer of the present invention is obtained by mixing the reaction mixture and a solvent that hardly dissolves the produced polymer to precipitate the polymer, and separating the precipitated polymer from the reaction mixture by filtration. It can be taken out.
After mixing the reaction mixture with a solvent that does not dissolve or hardly dissolves the produced polymer, an acid may be added, and the precipitated polymer may be separated from the reaction mixture by filtration.
Examples of the solvent that does not dissolve or hardly dissolve the produced polymer include water, methanol, ethanol, acetonitrile, and the like, and water and methanol are preferable.
Examples of the acid include hydrochloric acid, sulfuric acid and the like. The amount of the acid used may be an amount necessary for acidifying the reaction mixture.

When the structural unit derived from the phenylsulfonic acid compound represented by formula (7) of the obtained polymer contains R ¹ O— and R ¹ is a hydrocarbon group, a deprotection reaction is performed, and R ¹ needs to be a hydrogen atom or a cation. Such deprotection reaction is performed according to the method described in JP-A-2007-270118.
The ion exchange capacity (measured by a titration method) of the polymer thus obtained includes, for example, a range of 3.2 meq / g to 8 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.

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

The polymer described in Example 5 was analyzed by gel permeation chromatography (hereinafter abbreviated as GPC) (analysis conditions are as follows), and the polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight ( Mn) was calculated.
<Analysis conditions>
GPC measuring device: CTO-10A (manufactured by Shimadzu Corporation)
Column: TSK-GEL GMHHR-M (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Mobile phase: N, N-dimethylacetamide 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):
The polymer used for the measurement was formed into a film by a solution casting method to obtain a polymer film, and the obtained polymer film was cut to an appropriate weight. The dry weight of the cut polymer film was measured using a halogen moisture meter set at a heating temperature of 105 ° C. Next, the polymer membrane thus dried was immersed in 5 mL of a 0.1 mol / L sodium hydroxide aqueous solution, and further 50 mL of ion exchange water was added and left for 2 hours. Then, titration was performed by gradually adding 0.1 mol / L hydrochloric acid to the solution in which the polymer film was immersed, and the neutralization point was determined. Then, the ion exchange capacity (unit: meq / g) of the polymer was calculated from the dry weight of the cut polymer film and the amount of hydrochloric acid required for neutralization.

３０％発煙硫酸７１２．３ｇに２５℃で市販品の２，５−ジフルオロ−１，４−ジブロモベンゼン１５０ｇを徐々に加え、１００℃に昇温して２時間保温した。反応混合物を冷水７１３．０ｇに注ぎ込み、生成した固体をろ過した。得られた固体に水２０００ｇを加えて溶解させ、５０重量％の水酸化ナトリウム水溶液を約１３０ｇ加えて生成した固体をろ過し、濃縮・乾燥することによって３，６−ジフルオロ−２，５−ジブロモベンゼンスルホン酸ナトリウム（中間体１）を１３４．５ｇ（収率６７．２％）を得た。
^１Ｈ−ＮＭＲ（Ｄ_２Ｏ、δ（ｐｐｍ））：７．５４−７．６３（ｄｄ、１Ｈ） [Example 1]
Synthesis of intermediate 1

150 g of a commercially available 2,5-difluoro-1,4-dibromobenzene was gradually added to 712.3 g of 30% fuming sulfuric acid at 25 ° C., and the temperature was raised to 100 ° C. and kept warm for 2 hours. The reaction mixture was poured into 713.0 g of cold water, and the generated solid was filtered. The obtained solid was dissolved by adding 2000 g of water, and about 130 g of 50% by weight sodium hydroxide aqueous solution was added, and the resulting solid was filtered, concentrated and dried to give 3,6-difluoro-2,5-dibromo. 134.5 g (yield 67.2%) of sodium benzenesulfonate (intermediate 1) was obtained.
¹ H-NMR (D ₂ O, δ (ppm)): 7.54-7.63 (dd, 1H)

