WO2009113619A1

WO2009113619A1 - Process for production of aromatic polymer and starting compound for the same

Info

Publication number: WO2009113619A1
Application number: PCT/JP2009/054777
Authority: WO
Inventors: 大輔中村; 貴司山田; 有弘八代
Original assignee: 住友化学株式会社
Priority date: 2008-03-13
Filing date: 2009-03-12
Publication date: 2009-09-17
Also published as: JP2009263634A

Abstract

Disclosed is a process for producing an aromatic polymer, which involves a polymerization step of polymerizing a monomer represented by general formula (1) [wherein groups represented by X1 and X2 independently represent a condensable reacting group; Ar1 represents an aromatic group which may have a substituent; a group represented by E1 represents an ion exchange group or an ion exchange precursor group; and n represents an integer of 1 to 4, provided that when multiple E1's exist, the multiple E1's may be the same as or different from each other] in the copresence of a base and a first transition metal salt or a polymerization step of polymerizing a monomer represented by general formula (1) wherein E1 is a group represented by -(P(=O)(OR1)(OR2)) in the presence of a base.

Description

Method for producing aromatic polymer and raw material compound thereof

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

A polymer having an ion exchange group is used as a polymer electrolyte, and the polymer electrolyte is used as a polymer electrolyte membrane of a solid polymer fuel cell. A polymer electrolyte fuel cell (hereinafter may be abbreviated as “fuel cell”) is a power generation device that generates electricity through a chemical reaction between hydrogen and oxygen. High expectations are placed in the automotive industry and other fields. In recent years, inexpensive hydrocarbon polymer electrolytes have attracted attention as polymer electrolyte membranes for fuel cells, instead of conventional fluorine polymer electrolytes. Furthermore, as the hydrocarbon polymer electrolyte membrane, for example, an aromatic polymer electrolyte excellent in heat resistance is known (for example, Patent Document 1).

As a method for producing an aromatic polymer electrolyte, for example, a specific aromatic polymer compound called a polyether aromatic polymer is brominated with a brominating agent, and then in the presence of nickel halide in an organic solvent. A method is known in which a trialkyl phosphite is allowed to act to produce a phosphonic acid diester compound and the diester is further hydrolyzed to obtain an aromatic polymer (for example, see Patent Document 2). It was.

Japanese Patent No. 3861367 JP 2003-238678 A

However, the above-described method for producing an aromatic polymer has a large number of reaction steps and is not satisfactory. Moreover, it was not easy to adjust the ion exchange group density of the resulting aromatic polymer. Therefore, a method for producing an aromatic polymer having a small number of reaction steps and a method for producing an aromatic polymer capable of easily adjusting the ion exchange group density of the obtained aromatic polymer have been desired.

Under such circumstances, an object of the present invention is to provide a method for producing an aromatic polymer in which the number of reaction steps is small and the ion exchange group density can be easily adjusted, and a raw material compound used in the method. is there.

That is, the present invention provides the following [1].
[1] General formula (1)

(In the formula, groups represented by X ¹ and X ² each independently represent a condensable reactive group. Ar ¹ represents an optionally substituted aromatic group. The group represented by E ¹ is Represents an ion exchange group or an ion exchange precursor group, and n represents an integer of 1 to 4. When a plurality of E ¹ are present, the plurality of E ¹ may be the same or different. )
A polymerization step of polymerizing the monomer represented by the presence of a base and a first transition metal salt, or
Production of an aromatic polymer comprising a polymerization step of polymerizing the above monomer in which E ¹ is a group represented by — (P (═O) (OR ¹ ) (OR ² )) in the presence of a base Method.

The present invention provides the following [2] to [23] as preferred embodiments according to the above [1]. [2] General formula (1)

(In the formula, groups represented by X ¹ and X ² each independently represent a condensable reactive group. Ar ¹ represents an optionally substituted aromatic group. The group represented by E ¹ is Represents an ion exchange group or an ion exchange precursor group, and n represents an integer of 1 to 4. When a plurality of E ¹ are present, the plurality of E ¹ may be the same or different. )
The method for producing an aromatic polymer according to [1], comprising a polymerization step in which a monomer represented by the formula (I) is polymerized in the presence of a base and a first transition metal salt.
[3] and the polymerization step, in the general formula (1), a group represented by E ¹ at least part of (but group represented by E ¹ excluding the case where the ion-exchange group), with E ² Comprising the reaction step of converting to the group shown

(In the formula, Ar ² represents an aromatic group which may have a substituent. The group represented by E ² represents an ion-exchange group or an ion-exchange precursor group different from E ^1. m is 1 to 4) It represents an integer, Z is a group represented by -O- or -S-. in the case where E ² there are a plurality, E ² existing in plural numbers may each be the same or different.)
The manufacturing method of the aromatic polymer as described in [1] or [2] which has a repeating unit represented by these.
[4] The reaction step, a strong acid, trialkylsilyl halides, by the action of one or more members selected from the group consisting of base and nucleophile, at least part of the group represented by E ^1, in E ² The method for producing an aromatic polymer according to [3], which is a step of converting to the group shown.
[5] The method for producing an aromatic polymer according to any one of [1] to [4], wherein the ion exchange group is a phosphonic acid group, and the ion exchange precursor group is a phosphonic acid precursor group.
[6] The method for producing an aromatic polymer according to any one of [1] to [4], wherein the ion exchange group is a sulfonic acid group, and the ion exchange precursor group is a sulfonic acid precursor group.
[7] In the polymerization step, the monomer represented by the general formula (1) and the general formula (3)

(In the formula, groups represented by X ³ and X ⁴ each independently represent a condensable reactive group. Ar ³ represents an aromatic group which may have a substituent.)
The method for producing an aromatic polymer according to any one of [1] to [6], wherein the monomer represented by
[8] The method for producing an aromatic polymer according to any one of [1] to [7], wherein the groups represented by X ¹ and X ² are each independently a hydroxyl group or a mercapto group.
[9] The base is an alkali metal carbonate, alkali metal bicarbonate, alkali metal hydroxide, alkali metal hydride, alkaline earth metal carbonate, alkaline earth metal bicarbonate, alkaline earth metal hydroxide. And the method for producing an aromatic polymer according to any one of [1] to [8], which is at least one base selected from the group consisting of alkaline earth metal hydrides.
[10] The method for producing an aromatic polymer according to any one of [1] to [9], wherein the first transition metal salt is a copper salt.
[11] The method for producing an aromatic polymer according to [10], wherein the copper salt is a monovalent copper salt.
[12] The method for producing an aromatic polymer according to [11], wherein the monovalent copper salt is at least one selected from the group consisting of CuCl, CuBr, and CuI.
[13] General formula (4)

(In the formula, X ⁵ and X ⁶ each independently represent a condensable reactive group. Ar ⁴ represents an aromatic group which may have a substituent. P represents an integer of 1 to 4. R ¹ represents a hydrogen atom, an inorganic or organic cation, R ² represents an alkyl group or an aryl group. in the case where R ¹ and R ² there are a plurality, R ¹ and R ² existing in plural numbers, respectively identical It may or may not be.)
The manufacturing method of the aromatic polymer as described in [1] provided with the superposition | polymerization process which polymerizes the monomer represented by these in presence of a base.
[14] The method for producing an aromatic polymer according to [13], wherein the base is a base composed of a metal compound other than the first transition metal salt.
[15] At least part of the group represented by — (P (═O) (OR ¹ ) (OR ² )) in the general formula (4) and — (P (═O) (OH) ) (OR ³ )) and a reaction step for converting to a group represented by formula (5)

(In the formula, Ar ⁵ represents an aromatic group which may have a substituent. Q represents an integer of 1 to 4. Z ² represents —O—, —S— or —NR ⁴ — (R ⁴ the .R ³ represents a group represented by.) represents a hydrogen atom, an alkyl group or an aryl group represents a hydrogen atom, an alkyl group or an aryl group. in the case where R ³ there are a plurality, R ³ existing in plural Each may be the same or different.)
The method for producing an aromatic polymer according to [13] or [14], which has a repeating unit represented by:
[16] In the reaction step, a strong acid and / or a trialkylsilyl halide is allowed to act so that at least a part of the group represented by — (P (═O) (OR ¹ ) (OR ² )) is — ( The method for producing an aromatic polymer according to [15], which is a step of converting to a group represented by P (═O) (OH) (OR ³ )).
[17] In the polymerization step, the monomer represented by the general formula (4) and the general formula (6)

(In the formula, X ⁷ and X ⁸ each independently represent a condensable reactive group. Ar ⁶ represents an aromatic group which may have a substituent.)
Any one of [13] to [16], wherein a monomer having no group represented by-(P (= O) (OR ¹ ) (OR ² )) represented by A method for producing an aromatic polymer.
[18] The method for producing an aromatic polymer according to any one of [13] to [17], wherein both X ⁵ and X ⁶ are nucleophilic reactive groups.
[19] The method for producing an aromatic polymer according to [18], wherein the nucleophilic reactive group is a hydroxyl group.
[20] The method for producing an aromatic polymer according to any one of [13] to [19], wherein R ² is an alkyl group.
[21] The method for producing an aromatic polymer according to any one of [13] to [20], wherein the polymerization is performed at 100 ° C. or higher in the polymerization step.
[22] The method for producing an aromatic polymer according to any one of [13] to [21], wherein the base is an alkali metal salt.
[23] The method for producing an aromatic polymer according to any one of [13] to [22], wherein R ¹ is an organic cation.
[24] The same benzene as the benzene ring in which the group represented by — (P (═O) (OR ¹ ) (OR ² )) in the general formula (4) is substituted with X ⁵ and / or X ⁶ The method for producing an aromatic polymer according to any one of [13] to [23], wherein the ring is substituted.

Moreover, this application provides the following [25] and [26] as a raw material compound used for the manufacturing method of the aromatic high molecular phosphonic acid of this invention.
[25] General formula (7)

(In the formula, Ar ⁴ represents an aromatic group which may have a substituent. Q represents an integer of 1 to 4. R ¹ represents a hydrogen atom, an inorganic cation or an organic cation, and R ² represents an alkyl group. represents a group or an aryl group. in the case where R ¹ and R ² there are a plurality, R ¹ and R ² existing in plural numbers may each be the same or different.)
A compound represented by
[26] The compound according to [25], wherein Ar ⁴ is a biphenyl group which may have a substituent.

According to the present invention, since the monomer having the ion exchange group substituted in advance is polymerized, the ion exchange group density of the obtained aromatic polymer can be easily adjusted, and has various structures easily. Aromatic polymers can be produced. In addition, by using a monomer having a high ion exchange group substitution rate, an aromatic polymer having a high ion exchange group density can be obtained. Furthermore, since the production method of the present invention has high reactivity and conversion efficiency, the volumetric efficiency can be increased, leading to a reduction in process load.

Also, when the polymerization step is carried out in the coexistence of a base and a first transition metal salt, the monomer conversion rate is high and an aromatic polymer can be produced under mild reaction conditions. In the present invention, it is possible to use a monomer having a low reaction activity by a known polymerization method and a monomer that is easily decomposed by heat. Furthermore, the production method of the present invention is extremely useful industrially because the type of reaction solvent has little influence on polymerization.

A fuel cell using an aromatic polymer obtained by the production method of the present invention as a polymer electrolyte membrane can provide a fuel cell excellent in long-term stability while maintaining practically sufficient power generation performance. It is extremely useful industrially. In particular, a fuel cell using an aromatic polymer whose free acid form is a phosphonic acid group as a polymer electrolyte membrane is extremely useful industrially because it can provide a fuel cell with excellent durability.

Hereinafter, a preferred first embodiment of the present invention will be described in detail.

As described above, the method for producing an aromatic polymer according to the first embodiment is a polymerization in which the monomer represented by the general formula (1) is polymerized in the presence of a base and a first transition metal salt. A process is provided. Preferably, the above polymerization step, in the general formula (1), a group represented by E ¹ at least part of (but group represented by E ¹ excluding the case where the ion-exchange group), with E ² It is a manufacturing method of the aromatic polymer which has a repeating unit represented by General formula (2) provided with the reaction process converted into the group shown. The aromatic polymer obtained here is also referred to as an aromatic polymer electrolyte.

Therefore, in the following, the monomer used in the first embodiment, the polymerization step, the aromatic polymer electrolyte obtained by the production method of the first embodiment, the base, the first transition metal salt, and the reaction step in order. explain.

The monomer used in the first embodiment is a monomer represented by the general formula (1).

In the formula, groups represented by X ¹ and X ² each independently represent a condensable reactive group. Ar ¹ represents an aromatic group which may have a substituent. The group represented by E ¹ represents an ion exchange group or an ion exchange precursor group. n represents an integer of 1 to 4. When a plurality of E ¹ are present, the plurality of E ¹ may be the same or different.

Preferably, in addition to the monomer represented by the general formula (1), it is preferable to use a monomer represented by the general formula (3).

