JP2003242833A - Proton conductive polymeric solid electrolyte, its producing method, electrolytic membrane consisting thereof, its producing method, electrochemical element using electrolyte and/or electrolytic membrane, and its producing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly proton conductive polymeric solid electrolyte having superior strength, heat resistance, acid resistance, and oxidation and reduction resistance stability, its producing method, an electrolytic membrane consisting thereof, its producing method, an electrochemical element having durability, reliability and current property using the electrolyte and/or the electrolytic membrane, and its producing method. <P>SOLUTION: The highly proton conductive polymeric solid electrolyte comprising a polymer containing quinoxaline skeletons and an acid compound, its producing method, the electrolytic membrane consisting thereof, its producing method, the electrochemical element using the electrolyte and/or the electrolytic membrane, and its producing method. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high proton conductive polymer solid electrolyte excellent in strength, heat resistance, acid resistance and oxidation-reduction stability, a method for producing the electrolyte, an electrolyte membrane comprising the electrolyte, The present invention relates to a method for manufacturing an electrolyte membrane.

[0002] The present invention further relates to an electrochemical device using the high proton conductive polymer solid electrolyte and / or the electrolyte membrane and having excellent durability, reliability and current characteristics, and a method for producing the device.

[0003]

2. Description of the Related Art Proton-conductive electrolytes such as sulfuric acid take advantage of the characteristic of high electrical conductivity due to the small ionic radius of protons. Are often used for so-called electrochemical devices such as display devices which require the following.

Specifically, "Electrochemistry", 1998, No. 6
No. 6, No. 9, page 884, a carbon material having a large specific surface area, such as activated carbon or carbon black, is used as a polarizable electrode material and a proton conductive electrolyte is used as an organic or aqueous liquid (so-called electrolyte solution). 2) illustrates an electric double layer capacitor. Further, for example, "Electronic Technology" 1999,
No. On pages 11, 58, an electric double layer capacitor using a sulfuric acid aqueous solution is described.

However, all of these use the electrolyte in a liquid state. 2. Description of the Related Art Conventionally, electrolyte materials for electrochemical devices such as batteries and capacitors have been used in many cases in liquid form, including proton-conductive electrolytes. On the other hand, in recent years, electrolytes have been developed to improve the processability of elements, respond to the demand for lighter and smaller elements and devices incorporating them, and to meet increasing demands for reliability and safety of elements. There is an increasing demand for solidification of materials, and various developments are being made to meet this demand. The same applies to proton conductive electrolytes, and various developments have been made for solidifying the electrolyte material.

For example, JP-A-7-22034 and JP-A-7-326363 describe proton conductive polymer solid electrolytes such as Nafion. However, the proton conductive polymer solid electrolyte disclosed herein is expensive in raw material and difficult to produce, and further has problems in thermal stability and water retention of an electrolyte membrane made of the electrolyte.

On the other hand, Japanese Patent Laid-Open No. 2000-273159
Japanese Patent Application Laid-Open Publication No. H11-157, pp. 147-64 discloses a proton-conductive polymer solid electrolyte comprising a complex of polyquinoline or polyquinoxaline and phosphoric acid or a phosphoric acid ester. However, the dissociation degree of phosphoric acid is low and the conductivity is insufficient, and there are also problems with the heat resistance of the electrolyte itself and the strength of the membrane made of the electrolyte.

As described above, the performance of electrolyte materials for electrochemical devices such as batteries and capacitors, which have been required in recent years, is not sufficient, and a more excellent proton-conductive polymer solid electrolyte and an electrolyte composed of the electrolyte are used. There is a need for an electrolyte membrane.

[0009]

SUMMARY OF THE INVENTION One of the objects of the present invention is the strength, heat resistance, acid resistance and oxidation resistance which are problems of the conventional proton conductive polymer solid electrolyte and the electrolyte membrane comprising the electrolyte. An object of the present invention is to provide a proton-conductive polymer solid electrolyte having excellent reduction stability, a method for producing the electrolyte, an electrolyte membrane comprising the electrolyte, and a method for producing the electrolyte membrane.