実施例１で合成した中間体１を１３４．５ｇ、Ｎ，Ｎ−ジメチルホルムアミドを１３５０ｇ加え、１００℃に加熱して溶解させた後に減圧濃縮し、Ｎ，Ｎ−ジメチルホルムアミドを６９６ｇ留去した。濃縮マス水分値は２５１ｐｐｍであった。２５℃冷却後、銅粉末４６．０ｇと１価のヨウ化銅３４．３ｇを加え１００℃に昇温し、２時間保温した。反応混合物を水１２８０ｇに注ぎ込み、不溶物を濾別し、濾液を濃縮乾固し、４，４’−ジブロモ−２，５，２’，５’−テトラフルオロ−６，６’−ビフェニルジスルホン酸ナトリウム（中間体２）を９１．２ｇ（収率８５．９％）を得た。
マススペクトル（ＥＳＩ、ｍ／ｚ）：（Ｍ^−１）５４２．８（スルホン酸として検出） [Example 2]
Synthesis of intermediate 2

134.5 g of intermediate 1 synthesized in Example 1 and 1350 g of N, N-dimethylformamide were added, dissolved by heating to 100 ° C., and then concentrated under reduced pressure, and 696 g of N, N-dimethylformamide was distilled off. The concentrated mass moisture value was 251 ppm. After cooling at 25 ° C., 46.0 g of copper powder and 34.3 g of monovalent copper iodide were added, the temperature was raised to 100 ° C., and the temperature was kept for 2 hours. The reaction mixture is poured into 1280 g of water, the insoluble material is filtered off, the filtrate is concentrated to dryness, and 4,4′-dibromo-2,5,2 ′, 5′-tetrafluoro-6,6′-biphenyldisulfonic acid. 91.2 g (yield 85.9%) of sodium (intermediate 2) was obtained.
Mass spectrum (ESI, m / z): (M ⁻¹ ) 542.8 (detected as sulfonic acid)

オキシ塩化リンを４５３．８ｇ、五塩化リンを２４１．１ｇ、そして実施例２で合成した中間体２を９０．１ｇ加え、室温で３時間保温した。その後反応マスを１５℃に冷却し、氷水１３７９ｇに滴下した。滴下終１５分保温した後、生成した固体をろ過し、得られた固体にトルエンを５００ｇ加え、溶解させた。そこに水２０００ｇで繰り返し洗浄してｐＨを４以上に上げ他の油層を濃縮、乾燥し４，４’−ジブロモ−２，５，２’，５’−テトラフルオロ−６，６’−ビフェニルジスルホン酸クロリド（中間体３）を７６．１ｇ（収率９２．９％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δ（ｐｐｍ））：７．７２−７．８３（ｄｄ、１Ｈ） [Synthesis Example 1]
Synthesis of intermediate 3

453.8 g of phosphorus oxychloride, 241.1 g of phosphorus pentachloride, and 90.1 g of intermediate 2 synthesized in Example 2 were added, and the mixture was kept at room temperature for 3 hours. The reaction mass was then cooled to 15 ° C. and added dropwise to 1379 g of ice water. After keeping the temperature at the end of dropping for 15 minutes, the produced solid was filtered, and 500 g of toluene was added to the obtained solid to dissolve it. It was washed repeatedly with 2000 g of water, the pH was raised to 4 or more, and the other oil layer was concentrated and dried, and 4,4′-dibromo-2,5,2 ′, 5′-tetrafluoro-6,6′-biphenyldisulfone. 76.1 g (yield 92.9%) of acid chloride (intermediate 3) was obtained.
¹ H-NMR (CDCl ₃ , δ (ppm)): 7.72-7.83 (dd, 1H)