In the formula, X ³ and X ⁴ each independently represent a condensable reactive group. Ar ³ represents an aromatic group which may have a substituent.

X ¹ to X ⁴ in the general formulas (1) and (3) each independently represent a condensable reactive group. The condensable reactive group means a functional group that can be bonded via a divalent or trivalent group or atomic group by causing a condensation reaction with another condensable functional group. Examples of the condensable reactive group include a nucleophilic reactive group and a leaving group. Here, the nucleophilic reactive group represents a group having nucleophilicity, acts on the carbon atom to which the leaving group is bonded, and is newly added with the elimination of the leaving group by ipso substitution. A bond can be formed through a valent or trivalent group or atomic group. Moreover, a leaving group refers to the group which leaves | leaves with the addition of the nucleophilic reactive group to the carbon atom (epsocarbon) which the leaving group has couple | bonded.

Each of X ¹ to X ⁴ may be a nucleophilic reactive group or a leaving group, but when homopolymerization is performed with one kind of monomer described in the general formula (1), X ¹ And X ² , one is a nucleophilic reactive group and the other is a leaving group. Moreover, when copolymerizing 1 type of monomer of the said General formula (1), and 1 type of monomer of the said General formula (3), they are mention | raise | lifted following combination. That is,
(A) A case where X ¹ and X ² are nucleophilic reactive groups and X ³ and X ⁴ are leaving groups.
(B) When X ¹ and X ² are leaving groups and X ³ and X ⁴ are nucleophilic reactive groups.
(C) When X ¹ and X ³ are leaving groups, and X ² and X ⁴ are nucleophilic reactive groups.
However, the present invention is not limited to the case where two or more types of monomers described in the general formula (1) are used and / or the case where two or more types of monomers described in the general formula (3) are used.

Examples of the nucleophilic reactive group include a hydroxyl group and a mercapto group. Among these, a hydroxyl group is preferable. Representative examples of the leaving group include a fluoro group, a chloro group, a bromo group, an iodo group, a tosyl group, and a triflate group. Of these, the leaving group is preferably a chloro group.

The group represented by E ¹ in the general formula (1) represents an ion exchange group or an ion exchange precursor group. An ion exchange precursor group refers to the group used as an ion exchange group, without changing structures other than the ion exchange precursor group of an aromatic polymer electrolyte precursor. The ion exchange precursor group becomes an ion exchange group through a reaction of preferably within 3 stages, more preferably within 2 stages, still more preferably 1 stage. Representative examples of ion exchange groups include sulfonic acid groups, phosphonic acid groups, phosphinic acid groups, carboxylic acid groups, and the like. Among these, a sulfonic acid group and a phosphonic acid group are preferable, and a phosphonic acid group is preferable from the viewpoint of improving the solubility of the monomer by acting with the first transition metal salt. Representative examples of ion exchange precursor groups include sulfonic acid precursor groups, phosphonic acid precursor groups, phosphinic acid precursor groups, carboxylic acid precursor groups, and the like. The sulfonic acid precursor group is a group that becomes a sulfonic acid group through the above reaction, and the phosphonic acid precursor group is a group that becomes a phosphonic acid group through the above reaction, and phosphinic acid. The precursor group is a group that becomes a phosphinic acid group through the above reaction, and the carboxylic acid precursor group is a group that becomes a carboxylic acid group through the above reaction. Among these, a sulfonic acid precursor group and a phosphonic acid precursor group are preferable by acting with the first transition metal salt, and a phosphonic acid precursor group is preferable from the viewpoint of improving the solubility of the monomer.

Examples of the sulfonic acid precursor group include the following.
Sulfonic acid ester group: sulfonic acid neopentyl group, sulfonic acid t-butyl group and other sulfinic acid ester groups: sulfinic acid neopentyl group, sulfinic acid t-butyl group and other mercapto groups: sulfone such as methyl mercapto group, ethyl mercapto group and propyl mercapto group Acid base: sodium sulfonate group, potassium sulfonate group, lithium sulfonate group, ammonium sulfonate group, monomethylammonium sulfonate group, monoethylammonium sulfonate group, mono-n-propylammonium sulfonate group, mono-sulfonate group n-butylammonium group, dimethylammonium sulfonate group, diethylammonium sulfonate group, di-n-propylammonium group sulfonate, di-n-butylammonium sulfonate group, trime sulfonate Ruammonium group, triethylammonium sulfonate group, tri-n-propylammonium sulfonate group, tri-n-butylammonium sulfonate group, tetramethylammonium sulfonate group, tetraethylammonium sulfonate group, tetra-n-propyl sulfonate group Ammonium group, tetra-n-butylammonium sulfonate group, etc.

Examples of the phosphonic acid precursor group include the following.
Phosphonic acid diester group: phosphonic acid monoester group: phosphonic acid diethyl group, phosphonic acid di-n-butyl group, phosphonic acid di-t-butyl group, phosphonic acid dimethyl group, phosphonic acid diisopropyl group, phosphonic acid diphenyl group, etc. Phosphonic acid monoester bases such as acid monoethyl group, phosphonic acid mono-t-butyl group, phosphonic acid monomethyl group, and phosphonic acid monodiisopropyl group: ethyl phosphonate-sodium group, ethyl phosphonate-potassium group, ethyl phosphonate-lithium group Phosphonic acid ethyl-ammonium group, phosphonic acid ethyl-monomethylammonium group, phosphonic acid ethyl-monoethylammonium group, phosphonic acid ethyl-mono-n-propylammonium group, phosphonic acid ethyl-mono-n-butylammonium group, phospho Ethyl dimethylammonium group, ethyl phosphonate-diethylammonium group, ethyl phosphonate-di-n-propylammonium group, ethyl phosphonate-di-n-butylammonium group, ethyl phosphonate-trimethylammonium group, ethyl phosphonate -Triethylammonium group, ethyl phosphonate-tri-n-propylammonium group, ethyl phosphonate-tri-n-butylammonium group, ethyl phosphonate-tetramethylammonium group, ethyl phosphonate-tetraethylammonium group, ethyl phosphonate- Tetra-n-propylammonium group, ethyl phosphonate-tetra-n-butylammonium group, t-butyl-sodium phosphonate, t-butyl-potassium phosphonate, t-butyl-lithium phosphonate T-butyl-ammonium phosphonate, t-butyl-monomethylammonium phosphonate, t-butyl-monoethylammonium phosphonate, t-butyl-mono-n-propylammonium phosphonate, t-butyl-phosphonate Mono-n-butylammonium group, t-butyl-dimethylammonium phosphonate, t-butyl-diethylammonium phosphonate, t-butyl-di-n-propylammonium phosphonate, t-butyl-di-phosphonate n-butylammonium group, t-butyl-trimethylammonium phosphonate, t-butyl-triethylammonium phosphonate, t-butyl-tri-n-propylammonium phosphonate, t-butyl-tri-n-phosphonate Butylammonium group, phosphonic acid t-butyl Ru-tetramethylammonium group, t-butyl-tetraethylammonium phosphonate, t-butyl-tetra-n-propylammonium phosphonate, t-butyl-tetra-n-butylammonium phosphonate, methyl-sodium phosphonate Group, phosphonate methyl-potassium group, phosphonate methyl-lithium group, phosphonate methyl-ammonium group, phosphonate methyl-monomethylammonium group, phosphonate methyl-monoethylammonium group, phosphonate methyl-mono-n-propylammonium group Group, phosphonate methyl-mono-n-butylammonium group, phosphonate methyl-dimethylammonium group, phosphonate methyl-diethylammonium group, phosphonate methyl-di-n-propylammonium group, phosphonate methyl-di n-butylammonium group, phosphonate methyl-trimethylammonium group, phosphonate methyl-triethylammonium group, phosphonate methyl-tri-n-propylammonium group, phosphonate methyl-tri-n-butylammonium group, phosphonate methyl- Tetramethylammonium group, phosphonate methyl-tetraethylammonium group, phosphonate methyl-tetra-n-propylammonium group, phosphonate methyl-tetra-n-butylammonium group, phosphonate isopropyl-sodium group, phosphonate isopropyl-potassium group Isopropyl phosphonate-lithium group, isopropyl ammonium phosphonate group, isopropyl phosphonate monomethyl ammonium group, isopropyl phosphonate monoethyl ammonium group, Isopropyl sulfonate-mono-n-propylammonium group, isopropyl phosphonate-mono-n-butylammonium group, isopropyl phosphonate-dimethylammonium group, isopropyl phosphonate-diethylammonium group, isopropyl phosphonate-di-n-propylammonium phosphonate Group, isopropyl phosphonate-di-n-butylammonium group, isopropyl phosphonate-trimethylammonium group, isopropyl phosphonate-triethylammonium group, isopropyl phosphonate-tri-n-propylammonium group, isopropyl phosphonate-tri-n- Butylammonium group, isopropyl phosphonate-tetramethylammonium group, isopropyl phosphonate-tetraethylammonium group, isopropyl phosphonate-tetra -N-propylammonium group, phosphonate isopropyl-tetra-n-butylammonium group, etc. Phosphonate groups: sodium phosphonate group, potassium phosphonate group, lithium phosphonate group, ammonium phosphonate group, phosphonic acid-monomethylammonium group Phosphonic acid-monoethylammonium group, phosphonic acid-mono-n-propylammonium group, phosphonic acid-mono-n-butylammonium group, phosphonic acid-dimethylammonium group, phosphonic acid-diethylammonium group, phosphonic acid-di- n-propylammonium group, phosphonic acid-di-n-butylammonium group, phosphonic acid-trimethylammonium group, phosphonic acid-triethylammonium group, phosphonic acid-tri-n-propylammonium group, phosphonic acid-tri- - butyl ammonium group, phosphonic acid - tetramethyl ammonium group, phosphonic acid - tetraethyl ammonium group, phosphonic acid - tetra -n- propyl ammonium group, phosphonic acid - tetra -n- butylammonium group, and the like. These may be monocation salts, dication salts, or mixtures thereof.

Examples of the phosphinic acid group precursor group include the following.
Phosphinic acid ester group: Phosphinic acid ethyl group, Phosphinic acid t-butyl group, Phosphinic acid methyl group, Phosphinic acid diisopropyl group, etc. Phosphinic acid groups: Phosphinic acid sodium group, Phosphinic acid potassium group, Phosphinic acid lithium group, Phosphinic acid ammonium group Phosphinic acid-monomethylammonium group, phosphinic acid-monoethylammonium group, phosphinic acid-mono-n-propylammonium group, phosphinic acid-mono-n-butylammonium group, phosphinic acid-dimethylammonium group, phosphinic acid-diethylammonium group Group, phosphinic acid-di-n-propylammonium group, phosphinic acid-di-n-butylammonium group, phosphinic acid-trimethylammonium group, phosphinic acid-triethylammonium group, Sphineic acid-tri-n-propylammonium group, phosphinic acid-tri-n-butylammonium group, phosphinic acid-tetramethylammonium group, phosphinic acid-tetraethylammonium group, phosphinic acid-tetra-n-propylammonium group, phosphinic acid A tetra-n-butylammonium group, etc.

Examples of the carboxylic acid group precursor group include the following.
Carboxylic acid ester group: Carboxylic acid neopentyl group, Carboxylic acid t-butyl group and other carboxylic acid groups: Sodium carboxylate group, Carboxylic acid potassium group, Carboxylic acid lithium group, Carboxylic acid ammonium group, Carboxylic acid-monomethylammonium group, Carboxylic acid -Monoethylammonium group, carboxylic acid-mono-n-propylammonium group, carboxylic acid-mono-n-butylammonium group, carboxylic acid-dimethylammonium group, carboxylic acid-diethylammonium group, carboxylic acid-di-n-propyl Ammonium group, carboxylic acid-di-n-butylammonium group, carboxylic acid-trimethylammonium group, carboxylic acid-triethylammonium group, carboxylic acid-tri-n-propylammonium group, carboxylic acid-tri-n-butylammonium Beam group, carboxylic acid - tetramethyl ammonium group, a carboxylic acid - tetraethyl ammonium groups, carboxylic acid - tetra -n- propyl ammonium groups, carboxylic acid - tetra -n- butylammonium group, and the like. These may be all in the salt form or partly in the acid form.
A formyl group, a hydroxymethyl group, or a hydroxymethyl group obtained by introducing a protecting group to a hydroxyl group.

Ar ¹ and Ar ³ in the first embodiment represent an aromatic group that may have a substituent. The aromatic group may contain a hetero element, and preferably has 4 or more carbon atoms, more preferably 10 or more from the viewpoint of enhancing the reactivity of the condensation reaction. Further, from the viewpoint of increasing the density of ion exchange groups and / or ion exchange precursor groups in the obtained aromatic polymer electrolyte, the number of carbon atoms is preferably 24 or less, and more preferably 18 or less.

Examples of the aromatic group include aromatic groups represented by the following formulas (a) to (z). (In the formula, * represents a bond with X ¹ or X ² or X ³ or X ^{4, respectively,} and a bond with another substituent was omitted.)