Another object of the present invention is to provide an electrochemical device using the proton-conductive polymer solid electrolyte and / or the electrolyte membrane and having excellent durability, reliability, and current characteristics, and a method of manufacturing the device. Is to provide.

[0011]

Means for Solving the Problems The present inventors have intensively studied to solve the above problems. As a result, the proton conductive polymer solid electrolyte composed of a polymer containing a quinoxaline skeleton and an acidic compound has high proton conductivity, has heat resistance under the conditions required for the solid electrolyte, and has acidic conditions, redox conditions. The inventors have found that the electrolyte membrane is stable with respect to the conditions and that the electrolyte membrane made of the electrolyte has excellent strength, and thus completed the present invention.

That is, the present invention (I) provides a proton conductive polymer solid electrolyte comprising: A) a polymer having a quinoxaline structure represented by the general formula (1); and B) an acidic compound. It is. General formula (1)

[0013]

Embedded image

(In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer. Independently, a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, and an alkyl group having 1 to 20 carbon atoms which may have a substituent Having 2 carbon atoms which may have a substituent
Represents an alkenyl group having 20 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent. )

The present invention (II) is a method for producing the proton conductive polymer solid electrolyte of the present invention (I).

Further, the present invention (III) is the same as the present invention (I)
A proton conducting polymer solid electrolyte membrane characterized by including the proton conducting polymer solid electrolyte described above.

Further, the present invention (IV) relates to the present invention (II)
This is a method for producing a proton-conductive polymer solid electrolyte membrane of I).

Furthermore, the present invention (V) is characterized by using the proton conductive polymer solid electrolyte membrane of the present invention (I) and / or the proton conductive polymer solid electrolyte membrane of the present invention (III). It is an electrochemical device.

Further, the present invention (VI) is a compound of the present invention (V)
This is a method for producing an electrochemical device.

Further, the present invention includes, for example, the following items. [1] A proton conductive solid polymer electrolyte comprising: A) a polymer having a quinoxaline structure represented by the general formula (1); and B) an acidic compound.

General formula (1)

Embedded image (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

[2] A proton conductive polymer solid electrolyte comprising: A) a polymer having a quinoxaline structure represented by the general formula (1) in a side chain thereof; and B) an acidic compound.

General formula (1)

Embedded image (Wherein at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the others are each independently a hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

[3] A proton-conductive solid polymer electrolyte comprising: A) a polymer containing a quinoxaline structure represented by the general formula (2) as a part of a repeating unit; and B) an acidic compound. .

General formula (2)

Embedded image (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

[4] A) A polymer containing a quinoxaline structure represented by the general formula (1) in a side chain and a quinoxaline structure represented by the general formula (2) as a part of a repeating unit, and B) A proton-conductive polymer solid electrolyte comprising an acidic compound.

General formula (1)

Embedded image (Wherein at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the others are each independently a hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

General formula (2)

Embedded image (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

[5] A) The quinoxaline structure represented by the general formula (2) is a quinoxaline structure represented by the general formula (3): The proton conductive polymer solid electrolyte as described in the above.

General formula (3)

Embedded image (Wherein, R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

[6] A) The quinoxaline structure represented by the general formula (2) is a quinoxaline structure represented by the general formula (4): The proton conductive polymer solid electrolyte as described in the above.

Formula (4)

Embedded image (Wherein, R ^{15 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent, X each independently represents an aryl group which may have a substituent, and Y each independently has a hetero atom or a hetero atom. A good carbon number represents an aryl group which may have a substituent of 4 or more and 20 or less, and n represents an integer of 0-5. )

[7] B) The acidic compound is sulfuric acid, nitric acid,
The proton conductivity according to any one of [1] to [6], wherein the proton conduction is at least one selected from the group consisting of acetic acid, fluorinated acetic acid, propionic acid, fluorinated propionic acid, butyric acid, and fluorinated butyric acid. Polymer solid electrolyte.

[8] The proton conductive polymer solid electrolyte according to any one of [1] to [6], wherein the B) acidic compound is an acid type monomer.