２，２−ジメチル−１−プロパノール２９．３ｇに脱水トルエン１４７．１ｇを加え、得られた混合物を５℃に冷却した。これにｎ−ブチルリチウムの１．６ｍｏｌ／Ｌへキサン溶液１８４．０ｇを滴下した。得られた混合物を２０℃で１．５時間保温した。
次いで、得られた反応混合物に合成例１で合成した中間体３（６５．０ｇ）の脱水トルエン溶液７１４．５ｇを滴下し、得られた混合物を５０℃で８時間保温した。
次いで、得られた反応混合物に水１１９ｇを加えて攪拌した後、生成した有機層と水層とを分離し、第一の有機層と水層とを得た。分離した有機層を水で２回洗浄したのち、得られた有機層を硫酸ナトリウムで乾燥した後、これを濃縮乾固した。
次いで、得られた固体をシリカゲルカラムで精製し（ヘキサン単溶媒）、フラクションを回収し精製固体５９．４ｇを得た。得られた固体にヘキサン３００ｇを加え、加熱溶解させた後、０℃で２時間保温し、析出した結晶を濾取した。濾取した固体を乾燥することにより、白色固体の４，４’−ジブロモ−２，５，２’，５’−テトラフルオロ−６，６’−ビフェニルジスルホン酸ビス（２，２−ジメチル−１−プロピル）４０．２ｇ（収率５８％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δ（ｐｐｍ））：０．９５（ｓ、１８Ｈ）、３．８１（ｓ，４Ｈ）、７．６１−７．６９（ｓ、２Ｈ） [Example 3]
Synthesis of bis (2,2-dimethyl-1-propyl) 4,4′-dibromo-2,5,2 ′, 5′-tetrafluoro-6,6′-biphenyldisulfonate

147.1 g of dehydrated toluene was added to 29.3 g of 2,2-dimethyl-1-propanol, and the resulting mixture was cooled to 5 ° C. To this, 184.0 g of a 1.6 mol / L hexane solution of n-butyllithium was added dropwise. The resulting mixture was incubated at 20 ° C. for 1.5 hours.
Next, 714.5 g of a dehydrated toluene solution of Intermediate 3 (65.0 g) synthesized in Synthesis Example 1 was added dropwise to the resulting reaction mixture, and the resulting mixture was kept at 50 ° C. for 8 hours.
Next, 119 g of water was added to the obtained reaction mixture and stirred, and then the produced organic layer and the aqueous layer were separated to obtain a first organic layer and an aqueous layer. The separated organic layer was washed twice with water, and the obtained organic layer was dried over sodium sulfate and then concentrated to dryness.
Subsequently, the obtained solid was purified with a silica gel column (hexane single solvent), and the fractions were collected to obtain 59.4 g of a purified solid. To the obtained solid, 300 g of hexane was added and dissolved by heating, and then kept at 0 ° C. for 2 hours, and the precipitated crystals were collected by filtration. The solid collected by filtration was dried to give white solid 4,4′-dibromo-2,5,2 ′, 5′-tetrafluoro-6,6′-biphenyldisulfonic acid bis (2,2-dimethyl-1). -Propyl) (40.2 g, yield 58%) was obtained.
¹ H-NMR (CDCl ₃ , δ (ppm)): 0.95 (s, 18H), 3.81 (s, 4H), 7.61-7.69 (s, 2H)

クロロ硫酸１５２．７ｇに２５℃で２，３ ，５，６，−テトラフルオロブロモベンゼン６０．０ｇを徐々に加え、１２０℃で２０時間保温した。得られた反応混合物を２５℃まで冷却し、水１５２７ｇに加えた後、トルエン４２９．１ｇを加えた。分液後の油層を水で洗浄し、硫酸ナトリウムを加えた後に固形分を濾別し、得られた濾液を濃縮乾固して２，３ ，５，６，−テトラフルオロ−４−ブロモベンゼンスルホン酸クロリド４７．０ｇを得た。
一方で、２，２−ジメチルプロパノール２０．４ｇをトルエン２３０．０ｇに溶解させ、０℃でｎ−ブチルリチウムのヘキサン溶液（１．６２Ｍ）１３０．１ｍＬを滴下した。その後、２５℃で１時間攪拌し、リチウム（２，２−ジメチルプロポキシド）を含む溶液を調製した。ここに前記２，３ ，５，６，−テトラフルオロ−４−ブロモベンゼンスルホン酸クロリド４７．０ｇをトルエン２３０．１ｇに溶解させて得られた溶液を滴下し、２５℃で１時間反応させた。得られた反応混合物に水３６８．１ｇを加え、分液後の油層を水で４回洗浄し、硫酸ナトリウムを加えた後に固形分を濾別し、得られた濾液を濃縮乾固して粗生成物５６．１ｇを得た。粗生成物にヘキサン１０６．５ｇを加えてよく攪拌しながら０℃で１時間保温し、濾過及び乾燥により白色固体２，３ ，５，６，−テトラフルオロ−４−ブロモベンゼンスルホン酸（２，２−ジメチルプロピル）５０．０ｇ（収率５１％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，δ（ｐｐｍ））：０．９５（ｓ，９Ｈ），３．９５（ｓ，２Ｈ）
^１９Ｆ−ＮＭＲ（ＣＤＣｌ_３、δ（ｐｐｍ））：−１２８．９．０（ｍ，２Ｆ）、−１３４．１（ｍ，２Ｆ） [Example 4]
Synthesis of 2,3,5,6, -tetrafluoro-4-bromobenzenesulfonic acid (2,2-dimethylpropyl)

