JP5962120B2 - Polymer and production method thereof - Google Patents

Description

  The present invention relates to a polymer having a sulfo group or a polymer serving as a precursor thereof. The present invention also relates to a method for producing these polymers.

  A polymer having a sulfo group has been studied as a material for an electrolyte membrane in a polymer electrolyte fuel cell. As this polymer, a perfluoroalkylene polymer represented by Nafion (registered trademark) has been studied for a long time, but there is a problem that it is expensive and has insufficient heat resistance and strength. . In order to solve such problems, polyarylene polymers have been studied in recent years. At that time, in order to obtain an electrolyte membrane having a large ion exchange capacity and excellent proton conductivity, the sulfo group content is reduced. Many things are being considered. For example, Patent Documents 1 and 2 disclose polyarylene polymers having a phenylene group having 2 to 3 sulfo groups as substituents as a structural unit of the main chain.

JP 2010-70750 A JP 2011-190237 A

  When the polyarylene polymer disclosed in Patent Documents 1 and 2 has a large ion exchange capacity, an electrolyte membrane that easily undergoes dimensional change during water absorption swelling may be provided. Accordingly, an object of the present invention is to provide a polyarylene polymer or a polymer serving as a precursor thereof that provides an electrolyte membrane having a large ion exchange capacity and excellent dimensional stability during water absorption swelling.

（Ａ¹〜Ａ⁴は、それぞれ独立に、下記式（１ａ）又は下記式（１ｂ）で表される基を表す。

（Ｒ⁰¹¹は、水素原子又は炭素数１〜２０のアルキル基を表す。前記アルキル基は、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基及び炭素数６〜２０のアリールスルホニル基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。）

（Ｍは、カチオンを表す。前記カチオンは、２価以上のカチオンである場合、前記−Ｏ⁻以外のアニオンと結合している。）
Ｒ⁰⁰¹〜Ｒ⁰⁰⁴は、それぞれ独立に、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のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基又はシアノ基を表す。前記アルキル基、前記アルコキシル基、前記アリール基、前記アリールオキシル基及び前記アシル基は、それぞれ独立に、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基及びシアノ基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。）
Ｍｗ／（α＊１０００）＞２５ （Ｘ） To achieve the above object, the present invention is a polymer having a structural unit represented by the following formula (001) in the main chain, the following _-SO 2 ^A 1 in the _polymer, -SO ^{2 A} 2, The total content α (mmol / g) of —SO ₂ A ³ and —SO ₂ A ⁴ is 2.0 or more, and the α and the weight average molecular weight Mw of the polymer satisfy the relationship of the following formula (X). A polymer is provided.

(A ^{1 to} A ⁴ each independently represents a group represented by the following formula (1a) or the following formula (1b).

(R ⁰¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group is a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. And may have at least one substituent selected from the group consisting of an aryloxyl group, an acyl group having 2 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms.)

(M represents a cation the cation may be a divalent or higher cation, the -O ^-. Is bonded to the other anions.)
R ^{001 to} R ⁰⁰⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl 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 aryloxyl group, a C2-C20 acyl group, or a cyano group is represented. The alkyl group, the alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. It may have at least one substituent selected from the group consisting of ˜20 aryloxyl groups and cyano groups. )
Mw / (α * 1000)> 25 (X)

（Ａ¹〜Ａ⁴は、それぞれ独立に、下記式（１ａ）又は下記（１ｂ）で表される基を表す。

（Ｒ⁰¹¹は、水素原子又は炭素数１〜２０のアルキル基を表す。前記アルキル基は、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基及び炭素数６〜２０のアリールスルホニル基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。）

（Ｍは、カチオンを表す。前記カチオンは、２価以上のカチオンである場合、前記−Ｏ⁻以外のアニオンと結合している。）
Ｒ⁰⁰¹〜Ｒ⁰⁰⁴は、それぞれ独立に、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のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基又はシアノ基を表す。前記アルキル基、前記アルコキシル基、前記アリール基、前記アリールオキシル基及び前記アシル基は、それぞれ独立に、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基及びシアノ基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。Ｘ^１及びＸ²は、それぞれ独立に、塩素原子、臭素原子又はヨウ素原子を表す。）
配位子（Ｌ１）：電子求引性基を有し、３位、６位、３’位及び６’位にそれぞれ水素原子が結合している２，２’−ビピリジン化合物と、電子求引性基を有し、２位及び９位にそれぞれ水素原子が結合している１，１０−フェナントロリン化合物とからなる群から選ばれる少なくとも１つの配位子。
配位子（Ｌ２）：電子供与性基を有し、３位、６位、３’位及び６’位にそれぞれ水素原子が結合している２，２’−ビピリジン化合物と、電子供与性基を有し、２位及び９位にそれぞれ水素原子が結合している１，１０−フェナントロリン化合物とからなる群から選ばれる少なくとも１つの配位子。
配位子（Ｌ３）：２，２’−ビピリジンと、１，１０−フェナントロリンとからなる群から選ばれる少なくとも１つの配位子。 Moreover, this invention is a suitable manufacturing method of the said polymer, Comprising: The aromatic compound (A) represented by following formula (5) is a nickel compound, a metal reducing agent, and the following ligand (L1). ), The following ligand (L2), and a method for producing a polymer that is polymerized in the presence of at least two kinds of ligands selected from the group consisting of the following ligand (L3).

(A ^{1 to} A ⁴ each independently represents a group represented by the following formula (1a) or the following (1b).

(R ⁰¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group is a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. And may have at least one substituent selected from the group consisting of an aryloxyl group, an acyl group having 2 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms.)

(M represents a cation the cation may be a divalent or higher cation, the -O ^-. Is bonded to the other anions.)
R ^{001 to} R ⁰⁰⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl 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 aryloxyl group, a C2-C20 acyl group, or a cyano group is represented. The alkyl group, the alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. It may have at least one substituent selected from the group consisting of ˜20 aryloxyl groups and cyano groups. X ¹ and X ² each independently represent a chlorine atom, a bromine atom or an iodine atom. )
Ligand (L1): a 2,2′-bipyridine compound having an electron withdrawing group and having hydrogen atoms bonded to the 3-position, 6-position, 3′-position and 6′-position, respectively, and electron-withdrawing And at least one ligand selected from the group consisting of 1,10-phenanthroline compounds each having a functional group and having hydrogen atoms bonded to the 2-position and the 9-position, respectively.
Ligand (L2): 2,2′-bipyridine compound having an electron-donating group and having hydrogen atoms bonded to the 3-position, 6-position, 3′-position and 6′-position, respectively, and an electron-donating group And at least one ligand selected from the group consisting of 1,10-phenanthroline compounds each having a hydrogen atom bonded to the 2-position and the 9-position.
Ligand (L3): At least one ligand selected from the group consisting of 2,2′-bipyridine and 1,10-phenanthroline.

  The polymer of the present invention provides an electrolyte membrane having a large ion exchange capacity and excellent dimensional stability during water absorption swelling.

（Ａ¹〜Ａ⁴は、それぞれ独立に、下記式（１ａ）又は下記式（１ｂ）で表される基を表す。

（Ｒ⁰¹¹は、水素原子又は炭素数１〜２０のアルキル基を表す。前記アルキル基は、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基及び炭素数６〜２０のアリールスルホニル基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。）

（Ｍは、カチオンを表す。前記カチオンは、２価以上のカチオンである場合、前記−Ｏ⁻以外のアニオンと結合している。）
Ｒ⁰⁰¹〜Ｒ⁰⁰⁴は、それぞれ独立に、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のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基又はシアノ基を表す。前記アルキル基、前記アルコキシル基、前記アリール基、前記アリールオキシル基及び前記アシル基は、それぞれ独立に、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基及びシアノ基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。）
Ｍｗ／（α＊１０００）＞２５ （Ｘ） The polymer of the present invention is a polymer having a structural unit represented by the following formula (001) in the main chain, the following _-SO 2 ^A 1 in the _{^{polymer, -SO 2 A 2, -SO 2}} A The total content α (mmol / g) of ³ and —SO ₂ A ⁴ exceeds 2.0, and the α and the weight average molecular weight Mw of the polymer satisfy the relationship of the following formula (X). .

(A ^{1 to} A ⁴ each independently represents a group represented by the following formula (1a) or the following formula (1b).

(R ⁰¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group is a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. And may have at least one substituent selected from the group consisting of an aryloxyl group, an acyl group having 2 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms.)

(M represents a cation the cation may be a divalent or higher cation, the -O ^-. Is bonded to the other anions.)
R ^{001 to} R ⁰⁰⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl 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 aryloxyl group, a C2-C20 acyl group, or a cyano group is represented. The alkyl group, the alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. It may have at least one substituent selected from the group consisting of ˜20 aryloxyl groups and cyano groups. )
Mw / (α * 1000)> 25 (X)

In the present invention, the weight average molecular weight (Mw) of the polymer and the total content α (mmol / mmol) of the —SO ₂ A ¹ , —SO ₂ A ² , —SO ₂ A ³ and —SO ₂ A ^{4 in} the polymer. g) is calculated as follows.
[Measurement of weight average molecular weight of polymer]
Analysis is performed by gel permeation chromatography (hereinafter abbreviated as GPC) (analysis conditions are as follows), and a weight average molecular weight (Mw) in terms of polystyrene is calculated from the analysis result.
GPC measuring device: L2000 made by Hitachi High-Tech
RI detector: RI-101 manufactured by SHODEX
Light scattering detector: Wyatt miniDawn
Column: Asahipak GF-7M HQ manufactured by SHODEX
Column temperature: 60 ° C
Flow rate: 0.3 mL / min
Mobile phase: 10 mM tetrabutylammonium bromide NMP / DMSO = 1/1 solution

[Measurement of Total Content α (mmol / g) of —SO ₂ A ¹ , —SO ₂ A ² , —SO ₂ A ³ and —SO ₂ A ^{4 in} the Polymer]
Polymer to be subjected to measurement, the ^{_{-SO 2 A 1, -SO 2 A}} 2, if _-SO 2 ^{A 3} and _-SO 2 ^{A 4} is all sulfo group (-SO ₂ -OH), a polymer A film formed by a solution casting method to form a polymer film, the formed polymer film is cut to an appropriate weight, and the dry weight of the cut polymer film is set to a heating temperature of 105 ° C. Measure using a meter. Next, after immersing this membrane in 5 mL of 0.1 mol / L sodium hydroxide aqueous solution, 50 mL of ion-exchanged water is further added and left for 2 hours. Thereafter, 0.1 mol / L hydrochloric acid is gradually added to the solution in which the polymer film is immersed to perform titration to obtain a neutralization point, and the dry weight of the used polymer film (the cut polymer film). From the amount of hydrochloric acid required for neutralization, the total content α of the above-mentioned —SO ₂ A ¹ , —SO ₂ A ² , —SO ₂ A ³ and —SO ₂ A ^{4 in} the polymer is calculated. When —SO ₂ A ¹ , —SO ₂ A ² , —SO ₂ A ³ and —SO ₂ A ⁴ are all sulfo groups (—SO ₂ —OH), the total content α represents an ion exchange capacity.
When A ^{1 to} A ⁴ are groups represented by the formula (1a) and R ⁰¹¹ is an alkyl group having 1 to 20 carbon atoms, they are represented by —SO ₂ A ¹ to —SO ₂ A ^4. The group is a precursor group of a sulfo group. In this case, the weight of the polymer to be subjected to measurement is measured in advance, followed by hydrolysis, etc., to convert —SO ₂ A ¹ to —SO ₂ A ⁴ into sulfo groups (—SO ₂ —OH). Such hydrolysis treatment is performed according to the method described in JP-A-2007-270118. After conversion to sulfo groups, in the same manner as described above, from the amount of hydrochloric acid required to neutralize the dry weight of the polymer, the _-SO 2 ^A 1 in the ^{_{polymer, -SO 2 A 2, -SO 2}} A ³ and the total content α of —SO ₂ A ⁴ are calculated.
In the case where A ^{1 to} A ⁴ are groups represented by the formula (1b) and M is a cation, a strong acid such as sulfuric acid can be used to convert —SO ₂ A ¹ to —SO ₂ A ⁴ to a sulfo group (— SO ₂ —OH). After conversion to sulfo groups, in the same manner as described above, from the amount of hydrochloric acid required to neutralize the dry weight of the polymer, the _-SO 2 ^A 1 in the ^{_{polymer, -SO 2 A 2, -SO 2}} A ³ and the total content α of —SO ₂ A ⁴ are calculated.

  The Mw is 10,000 to 10,000,000, more preferably 100,000 to 5,000,000, and further preferably 150,000 to 3,000,000.

The α (mmol / g) is preferably larger than 2.0 (mmol / g). When α is larger than 2.0 (mmol / g), the —SO ₂ A ¹ , —SO ₂ A ² , —SO ₂ A ³ and —SO ₂ A ⁴ are converted into a sulfo group (—SO ₂ —OH). In this case, proton conductivity becomes higher and functions as a polymer electrolyte for a fuel cell are more excellent, which is preferable. Α (mmol / g) is more preferably 3.0 (mmol / g) or more. . On the other hand, when α is 7.0 (mmol / g) or less, the water resistance becomes better, and it is more preferable that it is 6.0 (mmol / g) or less. The α (mmol / g) can be easily adjusted by the charging ratio of the reaction raw materials.

In the formula (001), when all of —SO ₂ A ¹ , —SO ₂ A ² , —SO ₂ A ³ and —SO ₂ A ⁴ are groups other than a sulfo group (—SO ₂ —OH), The structural unit represented by the formula (001) does not exhibit proton conductivity. However, the groups represented by —SO ₂ A ¹ , —SO ₂ A ² , —SO ₂ A ³ and —SO ₂ A ⁴ other than such a sulfo group can be easily converted into a sulfo group. A polymer having such a precursor group is included in the scope of the present invention as a polymer precursor exhibiting excellent proton conductivity.

The reason why the polymer electrolyte membrane containing the polymer satisfying the relationship of the formula (X) and having the structural unit represented by the formula (001) in the main chain exhibits excellent dimensional stability at the time of water absorption swelling is as follows. Not necessarily obvious. However, the present inventor estimates as follows.
When the weight average molecular weight is larger than a certain ratio with respect to the ion exchange capacity, the entanglement of the polymer chains and the interaction between the polymer chains act effectively, and the movement of the polymer chains during water absorption can be suppressed. Moreover, since it has the structural unit represented by the said Formula (001), since the weight fraction of a hydrophobic part becomes comparatively high, the dimensional change of the whole film | membrane can be suppressed as a result.

  When Mw / (α * 1000) = Q, Q> 25, Q ≧ 40 is preferable, and Q ≧ 50 is more preferable.

（Ｒ⁰¹¹は、水素原子又は炭素数１〜２０のアルキル基を表す。前記アルキル基は、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基及び炭素数６〜２０のアリールスルホニル基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。）

（Ｍは、カチオンを表す。前記カチオンは、２価以上のカチオンである場合、前記−Ｏ⁻以外のアニオンと結合している。） A ^{1 to} A ⁴ each independently represent a group represented by the following formula (1a) or the following formula (1b).

(R ⁰¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group is a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. And may have at least one substituent selected from the group consisting of an aryloxyl group, an acyl group having 2 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms.)

(M represents a cation the cation may be a divalent or higher cation, the -O ^-. Is bonded to the other anions.)

  Here, the “main chain” refers to the longest chain forming a polymer. This chain is composed of carbon atoms bonded to each other by a covalent bond. In this case, this chain may be interrupted by a nitrogen atom, an oxygen atom, a sulfur atom, or the like.

Hereinafter, the groups represented by the formula (1a) and the formula (1b) will be described with specific examples.
When A ^{1 to} A ⁴ are a group represented by the formula (1a) and R ⁰¹¹ is a hydrogen atom, the group represented by —SO ₂ A ¹ to —SO ₂ A ⁴ has a proton conductivity. The resulting sulfo group (—SO ₂ —OH) is expressed. If R ⁰¹¹ is an alkyl group having 1 to 20 carbon _atoms, a group represented by _{^{-SO 2 A 1 ~-SO 2}} A 4 is a precursor group of a sulfo group, for example easily sulfo group by hydrolysis treatment or the like Can be converted to This hydrolysis treatment will be described later.
In addition, when A ^{1 to} A ⁴ are a group represented by the formula (1b), a group represented by —SO ₂ A ¹ to —SO ₂ A ⁴ is a cation and a salt in the form of a salt. The sulfo group in a salt form as described above can be easily converted into a sulfo group by a known ion exchange treatment.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and 2,2-dimethylpropyl. Group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, 2-methylpentyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group Group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.

  The alkyl group includes a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and 6 to 20 carbon atoms. And may have at least one substituent selected from the group consisting of arylsulfonyl groups.

  Examples of the alkoxyl group having 1 to 20 carbon atoms include methoxyl group, ethoxyl group, propoxyl group, isopropoxyl group, butoxyl group, sec-butoxyl group, tert-butoxyl group, pentyloxyl group, 2,2-dimethyl group. Propoxyl group, hexyloxyl group, cyclohexyloxyl group, heptyloxyl group, octyloxyl group, nonyloxyl group, decyloxyl group, undecyloxyl group, dodecyloxyl group, tridecyloxyl group, tetradecyloxyl group, pentadecyloxyl group, Examples include a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms such as a hexadecyloxyl group, a heptadecyloxyl group, an octadecyloxyl group, a nonadecyloxyl group, and an icosyloxyl group. 6 alkoxy Group, more preferably a linear or branched alkoxyl group having 1 to 6 carbon atoms.

  Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 4-methylphenyl group, a 2-methylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 3-phenanthryl group, and a 2-anthryl group. It is done.