[0035]

[9] The acid type monomer is acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid,
The proton conductive polymer solid electrolyte according to [8], which is at least one selected from the group consisting of styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid, and vinyl phosphoric acid.

[10] The proton-conductive polymer solid electrolyte according to any one of [1] to [6], wherein the B) acidic compound is an acid-type polymer.

[11] The acid-type polymer according to [10], wherein the acid-type polymer is at least one selected from the group consisting of a carboxylic acid-based polymer, a sulfonic acid-based polymer and a phosphoric acid-based polymer. Proton conductive polymer solid electrolyte.

[12] The method for producing a proton conductive polymer solid electrolyte according to any one of [1] to [11], comprising the following steps: Step A) Step of mixing a polymer having a quinoxaline structure represented by the general formula (1) and B) an acidic compound to obtain a proton-conductive polymer solid electrolyte

General formula (1)

Embedded image (In the formula, at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

[13] The method according to [1] to [6], [8] or [1], comprising the following first step and second step.

[9]
The method for producing a proton-conductive polymer solid electrolyte according to any one of the above. First step A) A polymer having a quinoxaline structure represented by the general formula (1) and B) Acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl Mixing an acidic compound having at least one or more polymerizable functional groups selected from the group consisting of sulfonic acid and vinyl phosphoric acid to obtain a composition for producing a proton conductive polymer solid electrolyte

Step 2 Step of polymerizing the acidic compound contained in the composition for producing a proton-conductive polymer solid electrolyte obtained in the first step to obtain a proton-conductive polymer solid electrolyte.

General formula (1)

Embedded image (In the formula, at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

[14] The method according to [1] to [6], [8] or [1], comprising the following first and second steps:

[9]
The method for producing a proton-conductive polymer solid electrolyte according to any one of the above. First step A) A polymer having a quinoxaline structure represented by the general formula (1) in a side chain, and B) Acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfone Mixing an acidic compound having at least one polymerizable functional group selected from the group consisting of acid, vinyl sulfonic acid and vinyl phosphoric acid to obtain a composition for producing a proton conductive polymer solid electrolyte

Second Step A step of polymerizing the acidic compound contained in the composition for producing a proton-conductive polymer solid electrolyte obtained in the first step to obtain a proton-conductive polymer solid electrolyte General formula (1)

Embedded image (Wherein at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the others are each independently a hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

[15] The method according to [1] to [6], [8] or [1], comprising the following first and second steps:

[9]
The method for producing a proton-conductive polymer solid electrolyte according to any one of the above. First step A) A polymer containing a quinoxaline structure represented by the general formula (2) as a part of a repeating unit and B) Acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, hydrofluoric acid, Mixing an acidic compound having at least one or more polymerizable functional groups selected from the group consisting of hydrogenated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid to obtain a composition for producing a proton conductive polymer solid electrolyte

Second step: A step of polymerizing the acidic compound contained in the composition for producing a proton-conductive polymer solid electrolyte obtained in the first step to obtain a proton-conductive polymer solid electrolyte.

General formula (2)

Embedded image (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

[16] The method according to [1] to [6], [8] or [1], comprising the following first and second steps:

[9]
The method for producing a proton-conductive polymer solid electrolyte according to any one of the above. First step A) a polymer containing a quinoxaline structure represented by the general formula (1) in a side chain and a quinoxaline structure represented by the general formula (2) as a part of a repeating unit, and B) acrylic acid; Mixing an acidic compound having at least one or more polymerizable functional groups selected from the group consisting of fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid To obtain a composition for producing a proton conductive polymer solid electrolyte

Second step A step of polymerizing the acidic compound contained in the composition for producing a proton-conductive polymer solid electrolyte obtained in the first step to obtain a proton-conductive polymer solid electrolyte General formula (1)

Embedded image (Wherein at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the others are each independently a hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

General formula (2)

Embedded image (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

[17] The method for producing a proton conductive polymer solid electrolyte according to any one of [1] to [11], comprising the following first step and second step. First step A) a step of mixing a polymerizable compound having a quinoxaline structure represented by the general formula (1) and B) an acidic compound to obtain a composition for producing a proton-conductive polymer solid electrolyte.