60.0 g of 2,3,5,6, -tetrafluorobromobenzene was gradually added to 152.7 g of chlorosulfuric acid at 25 ° C., and the mixture was kept at 120 ° C. for 20 hours. The obtained reaction mixture was cooled to 25 ° C., added to 1527 g of water, and then 429.1 g of toluene was added. The separated oil layer was washed with water, sodium sulfate was added, the solid content was filtered off, and the resulting filtrate was concentrated to dryness to give 2,3,5,6, -tetrafluoro-4-bromobenzene. 47.0 g of sulfonic acid chloride was obtained.
On the other hand, 20.4 g of 2,2-dimethylpropanol was dissolved in 230.0 g of toluene, and 130.1 mL of a hexane solution (1.62M) of n-butyllithium was added dropwise at 0 ° C. Then, it stirred at 25 degreeC for 1 hour, and prepared the solution containing lithium (2, 2- dimethylpropoxide). A solution obtained by dissolving 47.0 g of 2,3,5,6, -tetrafluoro-4-bromobenzenesulfonic acid chloride in 230.1 g of toluene was added dropwise thereto and reacted at 25 ° C. for 1 hour. . 368.1 g of water was added to the obtained reaction mixture, the oil layer after the separation was washed 4 times with water, sodium sulfate was added and then the solid content was filtered off, and the resulting filtrate was concentrated to dryness to give a crude product. 56.1 g of product was obtained. 106.5 g of hexane was added to the crude product, and the mixture was kept warm at 0 ° C. for 1 hour with good stirring. By filtration and drying, a white solid 2,3,5,6, -tetrafluoro-4-bromobenzenesulfonic acid (2, 20.0 g (yield 51%) of 2-dimethylpropyl) was obtained.
¹ H-NMR (CDCl ₃ , δ (ppm)): 0.95 (s, 9H), 3.95 (s, 2H)
¹⁹ F-NMR (CDCl ₃ , δ (ppm)): −128.9.0 (m, 2F), −134.1 (m, 2F)

実施例４で得られた２，３ ，５，６，−テトラフルオロ−４−ブロモベンゼンスルホン酸（２，２−ジメチルプロピル）４６．０ｇと２，５−ジクロロフェニルボロン酸４６．３ｇと炭酸ナトリウム５１．４ｇとテトラキス(トリフェニルホスフィン)パラジウム（０）７．０ｇを加え、窒素置換してからジメトキシエタン４６０．０ｇと水１８４．０ｇとを混合し、よく攪拌しながら７０℃で７時間保温した。得られた反応混合物を２５℃まで冷却し、水５４０．２ｇとトルエン９７２．３ｇとを加え、分液後の油層を５％硫酸、水で洗浄し、硫酸ナトリウムを加えた後に固形分を濾別し、得られた濾液を濃縮乾固して粗生成物５８．２ｇを得た。粗生成物にトルエン２７０．１ｇ加えて溶解し、シリカゲルカラムクロマトグラフィー（展開溶媒：トルエン）で精製後、濃縮乾固した。ヘキサン４０５．０ｇを加えてよく攪拌しながら２５℃で１時間保温し、濾過及び乾燥により白色固体２’，５’−ジクロロ−２，３ ，５，６，−テトラフルオロ−４ −ビフェニルスルホン酸（２，２−ジメチルプロピル）１２．８ｇ（収率２４％）を得た。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、δ（ｐｐｍ））：１．０２(ｓ，９Ｈ)、４．０４(ｓ，２Ｈ)、７．２６−７．５４（ｃ，３Ｈ）
^１９Ｆ−ＮＭＲ（ＣＤＣｌ_３、δ（ｐｐｍ））：−１３５．０（ｍ，２Ｆ）、−１３６．１（ｍ，２Ｆ）
マススペクトル（ＦＤ−ＭＳ、ｍ／ｚ）：４４４（Ｍ^−１） [Example 5]
Synthesis of 2 ', 5'-dichloro-2,3,5,6, -tetrafluoro-4-biphenylsulfonic acid (2,2-dimethylpropyl)