Among them, Ar ¹ is preferably a phenylene group represented by the above (c) which may have a substituent, or a biphenyl group represented by (m), and may have a substituent. The biphenyl group represented by (m) is more preferable. Ar ³ is preferably a group represented by the above (x) which may have a substituent, or a group represented by (y), and in the above (y) which may have a substituent. It is more preferable that it is a group represented.

Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a cyano group, a nitro group, and benzoyl. Group.

The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include t-butyl group, isobutyl group, n-pentyl group, 2,2-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, 2-methylpentyl group and 2-ethylhexyl group.

The alkoxy group having 1 to 10 carbon atoms may be linear, branched or cyclic. For example, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, sec- Butyloxy group, t-butyloxy group, isobutyloxy group, n-pentyloxy group, 2,2-dimethylpropyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, 2-methylpentyloxy group, 2- An ethylhexyloxy group is mentioned.

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group, and examples of the aryloxy group having 6 to 10 carbon atoms include a phenoxy group and a naphthyloxy group.

These groups may be further substituted with a group selected from the group consisting of an amino group, a methoxy group, an ethoxy group, an isopropyloxy group, a phenyl group, and a phenoxy group.

Preferred monomers represented by the general formula (1) include monomers represented by the following formulas (aa) to (au). In the formula, phosphonic acid precursor groups are shown, but can be changed to the ion exchange groups or ion exchange precursor groups specifically mentioned above.

Among these, the above formulas (aa) and (ac) are preferable.

Preferred monomers represented by the general formula (3) include monomers represented by the following formulas (ca) to (cr).

Above all, the above formulas (cf), (cg), (ci), (cj), (cp), and (cq) are preferable because they are easily available and inexpensive.

As the monomer represented by the formula (1) of the first embodiment, it can be obtained as a commercial product or synthesized using a known method.

For example, when the group represented by E ¹ is a phosphonic acid precursor group, as a method for producing the monomer represented by the formula (1) of the first embodiment, X ¹ and X ² are a fluoro group and a chloro group. In the case of a leaving group such as a bromo group or an iodo group, the following production method can be exemplified, that is,
(1-1) A method of introducing a phosphonic acid diester group into an aromatic compound and then introducing the above leaving group and hydrolyzing it by a known method.
(1-2) A method of introducing a phosphonic acid diester group after introducing the above leaving group into an aromatic compound and hydrolyzing it by a known method.
As a method for introducing a phosphonic acid diester group, before introducing a phosphonic acid diester group into an aromatic compound, a reactive group selected from a chloro group, a bromo group, an iodo group, and the like is introduced, and then the following (2-1) to Examples thereof include a method for carrying out the substitution reaction listed in (2-5).
(2-1) Michaelis-Albuzov reaction in which a phosphoric acid triester is reacted using a Lewis acid such as nickel chloride.
(2-2) Michaelis-Becker reaction in which a phosphite diester is reacted using a base such as sodium hydride.
(2-3) A reaction in which a phosphorous acid diester is reacted using a zerovalent palladium catalyst such as tetrakis (triphenylphosphine) palladium.
(2-4) Grignard reaction in which magnesium is reacted to form a Grignard reagent and then a halogenated phosphoric acid diester is reacted.
(2-5) Reaction in which halogenated phosphoric acid diester is reacted after alkyllithium is reacted to form aryllithium.
Examples of the method for introducing the leaving group include a method in which a halogenating reagent selected from fluorine, chlorine, bromine, iodine and the like is allowed to act. In the method described in (1-2), when the reactive group and the leaving groups X ¹ and X ² are the same functional group, after introducing three or more functional groups into the aromatic compound The monomer represented by the formula (1) can be obtained by substituting a part of the functional group with a phosphonic acid group and hydrolyzing by a known method. As a specific method, for example, J. et al. Fluorine Chem. Known methods such as those described in 2004, 125, 1317 can be used.

When X ¹ and / or X ² is a nucleophilic reactive group, a protecting group is introduced into the nucleophilic reactive group, the nucleophilic reactive group is deactivated, and then the above substitution reaction is performed. Hydrolysis is preferred. The protecting group is not particularly limited as long as it is a group that can be deprotected after the above-described substitution reaction. Representative protecting groups for hydroxyl and mercapto groups include ethers such as benzyl and t-butyl groups. Group, an acetal group such as methoxymethyl group, an acyl group such as acetyl group and benzoyl group, and a silyl ether group such as t-butyldimethylsilyl group. Representative protecting groups for amine groups include carbamate groups such as t-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, imide groups such as phthaloyl group, p-toluene Examples thereof include sulfonamide groups such as a sulfonyl group and a 2-nitrobenzenesulfonyl group.

When X ¹ and / or X ² is a hydroxyl group, a halogenated phosphoric diester is allowed to act on the hydroxyl group to form a phosphate compound, which is then converted to a compound having a phosphonic diester group by a rearrangement reaction using a strong base. However, a method for hydrolysis may be used. As a specific method, for example, J. et al. Org. Chem. Known methods such as those described in 1984, 49, 4018 can be used.

As the monomer represented by the formula (3) of the first embodiment, for example, a commercially available product is used.

The aromatic polymer electrolyte obtained by the production method of the first embodiment comprises a monomer represented by the general formula (1) or a monomer represented by the general formulas (1) and (3) as a base. And a first transition metal salt. Other monomers may be used as long as the above effects are not impaired. Here, the aromatic polymer electrolyte is an ion exchange in which a divalent aromatic residue obtained by removing two hydrogen atoms from a compound having an aromatic ring is directly or via a connecting member as a structural unit. It means a polymer having a group and / or an ion exchange precursor group. The aromatic polymer electrolyte in the first embodiment may have a substituent. The aromatic polyelectrolyte in the first embodiment has an aromatic ring which may have a substituent in the main chain, and further an aromatic ring to which an ion exchange group and / or an ion exchange precursor group are directly bonded. It is preferable to have.

As the aromatic polymer electrolyte obtained by the production method of the first embodiment, those having a repeating unit represented by the general formula (2) are preferable.

In the formula, Ar ² represents an aromatic group which may have a substituent. The group represented by E ² represents an ion exchange group or an ion exchange precursor group different from E ¹ . m represents an integer of 1 to 4, and Z represents a group represented by —O— or —S—. When a plurality of E ² are present, the plurality of E ² may be the same or different.

Ar ² in the first embodiment represents an aromatic group that may have a substituent, and examples of the aromatic group include those described above. Specific examples include aromatic groups such as the above formulas (a) to (z) (in the formula, * represents a bond with a group represented by —Z—, and a bond with a substituent). Omitted.) Among these, the phenylene group represented by the above (c) or the biphenyl group represented by (m) is preferable. Examples of the substituent include those described above.

E ² in the first embodiment represents an ion exchange group or an ion exchange precursor group different from E ¹ . Specific examples of the ion exchange group and the ion exchange precursor group include those described above, preferably a phosphonic acid group and a phosphonic acid precursor group. Specific examples of the phosphonic acid precursor group include those described above.

Examples of the repeating unit represented by the general formula (2) include repeating units represented by the following formulas (da) to (ea). In the formula, phosphonic acid precursor groups are shown, but can be changed to the ion exchange groups or ion exchange precursor groups specifically mentioned above.

Among these, the above formulas (da) and (de) are preferable.

The aromatic polymer electrolyte having the repeating unit represented by the general formula (2) may be a homopolymer, a random copolymer, an alternating copolymer, a block copolymer, It may be a coalescence. These can be obtained according to known methods by selecting the corresponding monomers, their ratios, and the polymerization method. These polymerization degrees are preferably 5 or more and a weight average molecular weight of 10 ³ or more from the viewpoint of increasing mechanical strength. In addition, these polymerization degrees are 10 ⁴ or less and 10 ⁶ or less in terms of weight average molecular weight from the viewpoint of maintaining solubility in a solvent during film formation, workability such as cast film formation, and moldability. Preferably used. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

In the polymerization step of the first embodiment, when the monomer represented by the general formula (1) and the monomer represented by the general formula (3) are used, the weight ratio is 100: 0 to 1: 99 is preferable, and 50:50 to 10:90 is more preferable.

The polymerization step of the first embodiment is performed in the coexistence of a base and a first transition metal salt. Examples of the base include alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate, alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metals such as sodium hydroxide, potassium hydroxide and cesium hydroxide. Alkali metal hydrides such as hydroxide, sodium hydride, potassium hydride, alkaline earth metal carbonates such as calcium carbonate, alkaline earth metal hydrogen carbonates such as calcium bicarbonate, alkaline earths such as calcium hydroxide Examples thereof include metal hydroxides and alkaline earth metal hydrides such as calcium hydride. You may use 1 type, or 2 or more types from these. Among these, alkali metal carbonates are preferable from the viewpoint of increasing reactivity and easy handling, and among alkali metal carbonates, sodium carbonate, potassium carbonate, and cesium carbonate are preferable.

The amount of the base in the polymerization step of the first embodiment is not particularly limited as long as it does not inhibit the condensation reaction in the first embodiment, but preferably 1 with respect to the amount of the nucleophilic reactive group. 0.000 to 50 molar equivalents, more preferably 1.05 to 10 molar equivalents.

Examples of the first transition metal salt include ScCl ₃ , TiCl ₄ , VCl ₃ , CrCl ₃ , MnCl ₂ , FeCl ₂ , CoCl ₂ , NiCl ₂ , CuCl, CuBr, CuI, CuCl ₂ , CuBr ₂ , and CuI ₂ . Examples include halides of transition metal elements. The first transition metal element means a transition metal element in the fourth period in the periodic table. Among these, Fe, Co, Ni or Cu halides are preferable, and copper salts are more preferable. Examples of the copper salt include a monovalent copper salt and a divalent copper salt. From the viewpoint of promptly proceeding the reaction, a monovalent copper salt is preferable, and among them, CuCl, CuBr, and CuI are more preferable. The amount of the first transition metal salt is preferably 0.01 molar equivalents or more and more preferably 0.1 molar equivalents or more with respect to the amount of the leaving group, from the viewpoint of promptly proceeding the polymerization reaction. From the viewpoint of production, it is preferably 10 molar equivalents or less, more preferably 5 molar equivalents or less.

The polymerization step of the first embodiment is preferably performed in an organic solvent. The organic solvent may be any solvent that can dissolve the monomer and the resulting polyarylene ether, and is preferably an aprotic solvent. Specific examples of such solvents include aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as tetrahydrofuran, 1,3-dioxolane and 1,4-dioxane; dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, Examples include aprotic polar solvents such as N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, sulfolane and hexamethylphosphoric triamide. Such a solvent may be used independently and may be used in mixture of 2 or more types. The amount of the organic solvent to be used is preferably 1 or more times by weight and more preferably 5 or more times by weight with respect to the monomer to be used from the viewpoint of increasing the solubility of the monomer to be used and the produced polymer. Further, from the viewpoint of shortening the reaction time, it is preferably 200 times by weight or less, more preferably 100 times by weight or less.

The polymerization reaction of the first embodiment is preferably carried out in an atmosphere of an inert gas such as nitrogen gas. The reaction temperature in the polymerization step of the first embodiment is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 100 ° C. or higher from the viewpoint of shortening the reaction time and increasing the degree of polymerization. Moreover, from a viewpoint of suppressing decomposition | disassembly of a monomer, 200 degrees C or less is preferable, 180 degrees C or less is more preferable, and 170 degrees C or less is still more preferable.

In the production method of the first embodiment, at least a part of the polymerization step and the group represented by E ¹ in the general formula (1) (except that the group represented by E ¹ is an ion exchange group). the preferably comprises a reaction step of converting the group represented by E ^2. The reaction step may be performed simultaneously with the polymerization step or after the polymerization step, but is preferably performed after the polymerization step.

Examples of the reaction step of the first embodiment include known methods such as reacting one or more selected from the group consisting of strong acids, trialkylsilyl halides, bases, and nucleophiles.

Examples of the method of allowing a strong acid to act include a method of stirring a mixed solution obtained by dissolving or slurrying an aromatic polymer electrolyte in a solvent containing a strong acid at 0 ° C. to reflux temperature, preferably room temperature to reflux temperature. Examples of the strong acid include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, trifluoroacetic acid, and the like. Examples of such solvents include alcohols, ethers, ketones, nitriles, dimethyl sulfoxide, aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

As a method of causing the trialkylsilyl halide to act, a trialkylsilyl halide is converted into the above-mentioned ion-exchange precursor group in an amount of 2 to 2 in a mixed solution obtained by dissolving or partially dissolving an aromatic polymer electrolyte in a solvent such as ketones or nitriles. An example is a method in which 10 molar equivalents are added and the temperature is kept at about 0 to 100 ° C., then water or a weak acid is added and the temperature is kept at 0 to 100 ° C. Typical trialkylsilyl halides include trimethylsilyl iodide, trimethylsilyl bromide, trimethylsilyl chloride, triethylsilyl iodide, triethylsilyl bromide, triethylsilyl chloride and the like.