  Examples of the aryloxyl group having 6 to 20 carbon atoms include phenoxyl group, 4-methylphenoxyl group, 2-methylphenoxyl group, 1-naphthyloxyl group, 2-naphthyloxyl group, and 3-phenanthryloxyl. And those composed of an aryl group having 6 to 20 carbon atoms such as a 2-anthryloxyl group and an oxygen atom.

  Examples of the acyl group having 2 to 20 carbon atoms include aliphatic or aromatic having 2 to 20 carbon atoms such as acetyl group, propionyl group, butyryl group, isobutyryl group, benzoyl group, 1-naphthoyl group, and 2-naphthoyl group. An acyl group is mentioned.

  Examples of the arylsulfonyl group having 6 to 20 carbon atoms include a phenylsulfonyl group and a p-toluenesulfonyl group.

The cation is preferably a metal ion or an ammonium ion.
As the metal ion, an alkali metal ion or an alkaline earth metal ion is preferable because it can be easily converted into a sulfo group by an ion exchange means. Examples of alkali metal ions include lithium ions, sodium ions, and potassium ions. Examples of alkaline earth metal ions include magnesium ions, calcium ions, barium ions and the like. However, since the alkaline earth metal ions are divalent cations, wherein -O ^- is bonded to the other anions. Usually, 1 mol of alkaline earth metal ion is ionically bonded to 2 mol of sulfo group and is electrostatically equivalent, or 1 mol of sulfo group and other monovalent anion 1 per mol of alkaline earth metal ion. Mole is ionically bonded and becomes electrostatically equivalent. Such other monovalent anions include alkyl sulfonate anions, aryl sulfonate anions, alkyl sulfate anions, aryl sulfate anions, alkyl carboxylate anions, aryl carboxylate anions, chloro anions, bromo anions, iodo anions, hydroxylation. For example, product ions.

  As an ammonium ion, any of a primary ammonium ion, a secondary ammonium ion, a tertiary ammonium ion, or a quaternary ammonium ion may be sufficient. Primary ammonium ions include methylammonium ion, ethylammonium ion, 1-propylammonium ion, 2-propylammonium ion, n-butylammonium ion, 2-butylammonium ion, 1-pentylammonium ion and 2-pentylammonium ion. Ion, 3-pentylammonium ion, neopentylammonium ion, cyclopentylammonium ion, 1-hexylammonium ion, 2-hexylammonium ion, 3-hexylammonium ion, cyclohexylammonium ion and the like. Secondary ammonium ions include dimethyl ammonium ion, diethyl ammonium ion, di-1-propyl ammonium ion, di-2-propyl ammonium ion, di-n-butyl ammonium ion, di-2-butyl ammonium ion, di- 1-pentylammonium ion, di-2-pentylammonium ion, di-3-pentylammonium ion, dineopentylammonium ion, dicyclopentylammonium ion, di-1-hexylammonium ion, di-2-hexylammonium ion, di -3-hexylammonium ion, ammonium ion and the like. Tertiary ammonium ions include trimethylamine, triethylamine, tri-1-propylammonium ion, tri-2-propylammonium ion, tri-n-butylammonium ion, tri-2-butylammonium ion, and tri-1-pentylammonium ion. Ion, tri-2-pentylammonium ion, tri-3-pentylammonium ion, trineopentylammonium ion, tricyclopentylammonium ion, tri-1-hexylammonium ion, tri-2-hexylammonium ion, tri-3-hexyl Examples include ammonium ions and ammonium ions. As quaternary ammonium ions, tetramethylammonium ion, tetraethylammonium ion, tetra (1-propyl) ammonium ion, tetra (2-propyl) ammonium ion, tetra (1-butyl) ammonium ion, tetra (2-butyl) Ammonium ion, tetra (1-pentyl) ammonium ion, tetra (2-pentylamine) ammonium ion, tetra (3-pentyl) ammonium ion, tetra (neopentyl) ammonium ion, tetra (1-cyclopentyl) ammonium ion, tetra (1 -Hexyl) ammonium ion, tetra (2-hexyl) ammonium ion, tetra (3-hexylamine) ammonium ion, tetra (cyclohexyl) ammonium ion and the like. It is.

When the group represented by ^{_{-SO 2 A 1 ~-SO 2}} A 4 is a precursor group of a sulfonic acid, i.e., A ¹ to A ⁴ is a group represented by the formula (1a), R ¹¹ is If an alkyl group, a group represented by such ^{_{-SO 2 a 1 ~-sO 2}} a 4 is readily tendency converted into sulfo groups by hydrolysis treatment or the like. Such hydrolysis treatment is performed according to the method described in JP-A-2007-270118.
_Further, the structural unit group represented by _{^{-SO 2 A 1 ~-SO 2}} A 4 is represented by the formula (001) is a precursor group of a sulfonic acid, in the preparation of the polymers of the present invention described below, the formula ( There is also an advantage that the structural unit represented by (001) can be easily introduced.

In the formula (001), R ^{001 to} R ⁰⁰⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents an aryloxyl group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group. The alkyl group, the alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. It may have at least one substituent selected from the group consisting of ˜20 aryloxyl groups and cyano groups.

  Here, as an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, and an acyl group having 2 to 20 carbon atoms, , Examples similar to those described above are exemplified.

R ^{001 to} R ⁰⁰⁴ are preferably a hydrogen atom, a fluorine atom, an alkoxyl group, an aryl group, an aryloxyl group, or a cyano group, and more preferably a hydrogen atom. It is particularly preferable that all of R ^{001 to} R ⁰⁰⁴ are hydrogen atoms.

A ^{1 to} A ⁴ may be the same or different, but are preferably the same for ease of production.
It is preferable that at least one of preferable A ^{1 to} A ⁴ is a group represented by the formula (1a), and R ⁰¹¹ is a hydrogen atom. In view of ease of production, two or more of A ^{1 to} A ⁴ are groups represented by the formula (1a), and R ⁰¹¹ is more preferably a hydrogen atom, and A ^{1 to} A ⁴ Is more preferably a group represented by the formula (1a), and R ⁰¹¹ is more preferably a hydrogen atom.

  The polymer of the present invention has a water resistance when a copolymer comprising a structural unit represented by the formula (001) having an ion exchange group and a structural unit having no ion exchange group is used as a polymer electrolyte membrane. And the mechanical strength tends to be excellent. The copolymerization mode of these two kinds of structural units may be any of random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization, preferably random copolymerization, block copolymerization, and graft copolymerization. Random copolymerization and block copolymerization are preferred, and block copolymerization is particularly preferred. A combination of these copolymerization modes may be used.

（Ａｒ⁰⁰⁰は、２価の芳香族基を表す。前記芳香族基は、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基及びシアノ基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。前記アルキル基、前記アルコキシル基、前記アリール基、前記アリールオキシル基及び前記アシル基は、それぞれ独立に、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基及びシアノ基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。） As the structural unit having no ion exchange group, a structural unit represented by the following formula (002) is preferable. The structural unit represented by the following formula (002) is preferably a polymer having a main chain in the main chain.

(Ar ⁰⁰⁰ represents a divalent aromatic group. The aromatic group includes a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It may have at least one substituent selected from the group consisting of an aryloxyl group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and a cyano group, the alkyl group, the alkoxyl group, and the aryl. Group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms and a cyano group. It may have at least one substituent selected from the group consisting of:

In the formula (002), Ar ⁰⁰⁰ represents a divalent aromatic group. Here, the divalent aromatic group is a residue obtained by removing two hydrogen atoms from an aromatic compound. Hereinafter, the term “divalent aromatic group” is used in the same sense. Examples of the aromatic ring contained in the aromatic compound include aromatic hydrocarbon rings such as benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, and phenanthrene ring, aromatic rings such as thiophene ring, pyrrole ring, and pyridine ring. Heterocycles are mentioned. 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.

  The aromatic group includes a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. It may have at least one substituent selected from the group consisting of 20 acyl groups and cyano groups. The alkyl group, the alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. It may have at least one substituent selected from the group consisting of ˜20 aryloxyl groups and cyano groups. As the alkyl group having 1 to 20 carbon atoms, the alkoxyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aryloxyl group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms, The thing similar to what was done is illustrated.

Further, when the divalent aromatic group represented by Ar ⁰⁰⁰ has an acyl group, the two structural units having the acyl group are adjacent to each other, and the acyl groups in the two structural units are bonded to each other, In this way, after the acyl groups are bonded to each other, a rearrangement reaction may occur. In addition, it is possible to confirm, for example, by measurement of ¹³ C-nuclear magnetic resonance spectrum whether or not such a reaction that the substituents on the aromatic ring are bonded to each other or a rearrangement reaction is generated after the bonding is generated. it can.

Here, a suitable thing is illustrated about the structural unit represented by said Formula (002).

なお、これらの構造単位の例示において、「−Ｐｈ」はフェニル基を表す。

In the examples of these structural units, “-Ph” represents a phenyl group.

In the present invention, a suitable polymer electrolyte includes a structural unit having an ion exchange group having a structural unit represented by the following formula (001a), and a structural unit represented by the above formulas (002a) to (002s). And having a structural unit having no ion exchange group. Particularly preferred combinations of structural units having an ion exchange group and structural units having no ion exchange group include combinations of structural units of (001a) and (002a), (001a) and (002r).

  The polymer of the present invention is preferably a block copolymer having a block having an ion exchange group and a block having substantially no ion exchange group. As a particularly preferred copolymer, a block mainly composed of a structural unit represented by the formula (001) having an ion exchange group (block having an ion exchange group) and a block mainly composed of a structural unit not having an ion exchange group (ion Block having substantially no exchange group).

In the present invention, the “block copolymer” is a polymer having a molecular structure in which a polymer having an ion exchange group and a polymer having substantially no ion exchange group are linked by a covalent bond to form a long chain. Say. In the present invention, the polymer is referred to as “block”. What is a block?
Three or more repeats having the same skeleton are connected. Preferably, 5 or more of 1 type of repeating units are connected. Here, the skeleton means a main chain constituting a polymer and containing no substituent.

Here, the “block having an ion-exchange group” means that the ion-exchange group is a block containing an average of 0.5 or more per structural unit constituting the block. It is more preferable that an average of 1.0 or more per one is included.
On the other hand, “a block having substantially no ion exchange group” means that the ion exchange group is a block having an average of less than 0.5 per structural unit constituting the block, The average per unit is preferably 0.1 or less, and more preferably 0.05 or less on average.
Typically, a block copolymer in a form in which a block having an ion exchange group and a block having substantially no ion exchange group are bonded by a direct bond or bonded by an appropriate atom or atomic group. is there.

（Ａｒ^１〜Ａｒ^４は、それぞれ独立に、２価の芳香族基を表す。前記芳香族基は、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基及びシアノ基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。前記アルキル基、前記アルコキシル基、前記アリール基、前記アリールオキシル基及び前記アシル基は、それぞれ独立に、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基及びシアノ基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。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す。ａ、ｂ及びｃは、それぞれ独立に、０又は１を表す。ｈは、２以上の整数を表す。） It is preferable that the block having substantially no ion exchange group has a structure represented by the following formula (003) in the main chain.

(Ar ^{1 to} Ar ⁴ each independently represents a divalent aromatic group. The aromatic group includes a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, and a carbon number. The alkyl group may have at least one substituent selected from the group consisting of an aryl group having 6 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and a cyano group. , The alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl 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. aryloxyl and good .Y ¹ and Y ² have at least one substituent selected from the group consisting of cyano groups, each independently, a single bond, a carbonyl group, sulfo Group, isopropylidene group, .Z ¹ and ^{Z 2} represents a hexafluoroisopropylidene group or a fluorene-9,9-diyl group, each independently, .a representing an oxygen atom or a sulfur atom, b and c, Each independently represents 0 or 1. h represents an integer of 2 or more.)

  a, b and c each independently represents 0 or 1; h is an integer greater than or equal to 2, Preferably, the integer of the range of 2-200, etc. can be mentioned, for example, More preferably, the integer of the range of 5-200, etc. can be mentioned, for example.

Ar ^{1 to} Ar ⁴ each independently represents a divalent aromatic group. The aromatic group includes a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. It may have at least one substituent selected from the group consisting of 20 acyl groups and cyano groups. The alkyl group, the alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. It may have at least one substituent selected from the group consisting of ˜20 aryloxyl groups and cyano groups. As the alkyl group having 1 to 20 carbon atoms, the alkoxyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aryloxyl group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms, The thing similar to what was done is illustrated.

Y ¹ and Y ² each independently represent a single bond, a carbonyl group, a sulfonyl group, an isopropylidene group, a hexafluoroisopropylidene group, or a fluorene-9,9-diyl group. Z ⁰⁰¹ and Z ⁰⁰² each independently represent an oxygen atom or a sulfur atom, preferably an oxygen atom.

  Examples of the weight average formula weight in terms of polystyrene of the structure represented by the formula (003) include, for example, a range of 1,000 to 2,000,000, and preferably, for example, 1,000 to The range of 500,000 can be raised. Examples of preferable weight average formula 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 2,000,000. Preferably, the range of 2,000-1,000,000 etc. can be mentioned, for example, More preferably, the range of 3,000-800,000 etc. are mentioned, for example.

  Specific examples of the structure represented by the formula (003) include structures represented by the following formulas (003a) to (003z). In the following formulae, nn represents the same meaning as described above, and specifically includes, for example, a range of 2 to 200, preferably a range of 5 to 200, and the like. The polystyrene-converted weight average formula amount of the structural unit represented by the formula (003) can include, for example, at least 1,000, and preferably includes, for example, at least 2,000. More preferable examples include at least 3,000.

  The introduction amount of ion exchange groups in the entire polymer of the present invention is preferably larger than 2.0 (meq / g) in terms of ion exchange capacity. When the ion exchange capacity is larger than 2.0 (meq / g), the proton conductivity becomes higher and the function as a polymer electrolyte for a fuel cell is more excellent, and preferably 3.0 (meq / g) or more. More preferably. On the other hand, when the ion exchange capacity indicating the amount of introduced ion exchange groups is 7.0 meq / g or less, the water resistance is preferably improved, and more preferably 6.0 (meq / g) or less.

  As a method for measuring the ion exchange capacity, a polymer to be measured is formed into a polymer film by a solution casting method, and the formed polymer film is cut to an appropriate weight, and the cut polymer film Is measured using a halogen moisture meter set at a heating temperature of 105 ° C. Next, after immersing this membrane in 5 mL of a 0.1 mol / L sodium hydroxide aqueous solution, 50 mL of ion-exchanged water is further added and left for 2 hours. Thereafter, 0.1 mol / L hydrochloric acid is gradually added to the solution in which the polymer film is immersed to perform titration to obtain a neutralization point, and the dry weight of the used polymer film (the cut polymer film). From the amount of hydrochloric acid required for neutralization, the ion exchange capacity of the polymer is determined.

The “ion exchange group” represents a group related to ion exchange. Examples of the ion exchange group include a phosphone group (—PO ₃ H ₂ ), a carboxyl group (—COOH), a sulfo group (—SO ₃ H), and a sulfonimide group (—SO ₂ —NH—SO ₂ —R. R represents a monovalent substituent such as an alkyl group or an aryl group.), Phenolic hydroxyl group (—OH), hydroxyl group (—OH), mercapto group (—SH), primary amino group (—NH ₂ ), two A quaternary amino group (—NHR, R is as defined above), a tertiary amino group (—NRR ′, R is as defined above), and a quaternary ammonium group (—N ⁺ RR′R ′ ′). R is as defined above), and nitrogen-containing heterocyclic groups such as pyridine, pyrrole and imidazole.

In the present invention, a suitable polymer electrolyte is any one of a block having an ion exchange group having a structural unit represented by the following formula (001a) and a structure represented by the above formulas (003a) to (003z). It has the block which does not have an ion exchange group which has the above substantially. In addition, a block having an ion exchange group having a structural unit represented by (001a) and any one or more of structural units represented by the formulas (002a) to (002s), and the formula (003a) to A polymer electrolyte having a block substantially free of ion-exchange groups having any one or more of the structures represented by (003z) is also suitable. Further preferred combinations of structural units having ion exchange groups and structures not having ion exchange groups include the combinations shown in <004a> to <004z> in Table 2 below.

  More preferably, <004a>, <004b>, <004f>, <004h>, <004i>, <004k>, <004l>, <004m>, <004n>, and more preferably <004a>, <004h>, <004i>, <004l>, <004m> or <004n>, particularly preferably <004a>, <004l>, <004m> or <004n>, <004a>, <004l> <004m> is more particularly preferable.

  The content of the block having substantially no ion exchange group in the polymer having the block having ion exchange group and the block having substantially no ion exchange group is, for example, 5% by weight. As mentioned above, the range of 95 weight% or less etc. can be mentioned, Preferably, the range of 10 weight% or more and 70 weight% or less etc. are mentioned, for example.

（Ａ¹〜Ａ⁴は、それぞれ独立に、下記式（１ａ）又は下記（１ｂ）で表される基を表す。

（Ｒ⁰¹¹は、水素原子又は炭素数１〜２０のアルキル基を表す。前記アルキル基は、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基及び炭素数６〜２０のアリールスルホニル基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。）

（Ｍは、カチオンを表す。前記カチオンは、２価以上のカチオンである場合、前記−Ｏ⁻以外のアニオンと結合している。）
Ｒ⁰⁰¹〜Ｒ⁰⁰⁴は、それぞれ独立に、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のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基又はシアノ基を表す。前記アルキル基、前記アルコキシル基、前記アリール基、前記アリールオキシル基及び前記アシル基は、それぞれ独立に、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基及びシアノ基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。Ｘ^１及びＸ²は、それぞれ独立に、塩素原子、臭素原子又はヨウ素原子を表す。） Next, a preferred method for producing a polymer of the present invention will be described.
Examples of the polymerization method for obtaining the present polymer include a method of polymerizing the aromatic compound (A) represented by the following formula (5) in the presence of a nickel compound.