46.0 g of 2,3,5,6, -tetrafluoro-4-bromobenzenesulfonic acid (2,2-dimethylpropyl) obtained in Example 4, 46.3 g of 2,5-dichlorophenylboronic acid and sodium carbonate 51.4 g and 7.0 g of tetrakis (triphenylphosphine) palladium (0) were added, the atmosphere was replaced with nitrogen, 460.0 g of dimethoxyethane and 184.0 g of water were mixed, and the mixture was kept at 70 ° C. for 7 hours while stirring well. did. The obtained reaction mixture was cooled to 25 ° C., 540.2 g of water and 972.3 g of toluene were added, the oil layer after separation was washed with 5% sulfuric acid and water, sodium sulfate was added, and the solid content was filtered. Separately, the obtained filtrate was concentrated to dryness to obtain 58.2 g of a crude product. The crude product was dissolved by adding 270.1 g of toluene, purified by silica gel column chromatography (developing solvent: toluene), and concentrated to dryness. 405.0 g of hexane was added, and the mixture was kept warm at 25 ° C. for 1 hour with good stirring, followed by filtration and drying. 12.8 g (24% yield) of (2,2-dimethylpropyl) was obtained.
¹ H-NMR (CDCl ₃ , δ (ppm)): 1.02 (s, 9H), 4.04 (s, 2H), 7.26-7.54 (c, 3H)
¹⁹ F-NMR (CDCl ₃ , δ (ppm)): −135.0 (m, 2F), −136.1 (m, 2F)
Mass spectrum (FD-MS, m / z): 444 (M ⁻¹ )

で示されるスミカエクセルＰＥＳ ３６００Ｐ（住友化学株式会社製；Ｍｗ＝３７，０００、Ｍｎ＝２２，０００）２．７５ｇを用い、亜鉛粉末２．１９ｇ及びＮ−メチル−２−ピロリドン６３．８ｇと混合し、４０℃に調整した。メタンスルホン酸１２．９ｍｇとＮ−メチル−２−ピロリドン０．８５ｇからなる溶液を加え、４０℃で３時間撹拌した。１５℃に冷却後、得られた溶液の水分含量は４７５ｐｐｍ重量部であった。窒素雰囲気下、得られた溶液に第１工程で得られた溶液を混合し、２０℃で１８時間撹拌した。得られたポリアリーレンのＭｗは５０，０００、Ｍｎは２２，０００であった。
得られた反応混合物を２ｍｏｌ／Ｌ塩酸２２６ｇに注ぎ込み析出物を濾過し、再度２ｍｏｌ／Ｌ塩酸８４ｇで浸漬し、濾過して得られたケーキをｐＨが４以上になるまで水洗を繰り返した。洗浄されたケーキにメタノール１５８ｇ加え、１時間還流した後ろ過して乾燥させた。得られた固体にＮ−メチル−２−ピロリドン８５．６ｇと３５重量％塩酸１１．０ｇを加え、１２０℃で２４時間攪拌した。
得られた混合物をアセトン３７３ｇに注ぎ込み、結晶を析出させた後、濾過し、得られたケーキを再度アセトンで洗浄し、塩酸で２回、熱水で５回洗浄し、乾燥することによって、４，４’−ジブロモ−２，５，２’，５’−テトラフルオロ−６，６’−ビフェニルジスルホン酸に由来する構造単位を有する重合体 ２．９８ｇを得た。得られた重合体のＭｗは８．５×１０^４、Ｍｎは６．２×１０^４であり、イオン交換容量は１．４７ｍｅｑ／ｇであった。 [Example 6]
Polymer synthesis (first step)
Under a nitrogen atmosphere, 3.64 g of anhydrous nickel bromide, 2.61 g of 2,2′-bipyridine, and 37.5 g of N-methyl-2-pyrrolidone were mixed and stirred at 65 ° C. for 2 hours. After cooling to 20 ° C., water was added so that the water content was 960 ppm by weight.
(Second step)
4.50 g of 4,4′-dibromo-2,5,2 ′, 5′-tetrafluoro-6,6′-biphenyldisulfonic acid bis (2,2-dimethyl-1-propyl) obtained in Example 3 (10.96 mmol) and the following formula