As a method of allowing the base to act, an aqueous solution containing a base in an amount of 1 mole or more in terms of ion-exchange precursor group, usually in a large excess, and an aromatic polymer electrolyte with alcohols, ethers, ketones, nitriles, dimethyl sulfoxide An example is a method in which a mixed solution dissolved or partially dissolved in an aprotic solvent such as the above is mixed so that the aromatic polymer electrolyte is at least partially dissolved, and the reaction is performed at room temperature to reflux temperature. Representative bases include alkali metal hydroxides and alkaline earth metal hydroxides, preferably lithium hydroxide, sodium hydroxide and potassium hydroxide, but are not limited thereto. It is not a thing.

As an example of de-O-alkylation using the above nucleophilic reagent, a mixed solution obtained by dissolving or partially dissolving an aromatic polymer electrolyte in a solvent containing a nucleophilic reagent is 0 ° C. to reflux temperature, preferably 24 Examples of the method include stirring at a temperature of from 200 ° C. to 200 ° C. Examples of such solvents include alcohols, ethers, ketones, nitriles, dimethyl sulfoxide, aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone. Typical nucleophiles include amines, alkali metal halides, etc., preferably secondary amines or lithium bromide.

Next, a preferred second embodiment of the present invention will be specifically described.

As described above, the method for producing an aromatic polymer according to the second embodiment includes a polymerization step of polymerizing the monomer represented by the general formula (4) in the presence of a base. To do. Preferably, at least a part of the polymerization step and a group represented by — (P (═O) (OR ¹ ) (OR ² )) in the general formula (4) is represented by — (P (═O) (OH). ) (OR ³ )) and a reaction step for converting to a group represented by (OR ³ )). The aromatic polymer obtained here is also referred to as an aromatic polymer phosphonic acid.

Membranes made of hydrocarbon-based polymer electrolytes do not have sufficient long-term operational stability of fuel cells (hereinafter referred to as “long-term stability”) compared to membranes made of fluorine-based polymer electrolytes. As one of the factors hindering stability, it is presumed that the film is deteriorated by a peroxide (for example, hydrogen peroxide) generated during battery operation or a radical generated from the peroxide. A membrane made of an aromatic polymer electrolyte (aromatic polymer phosphonic acid) obtained by the method for producing an aromatic polymer according to the second embodiment has durability against peroxides and radicals (hereinafter referred to as “radicals”). It is excellent in "resistance", and the long-term stability of the polymer electrolyte fuel cell can be achieved.

Therefore, hereinafter, the monomer used in the second embodiment, the polymerization step, the aromatic polymer phosphonic acid obtained by the production method of the second embodiment, the base, and the reaction step will be described in order.

The monomer used in the second embodiment is a monomer represented by the general formula (4).

In the formula, X ⁵ and X ⁶ each independently represent a condensable reactive group. Ar ⁴ represents an aromatic group which may have a substituent. p represents an integer of 1 to 4. R ¹ represents a hydrogen atom, an inorganic cation or an organic cation, and R ² represents an alkyl group or an aryl group. When a plurality of R ¹ and R ² are present, the plurality of R ¹ and R ² may be the same or different.

Preferably, in addition to the monomer represented by the general formula (4), a group represented by the above-described — (P (═O) (OR ¹ ) (OR ² )) represented by the general formula (6) It is preferable to use a monomer that does not have.

In the formula, X ⁷ and X ⁸ each independently represent a condensable reactive group. Ar ⁶ represents an aromatic group which may have a substituent.

X ⁵ to X ⁸ in the general formulas (4) and (6) each independently represent a condensable reactive group. The condensable reactive group means a functional group that can be bonded via a divalent or trivalent group or atomic group by causing a condensation reaction with another condensable functional group. Examples of the condensable reactive group include a nucleophilic reactive group and a leaving group. Here, the nucleophilic reactive group represents a group having nucleophilicity, acts on the carbon atom to which the leaving group is bonded, and is newly added with the elimination of the leaving group by ipso substitution. A bond can be formed through a valent or trivalent group or atomic group. Moreover, a leaving group refers to the group which leaves | leaves with the addition of the nucleophilic reactive group to the carbon atom (epsocarbon) which the leaving group has couple | bonded.

Each of X ⁵ to X ⁸ may be a nucleophilic reactive group or a leaving group, but when homopolymerization is performed with one kind of monomer described in the general formula (4), X ⁵ And X ⁶ , one is a nucleophilic reactive group and the other is a leaving group. Moreover, when copolymerizing 1 type of monomer of the said General formula (4), and 1 type of monomer of the said General formula (6), they are mention | raise | lifted following combination. That is,
(A-2) A case where X ⁵ and X ⁶ are nucleophilic reactive groups and X ⁷ and X ⁸ are leaving groups.
(B-2) When X ⁵ and X ⁶ are leaving groups, and X ⁷ and X ⁸ are nucleophilic reactive groups.
(C-2) A case where X ⁵ and X ⁷ are leaving groups and X ⁶ and X ⁸ are nucleophilic reactive groups.
However, the present invention is not limited to the case where two or more types of monomers described in the general formula (4) are used and / or the case where two or more types of monomers described in the general formula (6) are used.

Examples of the nucleophilic reactive group include a hydroxyl group, a mercapto group, and an amino group. The amino group represents a group represented by —NHR ⁴ (R ⁴ represents a hydrogen atom, an alkyl group or an aryl group). Among these, a hydroxyl group and a mercapto group are preferable because of high reactivity as a nucleophilic reactive group, and a hydroxyl group is more preferable. Representative examples of the leaving group include a fluoro group, a chloro group, a bromo group, an iodo group, a tosyl group, and a triflate group. Of these, the leaving group is preferably a fluoro group or a chloro group.

Each R ¹ independently represents a hydrogen atom, an inorganic cation or an organic cation. Representative examples of inorganic cations include cations such as alkali metals and alkaline earth metals, but are not limited thereto. Among these, lithium cation, sodium cation, and potassium cation are preferable. Representative examples of organic cations include, but are not limited to, primary ammonium cations, secondary ammonium cations, tertiary ammonium cations, and quaternary ammonium cations. Of these, primary ammonium cations and secondary ammonium cations are preferable. Among primary ammonium cations and secondary ammonium cations, a primary amine having a boiling point of 100 ° C. or higher and a protonated product of a secondary amine are preferable, and among them, dibutylammonium ion is preferable. R ¹ is preferably an organic cation from the viewpoint of enhancing the solubility in a solvent preferably used in the polymerization step described later.

Each R ² independently represents an alkyl group or an aryl group. These groups may be partially substituted with other groups. Representative examples of alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -Butyl group, t-butyl group, t-pentyl group, isooctyl group, t-octyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, 1-methylcyclopentyl group, 1-methyl Cyclohexyl group, 1-methyl-4-isopropylcyclohexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, etc. However, it is not limited to these. Typical examples of the aryl group include a hydrocarbon group such as a phenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a naphthyl group, a biphenylyl group, a diphenylpropyl group, a fluorenyl group, and a carbazole group. A group containing a hetero atom such as, but not limited to, a thiophene group, a dibenzothiophene group, a furyl group, a dibenzofuryl group, a diphenylamino group, and a 4-phenoxyphenyl group. Among these, in the reaction step described later, an alkyl group is preferable from the viewpoint of easily converting the group represented by — (P (═O) (OR ¹ ) (OR ² )) into a phosphonic acid group. Among these, an ethyl group is preferable.

Examples of the group represented by — (P (═O) (OR ¹ ) (OR ² )) include phosphonic acid monomethyl group, phosphonic acid monoethyl group, phosphonic acid monoisopropyl group, phosphonic acid mono t-butyl group, and phosphonic acid. Phosphonic acid monoester group such as monophenyl group, phosphonic acid (mono inorganic salt) such as phosphonic acid (lithium) (monoethyl) group, phosphonic acid (sodium) (monoethyl) group, phosphonic acid (potassium) (monoethyl) group ( Phosphonic acid (monoamine salt) such as monoester) group, phosphonic acid (monodibutylamine salt) (monoethyl) group, phosphonic acid (monoaniline salt) (monoethyl) group, phosphonic acid (monobenzylamine salt) (monoethyl) group (Monoester) group, and from the viewpoint of easily ensuring solubility in the solvent used in the polymerization step, An acid (monoamine salt) (monoester) group is preferred, and among these, a phosphonic acid (monodibutylamine salt) (monoethyl) group is preferred.

The group represented by — (P (═O) (OR ¹ ) (OR ² )) is the same as the benzene ring substituted with X ⁵ and / or X ⁶ from the viewpoint of increasing the reactivity of the condensation reaction. More preferably, the benzene ring is substituted.

Ar ⁴ and Ar ⁶ in the second embodiment represent an aromatic group that may have a substituent. The aromatic group may contain a hetero element, and preferably has 4 or more carbon atoms, more preferably 10 or more from the viewpoint of enhancing the reactivity of the condensation reaction. Moreover, it is preferable that carbon number is 18 or less from a viewpoint of raising the phosphonic acid group density of the aromatic polymer phosphonic acid obtained, and it is more preferable that it is 14 or less.

Examples of the aromatic group include aromatic groups represented by the following formulas (1-a) to (1-z). (In the formula, * represents a bond with X ⁵ or X ⁶ or X ⁷ or X ^{8 respectively,} and a bond with another substituent was omitted.)

Among them, Ar ⁴ is preferably a phenylene group represented by the above (1-c) which may have a substituent or a biphenyl group represented by (1-m), and has a substituent. The biphenyl group represented by the above (1-m) may be more preferable. Ar ⁶ is preferably a group represented by the above (1-x) which may have a substituent or a group represented by (1-y), and may have a substituent. A group represented by (1-y) is more preferable.

The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include a tert-butyl group, an isobutyl group, an n-pentyl group, a 2,2-dimethylpropyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a 2-methylpentyl group, and a 2-ethylhexyl group.

The alkoxy group having 1 to 10 carbon atoms may be linear, branched or cyclic. For example, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, sec- Butyloxy group, tert-butyloxy group, isobutyloxy group, n-pentyloxy group, 2,2-dimethylpropyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, 2-methylpentyloxy group, 2- An ethylhexyloxy group is mentioned.

Preferred monomers represented by the general formula (4) include monomers represented by the following formulas (2-aa) to (2-bj).

Among these, the above formulas (2-ae) and (2-ak) are preferable.

Preferred monomers represented by the general formula (6) include monomers represented by the following formulas (3-ca) to (3-cx).

Among them, the above formulas (3-cf), (3-cg), (3-ci), (3-cj), (3-cs), (3-cu) are preferable because they are easily available and inexpensive. It is preferable.

As a method for producing the monomer represented by the formula (4) according to the second embodiment, when X ⁵ and X ⁶ are leaving groups such as a fluoro group, a chloro group, a bromo group, and an iodo group, The production method of
(1-3) A method in which a phosphonic acid diester group is introduced into an aromatic compound, and then the above leaving group is introduced and hydrolyzed by a known method.
(1-4) A method of introducing a phosphonic acid diester group after introducing the above leaving group into an aromatic compound and hydrolyzing it by a known method.
As a method for introducing a phosphonic acid diester group, before introducing a phosphonic acid diester group into an aromatic compound, a reactive group selected from a chloro group, a bromo group, an iodo group and the like is introduced, and then the following (2-6) to And a method for carrying out the substitution reaction listed in (2-10).
(2-6) Michaelis-Albuzov reaction in which a phosphoric acid triester is reacted using a Lewis acid such as nickel chloride.
(2-7) Michaelis-Becker reaction in which a phosphite diester is reacted with a base such as sodium hydride.
(2-8) A reaction in which a phosphorous acid diester is reacted using a zerovalent palladium catalyst such as tetrakis (triphenylphosphine) palladium.
(2-9) Grignard reaction in which magnesium is reacted to form a Grignard reagent and then a halogenated phosphoric acid diester is reacted.
(2-10) Reaction in which halogenated phosphoric acid diester is reacted after alkyllithium is reacted to form aryllithium.
Examples of the method for introducing the leaving group include a method in which a halogenating reagent selected from fluorine, chlorine, bromine, iodine and the like is allowed to act. In the method described in (1-4), when the reactive group and the leaving groups X ⁵ and X ⁶ are the same functional group, after introducing three or more functional groups into the aromatic compound The monomer represented by the formula (4) can be obtained by substituting a part of the functional group with a phosphonic acid group and hydrolyzing by a known method. As a specific method, for example, J. et al. Fluorine Chem. Known methods such as those described in 2004, 125, 1317 can be used.