Second step: a step of polymerizing the polymerizable compound contained in the composition for producing a proton-conductive solid polymer electrolyte obtained in the first step to obtain a proton-conductive solid polymer electrolyte.

General formula (1)

Embedded image (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

[18] The method for producing a proton conductive solid polymer electrolyte according to any one of [1] to [11], comprising the following first step and second step. First step A) A step of mixing a polymerizable compound having a quinoxaline structure represented by the general formula (1) and B) an acid-type polymer to obtain a composition for producing a proton-conductive polymer solid electrolyte.

Second step: A step of polymerizing the polymerizable compound contained in the composition for producing a proton-conductive solid polymer electrolyte obtained in the first step to obtain a proton-conductive solid polymer electrolyte, general formula (1)

Embedded image (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

[19] A proton conductive polymer solid electrolyte membrane comprising the proton conductive polymer solid electrolyte according to any one of [1] to [11].

[20] The film thickness is 5 μm to 200 μm
[19] The proton conductive polymer solid electrolyte membrane according to [19], wherein:

[21] The proton conductive polymer solid electrolyte membrane according to any one of [19] and [20], further comprising a non-electron conductive reinforcing agent.

[22] The proton conductive polymer solid electrolyte membrane according to [21], wherein the non-electron conductive reinforcing agent is an oxide particle.

[23] The oxide particles are made of Al, Si and T
The proton conductive polymer solid electrolyte membrane according to [22], which is an oxide of at least one element selected from i.

[24] The oxide particles having a particle diameter of 0.00
It is in the range of 1 μm to 10 μm [2
2] or the proton conductive polymer solid electrolyte membrane according to [23].

[25] The method for producing a proton conductive polymer solid electrolyte membrane according to any one of [19] to [24], comprising the following first step and second step. First step A step of applying a solution of at least one of any of the polymers represented by the following (a) to (d) to a substrate and then distilling off the solvent to obtain a polymer film (a): Polymer containing quinoxaline structure represented by general formula (1) (b) Polymer containing quinoxaline structure represented by general formula (2) as a part of repeating unit (c) Represented by general formula (3) Containing a quinoxaline structure as a part of a repeating unit (d) A polymer containing a quinoxaline structure represented by the general formula (4) as a part of a repeating unit

General formula (1)

Embedded image (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

Formula (2)

Embedded image (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

Formula (3)

Embedded image (Wherein, R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

General formula (4)

Embedded image (Wherein, R ^{15 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent, X each independently represents an aryl group which may have a substituent, Y is each independently a heteroatom alone, Represents an aryl group having 4 to 20 carbon atoms, and n represents an integer of 0 to 5. )

Second step B) Step of adding an acidic compound to the polymer membrane obtained in the first step to obtain a proton-conductive polymer solid electrolyte membrane

[26] The method for producing a proton-conductive polymer solid electrolyte membrane according to any one of [19] to [24], comprising the following first to third steps: First step A step of applying a solution of at least one of any of the polymers represented by the following (a) to (d) to a substrate and then distilling off the solvent to obtain a polymer film (a): Polymer containing quinoxaline structure represented by general formula (1) (b) Polymer containing quinoxaline structure represented by general formula (2) as a part of repeating unit (c) Represented by general formula (3) Containing a quinoxaline structure as a part of a repeating unit (d) A polymer containing a quinoxaline structure represented by the general formula (4) as a part of a repeating unit

General formula (1)

Embedded image (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

General formula (2)

Embedded image (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

Formula (3)

Embedded image (Wherein, R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

Formula (4)

Embedded image (Wherein, R ^{15 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent, X each independently represents an aryl group which may have a substituent, Y is each independently a heteroatom alone, Represents an aryl group having 4 to 20 carbon atoms, and n represents an integer of 0 to 5. )

Second Step A step of adding an acid-type monomer to the polymer membrane obtained in the first step to obtain a proton-conductive polymer solid electrolyte precursor membrane.