(A ^{1 to} A ⁴ each independently represents a group represented by the following formula (1a) or the following (1b).

(R ⁰¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group is a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. And may have at least one substituent selected from the group consisting of an aryloxyl group, an acyl group having 2 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms.)

(M represents a cation the cation may be a divalent or higher cation, the -O ^-. Is bonded to the other anions.)
R ^{001 to} R ⁰⁰⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl 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 aryloxyl group, a C2-C20 acyl group, or a cyano group is represented. The alkyl group, the alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. It may have at least one substituent selected from the group consisting of ˜20 aryloxyl groups and cyano groups. X ¹ and X ² each independently represent a chlorine atom, a bromine atom or an iodine atom. )

Examples of the nickel compound include zero-valent nickel compounds such as nickel (0) bis (cyclooctadiene), nickel (0) (ethylene) bis (triphenylphosphine), nickel (0) tetrakis (triphenylphosphine), and halogenated compounds. Nickel (eg, nickel fluoride, nickel chloride, nickel bromide, nickel iodide), nickel carboxylate (eg, nickel formate, nickel acetate), nickel sulfate, nickel carbonate, nickel nitrate, nickel acetylacetonate, (dimethoxy Examples thereof include divalent nickel compounds such as ethane) nickel chloride, and preferably nickel (0) bis (cyclooctadiene) and nickel halide.
As usage-amount of a nickel compound, the range etc. of 0.001-5 mol are mentioned with respect to 1 mol of all the aromatic compounds which participate in reaction, for example.

  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. In the case of using a nitrogen-containing bidentate ligand, from the viewpoint of increasing Mw, for example, a range of 0.2 to 2 mol can be mentioned with respect to 1 mol of the nickel compound, preferably For example, the range of 1-1.5 mol is mentioned.

  When polymerizing using a divalent nickel compound as a catalyst, it is preferable to use a metal reducing agent in combination. The metal reducing agent means a metal that can reduce divalent nickel to zero-valent nickel. Specifically, zinc, magnesium, manganese, aluminum, sodium, etc. are mentioned, zinc, magnesium, and manganese are preferable, and zinc is more preferable. Usually, a commercially available metal reducing agent is used. Examples of the properties of the metal reducing agent include powders and chips. As a usage-amount in the case of using a metal reducing agent, the range of 0.5-10 mol etc. can be mentioned with respect to 1 mol of all the aromatic compounds which participate in reaction from a viewpoint of enlarging Mw. .

（Ａ¹〜Ａ⁴は、それぞれ独立に、下記式（１ａ）又は下記（１ｂ）で表される基を表す。

（Ｒ⁰¹¹は、水素原子又は炭素数１〜２０のアルキル基を表す。前記アルキル基は、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基及び炭素数６〜２０のアリールスルホニル基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。）

（Ｍは、カチオンを表す。前記カチオンは、２価以上のカチオンである場合、前記−Ｏ⁻以外のアニオンと結合している。）
Ｒ⁰⁰¹〜Ｒ⁰⁰⁴は、それぞれ独立に、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のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基又はシアノ基を表す。前記アルキル基、前記アルコキシル基、前記アリール基、前記アリールオキシル基及び前記アシル基は、それぞれ独立に、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基及びシアノ基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。Ｘ^１及びＸ²は、それぞれ独立に、塩素原子、臭素原子又はヨウ素原子を表す。）
配位子（Ｌ１）：電子求引性基を有し、３位、６位、３’位及び６’位にそれぞれ水素原子が結合している２，２’−ビピリジン化合物と、電子求引性基を有し、２位及び９位にそれぞれ水素原子が結合している１，１０−フェナントロリン化合物とからなる群から選ばれる少なくとも１つの配位子。
配位子（Ｌ２）：電子供与性基を有し、３位、６位、３’位及び６’位にそれぞれ水素原子が結合している２，２’−ビピリジン化合物と、電子供与性基を有し、２位及び９位にそれぞれ水素原子が結合している１，１０−フェナントロリン化合物とからなる群から選ばれる少なくとも１つの配位子。
配位子（Ｌ３）：２，２’−ビピリジンと、１，１０−フェナントロリンとからなる群から選ばれる少なくとも１つの配位子。 Next, a particularly preferable method for producing the polymer of the present invention will be described.
In the present invention, in order to obtain a polymer satisfying Q ≧ 50, the aromatic compound (A) represented by the following formula (5) is converted into a nickel compound, a metal reducing agent, the following ligand (L1), The polymerization is preferably performed in the presence of at least two kinds of ligands selected from the group consisting of the following ligand (L2) and the following ligand (L3).

(A ^{1 to} A ⁴ each independently represents a group represented by the following formula (1a) or the following (1b).

(R ⁰¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group is a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. And may have at least one substituent selected from the group consisting of an aryloxyl group, an acyl group having 2 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms.)

(M represents a cation the cation may be a divalent or higher cation, the -O ^-. Is bonded to the other anions.)
R ^{001 to} R ⁰⁰⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl 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 aryloxyl group, a C2-C20 acyl group, or a cyano group is represented. The alkyl group, the alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. It may have at least one substituent selected from the group consisting of ˜20 aryloxyl groups and cyano groups. X ¹ and X ² each independently represent a chlorine atom, a bromine atom or an iodine atom. )
Ligand (L1): a 2,2′-bipyridine compound having an electron withdrawing group and having hydrogen atoms bonded to the 3-position, 6-position, 3′-position and 6′-position, respectively, and electron-withdrawing And at least one ligand selected from the group consisting of 1,10-phenanthroline compounds each having a functional group and having hydrogen atoms bonded to the 2-position and the 9-position, respectively.
Ligand (L2): 2,2′-bipyridine compound having an electron-donating group and having hydrogen atoms bonded to the 3-position, 6-position, 3′-position and 6′-position, respectively, and an electron-donating group And at least one ligand selected from the group consisting of 1,10-phenanthroline compounds each having a hydrogen atom bonded to the 2-position and the 9-position.
Ligand (L3): At least one ligand selected from the group consisting of 2,2′-bipyridine and 1,10-phenanthroline.

Preferable specific examples of A ^{1 to} A ⁴ in the formula (5) include those similar to A ^{1 to} A ⁴ in the formula (001), respectively, and preferable ones are also the same. Preferred specific examples of the formula (1a) and the formula (1b) in the formula (5) include those similar to the formula (1a) and the formula (1b) in the formula (001), respectively. The preferred ones are the same. Preferable specific examples of R ^{001 to} R ⁰⁰⁴ in the formula (5) are the same as those of R ^{001 to} R ⁰⁰⁴ in the formula (001), and preferable examples are also the same. However, R ^{001 to} R ⁰⁰⁴ in the formula (5) are preferably atoms or groups other than (g1) or atoms or groups other than (h1).

Here, (g1) is 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 aryloxyl group having 6 to 20 carbon atoms. The C1-C20 alkyl group which may have one substituent is represented.
The alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aryloxyl group having 6 to 20 carbon atoms and the alkyl group having 1 to 20 carbon atoms in (g1) are the same as those described above. Things.

  In the case of having (g1), as (g1), an unsubstituted alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms having a fluorine atom such as a trifluoromethyl group, and a carbon such as a methoxymethyl group An alkyl group having 1 to 20 carbon atoms having an alkoxyl group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms having a cyano group such as a cyanomethyl group are preferable.

Here, (h1) is 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 aryloxyl group having 6 to 20 carbon atoms. The C2-C20 acyl group which may have one substituent is represented.
In (h1), the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the aryloxyl group having 6 to 20 carbon atoms and the acyl group having 2 to 20 carbon atoms are the same as those described above. Are illustrated.

  In the case of having (h1), as (h1), an unsubstituted acyl group having 2 to 20 carbon atoms and an acyl having 2 to 20 carbon atoms having an aryloxyl group having 6 to 20 carbon atoms such as a phenoxybenzoyl group Groups are preferred.

X ¹ and X ² are iodine atom, bromine atom and chlorine atom, preferably chlorine atom and bromine atom.

  A commercially available thing may be used as an aromatic compound (A), and what was manufactured according to the well-known method may be used. Examples of the aromatic compound (A) include tetramethyl 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonate, 4,4′-dichlorobiphenyl-2,2 ′, 6, 6'-tetrasulfonic acid tetraethyl, 4,4'-dichlorobiphenyl-2,2 ', 6,6'-tetrasulfonic acid tetrapropyl, 4,4'-dichlorobiphenyl-2,2', 6,6'- Tetraisopropyl tetrasulfonate, 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrabutyl tetrasulfonate, 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid Tetraisobutyl, 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetrakis (2,2-dimethylpropyl), 4,4′-dichlorobiphenyl-2 2 ′, 6,6′-tetrasulfonic acid tetracyclohexyl, 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetraoctyl, 4,4′-dichlorobiphenyl-2,2 ′ , 6,6′-tetrasulfonic acid tetrapentadecyl, 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetricosyl,

  3,3′-dimethoxy-4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetrakis (2,2-dimethylpropyl), 5,5′-dimethoxy-4,4′- Dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetrakis (2,2-dimethylpropyl), 3,3′-diphenyl-4,4′-dichlorobiphenyl-2,2 ′, 6,6 ′ -Tetrakissulfonic acid tetrakis (2,2-dimethylpropyl),

4,4′-dibromobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetramethyl, 4,4′-dibromobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetraethyl, 4,4 '-Dibromobiphenyl-2,2', 6,6'-tetrasulfonic acid tetrapropyl, 4,4'-dibromobiphenyl-2,2 ', 6,6'-tetrasulfonic acid tetraisopropyl, 4,4'- Dibromobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetrabutyl, 4,4′-dibromobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetraisobutyl, 4,4′-dibromobiphenyl- 2,2 ′, 6,6′-tetrasulfonic acid tetrakis (2,2-dimethylpropyl), 4,4′-dibromobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetracyclohexyl, 4,4 '-Jib Lomobiphenyl-2,2 ′, 6,6′-tetraoctyl tetrasulfonate, tetrapentadecyl 4,4′-dibromobiphenyl-2,2 ′, 6,6′-tetrasulfonate, 4,4′-dibromo Examples include biphenyl-2,2 ′, 6,6′-tetracosyl tetricosyl.
Among them, 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetraisopropyl, 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetrakis ( 2,2-dimethylpropyl), 4,4′-dibromobiphenyl-2,2 ′, 6,6′-tetraisopropyl tetrasulfonate and 4,4′-dibromobiphenyl-2,2 ′, 6,6′- Tetrasulfonic acid tetrakis (2,2-dimethylpropyl) is preferred.

  The aromatic compound (A) can be produced, for example, according to the method described in WO2011 / 030921.

  The aromatic compound (B) is structurally different from the aromatic compound (A), and is selected from the group consisting of an aromatic ring and a chlorine atom, a bromine atom and an iodine atom bonded to the aromatic ring. An aromatic compound having a leaving group. Preferably, it is an aromatic compound which does not have the following (c1), (g1) and (h1) described above on the carbon atom adjacent to the carbon atom to which the leaving group is bonded. More preferably, it is an aromatic compound in which a hydrogen atom is bonded to a carbon atom adjacent to the carbon atom to which the leaving group is bonded. Examples of (g1) and (h1) are the same as those described above. Moreover, a preferable example when it has (g1) and (h1) is the same as that mentioned above.

  The aromatic compound (B) is structurally different from the aromatic compound (A). Hereinafter, the aromatic compound (A) and the aromatic compound (B) may be collectively referred to as an aromatic compound.

  Examples of the aromatic ring contained in the aromatic compound include aromatic hydrocarbon rings such as benzene ring, biphenyl ring, naphthalene ring, fluorene ring, anthracene ring, and phenanthrene ring, aromatic rings such as thiophene ring, pyrrole ring, and pyridine ring. Heterocycles are mentioned.

（式（１０）中、Ａ^１は炭素数１〜２０のアルコキシル基を表す。ここで、前記アルコキシル基は、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基及び炭素数６〜２０のアリールスルホニル基からなる群から選ばれる少なくとも一つの基を有していてもよい。） Here, (c1) represents a group represented by the following formula (10).

(In the formula (10), ^{A 1} represents an alkoxyl group having 1 to 20 carbon atoms. Herein, the alkoxyl group, a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, (It may have at least one group selected from the group consisting of an aryloxyl group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms.)

  Examples of the alkoxyl group having 1 to 20 carbon atoms in the formula (10) of (c1) include the same ones as described above.

Such an alkoxyl group includes a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and 6 to 20 carbon atoms. It may have at least one group selected from the group consisting of arylsulfonyl groups.
C1-C20 alkoxyl group, C1-C20 alkoxyl group, C6-C20 aryl group, C6-C20 aryloxyl group, C2-C20 acyl group, and C6-C20 Examples of the 20 arylsulfonyl group are the same as those described above.

If having (c1), as the (c1), ^{A 1} is isopropoxyl group, 2,2-dimethyl-propoxyl group, a group represented by the formula is a cyclohexyl oxyl group (10) preferably.

Said (c1), (g1) and (h1) may be bonded to a carbon atom other than the carbon atom adjacent to the carbon atom to which the leaving group is bonded.
Said (c1), (g1) and (h1) are groups which do not participate in the coupling reaction of an aromatic compound.

The aromatic ring may have a group other than the above (c1), (g1) and (h1) and not involved in the coupling reaction of the aromatic compound.
Examples of the group that does not participate in the reaction other than (c1), (g1), and (h1) include the following (a1), (b1), (d1), (e1), and (f1).
(A1) a fluorine atom;
(B1) a cyano group;
(D1) having at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxyl group having 6 to 20 carbon atoms An optionally substituted alkoxyl group having 1 to 20 carbon atoms;
(E1) A carbon atom having 6 to 20 carbon atoms which may have at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxyl group having 1 to 20 carbon atoms and an aryloxyl group having 6 to 20 carbon atoms An aryl group of
(F1) 6 to 20 carbon atoms which may have at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxyl group having 1 to 20 carbon atoms and an aryloxyl group having 6 to 20 carbon atoms. An aryloxyl group of

In (d1), (e1) and (f1), the alkoxy group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms and the aryloxyl group having 6 to 20 carbon atoms are the same as those described above. Is mentioned.
(D1) is preferably a C1-C20 alkoxyl group having a C1-C20 alkoxyl group such as a C1-C20 unsubstituted alkoxyl group or a methoxymethoxyl group.
(E1) is preferably an unsubstituted aryl group having 6 to 20 carbon atoms.
(F1) is preferably an unsubstituted aryloxyl group having 6 to 20 carbon atoms.
As the group not involved in the reaction, the above (c1), (d1), (g1) and (h1) are preferable.

As an aromatic compound (B), a commercially available thing may be used and what was manufactured according to the well-known method may be used.
Examples of the aromatic compound (B) include 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,4-diiodobenzene, 3,5-dichlorotoluene, 3,5-dibromotoluene, 3,5. -Diiodotoluene, 3,4-dibromotoluene,
2,5-dichloroanisole, 2,4-dichloroanisole, 3,5-dichloroanisole, 2,5-dibromoanisole, 2,4-dibromoanisole, 3,5-dibromoanisole, 3,5-diiodoanisole, 1,3-dichloro-4-acetoxybenzene, 1,4-dibromo-3-acetoxybenzene, 1,3-diiodo-4-acetoxybenzene, 1,4-dichloro-2-phenoxybenzene, 1,5-dichloro- 3-phenoxybenzene, 1,4-dibromo-2-phenoxybenzene, 1,5-dibromo-3-phenoxybenzene,

3,5-dichloro-4'-phenoxybenzophenone, 1,3-dibromo-5-ethylbenzene, 1,4-dibromo-2-methoxybenzene, dimethyl 2,5-dibromoterephthalate, 1,4-dibromonaphthalene, 1, 1'-dibromo-4,4'-biphenyl, 1,4-dibromo-2,5-dihexyloxybenzene, 1-bromo-4-chlorobenzene, 3-bromo-5-chlorotoluene, 3-bromo-5-chloro 2-propylbenzene, 3,5-dibromo-4′-phenoxybenzophenone, 2,5-dibromothiophene, 5,5′-dibromo-2,2′-bithiophene, 2,5-dichloro-3-phenylthiophene, 2,5-dichloropyridine, 3,5-dichloropyridine, 2,5-dibromopyridine, 4-methyl-2,6-dichloropyri Gin, 4-hexyl-2,6-dichloropyridine, 5,5′-dichloro-2,2′-bipyridine, 3,3′-dimethyl-5,5′-dichloro-2,2′-bipyridine, 3, 3′-dioctyl-5,5′-dibromo-2,2′-bipyridine,
2,7-dibromo-9,9-dihexyl-9H-fluorene, 2,7-dibromo-9,9-dioctyl-9H-fluorene, 2,7-dibromo-9,9-didodecyl-9H-fluorene, 2, 7-dichloro-9,9-dihexyl-9H-fluorene, 2,7-dichloro-9,9-dioctyl-9H-fluorene, 2,7-dichloro-9,9-didodecyl-9H-fluorene, 2-bromo- 7-chloro-9,9-dihexyl-9H-fluorene, 2-bromo-7-chloro-9,9-dioctyl-9H-fluorene, 2-bromo-7-chloro-9,9-didodecyl-9H-fluorene,
1,2-ethylene glycol bis (p-chlorobenzoate), 1,2-ethylene glycol bis (m-chlorobenzoate), 1,4-butanediol bis (p-chlorobenzoate), 1,4-butanediol bis ( m-chlorobenzoate), 1,7-heptanediol bis (p-chlorobenzoate), 1,7-heptanediol bis (m-chlorobenzoate) and the like.