When X ⁵ and / or X ⁶ is a nucleophilic reactive group, a protective group is introduced into the nucleophilic reactive group, the nucleophilic reactive group is deactivated, and then the above substitution reaction is performed. Hydrolysis is preferred. The protecting group is not particularly limited as long as it is a group that can be deprotected after the above-described substitution reaction. Representative protecting groups for hydroxyl and mercapto groups include ethers such as benzyl and t-butyl groups. Group, an acetal group such as methoxymethyl group, an acyl group such as acetyl group and benzoyl group, and a silyl ether group such as t-butyldimethylsilyl group. Representative protecting groups for amine groups include carbamate groups such as t-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, imide groups such as phthaloyl group, p-toluene Examples thereof include sulfonamide groups such as a sulfonyl group and a 2-nitrobenzenesulfonyl group.

When X ⁵ and / or X ⁶ is a hydroxyl group, a halogenated phosphoric diester is allowed to act on the hydroxyl group to form a phosphate compound, which is then converted to a compound having a phosphonic diester group by a rearrangement reaction using a strong base. However, a method for hydrolysis may be used. As a specific method, for example, J. et al. Org. Chem. Known methods such as those described in 1984, 49, 4018 can be used.

As the monomer represented by the formula (6) of the second embodiment, for example, a commercially available product is used.

The aromatic polymer phosphonic acid obtained by the production method of the second embodiment is based on the monomer represented by the general formula (4) or the monomer represented by the general formula (4) and (6). It is obtained by a manufacturing method provided with the superposition | polymerization process polymerized in presence of this. Other monomers may be used as long as the above effects are not impaired. Here, the aromatic polymer phosphonic acids are phosphones linked directly or via a connecting member with a divalent aromatic residue obtained by removing two hydrogen atoms from a compound having an aromatic ring as a structural unit. It means a polymer having an acid group. The aromatic polymer phosphonic acids in the second embodiment may have a substituent. The aromatic polymer phosphonic acid in the second embodiment preferably has an aromatic ring which may have a substituent in the main chain, and further has an aromatic ring to which a phosphonic acid group is directly bonded. Here, the phosphonic acid group refers to a group that becomes a phosphonic acid group without changing the structure other than the phosphonic acid group of the aromatic polymer phosphonic acid. The phosphonic acid group is preferably converted into a phosphonic acid group through a reaction of 3 steps or less, more preferably 2 steps or less, and still more preferably 1 step.

As the aromatic polymer phosphonic acids obtained by the production method of the second embodiment, those having a repeating unit represented by the general formula (5) are preferable.

In the formula, Ar ⁵ represents an aromatic group which may have a substituent. q represents an integer of 1 to 4. —Z ² — represents a group represented by —O—, —S— or —NR ⁴ — (R ⁴ represents a hydrogen atom, an alkyl group or an aryl group). R ³ represents a hydrogen atom, an alkyl group or an aryl group. When a plurality of R ³ are present, the plurality of R ³ may be the same or different.

Ar ⁵ in the second embodiment represents an aromatic group which may have a substituent, and examples of the aromatic group include those described above. Specific examples include aromatic groups such as the above formulas (1-a) to (1-z) (wherein * represents a bond with a group represented by —Z ² — and The bond with the group is omitted.) Among these, a phenylene group represented by the above (1-c) or a biphenyl group represented by (1-m) is preferable. Examples of the substituent include those described above.

R ³ and R ⁴ each represent a hydrogen atom, an alkyl group or an aryl group, and typical examples of the alkyl group and the aryl group include those described above. Among these, as R ³ , an ethyl group is preferable, and as R ⁴ , a phenyl group is preferable.

Specific examples of the group represented by — (P (═O) (OH) (OR ³ )) in the general formula (5) include the above-described phosphonic acid monoester group and phosphonic acid group.

Examples of the repeating unit represented by the general formula (5) include repeating units represented by the following formulas (4-da) to (4-dt). In addition, a group represented by — (P (═O) (OH) (OEt)) in a repeating unit represented by the following formulas (4-da) to (4-dt) is represented by — (P (═O) ( OH) (OH)) may be substituted.

Among these, the above formulas (4-da) and (4-dc) are preferable.

As the weight content of P (phosphorus atom) in the aromatic polymer phosphonic acids having the repeating unit represented by the general formula (5), the radical resistance is increased with respect to the weight of the aromatic polymer phosphonic acids. From a viewpoint, 0.1 weight% or more is preferable and 1.0 weight% or more is more preferable. Further, from the viewpoint of suppressing solubility when the aromatic polymer phosphonic acid of the second embodiment is used as a polymer electrolyte membrane, 20% by weight or less is preferable, and 15% by weight or less is more preferable. As the weight content of P, triphenylphosphine oxide was added as an internal standard substance to the sample, and a ³¹ P-NMR spectrum was measured under conditions without proton decoupling using NMR. From the obtained NMR spectrum, It is obtained by comparing the area value of the sample with the area value of triphenylphosphine oxide.

The aromatic polymer phosphonic acid having a repeating unit represented by the general formula (5) may be a homopolymer, a random copolymer, an alternating copolymer, a block copolymer. It may be a polymer. These can be obtained according to known methods by selecting the corresponding monomers, their ratios, and the polymerization method. These polymerization degrees are preferably 5 or more and a weight average molecular weight of 10 ³ or more from the viewpoint of increasing mechanical strength. In addition, these polymerization degrees are 10 ⁴ or less and 10 ⁶ or less in terms of weight average molecular weight from the viewpoint of maintaining solubility in a solvent during film formation, workability such as cast film formation, and moldability. Preferably used. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

In the polymerization step of the second embodiment, when the monomer represented by the general formula (4) and the monomer represented by the general formula (6) are used, the weight ratio is 100: 0 to 1: 99 is preferable, and 50:50 to 10:90 is more preferable.

The polymerization step of the second embodiment is performed in the presence of a base. The base is preferably a base composed of a metal compound other than the first transition metal salt. Examples of the base include alkali metal salts and alkaline earth metal salts. Among these, alkali metal salts are preferable, and examples of the alkali metal salts include alkali metal carbonates and hydrogen carbonates. Among these, alkali metal carbonates are preferable. Among the alkali metal carbonates, sodium carbonate, potassium carbonate, and cesium carbonate are preferable.

The amount of the base in the polymerization step of the second embodiment is not particularly limited as long as it does not inhibit the condensation reaction in the second embodiment, but preferably the nucleophilic reactive group and the-(P (= O ) (OR ¹ ) (OR ² )) and the total amount of the substance is 1.00 to 50 molar equivalents, and more preferably 1.05 to 10 molar equivalents.

The reaction temperature in the polymerization step of the second embodiment is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and further preferably 120 ° C. or higher from the viewpoint of shortening the reaction time and increasing the degree of polymerization. Moreover, from a viewpoint of suppressing the side reaction by a phosphonic acid group, 300 degrees C or less is preferable and 200 degrees C or less is more preferable.

The polymerization step of the second embodiment is preferably performed in an organic solvent. Examples of the organic solvent include aprotic solvents such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.

In the production method of the second embodiment, at least a part of the polymerization step and a group represented by — (P (═O) (OR ¹ ) (OR ² )) in the general formula (4) are represented by — (P It is preferable to provide a reaction step of converting to a group represented by (= O) (OH) (OR ³ )). The reaction step may be performed simultaneously with the polymerization step or after the polymerization step, but is preferably performed after the polymerization step.

As the reaction step of the second embodiment, it is preferable to act a strong acid and / or a trialkylsilyl halide.

Examples of the method of allowing a strong acid to act include a method of stirring a mixed solution obtained by dissolving or slurrying an aromatic polymer phosphonic acid in a solvent containing a strong acid at 0 ° C. to reflux temperature, preferably from room temperature to reflux temperature. Examples of the strong acid include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, trifluoroacetic acid, and the like. Examples of such solvents include alcohols, ethers, ketones, nitriles, dimethyl sulfoxide, aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

As a method of allowing a trialkylsilyl halide to act, a trialkylsilyl halide is dissolved in a mixed solution obtained by dissolving or partially dissolving an aromatic polymer phosphonic acid in a solvent such as ketones or nitriles. An example is a method in which 2 to 10 molar equivalents in terms of a group represented by (OR ¹ ) (OR ² )) are added and kept at about 0 to 100 ° C., then water or a weak acid is added, and then kept at 0 to 100 ° C. Typical trialkylsilyl halides include trimethylsilyl iodide, trimethylsilyl bromide, trimethylsilyl chloride, triethylsilyl iodide, triethylsilyl bromide, triethylsilyl chloride and the like.

Next, the aromatic polymer electrolyte obtained by the above embodiment or the aromatic phosphonic acid obtained by the above embodiment (hereinafter, the aromatic polymer electrolyte and the aromatic phosphonic acid are collectively referred to as “aromatic”. The case where it is expressed as a "system polymer electrolyte") as a diaphragm (polymer electrolyte membrane) of an electrochemical device such as a fuel cell will be described.

In this case, the aromatic polymer electrolyte obtained by the above embodiment is usually used in the form of a membrane. Although there is no restriction | limiting in particular in the method to convert into a film | membrane, For example, the method (solution cast method) which forms into a film from a solution state is used preferably.

Specifically, an aromatic polymer electrolyte is dissolved in an appropriate solvent, and the solution is cast on a support substrate such as a glass plate or polyethylene terephthalate (hereinafter sometimes referred to as PET), and then the solvent is added. Is removed to remove the film. The solvent used for film formation is not particularly limited as long as it can dissolve the aromatic polymer electrolyte and can be removed thereafter. N, N-dimethylformamide, N, N-dimethylacetamide, N— Aprotic polar solvents such as methyl-2-pyrrolidone and dimethyl sulfoxide; chlorine-containing solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene and dichlorobenzene; alcohols such as methanol, ethanol and propanol; ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, and water are preferably used. These can be used singly, but two or more solvents can be mixed and used as necessary. Among them, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone are preferable because of high polymer solubility.

The thickness of the film is not particularly limited, but is preferably 10 to 300 μm, particularly preferably 20 to 100 μm. When the film is thinner than 10 μm, the practical strength may not be sufficient, and when the film is thicker than 300 μm, the film resistance tends to increase and the characteristics of the electrochemical device tend to deteriorate. The thickness of the film can be controlled by the concentration of the solution and the coating thickness on the substrate.

In addition, for the purpose of improving various physical properties of the polymer electrolyte membrane, plasticizers, stabilizers, release agents, etc., used for ordinary polymers can be added to the aromatic polymer electrolyte obtained by the above embodiment. . Also, other polymers can be combined with the copolymer of the above embodiment by a method such as co-casting in the same solvent.

In fuel cell applications, it is also known to add inorganic or organic fine particles as water retention agents in order to facilitate water management. Any of these known methods can be used as long as they are not contrary to the object of the present invention. Further, for the purpose of improving the mechanical strength of a polymer electrolyte membrane comprising a polymer electrolyte containing an aromatic polymer electrolyte obtained by the above embodiment, the polymer electrolyte is irradiated with an electron beam or radiation. The polymer electrolyte constituting the membrane can also be crosslinked.

Further, in order to further improve the strength, flexibility, and durability of the polymer electrolyte membrane, the polymer electrolyte is obtained by impregnating the porous base material with the aromatic polymer electrolyte obtained by the above embodiment and combining it. A composite membrane can also be used. 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 porous membranes, woven fabrics, non-woven fabrics, and fibrils, and they can be used regardless of their shapes and materials.

When the polymer electrolyte composite membrane using the aromatic polymer electrolyte obtained by the above embodiment is used as a diaphragm of a fuel cell, the porous substrate has a thickness of 1 to 100 μm, preferably 3 to 30 μm, and further It is preferably 5 to 20 μm, the pore diameter is 0.01 to 100 μm, preferably 0.02 to 10 μm, and the porosity is 20 to 98%, preferably 40 to 95%.

If the film thickness of the porous substrate is too thin, the effect of reinforcing the strength after combining or the reinforcing effect of imparting flexibility and durability is insufficient, and gas leakage (cross leak) is likely to occur. On the other hand, if the film thickness is too thick, the electric resistance becomes high, and the resulting composite film is insufficient as a diaphragm for the polymer electrolyte fuel cell. When the pore diameter is too small, it is difficult to fill the copolymer of the above embodiment, and when it is too large, the reinforcing effect on the polymer solid electrolyte is weakened. If the porosity is too small, the resistance of the composite film is increased, and if it is too large, the strength of the porous substrate itself is generally weakened and the reinforcing effect is reduced.

From the viewpoint of heat resistance and the effect of reinforcing physical strength, the porous substrate is preferably a substrate made of an aliphatic polymer, an aromatic polymer, or a fluorine-containing polymer.

Next, a fuel cell using an aromatic polymer electrolyte obtained by the above embodiment will be described. Examples of the fuel cell using the polymer electrolyte membrane include a solid polymer fuel cell using hydrogen gas as a fuel and a direct methanol solid polymer fuel cell directly supplying methanol as a fuel. The obtained aromatic polymer electrolyte can be suitably used for both.

The fuel cell using the aromatic polymer electrolyte obtained by the above embodiment is obtained by using the copolymer of the above embodiment as a polymer electrolyte membrane and / or a polymer electrolyte composite membrane, or obtained by the above embodiment. And the like using the obtained polymer electrolyte as the polymer electrolyte in the catalyst layer.