Third step: a step of polymerizing an acid-type monomer contained in the proton conductive polymer solid electrolyte precursor membrane obtained in the second step to obtain a proton conductive polymer solid electrolyte membrane.

[27] The acid type monomer is acrylic acid,
Fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid,
The method for producing a proton-conductive polymer solid electrolyte membrane according to [26], which is an acidic compound having at least one polymerizable functional group selected from the group consisting of vinyl sulfonic acid and vinyl phosphoric acid.

[28] The method for producing a proton conductive polymer solid electrolyte membrane according to any one of [19] to [24], comprising the following first step and second step. First step A) At least one polymer of any polymer represented by the following (a) to (d) (a) Polymer containing quinoxaline structure represented by general formula (1) ( b) A polymer containing the quinoxaline structure represented by the general formula (2) as a part of the repeating unit (c) A polymer (d) containing the quinoxaline structure represented by the general formula (3) as a part of the repeating unit A polymer containing a quinoxaline structure represented by the general formula (4) as a part of a repeating unit

General formula (1)

Embedded image (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

Formula (2)

Embedded image (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

Formula (3)

Embedded image (Wherein, R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

Formula (4)

Embedded image (Wherein, R ^{15 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent, X each independently represents an aryl group which may have a substituent, Y is each independently a heteroatom alone, Represents an aryl group having 4 to 20 carbon atoms, and n represents an integer of 0 to 5. ) And B) a step of obtaining a composition for producing a proton-conductive polymer solid electrolyte membrane containing an acidic compound

Step 2 Step of obtaining a proton-conductive polymer solid electrolyte membrane by molding the composition for producing a proton-conductive polymer solid electrolyte membrane obtained in the first step under pressure and / or heat.

[29] The method for producing a proton-conductive polymer solid electrolyte membrane according to any one of [19] to [24], comprising the following first step and second step. First step A) At least one polymer of any polymer represented by the following (a) to (d) (a) Polymer containing quinoxaline structure represented by general formula (1) ( b) A polymer containing the quinoxaline structure represented by the general formula (2) as a part of the repeating unit (c) A polymer (d) containing the quinoxaline structure represented by the general formula (3) as a part of the repeating unit A polymer containing a quinoxaline structure represented by the general formula (4) as a part of a repeating unit

General formula (1)

Embedded image (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. )

General formula (2)

Embedded image (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

General formula (3)

Embedded image (Wherein, R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. )

General formula (4)

Embedded image (Wherein, R ^{15 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent, X each independently represents an aryl group which may have a substituent, Y is each independently a heteroatom alone, Represents an aryl group having 4 to 20 carbon atoms, and n represents an integer of 0 to 5. And b) a step of obtaining a composition for producing a proton-conductive polymer solid electrolyte membrane containing an acid-type monomer.

Second step The proton conductive polymer solid electrolyte membrane is obtained by pressurizing and heating while polymerizing the acid type monomer in the composition for producing a proton conductive solid polymer electrolyte membrane obtained in the first step. Process

[30] The acid type monomer is acrylic acid,
Fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid,
[29] The method for producing a proton conductive polymer solid electrolyte membrane according to [29], wherein the acidic compound has at least one or more polymerizable functional groups selected from the group consisting of vinyl sulfonic acid and vinyl phosphoric acid.

[31] The proton-conductive polymer solid electrolyte according to any one of [1] to [11] and / or [1]
[9] An electrochemical device using the proton conductive polymer solid electrolyte membrane according to any one of [24] to [24].

[32] The proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or [1]
[9] A battery using the proton-conductive polymer solid electrolyte membrane according to any one of [24] to [24].

[33] The proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or [1]
[9] A fuel cell using the proton-conductive polymer solid electrolyte membrane according to any one of [24] to [24].

[34] The proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or [1]
[9] An electric double-layer capacitor using the proton-conductive polymer solid electrolyte membrane according to any one of [24] to [24].