（Ａｒ^１〜Ａｒ^４は、それぞれ独立に、２価の芳香族基を表す。前記芳香族基は、フッ素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基、炭素数２〜２０のアシル基及びシアノ基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。前記アルキル基、前記アルコキシル基、前記アリール基、前記アリールオキシル基及び前記アシル基は、それぞれ独立に、フッ素原子、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリールオキシル基及びシアノ基からなる群から選ばれる少なくとも１つの置換基を有していてもよい。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す。ａ、ｂ及びｃは、それぞれ独立に、０又は１を表す。ｈは、２以上の整数を表す。Ｘ⁵及びＸ⁶は、それぞれ独立に、塩素原子、臭素原子又はヨウ素原子を表す。） A different example of the aromatic compound (B) includes an aromatic compound represented by the following formula (6).

(Ar ^{1 to} Ar ⁴ each independently represents a divalent aromatic group. The aromatic group includes a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, and a carbon number. The alkyl group may have at least one substituent selected from the group consisting of an aryl group having 6 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and a cyano group. , The alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl 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. aryloxyl and good .Y ¹ and Y ² have at least one substituent selected from the group consisting of cyano groups, each independently, a single bond, a carbonyl group, sulfo Group, isopropylidene group, .Z ¹ and ^{Z 2} represents a hexafluoroisopropylidene group or a fluorene-9,9-diyl group, each independently, .a representing an oxygen atom or a sulfur atom, b and c, Each independently represents 0 or 1. h represents an integer of 2 or more, and X ⁵ and X ⁶ each independently represent a chlorine atom, a bromine atom or an iodine atom.)

In the formula ^{(6), Ar 1 ~Ar 4} , Y 1, Y 2, Z 1, Z 2, a, b, c and h, respectively, in the formula ^{(003), Ar 1 ~Ar 4} , Y ¹ , Y ² , Z ¹ , Z ² , a, b, c and h are the same, and preferred examples are also the same.

However, in the formula (6), the carbon atom adjacent to the carbon atom of Ar ¹ to which X ⁵ is bonded and Ar ² to which X ⁶ is bonded is
(A2) having at least one substituent selected from the group consisting of a fluorine atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryloxyl group having 6 to 20 carbon atoms From an optionally substituted alkyl group having 1 to 20 carbon atoms and (e2) 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 aryloxyl group having 6 to 20 carbon atoms. An acyl group having 2 to 20 carbon atoms, which may have at least one substituent selected from the group consisting of; the carbon atoms adjacent to the carbon atoms of Ar ¹ and Ar ² to which X ² is bonded; (A2) and (e2) are not bonded.
Is preferably not bound.
X ⁵ and X ⁶ are each preferably a chlorine atom or a bromine atom.

Specific examples of the aromatic compound represented by the formula (6) include compounds shown below, compounds in which chlorine atoms at both ends of the compounds shown below are replaced by bromine atoms, and the like. In the following formulae, h represents the same meaning as described above.

As the aromatic compound represented by the formula (6), those prepared according to a known method such as Japanese Patent No. 2,745,727 may be used, or those commercially available are used. It may be used. As what is marketed, Sumitomo Chemical Co., Ltd. Sumika Excel PES etc. are mentioned, for example.
Examples of the aromatic compound represented by the formula (6) include a polystyrene-equivalent weight average molecular weight in the range of 1,000 to 2,000,000, for example. The range of 000 to 500,000 can be raised. 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 2,000,000. Preferably, the range of 2,000-1,000,000 can be mentioned, for example, More preferably, the range of 3,000-800,000 etc. are mentioned, for example.

As a specific example in the case of reacting the aromatic compound (A) with an aromatic compound (B) different from the aromatic compound (A),
When the aromatic compound represented by the formula (5) different from the aromatic compound (A) is used as the aromatic compound (B); and the aromatic compound (B) as the formula (6) The case where the aromatic compound represented is used is mentioned.
When the aromatic compound (A) and the aromatic compound (B) different from the aromatic compound (A) are reacted, the usage amounts of the aromatic compound (A) and the aromatic compound (B) are adjusted respectively. By this, the content of the repeating unit derived from the aromatic compound (A) and the repeating unit derived from the aromatic compound (B) in the obtained polymer can be adjusted.

  The nickel compound is a compound containing nickel, for example, a zerovalent nickel compound such as nickel (0) bis (cyclooctadiene), nickel (0) tetrakis (triphenylphosphine); nickel halide (for example, fluoride) Nickel, nickel chloride, nickel bromide, nickel iodide, etc.), nickel carboxylate (eg, nickel formate, nickel acetate, etc.), nickel sulfate, nickel carbonate, nickel nitrate, nickel acetylacetonate, (dimethoxyethane) nickel chloride And divalent nickel compounds such as nickel (0) bis (cyclooctadiene) and nickel halide are preferable.

The amount of the nickel compound used may be, for example, in the range of 0.001 to 0.8 mol, preferably 0.01 to 0.3, with respect to 1 mol of all aromatic compounds involved in the reaction. Examples include a molar range.
When the nickel compound is 0.001 mol or more, the yield of the polymer tends to be improved, and when it is 0.8 mol or less, the operation of taking out the polymer after completion of the reaction becomes easy. It is preferable because of its tendency.

The metal reducing agent means a metal that can reduce divalent nickel to zero-valent nickel. Specifically, zinc, magnesium, manganese, aluminum, sodium, etc. are mentioned, zinc, magnesium, and manganese are preferable, and zinc is more preferable. Usually, a commercially available metal reducing agent is used. Examples of the properties of the metal reducing agent include powders and chips.
The amount of the metal reducing agent used may be, for example, in the range of 1 to 10 mol, preferably in the range of 1 to 5 mol, with respect to 1 mol of all aromatic compounds involved in the reaction.

  As the ligand, at least two kinds of ligands selected from the group consisting of a ligand (L1), a ligand (L2) and a ligand (L3) are used. As a combination of at least two kinds, a combination of a ligand (L1) and a ligand (L2), a combination of a ligand (L1) and a ligand (L3), a ligand (L2) and a ligand A combination of (L3) and a combination of ligand (L1), ligand (L2) and ligand (L3) can be mentioned, and a combination of ligand (L1) and ligand (L2) is preferred.

The ligand (L1) has an electron-withdrawing group and has a 2,2′-bipyridine compound in which a hydrogen atom is bonded to each of the 3-position, 6-position, 3′-position and 6′-position, At least one ligand selected from the group consisting of a 1,10-phenanthroline compound having an attractive group and having a hydrogen atom bonded to the 2-position and the 9-position, respectively.
Here, the electron withdrawing group means a substituent having a positive value of σ defined by the Hammett formula described in Chemical Reviews 1991, 91, 165-195.

Examples of the electron withdrawing group include a fluorine atom, a fluorinated alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a cyano group, and a nitro group. Can be mentioned.
Examples of the fluorinated alkyl group having 1 to 20 carbon atoms include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, A perfluoroisopropyl group and the like can be mentioned.
Examples of the alkoxycarbonyl group having 1 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group and the like.
Examples of the acyl group having 2 to 20 carbon atoms include aliphatic or aromatic having 2 to 20 carbon atoms such as acetyl group, propionyl group, butyryl group, isobutyryl group, benzoyl group, 1-naphthoyl group, and 2-naphthoyl group. An acyl group etc. are mentioned.
Preferred examples of the electron withdrawing group include a fluorine atom, a fluorinated alkyl group having 1 to 20 carbon atoms, and an alkoxycarbonyl group having 2 to 20 carbon atoms, and more preferably a methoxycarbonyl group, A fluoromethyl group etc. are mentioned.

The 2,2′-bipyridine compound in the ligand (L1) has at least one electron-withdrawing group in the molecule, and is a hydrogen atom at the 3-position, 6-position, 3′-position and 6′-position. 2,2′-bipyridine compound to which is bonded, and groups other than the electron withdrawing group may be present at positions other than the 3-position, 6-position, 3′-position and 6′-position.
The 1,10-phenanthroline compound in the ligand (L1) has at least one electron-withdrawing group in the molecule, and 1,10- which has a hydrogen atom bonded to the 2nd and 9th positions. It may be a phenanthroline compound, and may have a group other than the electron withdrawing group at a position other than the 2-position and the 9-position.

The ligand (L1) preferably has at least two electron-withdrawing groups.
When the ligand (L1) is a 2,2′-bipyridine compound, each of the two pyridine rings preferably has one electron withdrawing group.
When the ligand (L1) is a 1,10-phenanthroline compound, each of the rings containing a nitrogen atom preferably has one electron withdrawing group.
The ligand (L1) has at least two electron-withdrawing groups, and 2,2′- in which a hydrogen atom is bonded to the 3-position, 6-position, 3′-position and 6′-position. Bipyridine compounds are preferred.

（Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又は電子求引性基を表し、少なくとも１つが電子求引性基である。） Examples of the 2,2′-bipyridine compound having at least two electron-withdrawing groups and having hydrogen atoms bonded to the 3-position, 6-position, 3′-position and 6′-position include the following formula ( The bipyridine compound etc. which are represented by 1) can be mentioned.

(R ¹ and R ² each independently represents a hydrogen atom or an electron withdrawing group, and at least one is an electron withdrawing group.)

Examples of the bipyridine compound represented by the formula (1) include 4,4′-difluoro-2,2′-bipyridine, 5,5′-difluoro-2,2′-bipyridine, and 4,4′-bis. (Trifluoromethyl) -2,2′-bipyridine, 5,5′-bis (trifluoromethyl) -2,2′-bipyridine, 4,4′-bis (methoxycarbonyl) -2,2′-bipyridine, 5,5′-bis (methoxycarbonyl) -2,2′-bipyridine, 4,4′-bis (ethoxycarbonyl) -2,2′-bipyridine, 5,5′-bis (ethoxycarbonyl) -2,2 '-Bipyridine and the like can be mentioned. Preferably, for example, 4,4'-bis (trifluoromethyl) -2,2'-bipyridine, 4,4'-bis (methoxycarbonyl) -2,2'-bipyridine and the like. Is mentioned.

（Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子又は電子求引性基を表し、少なくとも１つが電子求引性基である。）
前記式（２）で表されるフェナントロリン化合物としては、例えば、４，７−ジクロロ−１，１０−フェナントロリン等が挙げられる。 Examples of the 1,10-phenanthroline compound having at least two electron-attracting groups and having a hydrogen atom bonded to the 2-position and the 9-position include, for example, a phenanthroline compound represented by the following formula (2): Etc.

(R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or an electron withdrawing group, and at least one is an electron withdrawing group.)
Examples of the phenanthroline compound represented by the formula (2) include 4,7-dichloro-1,10-phenanthroline.

As the ligand (L1), two or more kinds of 2,2′-bipyridine compounds may be used, two or more kinds of 1,10-phenanthroline compounds may be used, or 2,2′-bipyridine compounds. And a 1,10-phenanthroline compound may be used in combination.
As the ligand (L1), a 2,2′-bipyridine compound represented by the formula (1) is more preferable.

The ligand (L2) has an electron donating group, a 2,2′-bipyridine compound in which a hydrogen atom is bonded to each of the 3-position, 6-position, 3′-position and 6′-position, and an electron-donating property. It is at least one ligand selected from the group consisting of a 1,10-phenanthroline compound having a group and having a hydrogen atom bonded to the 2-position and the 9-position, respectively.
Here, the electron donating group means a substituent having a negative value of σ defined by the Hammett formula described in Chemical Reviews 1991, 91, 165-195.

Examples of the electron donating group include an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a dialkylamino group having 1 to 20 carbon atoms.
Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and 2,2-dimethylpropyl. Group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, 2-methylpentyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group Group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like, preferably methyl group, tert-butyl group and the like.
Examples of the alkoxyl group having 1 to 20 carbon atoms include methoxyl group, ethoxyl group, propoxyl group, isopropoxyl group, n-butoxyl group, sec-butoxyl group, tert-butoxyl group, pentyloxyl group, 2,2 -Dimethylpropoxyl, hexyloxyl, cyclohexyloxyl, heptyloxyl, octyloxyl, nonyloxyl, decyloxyl, undecyloxyl, dodecyloxyl, tridecyloxyl, tetradecyloxyl, pentadecyloxyl Group, hexadecyloxyl group, heptadecyloxyl group, octadecyloxyl group, nonadecyloxyl group, icosyloxyl group and the like, preferably methoxyl group and the like.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 4-methylphenyl group, a 2-methylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 3-phenanthryl group, and a 2-anthryl group. Preferably, a phenyl group etc. are mentioned, for example.
Examples of the dialkylamino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a di-propylamino group, a diisopropylamino group, a dibutylamino group, and a di (2,2-dimethylpropyl) amino group. Preferably, a dimethylamino group etc. are mentioned, for example.
Preferred examples of the electron donating group include an alkyl group having 1 to 20 carbon atoms and an alkoxyl group having 1 to 20 carbon atoms, and more preferred examples include a tert-butyl group and a methoxyl group.

The 2,2′-bipyridine compound in the ligand (L2) has at least one electron donating group in the molecule, and a hydrogen atom is present at the 3-position, 6-position, 3′-position and 6′-position. What is necessary is just the 2,2'- bipyridine compound couple | bonded, and you may have groups other than an electron-donating group in positions other than 3-position, 6-position, 3'-position, and 6'-position.
The 1,10-phenanthroline compound in the ligand (L2) has 1,10-phenanthroline having at least one electron donating group in the molecule and having hydrogen atoms bonded to the 2nd and 9th positions. It may be a compound and may have a group other than the electron donating group at a position other than the 2-position and the 9-position.

The ligand (L2) preferably has at least two electron donating groups.
When the ligand (L2) is a 2,2′-bipyridine compound, each of the two pyridine rings preferably has one electron donating group.
When the ligand (L2) is a 1,10-phenanthroline compound, each of the rings containing a nitrogen atom preferably has one electron donating group.
As the ligand (L2), 2,2′-bipyridine having at least two electron-donating groups and having a hydrogen atom bonded to the 3-position, 6-position, 3′-position and 6′-position Compounds are preferred.

（Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又は電子供与性基を表し、少なくとも１つが電子供与性基である。） Examples of the 2,2′-bipyridine compound having at least two electron-donating groups and having a hydrogen atom bonded to the 3-position, 6-position, 3′-position and 6′-position include the following formula ( Examples thereof include bipyridine compounds represented by 3).

(R ⁶ and R ⁷ each independently represents a hydrogen atom or an electron-donating group, and at least one is an electron-donating group.)

  Examples of the bipyridine compound represented by the formula (3) include 4,4′-dimethyl-2,2′-bipyridine, 4,4′-dinonyl-2,2′-bipyridine, and 4,4′-dimethoxy. -2,2'-bipyridine, 4,4'-diphenyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4 ', 5,5'-tetramethyl-2 , 2′-bipyridine, 4,4′-bis (1,1-dimethylethyl) -2,2′-bipyridine, 4,4′-bis (dimethylamino) -2,2′-bipyridine, and the like. Preferable examples include 4,4′-bis (1,1-dimethylethyl) -2,2′-bipyridine.

（Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立に、水素原子又は電子求引性基を表し、少なくとも１つが電子供与性基である。）
前記式（４）で表されるフェナントロリン化合物としては、例えば、３，４，７，８−テトラメチル−１，１０−フェナントロリン等が挙げられる。 Examples of the 1,10-phenanthroline compound having at least two electron donating groups and having a hydrogen atom bonded to the 2nd and 9th positions 10 include, for example, a phenanthroline compound represented by the following formula (4): Etc.

(R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or an electron withdrawing group, and at least one is an electron donating group.)
Examples of the phenanthroline compound represented by the formula (4) include 3,4,7,8-tetramethyl-1,10-phenanthroline.

As the ligand (L2), two or more kinds of 2,2′-bipyridine compounds may be used, two or more kinds of 1,10-phenanthroline compounds may be used, or 2,2′-bipyridine compounds. And a 1,10-phenanthroline compound may be used in combination.
As the ligand (L2), a 2,2′-bipyridine compound represented by the formula (3) is more preferable.

  The ligand (L3) is at least one ligand selected from the group consisting of 2,2'-bipyridine and 1,10-phenanthroline. 2,2'-bipyridine is preferred.