A fuel cell in which the aromatic polymer electrolyte obtained by the above embodiment is used as a polymer electrolyte membrane or a polymer electrolyte composite membrane has a catalyst and gas diffusion on both sides of the polymer electrolyte membrane or the polymer electrolyte composite membrane. It can be manufactured by joining the layers. 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.

Here, the catalyst is not particularly limited as long as it can activate the oxidation-reduction reaction with hydrogen or oxygen, and a known catalyst can be used, but platinum fine particles are preferably used. The platinum fine particles are often preferably those supported on particulate or fibrous carbon such as activated carbon or graphite. Also, platinum supported on carbon is mixed with an alcohol solution of perfluoroalkyl sulfonic acid resin as a polymer electrolyte and pasted into a gas diffusion layer, polymer electrolyte membrane or polymer electrolyte composite membrane. -A catalyst layer is obtained by drying. 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.

A fuel cell using the aromatic polymer electrolyte obtained by the above embodiment as the polymer electrolyte in the catalyst layer can be obtained by the above embodiment instead of the perfluoroalkylsulfonic acid resin constituting the catalyst layer. The thing using an aromatic polymer electrolyte can be mention | raise | lifted. When the catalyst layer using the copolymer of the above embodiment is used, the polymer electrolyte membrane is not limited to the membrane using the copolymer obtained by the above embodiment, and a known polymer electrolyte membrane may be used. it can.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Before proceeding to examples of the present invention, a method for measuring various physical properties of a sample and each synthesis example will be described below.

[Monomer purity (%), monomer conversion (mol%)]
It measured and calculated | required on the following conditions A or B by the liquid chromatography (LC).
Condition A:
・ LC measuring device LC-10A made by Shimadzu Corporation
・ Column L-Column ODS (5μm, 4.6mmφ × 15cm)
・ Column temperature 40 ℃
-Mobile phase solvent A liquid: 0.1 wt% tetrabutylammonium bromide / water B liquid: 0.1 wt% tetrabutylammonium bromide / (water / acetonitrile = 1/9 (weight ratio))
Mobile phase gradient 0 → 20 min (A liquid: 70 wt% → 10 wt%, B liquid: 30 wt% → 90 wt%), 20 → 35 min (A liquid: 10 wt%, B liquid: 90 wt%)
・ Solvent flow 1.0mL / min
・ Detection method UV (254nm)
The monomer conversion was determined by comparing the UV area value with biphenyl added as a standard substance.
Conversion of monomer (mol%) = 1- (amount of monomer substance after polymerization reaction / amount of monomer substance before polymerization reaction) × 100
Condition B:
・ LC measuring device Shimadzu LC-20AD
・ Column L-Column ODS (5μm, 4.6mmφ × 15cm)
・ Column temperature 40 ℃
-Mobile phase solvent A liquid: 0.1 wt% tetrabutylammonium bromide / water B liquid: 0.1 wt% tetrabutylammonium bromide / (water / acetonitrile = 1/9 (weight ratio))
Mobile phase gradient 0 → 20 min (A liquid: 70 wt% → 10 wt%, B liquid: 30 wt% → 90 wt%), 20 → 35 min (A liquid: 10 wt%, B liquid: 90 wt%)
・ Solvent flow 1.0mL / min
・ Detection method UV (254nm)
The monomer conversion was determined by comparing the UV area value with diphenylsulfone added as a standard substance.
Conversion of monomer (mol%) = 1- (amount of monomer substance after polymerization reaction / amount of monomer substance before polymerization reaction) × 100

[Molecular weight]
The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were measured by gel permeation chromatography (GPC) under the following conditions.
-GPC measuring device HLC-8220 manufactured by TOSOH
・ Column TSKgel GMH-M manufactured by TOSOH
・ Column temperature 40 ℃
Mobile phase solvent DMAc (LiBr added to 10 mmol / dm ³ )
・ Solvent flow rate 0.5mL / min
・ Detection method UV (300nm)

[ ³¹ P content (unit:% by weight)]
A sample and an internal standard substance (triphenylphosphine oxide) were added in a DMSO-d ⁶ solvent, and a ³¹ P-NMR spectrum was measured using NMR (600 MHz) without proton decoupling. The area value of the sample was compared with the area value of triphenylphosphine oxide to determine the ³¹ P content. The theoretical value was derived by stoichiometric calculation from the monomer charge ratio.

[Radical resistance (unit:% by weight)]
The sample was immersed for 2 hours in a 70 ° C. aqueous solution containing 3 wt% hydrogen peroxide and 8 ppm (parts per million by weight) Fe (II) Cl ₂ . The weight of the sample before and after immersion was measured, and the weight retention rate was calculated by the following formula. Higher weight retention means higher radical resistance.
Weight retention ratio (% by weight) = (weight of sample after immersion (mg) / weight of sample before immersion (mg))) × 100

Synthesis example 1
In a flask purged with argon, 120 g (644 mmol) of 4,4′-biphenol, 266 g (1.93 mol) of diethyl phosphite, 446 g of carbon tetrachloride, and 720 g of tetrahydrofuran were placed and cooled to 0 ° C. 196 g (1.93 mol) of triethylamine was added dropwise over 90 minutes so that the temperature of the reaction solution did not exceed 10 ° C. After stirring at 0 ° C. for 1 hour, the mixture was warmed to room temperature and stirred for 21 hours. 1440 g of water was added and stirred at room temperature for 1 hour. The reaction product was extracted into chloroform using a separatory funnel, the chloroform solution was washed with water, the oil layer was dehydrated with magnesium sulfate, and magnesium sulfate was filtered off. Chloroform was distilled off under reduced pressure to obtain a crude product. The crude product was purified using column chromatography to obtain 137 g (yield: 46%, LC area purity: 95.6% (condition A)) of the formula (8).
¹ H NMR (CDCl ₃ , 270 MHz) δ 1.35 (t, 12H), 4.11 (dq, 8H), 7.28 (d, 4H), 7.50 (d, 4H).
APPI-MS (chloroform solution) m / z [M + H] ⁺ : theoretical value 459.1, actual value 459.1

Synthesis example 2
The compound (137 g, 299 mmol) represented by formula (8) and 560 g of tetrahydrofuran were added to the dropping funnel substituted with argon to prepare a THF solution of the compound represented by formula (8). Into a flask purged with argon, 694 g of tetrahydrofuran was charged, cooled to −66 ° C. using a dry ice-acetone bath, and 546 g of a 2 mol / L lithium diisopropylamine tetrahydrofuran solution was added. Over a period of 3.5 hours, a THF solution of the compound represented by the formula (8) in the dropping funnel was dropped, and the mixture was stirred while keeping at -65 ° C for 1.5 hours. The reaction solution was neutralized with 8% hydrochloric acid, and extracted with diethyl ether and chloroform. The oil layer was washed with water and dehydrated with magnesium sulfate, and then distilled under reduced pressure to obtain a crude product. Recrystallization from ethanol gave 126 g of the compound represented by the formula (9) (yield: 92 mol%, LC surface percentage purity: 99.3% (condition A)).
¹ H NMR (CDCl ₃ , 270 MHz) δ 1.36 (t, 12H), 4.03-4.29 (m, 8H), 7.04 (dd, 2H), 7.48 (d, 2H), 7 .60 (d, 2H).
APPI-MS (chloroform solution) m / z [M + H] ⁺ : theoretical value 459.1, actual value 459.1

Synthesis Example 3 [Production of aromatic phosphonic acid compound]
To the flask purged with nitrogen was added the compound of formula (9) (50.0 g, 109 mmol), acetonitrile 250 g, sodium iodide 98.1 g (654 mmol), and trimethylsilyl chloride 71.1 g (654 mmol), and then at 40 ° C. for 1 hour. And stirred at room temperature for 1.5 hours. By-product sodium chloride was filtered off, and then acetonitrile was distilled off under reduced pressure. Chloroform was added, ultrasonic irradiation was performed, insolubles were filtered off, and chloroform was distilled off under reduced pressure. After water was added and dissolved, diethyl ether was added to extract the colored components into the oil layer. 80% of the aqueous layer was distilled off under reduced pressure, and the precipitated solid was collected by filtration, and 25.3 g (yield: 67 mol%, LC surface percentage purity: 99.3% (conditions) of the formula (10)) A)) obtained.
¹ H NMR (DMSO-d ⁶ , 270 MHz) δ 6.79 (dd, 2H), 7.51 (d, 2H), 7.90 (d, 2H).
ESI-MS (methanol solution) m / z [MH] ⁻ : Theoretical value 345.0, Actual value 344.9
³¹ P% by weight = 13.2 (theoretical value: 13.5)

Example (A-1) [Production of Aromatic Phosphonic Acid Monoester Compound]
The compound represented by formula (9) (5.00 g, 10.9 mmol), acetonitrile 25 g, and lithium bromide 3.56 g (32.7 mmol) were added to the argon-substituted flask, and the mixture was heated and stirred at 85 ° C. for 16.5 hours. . After cooling to room temperature, the solvent was distilled off under reduced pressure. Acetonitrile was added, and the mixture was heated to reflux with stirring for 1 hour, and the solid was collected by filtration. 4.12 g of the compound represented by the formula (11) (yield: 91 mol%, LC surface percentage purity: 97.4% (conditions) A)) obtained.
¹ H NMR (DMSO-d ⁶ , 270 MHz) δ 1.03 (t, 6H), 3.62 (dq, 4H), 6.71 (dd, 2H), 7.39 (d, 2H), 7.57 (D, 2H).
APPI-MS (methanol solution) m / z [M-2Li + 3H] ⁺ : Theoretical value 403.1, Measured value 403.1
³¹ P wt% = 18.4 (theoretical value: 17.9)

Example (A-2) [Production 2 of Aromatic Phosphonic Acid Monoester Compound]
To the flask purged with argon, the compound represented by the formula (9) (2.00 g, 4.36 mmol), piperazine (0.75 g, 8.73 mmol) and 18 g of N-methylpyrrolidone were added, and heated and stirred at 130 ° C. for 19 hours. did. After cooling to room temperature, N-methylpyrrolidone was distilled off under reduced pressure. Methanol was added and the resulting precipitate was filtered off. The obtained solid was repeatedly washed with methanol to obtain 0.79 g (yield: 45 mol%, LC area purity: 94.9% (condition A)) of the formula (12).
¹ H NMR (DMSO-d ⁶ , 270 MHz) δ 1.04 (t, 6H), 3.62 (dq, 4H), 6.75 (dd, 2H), 7.48-7.53 (m, 4H) .

Example (A-3) [Production of Aromatic Phosphonic Acid Monoester Compound 3]
To the flask purged with nitrogen, the compound represented by the formula (9) (75.8 g, 165 mmol), 128 g (993 mmol) of dibutylamine and 767 g of N-methylpyrrolidone were added and stirred at 130 ° C. for 7 hours. After allowing to cool, the precipitated solid was filtered off. To the obtained solid, 195 g of N-methylpyrrolidone was added and dissolved by heating at 130 ° C. After cooling to room temperature, the precipitated solid was collected by filtration. Recrystallization using N-methylpyrrolidone was performed again to obtain 100 g of a compound represented by the formula (13) (yield: 92 mol%, LC area percentage purity: 99.5% (condition A)).
¹ H NMR (CD ₃ OD, 270 MHz) δ 0.95 (t, 12H), 1.17 (t, 6H), 1.32-1.45 (m, 8H), 1.58-1.69 (m , 8H), 2.82-2.96 (m, 8H), 3.80 (dq, 4H), 6.84 (dd, 2H), 7.51 (d, 2H), 7.70 (d, 2H).
APPI-MS (methanol solution) m / z [M-2 dibutylammonium + 3H] ⁺ : Theoretical value 403.1, Actual value 403.0

Example (A-4) [Synthesis 1 of Aromatic Polymer Phosphonic Acid Monoester]
In a Schlenk flask equipped with an azeotropic distillation apparatus, 0.40 g (0.98 mmol) of a compound represented by the formula (12), 0.25 g (0.98 mmol) of 4,4′-sulfonyldiphenol, 0.57 g (4.13 mmol) of potassium carbonate was added, and 4.6 g of dimethyl sulfoxide and 5 g of toluene were added. Thereafter, the water in the system was azeotropically dehydrated by heating and distilling off toluene at a bath temperature of 120 ° C. for 3 hours. Subsequently, 0.50 g (1.97 mmol) of 4,4′-difluorodiphenylsulfone was added, the bath temperature was raised to 140 ° C., and the mixture was stirred while keeping for 5 hours. After allowing to cool, the reaction solution was added to a 50% hydrochloric acid / methanol solution, the deposited precipitate was filtered, and washed with ion-exchanged water until neutral, to obtain a compound represented by the formula (14).
Mn = 4900, Mw = 5500
³¹ P% by weight = 4.5 (theoretical value: 5.8)

In the formula, the symbol “ran” means a structure in which structural units coupled to the symbol are randomly connected. That is, the compound represented by the above formula (14) has a structure in which an aromatic phosphonic acid monoester compound residue and a 4,4′-sulfonyldiphenol residue are randomly linked.