[35] The proton conductive polymer solid electrolyte according to any one of [1] to [11] and / or [1]
[9] An electrochromic device using the proton-conductive polymer solid electrolyte membrane according to any one of [24] to [24].

[36] [1] to [1] between the positive electrode and the negative electrode
1) Production of a battery comprising the proton-conductive polymer solid electrolyte according to any one of [1] and / or the proton-conductive polymer solid electrolyte membrane according to any of [19] to [24]. Method.

[37] Between the fuel electrode and the air electrode [1]-
A fuel cell comprising the proton conductive polymer solid electrolyte according to any one of [11] and / or the proton conductive polymer solid electrolyte membrane according to any of [19] to [24]. Manufacturing method.

[38] [1] Between two polarizable electrodes
Or a proton-conductive polymer solid electrolyte membrane according to any one of [19] to [24]. Manufacturing method of double layer capacitor.

[39] Between the discoloring electrode and the counter electrode [1]-
An electrochromic comprising installing the proton conductive polymer solid electrolyte according to any one of [11] and / or the proton conductive polymer solid electrolyte membrane according to any of [19] to [24]. Device manufacturing method.

[0098]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

The present invention (I) is a proton-conductive polymer solid electrolyte comprising: A) a polymer having a quinoxaline structure represented by the general formula (1); and B) an acidic compound. is there.

General formula (1)

Embedded image

(In the formula, at least one of R ^{1 to} R ⁶ is a group bonding to the main chain of the polymer and / or at least two are groups forming the main chain of the polymer, and the others are respectively Independently, a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, and an alkyl group having 1 to 20 carbon atoms which may have a substituent Having 2 carbon atoms which may have a substituent
Represents an alkenyl group having 20 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent. )

First, “A) a polymer containing a quinoxaline structure represented by the general formula (1)” in the proton conductive solid polymer electrolyte of the present invention (I) will be described.

The “polymer having a quinoxaline structure” of the present invention (I) includes any polymer having a quinoxaline structure at least partially, whether it is a main chain or a side chain of the polymer. Can also be used. For example, a structure having a structure represented by, for example, a structural formula (1) in which a quinoxaline structure is not directly contained in a structure forming a main chain of a polymer but a part of the quinoxaline structure is bonded to the main chain. And a general formula (2) having a quinoxaline structure as a part of the structure forming the main chain of the polymer.
May have the structure represented by the formula as a repeating unit.

Structural formula (1)

Embedded image

General formula (2)

Embedded image

(Wherein, R ^{7 to} R ¹⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, and a substituent. 1 to 2 carbon atoms
0 alkyl group, alkenyl group having 2 to 20 carbon atoms which may have a substituent, 2 carbon atom which may have a substituent
Represents an alkynyl group having 20 to 20 carbon atoms or an aryl group which may have a substituent. )

Further, both a portion having a structure represented by structural formula (1) in which a part of the quinoxaline structure is bonded to the main chain and a portion having a structure represented by general formula (2) are included. It may be a polymer, and may further contain a repeating unit different from the quinoxaline structure. Further, a mixture thereof may be used.

In the present invention (I), “wherein at least one of R ^{1 to} R ⁶ in the formula (1) in the“ polymer having a quinoxaline structure ”is a group bonded to the main chain of the polymer. Is meant to include, for example, a structure represented by the structural formula (1).

Structural formula (1)

Embedded image

Here, the main chain and the quinoxaline structure may have not only those directly bonded as shown in the structural formula (1) but also other functional groups between them. For example, structural formula (2)
In the case of a polymer obtained by using an acrylic acid ester of an alcohol having a quinoxaline structure as a raw material, the polymer has a repeating unit represented by the structural formula (3) having an ester structure between the main chain and the quinoxaline structure. It becomes a polymer, but it does not matter much.

Structural formula (2)

Embedded image

Structural formula (3)

Embedded image

In the general formula (1), “wherein at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer” means, for example, an ester bond mentioned above as an example. It goes without saying that the main chain and the quinoxaline structure may be bonded in any form.