2.75 g of SUMIKAEXCEL PES 3600P (manufactured by Sumitomo Chemical Co., Ltd .; Mw = 37,000, Mn = 22,000) shown in FIG. And adjusted to 40 ° C. A solution consisting of 12.9 mg of methanesulfonic acid and 0.85 g of N-methyl-2-pyrrolidone was added and stirred at 40 ° C. for 3 hours. After cooling to 15 ° C., the water content of the resulting solution was 475 ppm by weight. Under a nitrogen atmosphere, the solution obtained in the first step was mixed with the obtained solution and stirred at 20 ° C. for 18 hours. Mw of the obtained polyarylene was 50,000 and Mn was 22,000.
The obtained reaction mixture was poured into 226 g of 2 mol / L hydrochloric acid, the precipitate was filtered, dipped again with 84 g of 2 mol / L hydrochloric acid, and the cake obtained by filtration was repeatedly washed with water until the pH became 4 or more. 158 g of methanol was added to the washed cake, refluxed for 1 hour, filtered and dried. To the obtained solid, 85.6 g of N-methyl-2-pyrrolidone and 11.0 g of 35 wt% hydrochloric acid were added, and the mixture was stirred at 120 ° C. for 24 hours.
The obtained mixture was poured into 373 g of acetone to precipitate crystals, and then filtered, and the obtained cake was washed again with acetone, washed twice with hydrochloric acid, washed 5 times with hot water, and dried to give 4 , 4′-Dibromo-2,5,2 ′, 5′-tetrafluoro-6,6′-biphenyldisulfonic acid 2.98 g of a polymer having a structural unit derived from it. Mw of the obtained polymer was 8.5 × 10 ⁴ , Mn was 6.2 × 10 ⁴ , and the ion exchange capacity was 1.47 meq / g.

で示される繰り返し単位から成る含むポリアリーレン１．７ｇを得た。得られた重合体のＭｗは１．２×１０^４、Ｍｎは３．１×１０^３であった。
上記で得られた重合体にＮ−メチル−２−ピロリドン８．８ｇと臭化リチウム１水和物１．４ｇとを加え、１２０℃で１８時間攪拌した。得られた反応混合物を１９％塩酸３４．５ｇに注ぎ込み、析出した固体を１９％塩酸、及び冷水で洗浄した。得られた固体を減圧乾燥することにより下記式

で示される繰り返し単位から成るポリアリーレン１．０ｇを得た（収率５０％）。 [Example 7]
Synthesis of Polymer 3.0 g and 2 ′, 5′-dichloro-2,3,5,6, -tetrafluoro-4-biphenylsulfonic acid (2,2-dimethylpropyl) obtained in Example 4 2.9 g of 2′-bipyridine, 2.4 g of N-methyl-2-pyrrolidone and 21.6 g of tetrahydrofuran were mixed and adjusted to 60 ° C. To this, 4.6 g of nickel (0) bis (cyclooctadiene) was added and a polymerization reaction was performed for 2 hours. The resulting reaction mixture was poured into 86.3 g of methanol, and the precipitated solid was washed with methanol and water. The obtained solid was mixed with 50.8 g of 20% nitric acid, 0.1 g of sodium nitrite was added, and the mixture was stirred at 25 ° C. for 1 hour, and 50.4 g of methanol and 50.4 g of water were added to the filtered solid And stirred at 70 ° C. for 1 hour. The cake obtained by filtration was washed twice with methanol and dried under reduced pressure to obtain the following formula.