Example (A-5) [Synthesis 2 of Aromatic Polymer Phosphonic Acid Monoester]
In a three-necked flask equipped with an azeotropic distillation apparatus, under a nitrogen atmosphere, 5.91 g (8.94 mmol) of a compound represented by the formula (13), 2.24 g (8.94 mmol) of 4,4′-sulfonyldiphenol, 4.94 g (35.8 mmol) of potassium carbonate, 53 g of dimethyl sulfoxide, and 31 g of toluene were added. Thereafter, the water in the system was azeotropically dehydrated by heating and distilling off toluene at a bath temperature of 145 ° C. for 5 hours. Next, 5.00 g (19.7 mmol) of 4,4′-difluorodiphenylsulfone was added, and the mixture was stirred while keeping the bath temperature at 145 ° C. for 15 hours. After allowing to cool, the reaction solution was added to a 35% hydrochloric acid / methanol (1/1) solution, the deposited precipitate was filtered, and washed with ion-exchanged water until neutral, to obtain the compound represented by the formula (14). It was.
Mn = 6300, Mw = 11000
³¹ % by weight = 5.2 (theoretical value: 5.6)

Example (A-6) [Synthesis of Aromatic Polymer Phosphonic Acid Monoester 3]
In a Schlenk flask equipped with an azeotropic distillation apparatus, under a nitrogen atmosphere, 0.66 g (1.00 mmol) of the compound represented by the formula (13), 0.20 g (0.79 mmol) of 4,4′-sulfonyldiphenol, 0.54 g (3.93 mmol) of potassium carbonate was added, and 5.4 g of dimethyl sulfoxide and 19 g of toluene were added. Thereafter, the water in the system was azeotropically dehydrated by heating and distilling off toluene at a bath temperature of 150 ° C. for 5 hours. Subsequently, 0.50 g (1.97 mmol) of 4,4′-difluorodiphenylsulfone was added, the bath temperature was raised to 140 ° C., and the mixture was stirred while keeping for 15 hours. After allowing to cool, the reaction solution was added to a 50% hydrochloric acid / methanol solution, the deposited precipitate was filtered, and washed with ion-exchanged water until neutral, to obtain a compound represented by the formula (14).
Mn = 6700, Mw = 13000
³¹ P% by weight = 5.6 (theoretical value: 6.0)

Example (A-7) [Synthesis of Aromatic Polymer Phosphonic Acid Monoester 4]
In a Schlenk flask equipped with an azeotropic distillation apparatus, in a nitrogen atmosphere, 0.52 g (0.79 mmol) of the compound represented by the formula (13), 0.20 g (0.79 mmol) of 4,4′-sulfonyldiphenol, 0.48 g (3.48 mmol) of potassium carbonate, 4.9 g of dimethyl sulfoxide, and 19 g of toluene were added. Thereafter, the water in the system was azeotropically dehydrated by heating and distilling off toluene at a bath temperature of 150 ° C. for 5 hours. Next, 0.54 g (1.74 mmol) of 4,4′-dichlorodiphenylsulfone and Cu (I) Cl 2 (90 mg, 0.91 mmol) were added, the bath temperature was raised to 160 ° C., and the mixture was stirred while maintaining for 27 hours. . After allowing to cool, the reaction solution was added to a 35% hydrochloric acid / methanol (1/1) solution, the deposited precipitate was filtered, and washed with ion-exchanged water until neutral, to obtain the compound represented by the formula (14). It was.
Mn = 6500, Mw = 13500
³¹ P% by weight = 5.0 (theoretical value: 5.5)

Example (B-1) [Synthesis 5 of Aromatic Polymer Phosphonic Acid Monoester]
In a Schlenk flask equipped with an azeotropic distillation apparatus, 1.12 g (1.79 mmol) of the compound represented by the formula (13), 0.45 g (1.79 mmol) of 4,4′-sulfonyldiphenol, under a nitrogen atmosphere, 1.04 g (7.51 mmol) of potassium carbonate and 150 mg of biphenyl were added, and 14.5 g of dimethyl sulfoxide and 7.4 g of toluene were added. Thereafter, the toluene in the system was azeotropically dehydrated by heating and distilling off toluene at a bath temperature of 140 ° C. for 7 hours. Next, 1.00 g (3.93 mmol) of 4,4′-dichlorodiphenylsulfone and 195 mg (1.97 mmol) of Cu (I) Cl were added, the bath temperature was raised to 160 ° C., and the mixture was stirred while keeping for 21 hours. After allowing to cool, the reaction solution was added to a 25% nitric acid aqueous solution, the deposited precipitate was filtered, and then washed with ion-exchanged water until neutral, to obtain a compound represented by the formula (14).
Mn = 6100, Mw = 13000
³¹ P wt% = 5.2 wt% (theoretical value: 5.8)
Conversion of compound represented by formula (13) (6 hours after addition of Cu (I) Cl) = 98 mol% (Condition A)

Example (B-2) [Synthesis of Aromatic Polymer Phosphonic Acid Monoester 6]
A compound represented by the formula (14) was obtained in the same manner as in Example (B-1) except that 1,3-dimethyl-2-imidazolidinone was used instead of dimethyl sulfoxide.
Mn = 5600, Mw = 10200
³¹ P% by weight = 4.8% by weight (theoretical value: 5.8)
Conversion of compound represented by formula (13) (6 hours after addition of Cu (I) Cl) = 83 mol% (Condition A)

Example (A-8) [Acid Hydrolysis of Aromatic Polymer Phosphonic Acid Monoester]
Under a nitrogen atmosphere, 5 g of the polymer obtained in Example (A-5) and 68 g of 35% hydrochloric acid were added to an eggplant flask equipped with a reflux condenser. The slurry liquid was heated to reflux with stirring at a bath temperature of 145 ° C. for 17 hours. After allowing to cool, the reaction solution was filtered and washed with ion-exchanged water until neutral. After drying, it was dissolved in N-methylpyrrolidone to make a 10% strength by weight solution, and then reprecipitated into a 10% by weight solution of 35% hydrochloric acid / methanol (1/10 (weight ratio)). The precipitate was filtered and then washed with ion exchanged water until neutrality to obtain a compound represented by the formula (15).
Mn = 14700, Mw = 19600
³¹ P% by weight = 5.4 (theoretical value: 5.9)

Example (B-3) [Synthesis of Aromatic Polymer Sulfonic Acid 1]
In a two-necked flask equipped with an azeotropic distillation apparatus, 2.66 g (14.27 mmol) of 4,4′-biphenol, 2.17 g (15.70 mmol) of potassium carbonate and 399 mg of diphenylsulfone were placed under a nitrogen atmosphere, and dimethyl sulfoxide was added. 38.6 g and 40 g of toluene were added. Thereafter, the toluene in the system was azeotropically dehydrated by heating and distilling off toluene at a bath temperature of 160 ° C. for 4 hours. Subsequently, 7.00 g (14.27 mmol) of the compound represented by the formula (16) and 706 mg (7.13 mmol) of Cu (I) Cl were added, and the mixture was stirred while keeping at a bath temperature of 100 ° C. for 6 hours. After allowing to cool, the reaction solution was added to acetone, the deposited precipitate was filtered, and ion exchanged water was added to the resulting precipitate to dissolve it, and then a cation exchange resin was added and stirred. After filtering off the cation exchange resin, the obtained aqueous solution was dried to obtain the compound represented by the formula (17).
Mn = 9400, Mw = 11900
Conversion of compound represented by formula (16) (6 hours after addition of Cu (I) Cl) = 96 mol% (Condition B)
IEC = 3.38 meq / g (theoretical value: 3.5 meq / g)

Example (B-4) [Synthesis of Aromatic Polymer Sulfonic Acid 2]
In a two-necked flask equipped with an azeotropic distillation apparatus, under a nitrogen atmosphere, 2.65 g (14.25 mmol) of 4,4′-biphenol, 2.17 g (15.67 mmol) of potassium carbonate, and 398 mg of diphenylsulfone were added, and dimethyl sulfoxide was added. 38.6 g and 40 g of toluene were added. Thereafter, the toluene in the system was azeotropically dehydrated by heating and distilling off toluene at a bath temperature of 160 ° C. for 4 hours. Subsequently, 7.00 g (14.25 mmol) of the compound represented by the formula (18) and 705 mg (7.12 mmol) of Cu (I) Cl were added, and the mixture was stirred while keeping at a bath temperature of 160 ° C. for 6 hours. After allowing to cool, the reaction solution was added to acetone, the deposited precipitate was filtered, and ion exchanged water was added to the resulting precipitate to dissolve it, and then a cation exchange resin was added and stirred. After filtering off the cation exchange resin, the obtained aqueous solution was dried to obtain the compound represented by the formula (17).
Mn = 12600, Mw = 19200
Conversion of compound represented by formula (18) (6 hours after addition of Cu (I) Cl) = 99 mol% (Condition B)
IEC = 3.33 meq / g (theoretical value: 3.5 meq / g)

Comparative Example (A-1)
In a three-necked flask equipped with an azeotropic distillation apparatus, under a nitrogen atmosphere, 5.00 g (10.9 mmol) of a compound represented by the formula (9), 1.58 g (11.5 mmol) of potassium carbonate, 31 g of dimethyl sulfoxide, and 15 g of toluene Was added. Thereafter, the water in the system was azeotropically dehydrated by heating and distilling off toluene at a bath temperature of 150 ° C. for 4 hours. Next, 2.77 g (10.9 mmol) of 4,4′-difluorodiphenylsulfone was added, and the bath temperature was kept at 150 ° C. for 3 hours while stirring. After allowing to cool, the reaction solution was diluted and the molecular weight was measured, but no polymer was confirmed.

Comparative Example (A-2)
In a Schlenk flask equipped with an azeotropic distillation apparatus, 0.50 g (1.44 mmol) of the compound represented by the formula (10), 0.326 g (1.28 mmol) of 4,4′-difluorodiphenylsulfone under a nitrogen atmosphere, 0.915 g (3.97 mmol) of potassium carbonate, 11 g of dimethyl sulfoxide, and 5 g of toluene were added. After reflux dehydration at a bath temperature of 150 ° C. for 9 hours, the mixture was kept at 150 ° C. for 5 hours. After cooling, the reaction solution was collected and the molecular weight was measured, but no polymer was confirmed.

Comparative Example (A-3)
In a Schlenk flask equipped with an azeotropic distillation apparatus, 1.00 g (2.18 mmol) of the compound represented by the formula (9), 0.36 g (1.45 mmol) of bis-4-hydroxysulfone, 4, 1.02 g (4.00 mmol) of 4′-difluorodiphenylsulfone, 0.55 g (4.00 mmol) of potassium carbonate, 9.5 g of dimethyl sulfoxide, and 10 g of toluene were added. The toluene in the system was azeotropically dehydrated by heating and distilling off the toluene at a bath temperature of 150 ° C. for 5 hours, and then stirred while keeping at a bath temperature of 150 ° C. for 9 hours. After cooling, the reaction solution was collected and the molecular weight was measured, but no polymer was confirmed.

Comparative Example (A-4)
In a Schlenk flask equipped with an azeotropic distillation apparatus, 0.50 g (1.44 mmol) of a compound represented by the formula (10), 0.24 g (0.96 mmol) of bis-4-hydroxysulfone, 4, 0.67 g (2.65 mmol) of 4′-difluorodiphenyl sulfone, 0.76 g (5.49 mmol) of potassium carbonate, 8.0 g of dimethyl sulfoxide, and 10 g of toluene were added. The toluene in the system was azeotropically dehydrated by heating and distilling off the toluene at a bath temperature of 150 ° C. for 5 hours, and then stirred while keeping at a bath temperature of 150 ° C. for 9 hours. After cooling, the reaction solution was collected and the molecular weight was measured, but no polymer was confirmed.