In the present invention (I), “a polymer containing a quinoxaline structure represented by the general formula (2) as a part of a repeating unit” refers to a quinoxaline structure having at least a part of a main chain of the polymer. Any material may be used as long as it has the following.

The term “polymer containing a quinoxaline structure as a part of a repeating unit” as used herein refers to a polymer consisting of only a quinoxaline structure, but having at least one other different structure in addition to the quinoxaline structure. May be included. In this case, a quinoxaline structure and another structure may be alternated, or a structure in which only a quinoxaline structure is repeated and a portion in which another structure is repeated may be alternately provided.

Further, the quinoxaline structure may or may not be a direct repeating structure. For example, in the general formula (4), a structure in which another structure is bonded to a quinoxaline structure is used as a basic structure of a repeating unit. Includes those represented.

General formula (4)

Embedded image

(Wherein, R ^{15 to} R ³⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, and a substituent. 1 to 2 carbon atoms
0 alkyl group, alkenyl group having 2 to 20 carbon atoms which may have a substituent, 2 carbon atom which may have a substituent
Represents an alkynyl group having 20 to 20 carbon atoms or an aryl group which may have a substituent, X represents an aryl group which may have a substituent, Y represents a hetero atom alone, a hetero atom 4 to 20 carbon atoms which may have
The following aryl groups are represented, and n represents an integer of 0 to 5. )

Further, “a polymer containing a quinoxaline structure represented by the general formula (1) in a side chain and containing a quinoxaline structure represented by the general formula (2) as a part of a repeating unit” includes A polymer having a structure in which a part of the polymer has, for example, a structure represented by the structural formula (1) in which a part of the quinoxaline structure is bonded to the main chain, and the other part has a quinoxaline structure in a part of the main chain of the polymer Any object can be used.

In this case, the portion containing the quinoxaline structure in the side chain and the portion containing the quinoxaline structure as the main chain structure are alternately present, and the portion containing the quinoxaline structure in the side chain is repeated. It may be a product obtained by repeating a portion containing a quinoxaline structure as a main chain structure later. Further, the compound may have a repeating unit different from the quinoxaline structure. In that case, the structures may be bonded to each other in an arbitrary order.

In the general formulas (1) to (4) of the present invention (I), R ^{1 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester. Group, sulfonic acid group, sulfonic acid ester group, alkyl group having 1 to 20 carbon atoms which may have a substituent, alkenyl group having 2 to 20 carbon atoms which may have a substituent, It represents an alkynyl group having 2 to 20 carbon atoms which may have a group or an aryl group which may have a substituent.

As used herein, “each independently” refers to R ¹
Both of ~R ³⁰ is not only said to be independent,
This shows that each quinoxaline structure of the polymer is independent. That is, for example, when any R ^α (α is an integer of 1 to 30) of the quinoxaline structure is a methyl group, R
^α indicates that it may be a methyl group or a functional group other than a methyl group. Therefore, when n quinoxaline structures are present in one polymer, any R ^α
Indicates that each of the n quinoxaline structures is an independent functional group.

R ¹ in the general formulas (1) to (4)
~R Specifically, for example, hydrogen atom ^30, a methyl group, a trifluoromethyl group, an alkyl group such as ethyl group, an ethenyl group, a 2-propenyl group, 1,3-butadienyl group, 4
Alkenyl groups such as -methoxy-2-butenyl group, ethynyl group, alkynyl groups such as 2-propynyl group, phenyl group, thienyl group, pyrrolyl group, 4-methoxyphenyl group, 3-trifluoromethylphenyl group, naphthyl group,
Examples thereof include an aryl group such as 3-methylthienyl group, a halogen atom such as fluorine and chlorine, a carboxylic acid group, a carboxylic acid ester group, a nitro group, a nitrile group, a sulfonic acid group, and a sulfonic acid ester group.