As the specific combination of the preferred ligand (L1) and ligand (L2) as the at least two kinds of ligands, for example,
4,4′-difluoro-2,2′-bipyridine and 4,4′-dimethyl-2,2′-bipyridine,
4,4′-difluoro-2,2′-bipyridine and 4,4′-dinonyl-2,2′-bipyridine,
4,4′-difluoro-2,2′-bipyridine and 4,4′-dimethoxy-2,2′-bipyridine,
4,4′-difluoro-2,2′-bipyridine and 4,4′-diphenyl-2,2′-bipyridine,
4,4′-difluoro-2,2′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine,
4,4′-difluoro-2,2′-bipyridine and 4,4 ′, 5,5′-tetramethyl-2,2′-bipyridine,
4,4′-difluoro-2,2′-bipyridine and 4,4′-bis (1,1-dimethylethyl) -2,2′-bipyridine,
4,4′-difluoro-2,2′-bipyridine and 4,4′-bis (dimethylamino) -2,2′-bipyridine,

5,5′-difluoro-2,2′-bipyridine and 4,4′-dimethyl-2,2′-bipyridine,
5,5′-difluoro-2,2′-bipyridine and 4,4′-dinonyl-2,2′-bipyridine,
5,5′-difluoro-2,2′-bipyridine and 4,4′-dimethoxy-2,2′-bipyridine,
5,5′-difluoro-2,2′-bipyridine and 4,4′-diphenyl-2,2′-bipyridine,
5,5′-difluoro-2,2′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine,
5,5′-difluoro-2,2′-bipyridine and 4,4 ′, 5,5′-tetramethyl-2,2′-bipyridine,
5,5′-difluoro-2,2′-bipyridine and 4,4′-bis (1,1-dimethylethyl) -2,2′-bipyridine,
5,5′-difluoro-2,2′-bipyridine and 4,4′-bis (dimethylamino) -2,2′-bipyridine,

4,4′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-dimethyl-2,2′-bipyridine,
4,4′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-dinonyl-2,2′-bipyridine,
4,4′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-dimethoxy-2,2′-bipyridine,
4,4′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-diphenyl-2,2′-bipyridine,
4,4′-bis (trifluoromethyl) -2,2′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine,
4,4′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4 ′, 5,5′-tetramethyl-2,2′-bipyridine,
4,4′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-bis (1,1-dimethylethyl) -2,2′-bipyridine,
4,4′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-bis (dimethylamino) -2,2′-bipyridine,

5,5′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-dimethyl-2,2′-bipyridine,
5,5′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-dinonyl-2,2′-bipyridine,
5,5′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-dimethoxy-2,2′-bipyridine,
5,5′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-diphenyl-2,2′-bipyridine,
5,5′-bis (trifluoromethyl) -2,2′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine,
5,5′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4 ′, 5,5′-tetramethyl-2,2′-bipyridine,
5,5′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-bis (1,1-dimethylethyl) -2,2′-bipyridine,
5,5′-bis (trifluoromethyl) -2,2′-bipyridine and 4,4′-bis (dimethylamino) -2,2′-bipyridine,

4,4′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-dimethyl-2,2′-bipyridine,
4,4′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-dinonyl-2,2′-bipyridine,
4,4′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-dimethoxy-2,2′-bipyridine,
4,4′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-diphenyl-2,2′-bipyridine,
4,4′-bis (methoxycarbonyl) -2,2′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine,
4,4′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4 ′, 5,5′-tetramethyl-2,2′-bipyridine,
4,4′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-bis (1,1-dimethylethyl) -2,2′-bipyridine,
4,4′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-bis (dimethylamino) -2,2′-bipyridine,

5,5′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-dimethyl-2,2′-bipyridine,
5,5′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-dinonyl-2,2′-bipyridine,
5,5′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-dimethoxy-2,2′-bipyridine,
5,5′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-diphenyl-2,2′-bipyridine,
5,5′-bis (methoxycarbonyl) -2,2′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine,
5,5′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4 ′, 5,5′-tetramethyl-2,2′-bipyridine,
5,5′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-bis (1,1-dimethylethyl) -2,2′-bipyridine,
5,5′-bis (methoxycarbonyl) -2,2′-bipyridine and 4,4′-bis (dimethylamino) -2,2′-bipyridine,

4,4′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-dimethyl-2,2′-bipyridine,
4,4′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-dinonyl-2,2′-bipyridine,
4,4′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-dimethoxy-2,2′-bipyridine,
4,4′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-diphenyl-2,2′-bipyridine,
4,4′-bis (ethoxycarbonyl) -2,2′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine,
4,4′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4 ′, 5,5′-tetramethyl-2,2′-bipyridine,
4,4′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-bis (1,1-dimethylethyl) -2,2′-bipyridine,
4,4′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-bis (dimethylamino) -2,2′-bipyridine,

5,5′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-dimethyl-2,2′-bipyridine,
5,5′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-dinonyl-2,2′-bipyridine,
5,5′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-dimethoxy-2,2′-bipyridine,
5,5′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-diphenyl-2,2′-bipyridine,
5,5′-bis (ethoxycarbonyl) -2,2′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine,
5,5′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4 ′, 5,5′-tetramethyl-2,2′-bipyridine,
5,5′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-bis (1,1-dimethylethyl) -2,2′-bipyridine, and
Examples include 5,5′-bis (ethoxycarbonyl) -2,2′-bipyridine and 4,4′-bis (dimethylamino) -2,2′-bipyridine.

The total amount of the ligand used may be, for example, in the range of 0.2 to 2 mol, preferably in the range of 0.5 to 1.7 mol, with respect to 1 mol of the nickel compound. Can be mentioned.
As the use amount of each of the ligand (L1) and the ligand (L2) as the ligand, for example, the ratio of one use amount to the total use amount 1 is, for example, 0.01. The range of -0.99 is mentioned, Preferably the range of 0.1-0.9 is mentioned. When using a ligand (L1) and a ligand (L2) as a ligand, it is more preferable that the usage-amount of a ligand (L2) is larger than the usage-amount of a ligand (L1).

The production method of the present invention is performed by mixing an aromatic compound, a nickel compound, a metal reducing agent, and the at least two kinds of ligands, and the mixing order is not limited. It is preferable to have a step of mixing seed ligands (hereinafter sometimes referred to as a complex preparation step). Here, the case where a preferable ligand (L1) and a ligand (L2) are used as said at least 2 types of ligand is demonstrated.
Specifically, for example, a step of mixing the ligand (L1), the ligand (L2) and the nickel compound in a solvent;
A step of taking out a nickel complex comprising a ligand (L1), a ligand (L2) and a nickel compound from the mixture obtained in the step;
The first step of mixing the ligand (L1) and the nickel compound in the solvent, the second step of mixing the ligand (L2) and the nickel compound in the solvent, and the mixture obtained in the first step And a step of mixing the mixture obtained in the second step;
A first ′ step for further extracting a nickel complex comprising a ligand (L1) and a nickel compound from the mixture obtained in the first step, the second step, the nickel complex obtained in the first ′ step and the first A step comprising mixing the mixture obtained in two steps;
The first step, the second step of extracting a nickel complex comprising a ligand (L2) and a nickel compound from the mixture obtained in the second step, the mixture obtained in the first step and the second step A step comprising mixing the nickel complex obtained in the step;
A first ′ step for further removing a nickel complex comprising a ligand (L1) and a nickel compound from the mixture obtained in the first step, and a ligand (L2) and a ligand obtained from the mixture obtained in the second step A step comprising: a second ′ step of extracting a nickel complex comprising a nickel compound; and a step of mixing the nickel complex obtained in the first ′ step and the nickel complex obtained in the second ′ step;
Etc.
In addition, it can be discriminated that the nickel complex is prepared in the catalyst preparation step by the change in the hue of the mixture.
As a preferable catalyst preparation process, it is a manufacturing method which has the process of mixing a ligand (L1), a ligand (L2), and a nickel compound in a solvent.

The catalyst preparation step is preferably performed in an atmosphere of an inert gas such as nitrogen gas.
The reaction temperature in a catalyst preparation process can mention the range of 0-250 degreeC, for example, Preferably the range of 30-100 degreeC can be mentioned.
Examples of the reaction time in the catalyst preparation step include a range of 0.5 to 48 hours.

  Via a step of polymerizing the aromatic compound (A) in the presence of the nickel complex obtained through the catalyst preparation step and the metal reducing agent (hereinafter, sometimes referred to as a reaction step), A polymer can be produced.

The reaction step is preferably performed in the presence of a solvent.
The solvent may be any solvent that can dissolve the aromatic compound to be used and the polymer to be produced. 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.
As a usage-amount of a solvent, the range of 1-200 weight part etc. can be mentioned with respect to 1 weight part of all the aromatic compounds to be used, Preferably, the range of 5-100 weight part etc. is preferable, for example. Can be mentioned. When the solvent is 1 part by weight or more, when the aromatic compound has at least two leaving groups, the molecular weight of the resulting polymer tends to increase, and when the solvent is 200 parts by weight or less, it is obtained. This is preferable because the viscosity of the reaction mixture containing the polymer tends to decrease and the handling becomes easy.

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

In order to improve the reaction rate of the reaction step, a halogen compound may be added to the reaction system.
Examples of the halogen compound include sodium halides such as sodium fluoride, sodium chloride, sodium bromide and sodium iodide, and potassium halides such as potassium fluoride, potassium chloride, potassium bromide and potassium iodide, such as fluorine. And quaternary ammonium halides such as tetraethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, and tetraethylammonium iodide. Preferable examples include sodium halide, and more preferable examples include sodium iodide.
The usage-amount is 0.001-1 mol normally with respect to 1 mol of all the aromatic compounds which participate in reaction, Preferably it is 0.05-0.2 mol.

  After completion of the reaction step, the produced polymer is precipitated by mixing the reaction mixture with a solvent that does not dissolve or hardly dissolves the produced polymer, and the precipitated polymer is filtered to remove the reaction mixture. It can be taken out by separating from. After mixing the solvent which does not dissolve | melt the produced | generated polymer with the solvent which is hard to melt | dissolve, and reaction mixture, the aqueous solution of acids, such as hydrochloric acid, may be added, and the precipitated polymer may be isolate | separated from a reaction mixture by filtration. The molecular weight and structure of the obtained polymer can be analyzed by ordinary analysis means such as gel permeation chromatography and NMR. 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.

  When the aromatic compound (A) is polymerized alone as the raw material monomer, specific examples of the polymer obtained include polymers composed of repeating units represented by the following formulas (23a) to (23c).

  Examples of the polymer include cases where the polymer has repeating units in the range of 2 to 10,000, and the weight average molecular weight of the polymer in terms of polystyrene is, for example, in the range of 1,000 to 6,000,000. Etc.

  When the aromatic compound represented by the formula (6) is used as the aromatic compound (A) and the aromatic compound (B) as the raw material monomer, specific examples of the resulting polymer include the formula (23a). Any one or more of the repeating units represented by any one or more of the repeating units represented by (23c) and (24a) to (24y) And a polymer having a repeating unit represented by the following repeating unit in the main chain. Examples of the weight average molecular weight of the polymer in terms of polystyrene include a range of 3,000 to 3,000,000.

Examples of the polymer having a block having a repeating unit represented by the formula (001) and a block having a structure represented by the formula (003) are represented by the formulas (23a) to (23c). And polymers having any one or more of the repeating units and any one or more of the blocks represented by the formulas (24a) to (24y).
Specific examples include polymers represented by the following (III-1) to (III-6). Here, in the following formula, h represents the same meaning as described above, and p represents an integer of at least 2.

  The content of each repeating unit in the polymer having two or more types of repeating units can be adjusted by appropriately adjusting the amount of the aromatic compound used.

In the polymer obtained as described above, the polymer having the structural unit represented by the formula (001) in the main chain includes the group represented by (1a), and R ⁰¹¹ is 1 to 1. In the case of 20 alkyl groups, it is preferable to perform a deprotection reaction to convert R ⁰¹¹ to a hydrogen atom, or to convert the group represented by (1a) to the group represented by (1b). Such deprotection reaction is performed according to the method described in JP-A-2007-270118.

  Any of the polymers thus obtained can be suitably used as a member for a fuel cell. The polymer of the present invention is preferably used as a polymer electrolyte of an electrochemical device such as a fuel cell, and particularly preferably used as a polymer electrolyte membrane. That is, the polymer electrolyte of the present invention is a polymer electrolyte containing the polymer of the present invention, and the polymer electrolyte membrane of the present invention is a polymer electrolyte membrane containing the polymer electrolyte of the present invention. In the following description, the case of the polymer electrolyte membrane will be mainly described.

  In this case, the polymer electrolyte of the present invention is converted into a membrane form. Although there is no restriction | limiting in particular in this method (film forming method), It is preferable to form into a film using the method (solution casting method) formed into a film from a solution state. The solution casting method is a method that has been widely used in the art as a polymer electrolyte membrane production, and is particularly useful industrially.

  Specifically, the polymer electrolyte of the present invention is dissolved in an appropriate solvent to prepare a polymer electrolyte solution, the polymer electrolyte solution is cast on a support substrate, and the solvent is removed to form a film. Is done. Examples of such a supporting substrate include glass plates and plastic films such as polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI).

  The solvent (cast solvent) used in the solution casting method is not particularly limited as long as it can sufficiently dissolve the polymer electrolyte of the present invention and can be removed thereafter. N-methyl-2-pyrrolidone (NMP ), Aprotic polar solvents such as N, N-dimethylacetamide (DMAc), N-dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO); dichloromethane, Chlorinated solvents such as chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; alcohols such as methanol, ethanol, propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether Ether, propylene glycol monomethyl ether, alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether are preferably used. These can be used singly, but two or more solvents can be mixed and used as necessary. Among them, NMP, DMAc, DMF, DMI, and DMSO are preferable because the polymer electrolyte of the present invention has high solubility and a polymer electrolyte membrane having high water resistance can be obtained.

  The thickness of the polymer electrolyte membrane thus obtained is not particularly limited, but is preferably 5 to 300 μm in a practical range as a polymer electrolyte membrane for fuel cells (diaphragm). A film having a film thickness of 5 μm or more is preferable because of its practical strength, and a film having a film thickness of 300 μm or less is preferable because the film resistance itself tends to decrease. The film thickness can be controlled by the concentration of the solution and the coating thickness of the coating film on the support substrate.

  In addition, for the purpose of improving various physical properties of the membrane, additives such as plasticizers, stabilizers, release agents and the like used in ordinary polymers are added to the polymer of the present invention to prepare a polymer electrolyte. Also good. It is also possible to prepare a polymer electrolyte by compound-alloying another polymer with the copolymer of the present invention by a method such as co-casting in the same solvent. As described above, when a polymer electrolyte is prepared by combining the polymer of the present invention with an additive and / or another polymer, the polymer electrolyte is desired when applied to a fuel cell member. Thus, the types and amounts of additives and / or other polymers are determined.

  Furthermore, in fuel cell applications, it is also known to add inorganic or organic fine particles as a water retention agent in order to effectively use water generated in the fuel cell. Any of these known methods can be used as long as they are not contrary to the object of the present invention. The polymer electrolyte membrane thus obtained may be subjected to a treatment such as irradiation with an electron beam or radiation for the purpose of improving its mechanical strength.

  In order to further improve the strength, flexibility and durability of the polymer electrolyte membrane using the polymer electrolyte of the present invention, a porous substrate is impregnated with the polymer electrolyte containing the polymer of the present invention to form a composite. By doing so, a polymer electrolyte composite membrane (hereinafter referred to as “composite membrane”) can be obtained. A known method can be used as the compounding method.

  The porous substrate is not particularly limited as long as it satisfies the above-mentioned purpose of use, and examples thereof include a porous membrane, a woven fabric, a non-woven fabric, and the like. It can be used regardless of the material. As the material for the porous substrate, an aliphatic polymer and an aromatic polymer are preferable in view of heat resistance and the effect of reinforcing physical strength.

  When the composite membrane using the polymer electrolyte of the present invention is used as a polymer electrolyte membrane, the thickness of the porous substrate is preferably 1 to 100 μm, more preferably 3 to 30 μm, particularly preferably 5 to 20 μm. It is. The pore diameter of the porous substrate is preferably 0.01 to 100 μm, more preferably 0.02 to 10 μm. The porosity of the porous substrate is preferably 20 to 98%, more preferably 40 to 95%.

  When the film thickness of the porous substrate is 1 μm or more, the effect of reinforcing the strength after compounding or the reinforcing effect of imparting flexibility and durability is more excellent, and gas leakage (cross leak) is less likely to occur. . Further, when the film thickness is 100 μm or less, the electric resistance becomes lower, and the obtained composite membrane becomes more excellent as a polymer electrolyte membrane for a fuel cell. When the pore diameter is 0.01 μm or more, the filling of the polymer of the present invention becomes easier, and when it is 100 μm or less, the reinforcing effect is further increased. When the porosity is 20% or more, the resistance as the polymer electrolyte membrane becomes smaller, and when it is 98% or less, the strength of the porous substrate itself becomes larger and the reinforcing effect is further improved, which is preferable.

  Also, a composite membrane using the polymer electrolyte of the present invention and a polymer electrolyte membrane using the polymer electrolyte of the present invention can be laminated and used as a proton conducting membrane.

Next, the fuel cell of the present invention will be described.
The membrane electrode assembly of the present invention (hereinafter sometimes referred to as “MEA”), which is a basic unit of a fuel cell, comprises the polymer electrolyte membrane of the present invention, the polymer electrolyte composite membrane of the present invention, and The polymer electrolyte of the present invention can be produced using at least one selected from the group consisting of a catalyst composition containing a catalyst component.
Here, the catalyst component is not particularly limited as long as it can activate the oxidation-reduction reaction with hydrogen or oxygen, and a known component can be used, but platinum or platinum alloy fine particles are used as the catalyst component. It is preferable. The fine particles of platinum or platinum-based alloys are often used by being supported on particulate or fibrous carbon such as activated carbon or graphite.
A catalyst prepared by mixing platinum supported on carbon or a platinum-based alloy (carbon-supported catalyst) with the solution of the polymer electrolyte of the present invention and / or the alcohol solution of the perfluoroalkylsulfonic acid resin as the polymer electrolyte. A catalyst layer is obtained by applying and drying the composition to a gas diffusion layer and / or a polymer electrolyte membrane and / or a polymer electrolyte composite membrane. As a specific method, for example, J. Org. Electrochem. Soc. : Known methods such as those described in Electrochemical Science and Technology, 1988, 135 (9), 2209 can be used. Thus, MEA is obtained by forming a catalyst layer on both surfaces of a polymer electrolyte membrane. In the production of the MEA, when a catalyst layer is formed on a base material to be a gas diffusion layer, the resulting MEA is a membrane-electrode having both a gas diffusion layer and a catalyst layer on both sides of a polymer electrolyte membrane. -Obtained in the form of a gas diffusion layer assembly. In addition, when the catalyst composition formed into a paste is applied to the polymer electrolyte membrane to form a catalyst layer on the polymer electrolyte membrane, a gas diffusion layer is further formed on the obtained catalyst layer to form a membrane. -An electrode-gas diffusion layer assembly is obtained.
A known material can be used for the gas diffusion layer, but a porous carbon woven fabric, carbon non-woven fabric or carbon paper is preferable in order to efficiently transport the raw material gas to the catalyst.
The fuel cell including the MEA manufactured in this way can be used in various formats using methanol as well as a format using hydrogen gas or reformed hydrogen gas as fuel.