1.7 g of polyarylene comprising a repeating unit represented by Mw of the obtained polymer was 1.2 × 10 ⁴ , and Mn was 3.1 × 10 ³ .
To the polymer obtained above, 8.8 g of N-methyl-2-pyrrolidone and 1.4 g of lithium bromide monohydrate were added and stirred at 120 ° C. for 18 hours. The obtained reaction mixture was poured into 34.5 g of 19% hydrochloric acid, and the precipitated solid was washed with 19% hydrochloric acid and cold water. By drying the obtained solid under reduced pressure, the following formula

As a result, 1.0 g of polyarylene comprising the repeating unit represented by the formula (yield 50%) was obtained.

  The present invention can provide a polymer having a novel ion exchange group.

Claims (14)

A polymer having an ion exchange group, wherein the repeating unit having the ion exchange group is composed of 1) polyarylene, 2) both a fluorine group and a sulfo group are directly bonded to the aromatic ring, and 3) the ion exchange capacity is increased. A polymer characterized by being in the range of 3.2 meq / g to 8 meq / g. The repeating unit having an ion exchange group has the formula (1)

(In the formula, w represents an integer of 0 to 2. w ′ represents an integer of 0 to 3. x represents an integer of 0 to 2. y represents an integer of 0 to 3. y ′ represents 0 to 0. Represents an integer of 4. y + y ′ represents an integer of 1 or more, z represents an integer of 0 to 3, z ′ represents an integer of 0 to 4, z + z ′ represents an integer of 1 or more, and z When 'is an integer of 1 or more, x represents an integer of 1 or more, and R ¹ is the same or different and is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 6 to 8 carbon atoms. An aryl group, an aryloxy group having 6 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a cyano group, wherein the alkyl group has 1 to 8 carbon atoms, the alkoxy group has 1 to 8 carbon atoms, the number of carbon atoms A hydrogen atom contained in an aryl group having 6 to 8 carbon atoms, an aryloxy group having 6 to 8 carbon atoms and an acyl group having 2 to 8 carbon atoms is a fluorine atom. , A cyano group, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, and an aryloxy group having 6 to 8 carbon atoms may be substituted. And two R ^{1 s} adjacent to each other at the bonding position may be bonded to form a ring together with the carbon atom on the benzene ring to which the R ¹ is bonded.)
The polymer according to claim 1, which is represented by:   The polymer according to claim 2, wherein x is 0 in the formula (1). The repeating unit having an ion exchange group represented by formula (1) is represented by formula (2).

(Wherein y1 is the same or different and represents an integer of 1 to 3)
The polymer according to claim 2, wherein The repeating unit having an ion exchange group represented by formula (1) is represented by formula (3).

(Wherein y2 and z1 represent an integer of 1 to 4. y2 + z1 represents an integer of 2 to 5)
The polymer according to claim 2, wherein The repeating unit having an ion exchange group represented by formula (1) is represented by formula (4).

(Wherein y2 represents an integer of 1 to 4)
The polymer according to claim 5, which is represented by: A polymer having an ion exchange group, wherein the repeating unit having no ion exchange group is represented by formula (5)

(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 polymer according to any one of claims 1 to 6, which is represented by: A polymer having an ion exchange group, wherein the repeating unit having no ion exchange group is represented by formula (6)

(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; 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 an aryloxy group having 6 to 20 carbon atoms. (It may be 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 from the group).
The polymer according to any one of claims 1 to 6, which is represented by: A dihalosulfo compound represented by the formula (7):

(In the formula, w represents an integer of 0 to 2. w ′ represents an integer of 0 to 3. x represents an integer of 0 to 2. y represents an integer of 0 to 2. y ′ represents 0 to 2. Represents an integer of 4. y + y ′ represents an integer of 1 or more, z represents an integer of 0 to 3, z ′ represents an integer of 0 to 4, z + z ′ represents an integer of 1 or more, and z When 'is an integer of 1 or more, x represents an integer of 1 or more, R ¹ is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, or the number of carbon atoms Represents an aryloxy group having 6 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a cyano group, where an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl having 6 to 8 carbon atoms Group, an aryloxy group having 6 to 8 carbon atoms and an acyl group having 2 to 8 carbon atoms include a fluorine atom, a cyano group, and a carbon number It may be substituted with at least one selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, and an aryloxy group having 6 to 8 carbon atoms, and the bonding positions are adjacent. Two R ¹ may combine to form a ring together with the carbon atom on the benzene ring to which the R ¹ is bonded, m represents 1 or 2, -OM represents -OM ₁ or -O ^- M ₂ ⁺ represent. here, M ₁ is .X representing the cation of .M ₂ ⁺ is an alkali metal cation or ammonium compounds represents an alkyl group having 1 to 20 carbon atoms represents a chlorine atom, a bromine atom or an iodine atom.) The dihalosulfo compound according to claim 9, which is represented by the formula (8).