Comparative Example (A-5)
In a Schlenk flask equipped with an azeotropic distillation apparatus, 0.34 g (0.98 mmol) of a compound represented by the formula (10), 0.25 g (0.98 mmol) of 4,4′-sulfonyldiphenol, Potassium carbonate 0.84 g (6.10 mmol) was added, and dimethyl sulfoxide 4.4 g and toluene 4 g were added. Thereafter, the water in the system was azeotropically dehydrated by distilling off toluene for 8 hours at a bath temperature of 145 ° C. Subsequently, 0.50 g (1.97 mmol) of 4,4′-difluorodiphenylsulfone was added, and the mixture was stirred while keeping at a bath temperature of 145 ° C. for 16 hours. After allowing to cool, the reaction solution was added to 6N hydrochloric acid, and the deposited precipitate was filtered, and then washed with ion-exchanged water until neutral, to obtain a solid, but the solid did not have a phosphonic acid group. It was.
Mn = 3700, Mw = 4700
³¹ P% by weight = 0.0 (theoretical value: 6.0)

Comparative Example (B-1)
In a flask equipped with an azeotropic distillation apparatus, under a nitrogen atmosphere, 2.18 g (3.48 mmol) of the compound represented by the formula (13), 0.87 g (3.48 mmol) of 4,4′-sulfonyldiphenol, carbonic acid, 2.02 g (14.6 mmol) of potassium and 30 mg of biphenyl were added, and 20 g of N-methylpyrrolidone and 10 g of toluene were added. Thereafter, the water in the system was azeotropically dehydrated by heating and distilling off toluene at a bath temperature of 120 ° C. for 3 hours. Then, 2.00 g (6.97 mmol) of 4,4′-dichlorodiphenylsulfone was added. This was divided into three parts under a nitrogen atmosphere, and the mixture was stirred while keeping the bath temperatures at 140 ° C., 160 ° C., and 180 ° C. for 5 hours. After standing to cool, each reaction solution was diluted with methanol, and each conversion rate was measured. Moreover, although the product obtained from each reaction solution was measured by GPC, the peak of the polymer was not confirmed.
Conversion of compound represented by formula (13) at bath temperature of 140 ° C. = 0 mol%
Conversion of compound represented by formula (13) at bath temperature of 160 ° C. = 5 mol%
Conversion of compound represented by formula (13) at bath temperature of 180 ° C. = 13 mol%

Comparative Example (B-2)
In a flask equipped with an azeotropic distillation apparatus, 2.18 g (3.48 mmol) of a compound represented by the formula (13), 0.87 g (3.48 mmol) of 4,4′-sulfonyldiphenol, 2.02 g (14.6 mmol) of potassium and 30 mg of biphenyl were added, and 20 g of 1,3-dimethyl-2-imidazolidinone and 10 g of toluene were added. Thereafter, the water in the system was azeotropically dehydrated by heating and distilling off toluene at a bath temperature of 120 ° C. for 4 hours. Then, 2.00 g (6.97 mmol) of 4,4′-dichlorodiphenylsulfone was added. This was divided into three parts under a nitrogen atmosphere, and stirred while keeping the bath temperatures at 160 ° C., 180 ° C., and 190 ° C. for 5 hours, respectively. After standing to cool, each reaction solution was diluted with methanol, and each conversion rate was measured. Moreover, although the product obtained from each reaction solution was measured by GPC, the peak of the polymer was not confirmed.
Conversion of compound represented by formula (13) at bath temperature of 160 ° C. = 2 mol%
Conversion of compound represented by formula (13) at bath temperature of 180 ° C. = 11 mol%
Conversion of compound represented by formula (13) at bath temperature of 190 ° C. = 24 mol%

Synthesis Example 4 [Production of polymer electrolyte (base polymer)]
A sulfone comprising a repeating unit represented by the following formula (19) using Sumika Excel PES5200P (manufactured by Sumitomo Chemical Co., Ltd.) with reference to the methods described in Examples 7 and 21 of JP-A-2007-284653. Block copolymer 1 having a segment having an acid group and a segment having no ion exchange group represented by the following formula (20) (ion exchange capacity = 2.5 meq / g, Mw = 340 × 10 ³ , Mn = 160 × 10 ³ (these values were measured by the method described in JP-A-2007-284653)).

Example (A-9) [Production 1 of polymer electrolyte membrane]
The polymer obtained in Example (A-8) and the block copolymer 1 were mixed at a weight ratio of 1: 9. A polymer electrolyte solution was prepared by dissolving in dimethyl sulfoxide so that the concentration of the obtained mixture was 9% by weight. Next, this polymer electrolyte solution was uniformly spread on a PET substrate. After application, the polymer electrolyte solution was dried at 80 ° C. under normal pressure. The obtained membrane was immersed in 2N sulfuric acid, washed with ion-exchanged water, further dried at room temperature, and then peeled from the PET substrate to obtain a polymer electrolyte membrane (film thickness 20 μm). The radical resistance of the obtained film was evaluated, and the results are shown in Table 1.

Comparative Example (A-6) [Polymer Electrolyte Membrane Production 2]
The block copolymer 1 was dissolved in dimethyl sulfoxide so as to have a concentration of 9% by weight to prepare a polymer electrolyte solution. Next, this polymer electrolyte solution was uniformly spread on a PET substrate. After application, the polymer electrolyte solution was dried at 80 ° C. under normal pressure. The obtained membrane was immersed in 2N sulfuric acid, washed with ion-exchanged water, further dried at room temperature, and then peeled from the PET substrate to obtain a polymer electrolyte membrane (film thickness 20 μm). The radical resistance of the obtained film was evaluated, and the results are shown in Table 1.

From the above results, by using the monomer represented by the general formula (1) and polymerizing in an organic solvent in the presence of a base and a copper salt, mild reaction conditions can be used regardless of the type of reaction solvent. The results show that the monomer conversion is high and an aromatic polymer electrolyte can be obtained. From the above results, it was revealed that the aromatic polymer phosphonic acids can be produced with a small number of reaction steps in the presence of a base by using the monomer represented by the general formula (4). Furthermore, from the results of Examples (A-5) and (A-6), the phosphonic acid group density of the obtained aromatic polymer phosphonic acids can be easily adjusted by changing the monomer charging ratio. It became clear. The aromatic polymer phosphonic acids obtained by the above production method are excellent in radical resistance as shown in Example (A-9). Therefore, the polymer electrolyte obtained by the above production method is used as a polymer electrolyte membrane. Since the fuel cell used as can provide a fuel cell with excellent long-term stability while maintaining practically sufficient power generation performance, it is extremely useful industrially.

Claims

General formula (1)
(In the formula, groups represented by X 1 and X 2 each independently represent a condensable reactive group. Ar 1 represents an optionally substituted aromatic group. The group represented by E 1 is Represents an ion exchange group or an ion exchange precursor group, and n represents an integer of 1 to 4. When a plurality of E 1 are present, the plurality of E 1 may be the same or different. )
A polymerization step of polymerizing the monomer represented by the presence of a base and a first transition metal salt, or
E 1 represents a group represented by — (P (═O) (OR 1 ) (OR 2 )) (R 1 represents a hydrogen atom, an inorganic cation or an organic cation, and R 2 represents an alkyl group or an aryl group. , R 1 and R 2 are present in a plurality, R 1 and R 2 may be the same or different from each other.) The monomer is polymerized in the presence of a base. A method for producing an aromatic polymer comprising a polymerization step.
General formula (1)

(In the formula, groups represented by X 1 and X 2 each independently represent a condensable reactive group. Ar 1 represents an optionally substituted aromatic group. The group represented by E 1 is Represents an ion exchange group or an ion exchange precursor group, and n represents an integer of 1 to 4. When a plurality of E 1 are present, the plurality of E 1 may be the same or different. )
The method for producing an aromatic polymer according to claim 1, further comprising a polymerization step of polymerizing the monomer represented by the formula in the presence of a base and a first transition metal salt.
Wherein the polymerization step, in the general formula (1), a group a group represented by E 1 at least part of (but group represented by E 1 excluding the case where the ion-exchange group), represented by E 2 General formula (2) comprising a reaction step of converting to

(In the formula, Ar 2 represents an aromatic group which may have a substituent. The group represented by E 2 represents an ion-exchange group or an ion-exchange precursor group different from E 1. m is 1 to 4) It represents an integer, Z is a group represented by -O- or -S-. in the case where E 2 there are a plurality, E 2 existing in plural numbers may each be the same or different.)
The manufacturing method of the aromatic polymer of Claim 1 or 2 which has a repeating unit represented by these.
In the reaction step, one or more selected from the group consisting of strong acids, trialkylsilyl halides, bases, and nucleophiles are allowed to act, and at least a part of the group represented by E 1 is converted to a group represented by E 2. The method for producing an aromatic polymer according to claim 3, wherein the method is a step of converting into an aromatic polymer.
The method for producing an aromatic polymer according to any one of claims 1 to 4, wherein the ion exchange group is a phosphonic acid group, and the ion exchange precursor group is a phosphonic acid precursor group.
The method for producing an aromatic polymer according to any one of claims 1 to 4, wherein the ion exchange group is a sulfonic acid group, and the ion exchange precursor group is a sulfonic acid precursor group.
In the polymerization step, the monomer represented by the general formula (1) and the general formula (3)

(In the formula, groups represented by X 3 and X 4 each independently represent a condensable reactive group. Ar 3 represents an aromatic group which may have a substituent.)
The method for producing an aromatic polymer according to any one of claims 1 to 6, wherein a monomer represented by the formula:
The method for producing an aromatic polymer according to any one of claims 1 to 7, wherein the groups represented by X 1 and X 2 are each independently a hydroxyl group or a mercapto group.
The base is an alkali metal carbonate, alkali metal bicarbonate, alkali metal hydroxide, alkali metal hydride, alkaline earth metal carbonate, alkaline earth metal bicarbonate, alkaline earth metal hydroxide and alkaline earth. The method for producing an aromatic polymer according to any one of claims 1 to 8, which is at least one base selected from the group consisting of metal hydrides.
The method for producing an aromatic polymer according to any one of claims 1 to 9, wherein the first transition metal salt is a copper salt.
The method for producing an aromatic polymer according to claim 10 , wherein the copper salt is a monovalent copper salt.
The method for producing an aromatic polymer according to claim 11, wherein the monovalent copper salt is at least one selected from the group consisting of CuCl, CuBr and CuI.
General formula (4)

(In the formula, X 5 and X 6 each independently represent a condensable reactive group. Ar 4 represents an aromatic group which may have a substituent. P represents an integer of 1 to 4. R 1 represents a hydrogen atom, an inorganic or organic cation, R 2 represents an alkyl group or an aryl group. in the case where R 1 and R 2 there are a plurality, R 1 and R 2 existing in plural numbers, respectively identical It may or may not be.)
The manufacturing method of the aromatic polymer of Claim 1 provided with the superposition | polymerization process which polymerizes the monomer represented by these in presence of a base.
The method for producing an aromatic polymer according to claim 13, wherein the base is a base composed of a metal compound other than the first transition metal salt.
In the polymerization step, at least a part of the group represented by — (P (═O) (OR 1 ) (OR 2 )) in the general formula (4) is substituted with — (P (═O) (OH) (OR 3 )) a reaction step for converting to a group represented by formula (5)

(In the formula, Ar 5 represents an aromatic group which may have a substituent. Q represents an integer of 1 to 4. Z 2 represents —O—, —S— or —NR 4 — (R 4 the .R 3 represents a group represented by.) represents a hydrogen atom, an alkyl group or an aryl group represents a hydrogen atom, an alkyl group or an aryl group. in the case where R 3 there are a plurality, R 3 existing in plural Each may be the same or different.)
The manufacturing method of the aromatic polymer of Claim 13 or 14 which has a repeating unit represented by these.
In the reaction step, a strong acid and / or a trialkylsilyl halide is allowed to act to convert at least a part of the group represented by — (P (═O) (OR 1 ) (OR 2 )) to — (P (= The method for producing an aromatic polymer according to claim 15, which is a step of converting to a group represented by O) (OH) (OR 3 )).
In the polymerization step, the monomer represented by the general formula (4) and the general formula (6)

(In the formula, X 7 and X 8 each independently represent a condensable reactive group. Ar 6 represents an aromatic group which may have a substituent.)
The aromatic group according to any one of claims 13 to 16, which is copolymerized with a monomer represented by the formula-(P (= O) (OR 1 ) (OR 2 )). Of production of a polymer.
The method for producing an aromatic polymer according to any one of claims 13 to 17, wherein both X 5 and X 6 are nucleophilic reactive groups.
The method for producing an aromatic polymer according to claim 18, wherein the nucleophilic reactive group is a hydroxyl group.
The method for producing an aromatic polymer according to any one of claims 13 to 19, wherein R 2 is an alkyl group.
The method for producing an aromatic polymer according to any one of claims 13 to 20, wherein the polymerization is performed at 100 ° C or higher in the polymerization step.
The method for producing an aromatic polymer according to any one of claims 13 to 21, wherein the base is an alkali metal salt.
The method for producing an aromatic polymer according to any one of claims 13 to 22, wherein R 1 is an organic cation.
In the general formula (4), a group represented by — (P (═O) (OR 1 ) (OR 2 )) replaces the same benzene ring as that substituted with X 5 and / or X 6. The method for producing an aromatic polymer according to any one of claims 13 to 23.
General formula (7)

(In the formula, Ar 4 represents an aromatic group which may have a substituent. Q represents an integer of 1 to 4. R 1 represents a hydrogen atom, an inorganic cation or an organic cation, and R 2 represents an alkyl group. represents a group or an aryl group. in the case where R 1 and R 2 there are a plurality, R 1 and R 2 existing in plural numbers may each be the same or different.)
A compound represented by
The compound according to claim 25, wherein Ar 4 is a biphenyl group which may have a substituent.