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

Molecular weight measurement:
The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were measured by gel permeation chromatography (GPC) under the following conditions.
[Condition 1]
GPC measuring device: L2000 made by Hitachi High-Tech
RI detector: RI-101 manufactured by SHODEX
Light scattering detector: Wyatt miniDawn
Column: Asahipak GF-7M HQ manufactured by SHODEX
Column temperature: 60 ° C
Flow rate: 0.3 mL / min
Mobile phase: 10 mM tetrabutylammonium bromide NMP / DMSO = 1/1 solution [Condition 2]
GPC measuring device: Shimadzu Corporation CTO-10A
Column: TSK-GEL manufactured by Tosoh Corporation
Detection wavelength: 300 nm
Column temperature: 40 ° C
Flow rate: 0.5mL / min
Mobile phase: N, N-dimethylformamide containing lithium bromide (lithium bromide concentration: 10 mmol / dm ³ )

Measurement of α (mmol / g):
The polymer used for the measurement is formed into a polymer film by solution casting, and the formed polymer film is cut to an appropriate weight, and the dry weight of the cut polymer film is set to a heating temperature of 105 ° C. It measured using the set halogen moisture content meter. Next, this membrane was immersed in 5 mL of a 0.1 mol / L sodium hydroxide aqueous solution, and then 50 mL of ion-exchanged water was added and left for 2 hours. Thereafter, 0.1 mol / L hydrochloric acid is gradually added to the solution in which the polymer film is immersed to perform titration to obtain a neutralization point, and the dry weight of the used polymer film (the cut polymer film). From the amount of hydrochloric acid required for neutralization, α (mmol / g) of the polymer was calculated.

Dimensional change rate during water absorption swelling:
The dimension (Ld) in the surface direction of the film dried at 23 ° C. and 50% relative humidity, and the dimension (Lw) in the surface direction immediately after the film was immersed and swollen in 80 ° C. hot water for 1 hour or more. ) Was measured and calculated as follows.
Dimensional change rate [%] = (Lw-Ld) / Ld x 100 [%]

Calculation of Q:
Q = Mw / (α * 1000).

で表されるＷＯ ２０１１／０３０９２１［実施例８］に記載の方法で合成した重合体（Ｍｗ ３，２００、Ｍｎ １，７００：前記分析条件２で測定）６．２６ｇと、２，２’−ビピリジン７．８５ｇと、Ｎ−メチル−２−ピロリドン２９ｇ、テトラヒドロフラン１９３ｇとを含む溶液を５０℃に昇温し、４，４’−ジクロロビフェニル−２，２’，６，６’−テトラスルホン酸テトラキス（２，２−ジメチル−１−プロピル）１５．０ｇと、ニッケル（０）ビス（シクロオクタジエン）１２．５ｇを加えてから７０℃に昇温し、２時間攪拌した。
得られた反応混合物をメタノール９９３ｇに注ぎ込み析出物を濾過し、濾過して得られたケーキをメタノールで３回、１７％塩酸で２回洗浄し、さらに濾液のｐＨが４を超えるまで水洗を行なった。次に、冷却器を備えたフラスコに、ケーキと、ケーキと水との合計重量が３９３ｇになるように水を加え、さらに、メタノール３９３ｇを加え、バス温９０℃で１時間過熱攪拌した。ケーキを濾過し、メタノールで１回洗浄し乾燥した。
乾燥したケーキをＮ−メチル−２−ピロリドン３４４ｇに溶解した後、３５％塩酸を１２．０ｇ加え１２０℃で１２時間攪拌した。
得られた混合物をアセトン９２９ｇに注ぎ込み、結晶を析出させた後、得られたケーキをアセトンで１回、１３．２％塩酸で３回、熱水で５回、水で１回洗浄し、乾燥することにより、下記式（００１ａ）で表される繰り返し単位と、下記式（００３ｐ）で表される構造とを含む高分子電解質を得た。収量は１３．５２ｇであった。

（ｈは繰り返し単位数を表す。）

上述のように重合して得られた高分子電解質をジエチレングリコールジエチルエーテルに溶解して、濃度が６質量％の高分子電解質溶液を調製した。
得られた高分子電解質溶液を、支持基材である巾３００ｍｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡績社製、Ｅ５０００グレード、厚さ１００μｍ）に流延塗布して、流延膜を形成した。その後、支持基板と流延膜とを１００℃に設定した熱風ヒーター乾燥炉へと搬送し、溶媒を除去して成膜した。
得られた膜を２Ｎ硫酸に２時間浸漬後、イオン交換水で水洗し、更に風乾した後に支持基材から剥離することで、高分子電解質膜を作製した。膜厚は１０μｍであった。

Ｍｗ ６．８９×１０⁵ ［ 条件１ ］
α ４．８（ｍｍｏｌ／ｇ）
寸法変化率 １０．１％
Ｑ １４４
Example 1
In a nitrogen reaction atmosphere in a glass reaction vessel equipped with a cooling device, the following formula (i)

6.26 g of a polymer synthesized by the method described in WO 2011/030921 [Example 8] (Mw 3,200, Mn 1,700: measured under the analysis condition 2) and 2,2′- A solution containing 7.85 g of bipyridine, 29 g of N-methyl-2-pyrrolidone and 193 g of tetrahydrofuran was heated to 50 ° C., and 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid. After adding 15.0 g of tetrakis (2,2-dimethyl-1-propyl) and 12.5 g of nickel (0) bis (cyclooctadiene), the temperature was raised to 70 ° C. and stirred for 2 hours.
The obtained reaction mixture was poured into 993 g of methanol, and the precipitate was filtered. The cake obtained by filtration was washed 3 times with methanol and twice with 17% hydrochloric acid, and further washed with water until the pH of the filtrate exceeded 4. It was. Next, water was added to a flask equipped with a cooler so that the total weight of the cake and the cake and water was 393 g, and 393 g of methanol was further added, followed by superheated stirring at a bath temperature of 90 ° C. for 1 hour. The cake was filtered, washed once with methanol and dried.
After the dried cake was dissolved in 344 g of N-methyl-2-pyrrolidone, 12.0 g of 35% hydrochloric acid was added and stirred at 120 ° C. for 12 hours.
The obtained mixture was poured into 929 g of acetone to precipitate crystals, and the obtained cake was washed once with acetone, three times with 13.2% hydrochloric acid, five times with hot water and once with water, and then dried. As a result, a polymer electrolyte containing a repeating unit represented by the following formula (001a) and a structure represented by the following formula (003p) was obtained. The yield was 13.52g.

(H represents the number of repeating units.)

The polymer electrolyte obtained by polymerization as described above was dissolved in diethylene glycol diethyl ether to prepare a polymer electrolyte solution having a concentration of 6% by mass.
The obtained polymer electrolyte solution was cast and applied to a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., E5000 grade, thickness 100 μm) having a width of 300 mm, which was a supporting substrate, to form a cast film. Thereafter, the support substrate and the cast film were transferred to a hot air heater drying furnace set at 100 ° C., and the solvent was removed to form a film.
The obtained membrane was immersed in 2N sulfuric acid for 2 hours, then washed with ion-exchanged water, further air-dried, and then peeled off from the support base material to produce a polymer electrolyte membrane. The film thickness was 10 μm.

Mw 6.89 × 10 ⁵ [Condition 1]
α 4.8 (mmol / g)
Dimensional change rate 10.1%
Q 144

で表されるＷＯ ２０１１／０３０９２１［実施例８］に記載の方法で合成した重合体（Ｍｗ ３，２００、Ｍｎ １，７００：前記分析条件２で測定）２０．８７ｇと、２，２’−ビピリジン２６．２ｇと、Ｎ−メチル−２−ピロリドン９８ｇ、テトラヒドロフラン６４２ｇとを含む溶液を５０℃に昇温し、４，４’−ジクロロビフェニル−２，２’，６，６’−テトラスルホン酸テトラキス（２，２−ジメチル−１−プロピル）５０．０ｇと、ニッケル（０）ビス（シクロオクタジエン）４１．７ｇを加えてから７０℃に昇温し、２時間攪拌した。
得られた反応混合物をメタノール３６８７ｇに注ぎ込み析出物を濾過し、濾過して得られたケーキをメタノールで３回、１７％塩酸で２回、水で１１回洗浄し乾燥した。
乾燥したケーキをＮ−メチル−２−ピロリドン１３３５ｇに溶解した後、３５％塩酸を４０．７ｇ加え１２０℃で１５時間攪拌した。
得られた混合物をアセトン４２１９ｇに注ぎ込み、結晶を析出させた後、得られたケーキをアセトンで１回、１３．２％塩酸で３回、熱水で５回、水で１回洗浄し、乾燥することにより、下記式（００１ａ）で表される繰り返し単位と、下記式（００３ｐ）で表される構造とを含む高分子電解質を得た。収量は３９．０９ｇであった。

（ｈは繰り返し単位数を表す。）

上述のように重合して得られた高分子電解質をジエチレングリコールジエチルエーテルに溶解して、濃度が５質量％の高分子電解質溶液を調製した。
得られた高分子電解質溶液を、支持基材である巾３００ｍｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡績社製、Ｅ５０００グレード、厚さ１００μｍ）に流延塗布して、流延膜を形成した。その後、支持基板と流延膜とを１００℃に設定した熱風ヒーター乾燥炉へと搬送し、溶媒を除去して成膜した。
得られた膜を２Ｎ硫酸に２時間浸漬後、イオン交換水で水洗し、更に風乾した後に支持基材から剥離することで、高分子電解質膜を作製した。膜厚は１０μｍであった。

Ｍｗ １７．６０×１０⁵［ 条件１ ］
α ４．８（ｍｍｏｌ／ｇ）
寸法変化率 ８．３％
Ｑ ３６５
Example 2
In a nitrogen reaction atmosphere in a glass reaction vessel equipped with a cooling device, the following formula (i)

20.87 g of a polymer synthesized by the method described in WO 2011/030921 [Example 8] (Mw 3,200, Mn 1,700: measured under the above-described analysis condition 2) and 2,2′- A solution containing 26.2 g of bipyridine, 98 g of N-methyl-2-pyrrolidone and 642 g of tetrahydrofuran was heated to 50 ° C., and 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid. After adding 50.0 g of tetrakis (2,2-dimethyl-1-propyl) and 41.7 g of nickel (0) bis (cyclooctadiene), the temperature was raised to 70 ° C. and stirred for 2 hours.
The obtained reaction mixture was poured into 3687 g of methanol, the precipitate was filtered, and the cake obtained by filtration was washed with methanol 3 times, 17% hydrochloric acid twice, water 11 times and dried.
The dried cake was dissolved in 1335 g of N-methyl-2-pyrrolidone, 40.7 g of 35% hydrochloric acid was added, and the mixture was stirred at 120 ° C. for 15 hours.
The obtained mixture was poured into 4219 g of acetone to precipitate crystals, and the resulting cake was washed once with acetone, three times with 13.2% hydrochloric acid, five times with hot water and once with water, and then dried. As a result, a polymer electrolyte containing a repeating unit represented by the following formula (001a) and a structure represented by the following formula (003p) was obtained. The yield was 39.09g.

(H represents the number of repeating units.)

The polymer electrolyte obtained by polymerization as described above was dissolved in diethylene glycol diethyl ether to prepare a polymer electrolyte solution having a concentration of 5% by mass.
The obtained polymer electrolyte solution was cast and applied to a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., E5000 grade, thickness 100 μm) having a width of 300 mm, which was a supporting substrate, to form a cast film. Thereafter, the support substrate and the cast film were transferred to a hot air heater drying furnace set at 100 ° C., and the solvent was removed to form a film.
The obtained membrane was immersed in 2N sulfuric acid for 2 hours, then washed with ion-exchanged water, further air-dried, and then peeled off from the support base material to produce a polymer electrolyte membrane. The film thickness was 10 μm.

Mw 17.60 × 10 ⁵ [Condition 1]
α 4.8 (mmol / g)
Dimensional change rate 8.3%
Q 365

で表されるＷＯ ２０１１／０３０９２１［実施例８］に記載の方法で合成した重合体（Ｍｗ ３，２００、Ｍｎ １，７００：前記分析条件２で測定）６．７３ｇをＮ−メチル−２−ピロリドン７５ｇに溶解させ、１．５％メタンスルホン酸を含むＮ−メチル−２−ピロリドン２．５６ｇを加えた後４０℃で３時間加熱し得られた溶液に加えた。その後、５０℃で２時間攪拌した。
得られた反応混合物を７．３％塩酸３０６ｇに注ぎ込み析出物を濾過し、濾過して得られたケーキを７．３％塩酸で１回洗浄し、さらに濾液のｐＨが４を超えるまで水洗を行なった。次に、冷却器を備えたフラスコに、ケーキと、ケーキと水との合計重量が３１１ｇになるように水を加え、さらに、メタノール３１１ｇを加え、バス温９０℃で１時間過熱攪拌した。ケーキを濾過し、メタノールで１回洗浄し乾燥した。
乾燥したケーキをＮ−メチル−２−ピロリドン１４３ｇに溶解した後、３５％塩酸を１０．１ｇ加え１２０℃で２０時間攪拌した。
得られた混合物をアセトン６７１ｇに注ぎ込み、結晶を析出させた後、得られたケーキをアセトンで１回、１３．２％塩酸で２回、熱水で５回、水で１回洗浄し、乾燥することにより、下記式（００１ａ）で表される繰り返し単位と、下記式（００３ｐ）で表される構造とを含む高分子電解質を得た。収量は３．６３ｇであった。

（ｈは繰り返し単位数を表す。）

上述のように重合して得られた高分子電解質をジエチレングリコールジエチルエーテルに溶解して、濃度が１０質量％の高分子電解質溶液を調製した。
得られた高分子電解質溶液を、支持基材である巾３００ｍｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡績社製、Ｅ５０００グレード、厚さ１００μｍ）に流延塗布して、流延膜を形成した。その後、支持基板と流延膜とを１００℃に設定した熱風ヒーター乾燥炉へと搬送し、溶媒を除去して成膜した。
得られた膜を２Ｎ硫酸に２時間浸漬後、イオン交換水で水洗し、更に風乾した後に支持基材から剥離することで、高分子電解質膜を作製した。膜厚は１０μｍであった。

Ｍｗ １．８２×１０⁵［ 条件１ ］
α ３．８（ｍｍｏｌ／ｇ）
寸法変化率 １１．４％
Ｑ ４８
Example 3
In a glass reaction vessel equipped with a cooling device, 5.45 g of nickel bromide and 3.89 g of 2,2′-bipyridine were dissolved in 75 g of N-methyl-2-pyrrolidone at 70 ° C. in a nitrogen atmosphere at room temperature. The solution obtained by stirring for 2 hours was charged with 3.26 g of zinc powder, tetrakis (2,2-dimethyl-1-propyl) 10,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid 10 0.0 g, the following formula (i)

A polymer synthesized by the method described in WO 2011/030921 [Example 8] (Mw 3,200, Mn 1,700: measured under the above-mentioned analysis condition 2) 6.73 g was added to N-methyl-2- It was dissolved in 75 g of pyrrolidone, 2.56 g of N-methyl-2-pyrrolidone containing 1.5% methanesulfonic acid was added, and the mixture was added to the resulting solution heated at 40 ° C. for 3 hours. Then, it stirred at 50 degreeC for 2 hours.
The obtained reaction mixture was poured into 306 g of 7.3% hydrochloric acid, the precipitate was filtered, the cake obtained by filtration was washed once with 7.3% hydrochloric acid, and further washed with water until the pH of the filtrate exceeded 4. I did it. Next, water was added to a flask equipped with a condenser so that the total weight of the cake and the cake and water was 311 g, and further 311 g of methanol was added, followed by superheated stirring at a bath temperature of 90 ° C. for 1 hour. The cake was filtered, washed once with methanol and dried.
After the dried cake was dissolved in 143 g of N-methyl-2-pyrrolidone, 10.1 g of 35% hydrochloric acid was added and stirred at 120 ° C. for 20 hours.
The obtained mixture was poured into 671 g of acetone to precipitate crystals, and the obtained cake was washed once with acetone, twice with 13.2% hydrochloric acid, five times with hot water and once with water, and then dried. As a result, a polymer electrolyte containing a repeating unit represented by the following formula (001a) and a structure represented by the following formula (003p) was obtained. The yield was 3.63g.

(H represents the number of repeating units.)

The polymer electrolyte obtained by polymerization as described above was dissolved in diethylene glycol diethyl ether to prepare a polymer electrolyte solution having a concentration of 10% by mass.
The obtained polymer electrolyte solution was cast and applied to a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., E5000 grade, thickness 100 μm) having a width of 300 mm, which was a supporting substrate, to form a cast film. Thereafter, the support substrate and the cast film were transferred to a hot air heater drying furnace set at 100 ° C., and the solvent was removed to form a film.
The obtained membrane was immersed in 2N sulfuric acid for 2 hours, then washed with ion-exchanged water, further air-dried, and then peeled off from the support base material to produce a polymer electrolyte membrane. The film thickness was 10 μm.