(Wherein, w represents an integer of 0 to 2, y1 represents an integer of 1 to 3. z represents an integer of 1 to 3. R ¹ represents an alkyl group having 1 to 8 carbon atoms, and 1 to 8 carbon atoms. An alkoxy group, an aryl group having 6 to 8 carbon atoms, an aryloxy group having 6 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a cyano group, wherein the alkyl group having 1 to 8 carbon atoms, the number of carbon atoms A hydrogen atom contained in an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aryloxy group having 6 to 8 carbon atoms, and an acyl group having 2 to 8 carbon atoms includes a fluorine atom, a cyano group, and 1 carbon atom. May be substituted with at least one selected from the group consisting of an alkoxy group having 8 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms and an aryloxy group having 6 to 8 carbon atoms. One of carbons on the benzene ring original to which the R ¹ and R ¹ is attached is bound Together may form a ring.-OM is -OM ₁ or ^-O -. Represents an _{M 2} ⁺ wherein, _{M 1} is an alkyl group having 1 to 20 carbon atoms, _{M 2} ⁺ is an alkali metal cation Alternatively, it represents a cation of an ammonium compound, and X represents a chlorine atom, a bromine atom or an iodine atom.) The dihalosulfo compound according to claim 9 or 10, which is represented by the formula (9).

(Wherein, y1 are the same or different, represents an integer of 1 to 3-OM. Is -OM ₁ or ^-O -. Represents an _{M 2} ^+, where, _{M 1} is an alkyl group having 1 to 20 carbon atoms, (M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound, and X represents a chlorine atom, a bromine atom, or an iodine atom.) The dihalosulfo compound represented by the following formula (10):

(In the formula, y2 represents an integer of _{1 to} 4. -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali. And represents a cation of a metal cation or an ammonium compound, and X represents a chlorine atom, a bromine atom or an iodine atom.) A step of polymerizing a monomer composition containing the dihalosulfo compound according to claim 9, and a group represented by the formula —SO ₂ OM included in the polymer obtained by the polymerization step as a group represented by the formula —SO ₂ OH The manufacturing method of the polymer characterized by including the process to convert. The polymer characterized by including the repeating unit represented by following formula (11).

(In the formula, -OM represents -OM ₁ or -O ^- M ₂ ⁺ . Here, M ₁ represents an alkyl group having 1 to 20 carbon atoms, and M ₂ ⁺ represents an alkali metal cation or a cation of an ammonium compound. W represents an integer of 0 to 2. w ′ represents an integer of 0 to 3. x represents an integer of 0 to 2. y represents an integer of 0 to 3. y ′ represents 0 to 4. Y + y ′ represents an integer of 1 or more, z represents an integer of 0 to 3, z ′ represents an integer of 0 to 4, z + z ′ represents an integer of 1 or more, and z ′ represents In the case of an integer of 1 or more, x represents an integer of 1 or more, R ¹ represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, or 6 to 6 carbon atoms. 8 represents an aryloxy group, an acyl group having 2 to 8 carbon atoms, or a cyano group, wherein alkyl having 1 to 8 carbon atoms , A hydrogen atom contained in an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aryloxy group having 6 to 8 carbon atoms and an acyl group having 2 to 8 carbon atoms is a fluorine atom, a cyano group, It may be substituted with at least one selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, and an aryloxy group having 6 to 8 carbon atoms, and the bonding position thereof. by bonding two adjacent R ¹ together with the carbon atoms on the benzene ring to which the R ¹ are bonded may form a ring.)