Mw 1.82 × 10 ⁵ [Condition 1]
α 3.8 (mmol / g)
Dimensional change rate 11.4%
Q 48

で表されるＷＯ ２０１１／０３０９２１［実施例８］に記載の方法で合成した重合体（Ｍｗ ３，２００、Ｍｎ １，７００：前記分析条件２で測定）１０．０８ｇと、２，２’−ビピリジン１０．７５ｇと、Ｎ−メチル−２−ピロリドン３０ｇ、テトラヒドロフラン２７０ｇとを含む溶液を５０℃に昇温し、４，４’−ジクロロビフェニル−２，２’，６，６’−テトラスルホン酸テトラキス（２，２−ジメチル−１−プロピル）１５．０ｇと、ニッケル（０）ビス（シクロオクタジエン）１７．１ｇを加えてから７０℃に昇温し、２時間攪拌した。
得られた反応混合物をメタノール１１５８ｇに注ぎ込み析出物を濾過し、濾過して得られたケーキをメタノールで３回、１７％塩酸で２回洗浄し、さらに濾液のｐＨが４を超えるまで水洗を行なった。次に、冷却器を備えたフラスコに、ケーキと、ケーキと水との合計重量が４６６ｇになるように水を加え、さらに、メタノール４６６ｇを加え、バス温９０℃で１時間過熱攪拌した。ケーキを濾過し、メタノールで１回洗浄し乾燥した。
乾燥したケーキをＮ−メチル−２−ピロリドン６４５ｇに溶解した後、３５％塩酸を１４．０ｇ加え１２０℃で２０時間攪拌した。
得られた混合物をアセトン１７００ｇに注ぎ込み、結晶を析出させた後、得られたケーキをアセトンで１回、１３．２％塩酸で３回、熱水で５回、水で１回洗浄し、乾燥することにより、下記式（００１ａ）で表される繰り返し単位と、下記式（００３ｐ）で表される構造とを含む高分子電解質を得た。収量は１６．９８ｇであった。

（ｈは繰り返し単位数を表す。）

上述のように重合して得られた高分子電解質をジエチレングリコールジエチルエーテルに溶解して、濃度が５質量％の高分子電解質溶液を調製した。
得られた高分子電解質溶液を、支持基材である巾３００ｍｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡績社製、Ｅ５０００グレード、厚さ１００μｍ）に流延塗布して、流延膜を形成した。その後、支持基板と流延膜とを１００℃に設定した熱風ヒーター乾燥炉へと搬送し、溶媒を除去して成膜した。
得られた膜を２Ｎ硫酸に２時間浸漬後、イオン交換水で水洗し、更に風乾した後に支持基材から剥離することで、高分子電解質膜を作製した。膜厚は１０μｍであった。

Ｍｗ ９．６３×１０⁵［ 条件１ ］
α ４．０（ｍｍｏｌ／ｇ）
寸法変化率 ５．６％
Ｑ ２４１
Example 4
In a nitrogen reaction atmosphere in a glass reaction vessel equipped with a cooling device, the following formula (i)

10.2011 g of a polymer synthesized by the method described in WO 2011/030921 [Example 8] (Mw 3,200, Mn 1,700: measured under the above-mentioned analysis condition 2) and 2,2′- A solution containing 10.75 g of bipyridine, 30 g of N-methyl-2-pyrrolidone and 270 g of tetrahydrofuran was heated to 50 ° C., and 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid. After adding 15.0 g of tetrakis (2,2-dimethyl-1-propyl) and 17.1 g of nickel (0) bis (cyclooctadiene), the temperature was raised to 70 ° C. and stirred for 2 hours.
The obtained reaction mixture was poured into 1158 g of methanol, the precipitate was filtered, the cake obtained by filtration was washed 3 times with methanol and twice with 17% hydrochloric acid, and further washed with water until the pH of the filtrate exceeded 4. It was. Next, water was added to a flask equipped with a condenser so that the total weight of the cake and the cake and water was 466 g, and 466 g of methanol was further added, followed by superheated stirring at a bath temperature of 90 ° C. for 1 hour. The cake was filtered, washed once with methanol and dried.
After the dried cake was dissolved in 645 g of N-methyl-2-pyrrolidone, 14.0 g of 35% hydrochloric acid was added and stirred at 120 ° C. for 20 hours.
The obtained mixture was poured into 1700 g of acetone to precipitate crystals, and the obtained cake was washed once with acetone, three times with 13.2% hydrochloric acid, five times with hot water and once with water, and then dried. As a result, a polymer electrolyte containing a repeating unit represented by the following formula (001a) and a structure represented by the following formula (003p) was obtained. The yield was 16.98g.

(H represents the number of repeating units.)

The polymer electrolyte obtained by polymerization as described above was dissolved in diethylene glycol diethyl ether to prepare a polymer electrolyte solution having a concentration of 5% by mass.
The obtained polymer electrolyte solution was cast and applied to a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., E5000 grade, thickness 100 μm) having a width of 300 mm, which was a supporting substrate, to form a cast film. Thereafter, the support substrate and the cast film were transferred to a hot air heater drying furnace set at 100 ° C., and the solvent was removed to form a film.
The obtained membrane was immersed in 2N sulfuric acid for 2 hours, then washed with ion-exchanged water, further air-dried, and then peeled off from the support base material to produce a polymer electrolyte membrane. The film thickness was 10 μm.

Mw 9.63 × 10 ⁵ [Condition 1]
α 4.0 (mmol / g)
Dimensional change rate 5.6%
Q 241

上述のように重合して得られた高分子電解質をジエチレングリコールジエチルエーテルに溶解して、濃度が４質量％の高分子電解質溶液を調製した。
得られた高分子電解質溶液を、支持基材である巾３００ｍｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡績社製、Ｅ５０００グレード、厚さ１００μｍ）に流延塗布して、流延膜を形成した。その後、支持基板と流延膜とを１００℃に設定した熱風ヒーター乾燥炉へと搬送し、溶媒を除去して成膜した。
得られた膜を２Ｎ硫酸に２時間浸漬後、イオン交換水で水洗し、更に風乾した後に支持基材から剥離することで、高分子電解質膜を作製した。膜厚は１０μｍであった。

Ｍｗ １．９９×１０⁵［ 条件１ ］
α ４．７（ｍｍｏｌ／ｇ）
寸法変化率 ０．４％
Ｑ ４２
Example 5
In a glass reaction vessel equipped with a cooling device, 29.9 g of nickel bromide and 21.4 g of 2,2′-bipyridine were dissolved in 192 g of N-methyl-2-pyrrolidone at room temperature in a nitrogen atmosphere at room temperature. The solution obtained by stirring for 2 hours was charged with 17.91 g of zinc powder, 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetrakis (2,2-dimethyl-1-propyl) 40 1.0 g, 22.5-g of 2,5-dichlorobenzophenone dissolved in 68 g of N-methyl-2-pyrrolidone and 260 g of dioxane, and 14.0 g of N-methyl-2-pyrrolidone containing 1.5% methanesulfonic acid was added. After that, it was heated at 40 ° C. for 3 hours and added to the resulting solution. Then, it stirred at 50 degreeC for 2 hours.
The obtained reaction mixture was poured into 2013 g of methanol, the precipitate was filtered, and the cake obtained by filtration was washed 3 times with methanol and twice with 17% hydrochloric acid, and further washed with water until the pH of the filtrate exceeded 4. It was. Next, water was added to a flask equipped with a condenser so that the total weight of the cake and the cake and water was 1243 g, and 1243 g of methanol was further added, followed by superheated stirring at a bath temperature of 90 ° C. for 1 hour. The cake was filtered, washed once with methanol and dried.
After the dried cake was dissolved in 965 g of N-methyl-2-pyrrolidone, 37.22 g of 35% hydrochloric acid was added and stirred at 120 ° C. for 20 hours.
The obtained mixture was poured into 1040 g of acetone to precipitate crystals, and the obtained cake was washed once with acetone, three times with 13.2% hydrochloric acid, twice with hot water and six times with water, and dried. As a result, a polymer electrolyte containing a repeating unit represented by the following formula (001a) and a structure represented by the following formula (002r) was obtained. The yield was 36.36g.

The polymer electrolyte obtained by polymerization as described above was dissolved in diethylene glycol diethyl ether to prepare a polymer electrolyte solution having a concentration of 4% by mass.
The obtained polymer electrolyte solution was cast and applied to a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., E5000 grade, thickness 100 μm) having a width of 300 mm, which was a supporting substrate, to form a cast film. Thereafter, the support substrate and the cast film were transferred to a hot air heater drying furnace set at 100 ° C., and the solvent was removed to form a film.
The obtained membrane was immersed in 2N sulfuric acid for 2 hours, then washed with ion-exchanged water, further air-dried, and then peeled off from the support base material to produce a polymer electrolyte membrane. The film thickness was 10 μm.

Mw 1.99 × 10 ⁵ [Condition 1]
α 4.7 (mmol / g)
Dimensional change rate 0.4%
Q42

で表されるＪＰ ２０１０／２７２３６３［実施例Ｂ２］に記載の方法で合成した重合体（Ｍｗ １１，０００、Ｍｎ １８，０００：前記分析条件２で測定）１７．８ｇと、２，２’−ビピリジン２４．８ｇと、Ｎ−メチル−２−ピロリドン８８ｇ、テトラヒドロフラン７９２ｇとを含む溶液を５０℃に昇温し、４，４’−ジクロロビフェニル−２，２’，６，６’−テトラスルホン酸テトラキス（２，２−ジメチル−１−プロピル）４４．０ｇと、ニッケル（０）ビス（シクロオクタジエン）３９．６ｇを加えてから７０℃に昇温し、２時間攪拌した。
得られた反応混合物をメタノール２７６５ｇに注ぎ込み析出物を濾過し、濾過して得られたケーキをメタノールで３回、１７％塩酸で２回洗浄し、さらに濾液のｐＨが４を超えるまで水洗を行なった。次に、冷却器を備えたフラスコに、ケーキと、ケーキと水との合計重量が１１５４ｇになるように水を加え、さらに、メタノール１１５４ｇを加え、バス温９０℃で１時間過熱攪拌した。ケーキを濾過し、メタノールで１回洗浄し乾燥した。
乾燥したケーキをＮ−メチル−２−ピロリドン１４２８ｇに溶解した後、３５％塩酸を４６．４ｇ加え１２０℃で１６時間攪拌した。
得られた混合物をアセトン４５９２ｇに注ぎ込み、結晶を析出させた後、得られたケーキをアセトンで１回、１３．２％塩酸で３回、熱水で５回、水で１回洗浄し、乾燥することにより、下記式（００１ａ）で表される繰り返し単位と、下記式（００３ｐ）で表される構造とを含む高分子電解質を得た。収量は４１．３１ｇであった。

（ｈは繰り返し単位数を表す。）

上述のように重合して得られた高分子電解質をジメチルスルホキシドに溶解して、濃度が３質量％の高分子電解質溶液を調製した。
得られた高分子電解質溶液を、支持基材である巾３００ｍｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡績社製、Ｅ５０００グレード、厚さ１００μｍ）に流延塗布して、流延膜を形成した。その後、支持基板と流延膜とを１００℃に設定した熱風ヒーター乾燥炉へと搬送し、溶媒を除去して成膜した。
得られた膜を２Ｎ硫酸に２時間浸漬後、イオン交換水で水洗し、更に風乾した後に支持基材から剥離することで、高分子電解質膜を作製した。膜厚は１０μｍであった。

Ｍｗ ２３．１８×１０⁵［ 条件１ ］
α ４．７（ｍｍｏｌ／ｇ）
寸法変化率 ７．１％
Ｑ ４９３
Example 6
In a glass reaction vessel equipped with a cooling device, under a nitrogen atmosphere, the following formula (ii)

17.8 g of a polymer synthesized by the method described in JP 2010/272363 [Example B2] represented by the formula (Mw 11,000, Mn 18,000: measured under the above-mentioned analytical condition 2), and 2,2′- A solution containing 24.8 g of bipyridine, 88 g of N-methyl-2-pyrrolidone and 792 g of tetrahydrofuran was heated to 50 ° C., and 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid. After adding 44.0 g of tetrakis (2,2-dimethyl-1-propyl) and 39.6 g of nickel (0) bis (cyclooctadiene), the mixture was heated to 70 ° C. and stirred for 2 hours.
The obtained reaction mixture was poured into 2765 g of methanol, and the precipitate was filtered. The cake obtained by filtration was washed 3 times with methanol and twice with 17% hydrochloric acid, and further washed with water until the pH of the filtrate exceeded 4. It was. Next, water was added to a flask equipped with a cooler so that the total weight of the cake and the cake and water was 1154 g, and 1154 g of methanol was further added, followed by superheated stirring at a bath temperature of 90 ° C. for 1 hour. The cake was filtered, washed once with methanol and dried.
After the dried cake was dissolved in 1428 g of N-methyl-2-pyrrolidone, 46.4 g of 35% hydrochloric acid was added and stirred at 120 ° C. for 16 hours.
The obtained mixture was poured into 4592 g of acetone to precipitate crystals, and the obtained cake was washed once with acetone, three times with 13.2% hydrochloric acid, five times with hot water and once with water, and then dried. As a result, a polymer electrolyte containing a repeating unit represented by the following formula (001a) and a structure represented by the following formula (003p) was obtained. The yield was 41.31 g.

(H represents the number of repeating units.)

The polymer electrolyte obtained by polymerization as described above was dissolved in dimethyl sulfoxide to prepare a polymer electrolyte solution having a concentration of 3% by mass.
The obtained polymer electrolyte solution was cast and applied to a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., E5000 grade, thickness 100 μm) having a width of 300 mm, which was a supporting substrate, to form a cast film. Thereafter, the support substrate and the cast film were transferred to a hot air heater drying furnace set at 100 ° C., and the solvent was removed to form a film.
The obtained membrane was immersed in 2N sulfuric acid for 2 hours, then washed with ion-exchanged water, further air-dried, and then peeled off from the support base material to produce a polymer electrolyte membrane. The film thickness was 10 μm.

Mw 23.18 × 10 ⁵ [Condition 1]
α 4.7 (mmol / g)
Dimensional change rate 7.1%
Q 493

で表されるＪＰ ２０１０／２７２３６３［実施例Ｂ１］に記載の方法で合成した重合体（Ｍｗ １０，０００、Ｍｎ １６，０００：前記分析条件２で測定）２１．５ｇをＮ−メチル−２−ピロリドン２０８ｇに溶解させ、１．５％メタンスルホン酸を含むＮ−メチル−２−ピロリドン３．７１ｇを加えた後４０℃で３時間加熱し得られた溶液に加えた。その後、７０℃で２時間攪拌した。
得られた反応混合物を２−ブタノン３３１ｇと、トルエン８０ｇと、Ｎ−メチル−２−ピロリドン４５ｇをと含む溶液に注ぎ込み、１８．９％塩酸１９７ｇを加え、８０度で１時間攪拌した。静置した後、有機層を分離した。分離した有機層にＮ−メチル−２−ピロリドン９５７ｇを加え、減圧条件下で溶媒７０２ｇを留去した。得られた混合物に３５％塩酸を２６．１ｇ加え１２０℃で２０時間攪拌した。
得られた混合物をアセトン１９３９ｇに注ぎ込み、結晶を析出させた後、得られたケーキをアセトンで１回、１３．２％塩酸で３回、熱水で５回、水で１回洗浄し、乾燥することにより、下記式（００１ａ）で表される繰り返し単位と、下記式（００３ｂ）で表される構造とを含む高分子電解質を得た。収量は３３．４８ｇであった。

（ｈは繰り返し単位数を表す。）

上述のように重合して得られた高分子電解質をジメチルスルホキシドに溶解して、濃度が１０質量％の高分子電解質溶液を調製した。
得られた高分子電解質溶液を、支持基材である巾３００ｍｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡績社製、Ｅ５０００グレード、厚さ１００μｍ）に流延塗布して、流延膜を形成した。その後、支持基板と流延膜とを１００℃に設定した熱風ヒーター乾燥炉へと搬送し、溶媒を除去して成膜した。
得られた膜を２Ｎ硫酸に２時間浸漬後、イオン交換水で水洗し、更に風乾した後に支持基材から剥離することで、高分子電解質膜を作製した。膜厚は１０μｍであった。

Ｍｗ １．７８×１０⁵［ 条件１ ］
α ３．５（ｍｍｏｌ／ｇ）
寸法変化率 ６．５％
Ｑ ５１
Example 7
In a glass reaction vessel equipped with a cooling device, in a nitrogen atmosphere at room temperature, 2.37 g of nickel bromide, 2.37 g of 4,4′-dimethyl-2,2′-bipyridine, 4,4′-bis (methoxy) Carbonyl) -2,2′-bipyridine (0.296 g) was dissolved in N-methyl-2-pyrrolidone (78 g), stirred at 70 ° C. for 1 hour, and then added with 260 g of toluene. 26.0 g of 4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetrakis (2,2-dimethyl-1-propyl), the following formula (iii)

21.5 g of a polymer synthesized by the method described in JP 2010/272363 [Example B1] (Mw 10,000, Mn 16,000: measured under the above-described analytical condition 2) was added to N-methyl-2- The resultant was dissolved in 208 g of pyrrolidone, 3.71 g of N-methyl-2-pyrrolidone containing 1.5% methanesulfonic acid was added, and the mixture was added to the resulting solution heated at 40 ° C. for 3 hours. Then, it stirred at 70 degreeC for 2 hours.
The obtained reaction mixture was poured into a solution containing 331 g of 2-butanone, 80 g of toluene, and 45 g of N-methyl-2-pyrrolidone, 197 g of 18.9% hydrochloric acid was added, and the mixture was stirred at 80 ° C. for 1 hour. After standing, the organic layer was separated. 957 g of N-methyl-2-pyrrolidone was added to the separated organic layer, and 702 g of the solvent was distilled off under reduced pressure. To the obtained mixture, 26.1 g of 35% hydrochloric acid was added and stirred at 120 ° C. for 20 hours.
The obtained mixture was poured into 1939 g of acetone to precipitate crystals, and the obtained cake was washed once with acetone, three times with 13.2% hydrochloric acid, five times with hot water and once with water, and then dried. As a result, a polymer electrolyte containing a repeating unit represented by the following formula (001a) and a structure represented by the following formula (003b) was obtained. The yield was 33.48g.

(H represents the number of repeating units.)

The polymer electrolyte obtained by polymerization as described above was dissolved in dimethyl sulfoxide to prepare a polymer electrolyte solution having a concentration of 10% by mass.
The obtained polymer electrolyte solution was cast and applied to a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., E5000 grade, thickness 100 μm) having a width of 300 mm, which was a supporting substrate, to form a cast film. Thereafter, the support substrate and the cast film were transferred to a hot air heater drying furnace set at 100 ° C., and the solvent was removed to form a film.
The obtained membrane was immersed in 2N sulfuric acid for 2 hours, then washed with ion-exchanged water, further air-dried, and then peeled off from the support base material to produce a polymer electrolyte membrane. The film thickness was 10 μm.

Mw 1.78 × 10 ⁵ [Condition 1]
α 3.5 (mmol / g)
Dimensional change rate 6.5%
Q 51

で表されるＷＯ ２０１１／０３０９２１［実施例８］に記載の方法で合成した重合体（Ｍｗ ３，２００、Ｍｎ １，７００：前記分析条件２で測定）３．１８ｇをＮ−メチル−２−ピロリドン６０ｇに溶解させ、１．５％メタンスルホン酸を含むＮ−メチル−２−ピロリドン１．８９ｇを加えた後４０℃で３時間加熱し得られた溶液に加えた。その後、５０℃で２時間攪拌した。
得られた反応混合物を７．３％塩酸２８４ｇに注ぎ込み析出物を濾過し、濾過して得られたケーキを７．３％塩酸で１回洗浄し、さらに濾液のｐＨが４を超えるまで水洗を行なった。次に、冷却器を備えたフラスコに、ケーキと、ケーキと水との合計重量が３１１ｇになるように水を加え、さらに、メタノール３１１ｇを加え、バス温９０℃で１時間過熱攪拌した。ケーキを濾過し、メタノールで１回洗浄し乾燥した。
乾燥したケーキをＮ−メチル−２−ピロリドン６３ｇに溶解した後、３５％塩酸を８．０９ｇ加え１２０℃で２０時間攪拌した。
得られた混合物をアセトン２３０ｇに注ぎ込み、結晶を析出させた後、得られたケーキをアセトンで１回、１３．２％塩酸で２回、熱水で５回、水で１回洗浄し、乾燥することにより、下記式（００１ａ）で表される繰り返し単位と、下記式（００３ｐ）で表される構造とを含む高分子電解質を得た。収量は３．６３ｇであった。

（ｈは繰り返し単位数を表す。）

上述のように重合して得られた高分子電解質をジメチルスルホキシドに溶解して、濃度が１０質量％の高分子電解質溶液を調製した。
得られた高分子電解質溶液を、支持基材である巾３００ｍｍのポリエチレンテレフタレート（ＰＥＴ）フィルム（東洋紡績社製、Ｅ５０００グレード、厚さ１００μｍ）に流延塗布して、流延膜を形成した。その後、支持基板と流延膜とを１００℃に設定した熱風ヒーター乾燥炉へと搬送し、溶媒を除去して成膜した。
得られた膜を２Ｎ硫酸に２時間浸漬後、イオン交換水で水洗し、更に風乾した後に支持基材から剥離することで、高分子電解質膜を作製した。膜厚は１０μｍであった。

Ｍｗ １．２０×１０⁵［ 条件１ ］
α ４．８（ｍｍｏｌ／ｇ）
寸法変化率 １９．１％
Ｑ ２５
Comparative Example 1
In a glass reaction vessel equipped with a cooling device, 3.88 g of nickel bromide was dissolved in 60 g of N-methyl-2-pyrrolidone at room temperature in a nitrogen atmosphere and stirred at 70 ° C. for 1 hour, then 2,2′- 2.77 g of bipyridine was added, and the resulting solution was added with 2.32 g of zinc powder, tetrakis (2,2-dimethyl-1-propyl) 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonate. 8.0 g, following formula (i)

A polymer synthesized by the method described in WO 2011/030921 [Example 8] (Mw 3,200, Mn 1,700: measured under the above analysis condition 2) 3.18 g of N-methyl-2- It was dissolved in 60 g of pyrrolidone, 1.89 g of N-methyl-2-pyrrolidone containing 1.5% methanesulfonic acid was added, and then the mixture was heated at 40 ° C. for 3 hours and added to the resulting solution. Then, it stirred at 50 degreeC for 2 hours.
The obtained reaction mixture was poured into 284 g of 7.3% hydrochloric acid, the precipitate was filtered, the cake obtained by filtration was washed once with 7.3% hydrochloric acid, and further washed with water until the pH of the filtrate exceeded 4. I did it. Next, water was added to a flask equipped with a condenser so that the total weight of the cake and the cake and water was 311 g, and further 311 g of methanol was added, followed by superheated stirring at a bath temperature of 90 ° C. for 1 hour. The cake was filtered, washed once with methanol and dried.
After the dried cake was dissolved in 63 g of N-methyl-2-pyrrolidone, 8.09 g of 35% hydrochloric acid was added and stirred at 120 ° C. for 20 hours.
The obtained mixture was poured into 230 g of acetone to precipitate crystals, and the obtained cake was washed once with acetone, twice with 13.2% hydrochloric acid, five times with hot water and once with water, and then dried. As a result, a polymer electrolyte containing a repeating unit represented by the following formula (001a) and a structure represented by the following formula (003p) was obtained. The yield was 3.63g.

(H represents the number of repeating units.)

The polymer electrolyte obtained by polymerization as described above was dissolved in dimethyl sulfoxide to prepare a polymer electrolyte solution having a concentration of 10% by mass.
The obtained polymer electrolyte solution was cast and applied to a polyethylene terephthalate (PET) film (Toyobo Co., Ltd., E5000 grade, thickness 100 μm) having a width of 300 mm, which was a supporting substrate, to form a cast film. Thereafter, the support substrate and the cast film were transferred to a hot air heater drying furnace set at 100 ° C., and the solvent was removed to form a film.
The obtained membrane was immersed in 2N sulfuric acid for 2 hours, then washed with ion-exchanged water, further air-dried, and then peeled off from the support base material to produce a polymer electrolyte membrane. The film thickness was 10 μm.

Mw 1.20 × 10 ⁵ [Condition 1]
α 4.8 (mmol / g)
Dimensional change rate 19.1%
Q 25

で表されるＷＯ ２０１１／０３０９２１［実施例８］に記載の方法で合成した芳香族化合物（Ｍｗ ３，２００、Ｍｎ １，７００：前記分析条件で測定）１８．８ｇをＮ−メチル−２−ピロリドン３１９ｇに溶解させ、５％メタンスルホン酸を含むＮ−メチル−２−ピロリドン６．９０ｇを加えた後４０℃で３時間加熱し得られた溶液に加えた。その後、７０℃で２時間重合反応を行い、下式（ｉ）で表される繰り返し単位と、下記式（００３ｐ）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４８０，０００、Ｍｎは１８２，０００［ 条件２ ］であった。

（ｈは繰り返し単位数を表す。）
Example 8
In a glass reaction vessel equipped with a cooling device, in a nitrogen atmosphere, at room temperature, 2.91 g of nickel bromide, 2.23 g of 4,4′-dimethyl-2,2′-bipyridine, 4,4′-bis (methoxy) Carbonyl) -2,2′-bipyridine (0.365 g) was dissolved in N-methyl-2-pyrrolidone (160 g), stirred at 70 ° C. for 1 hour, and then added with 479 g of toluene. 45.0 g of 4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetrakis (2,2-dimethyl-1-propyl), the following formula (vii)

18.8 g of an aromatic compound (Mw 3,200, Mn 1,700: measured under the above analysis conditions) synthesized by the method described in WO 2011/030921 [Example 8] It was dissolved in 319 g of pyrrolidone, 6.90 g of N-methyl-2-pyrrolidone containing 5% methanesulfonic acid was added, and the mixture was added to the resulting solution heated at 40 ° C. for 3 hours. Thereafter, a polymerization reaction was carried out at 70 ° C. for 2 hours to obtain a polymer containing a repeating unit represented by the following formula (i) and a structure represented by the following formula (003p). Mw of the obtained polymer was 480,000 and Mn was 182,000 [Condition 2].

(H represents the number of repeating units.)

（ｈは繰り返し単位数を表す。）
Example 9
In a glass reaction vessel equipped with a cooling device, in a nitrogen atmosphere at room temperature, nickel bromide 18.7 mg, 4,4′-dimethyl-2,2′-bipyridine 14.5 mg, 4,4′-bis (ethoxy) A solution obtained by dissolving 2.7 mg of carbonyl) -2,2′-bipyridine in 3 mL of N-methyl-2-pyrrolidone was dissolved in 57.4 mg of zinc powder, 4,4′-dichlorobiphenyl-2,2 ′, 6,6′-tetrasulfonic acid tetrakis (2,2-dimethyl-1-propyl) 283 mg, conjugated aromatic compound (Mw 3,200, Mn 1) synthesized by the method described in WO 2011/030921 [Example 8] , 700: measured under the above analysis conditions) 118 mg was dissolved in 3 mL of N-methyl-2-pyrrolidone, 0.65 mg of methanesulfonic acid was added, and the mixture was heated at 50 ° C. for 2 hours and added to the resulting solution. It was. Thereafter, a polymerization reaction was carried out at 70 ° C. for 4 hours to obtain a polymer containing a repeating unit represented by the following formula (i) and a structure represented by the following formula (003p). Mw of the obtained polymer was 369,000 and Mn was 162,000 [Condition 2].

(H represents the number of repeating units.)

（ｈは繰り返し単位数を表す。）
Example 10
In a glass reaction vessel equipped with a cooling apparatus, in a nitrogen atmosphere, at room temperature, 27.9 mg of nickel bromide, 24.2 mg of 4,4′-dimethoxy-2,2′-bipyridine, 4,4′-bis (methoxy) A solution obtained by dissolving 3.5 mg of carbonyl) -2,2′-bipyridine in 3 mL of N, N-dimethylacetamide was dissolved in 84.5 mg of zinc powder, 4,4′-dichlorobiphenyl-2,2 ′, 6. , 6′-tetrasulfonic acid tetrakis (2,2-dimethyl-1-propyl) 414 mg, a conjugated aromatic compound synthesized by the method described in WO 2011/030921 [Example 8] (Mw 3,200, Mn 1, 700 [Condition 2]) 173 mg was dissolved in 3 mL of N, N-dimethylacetamide, 0.95 mg of methanesulfonic acid was added and then heated at 50 ° C. for 2 hours and added to the resulting solution. Thereafter, a polymerization reaction was carried out at 70 ° C. for 4 hours to obtain a polymer containing a repeating unit represented by the following formula (i) and a structure represented by the following formula (003p). Mw of the obtained polymer was 525,000 and Mn was 217,000 [Condition 2].

(H represents the number of repeating units.)

（ｈは繰り返し単位数を表す。）
Example 11
In Example 10, 30.0 mg of 4,4′-bis (1,1-dimethylethyl) -2,2′-bipyridine was used instead of 24.2 mg of 4,4′-dimethoxy-2,2′-bipyridine. A polymer containing a repeating unit represented by the following formula (i) and a structure represented by the following formula (003p) was obtained. Mw of the obtained polymer was 307,000, and Mn was 143,000 [Condition 2].

(H represents the number of repeating units.)

（ｈは繰り返し単位数を表す。）
Example 12
The reaction was conducted in the same manner as in Example 10 except that 20.1 mg of 4,4′-dimethyl-2,2′-bipyridine was used instead of 24.2 mg of 4,4′-dimethoxy-2,2′-bipyridine. A polymer containing a repeating unit represented by the following formula (i) and a structure represented by the following formula (003p) was obtained. Mw of the obtained polymer was 502,000 and Mn was 218,000 [Condition 2].

(H represents the number of repeating units.)

（ｈは繰り返し単位数を表す。）
Example 13
The reaction was carried out in the same manner as in Example 10 except that 17.4 mg of 2,2′-bipyridine was used instead of 24.2 mg of 4,4′-dimethoxy-2,2′-bipyridine. A polymer containing a repeating unit represented by the following formula (003p) was obtained. Mw of the obtained polymer was 292,000 and Mn was 133,000 [Condition 2].

(H represents the number of repeating units.)

（ｈは繰り返し単位数を表す。）
Example 14
In Example 10, 4,4′-dimethoxy-2,2′-bipyridine 24.2 mg and 4,4′-bis (methoxycarbonyl) -2,2′-bipyridine 3.5 mg were used instead of 4,4′- Bis (1,1-dimethylethyl) -2,2′-bipyridine 19.3 mg, 4,4′-ditrifluoromethyl-2,2′-bipyridine 2.5. A reaction was carried out in the same manner except that mg was used to obtain a polymer containing a repeating unit represented by the following formula (i) and a structure represented by the following formula (003p). Mw of the obtained polymer was 50,000, and Mn was 26,000 [Condition 2].

(H represents the number of repeating units.)

（ｈは繰り返し単位数を表す。）
Example 15
The reaction was conducted in the same manner as in Example 10 except that 20.4 mg of 1,10-phenanthroline was used instead of 24.2 mg of 4,4′-dimethoxy-2,2′-bipyridine. The polymer containing the repeating unit and the structure represented by the following formula (003p) was obtained. Mw of the obtained polymer was 65,000, and Mn was 31,000 [Condition 2].

(H represents the number of repeating units.)

（ｈは繰り返し単位数を表す。） Example 16
In Example 10, the reaction was carried out in the same manner except that 29.7 mg of 4,7-diphenyl-1,10-phenanthroline was used instead of 24.2 mg of 4,4′-dimethoxy-2,2′-bipyridine. A polymer containing a repeating unit represented by the formula (i) and a structure represented by the following formula (003p) was obtained. Mw of the obtained polymer was 103,000, and Mn was 39,000 [Condition 2].

(H represents the number of repeating units.)

Claims (13)

A polymer having a structural unit represented by the following formula (001) in the main chain, the following —SO ₂ A ¹ , —SO ₂ A ² , —SO ₂ A ³ and —SO ₂ A ^{4 in the} polymer A polymer in which the total content α (mmol / g) exceeds 2.0, and the α and the weight average molecular weight Mw of the polymer satisfy the relationship of the following formula (X).

(A ^{1 to} A ⁴ each independently represents a group represented by the following formula (1a) or the following formula (1b).

(R ⁰¹¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group is a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. And may have at least one substituent selected from the group consisting of an aryloxyl group, an acyl group having 2 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms.)

(M represents a cation the cation may be a divalent or higher cation, the -O ^-. Is bonded to the other anions.)
R ^{001 to} R ⁰⁰⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl 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 aryloxyl group, a C2-C20 acyl group, or a cyano group is represented. The alkyl group, the alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. It may have at least one substituent selected from the group consisting of ˜20 aryloxyl groups and cyano groups. )
Mw / (α * 1000)> 25 (X) The polymer according to claim 1, further comprising a structural unit represented by the following formula (002) in the main chain.

(Ar ⁰⁰⁰ represents a divalent aromatic group. The aromatic group includes a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It may have at least one substituent selected from the group consisting of an aryloxyl group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and a cyano group, the alkyl group, the alkoxyl group, and the aryl. Group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms and a cyano group. It may have at least one substituent selected from the group consisting of:   The polymer of Claim 1 or 2 which has a block which has an ion exchange group, and a block which does not have an ion exchange group substantially.   The polymer according to claim 3, wherein the block having an ion exchange group has a structural unit represented by the formula (001) in the main chain. The polymer according to claim 3 or 4, wherein the block having substantially no ion exchange group has a structure represented by the following formula (003) in the main chain.

(Ar ^{1 to} Ar ⁴ each independently represents a divalent aromatic group. The aromatic group includes a fluorine atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, and a carbon number. The alkyl group may have at least one substituent selected from the group consisting of an aryl group having 6 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, and a cyano group. , The alkoxyl group, the aryl group, the aryloxyl group and the acyl group are each independently a fluorine atom, an alkoxyl 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. aryloxyl and good .Y ¹ and Y ² have at least one substituent selected from the group consisting of cyano groups, each independently, a single bond, a carbonyl group, sulfo Group, isopropylidene group, .Z ¹ and ^{Z 2} represents a hexafluoroisopropylidene group or a fluorene-9,9-diyl group, each independently, .a representing an oxygen atom or a sulfur atom, b and c, Each independently represents 0 or 1. h represents an integer of 2 or more.)   The polymer according to claim 5, wherein h is an integer of 5 or more. The polymer according to any one of claims 1 to 6, wherein each of A ^{1 to} A ⁴ is a group represented by the formula (1a), and R ⁰¹¹ is a hydrogen atom.   The electrolyte containing the polymer in any one of Claims 1-7.   An electrolyte membrane comprising the polymer electrolyte according to claim 8.   The electrolyte membrane according to claim 8, further comprising a porous substrate.   A catalyst composition comprising the polymer electrolyte according to claim 8 and a catalyst component.   The membrane electrode assembly which has at least 1 chosen from the group which consists of the electrolyte membrane of Claim 9 or 10, and the catalyst composition of Claim 11.   A fuel cell comprising the membrane electrode assembly according to claim 12.