Preferred are a hydrogen atom, methyl group, trifluoromethyl group, phenyl group, 3-trifluoromethylphenyl group, naphthyl group, fluorine, carboxylic acid group, carboxylic ester group, nitro group, nitrile group, sulfonic acid Group, a sulfonic acid ester group, more preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a phenyl group,
A naphthyl group, a fluorine, a nitro group, a nitrile group, a sulfonic group, and a sulfonic ester group.

Examples of the combination of R ^{1 to} R ³⁰ include a combination of a hydrogen atom and an electron donating group such as a methyl group or a phenyl group, or a combination of a hydrogen atom and a fluorine or trifluoromethyl group.
A combination of electron-withdrawing groups such as a nitro group and a nitrile group is preferred. It is also preferable to use these preferable elements alone, for example, all hydrogen atoms, all methyl groups, all fluorine and the like.

The “polymer having a quinoxaline structure represented by the general formula (1)” of the present invention (I) is preferably a polymer containing a quinoxaline structure represented by the general formula (2) as a part of a repeating unit. It is united.

General formula (2)

Embedded image

(Wherein, R ^{7 to} R ¹⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, and a substituent. 1 to 2 carbon atoms
0 alkyl group, alkenyl group having 2 to 20 carbon atoms which may have a substituent, 2 carbon atom which may have a substituent
Represents an alkynyl group having 20 to 20 carbon atoms or an aryl group which may have a substituent. )

More preferably, a polymer containing the quinoxaline structure represented by the general formula (3) as a part of the repeating unit, or a polymer containing the quinoxaline structure represented by the general formula (4) as a part of the repeating unit It is.

General formula (3)

Embedded image

(Wherein, R ^{11 to} R ¹⁴ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, and a substituent. 1 to 2 carbon atoms
0 alkyl group, alkenyl group having 2 to 20 carbon atoms which may have a substituent, 2 carbon atom which may have a substituent
Represents an alkynyl group having 20 to 20 carbon atoms or an aryl group which may have a substituent. )

General formula (4)

Embedded image

(Wherein, R ^{15 to} R ³⁰ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, and a substituent. 1 to 2 carbon atoms
0 alkyl group, alkenyl group having 2 to 20 carbon atoms which may have a substituent, 2 carbon atom which may have a substituent
Represents an alkynyl group having 20 to 20 carbon atoms or an aryl group which may have a substituent, X represents an aryl group which may have a substituent, Y represents a hetero atom alone, a hetero atom 4 to 20 carbon atoms which may have
The following aryl groups are represented, and n represents an integer of 0 to 5. )

R ^{11 to} R ¹⁴ in formula (3) are preferably a hydrogen atom, a methyl group, a trifluoromethyl group,
A phenyl group, a 3-trifluoromethylphenyl group, a naphthyl group, fluorine, a carboxylic acid group, a carboxylic acid ester group, a nitro group, a nitrile group, a sulfonic acid group, and a sulfonic acid ester group; Group, trifluoromethyl group, phenyl group, naphthyl group,
These are fluorine, nitro, nitrile, sulfonic acid, and sulfonic ester groups.

The combination of R ^{11 to} R ¹⁴ may be a combination of a hydrogen atom and an electron donating group such as a methyl group or a phenyl group, or a combination of a hydrogen atom and a fluorine or trifluoromethyl group.
A combination of electron-withdrawing groups such as a nitro group and a nitrile group is preferred. It is also preferable to use these preferable elements alone, for example, all hydrogen atoms, all methyl groups, all fluorine and the like.

R ^{15 to} R ³⁰ in formula (4) are preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a phenyl group, a 3-trifluoromethylphenyl group, a naphthyl group, a fluorine atom, a carboxylic acid group. Carboxylic acid ester group, nitro group, sulfonic acid group, sulfonic acid ester group, more preferably a hydrogen atom, methyl group, trifluoromethyl group, phenyl group, naphthyl group, fluorine,
A nitro group, a sulfonic group, and a sulfonic ester group.

The combination of R ^{15 to} R ³⁰ may be a combination of a hydrogen atom and an electron donating group such as a methyl group or a phenyl group, or a combination of a hydrogen atom and a fluorine or trifluoromethyl group.
A combination of electron-withdrawing groups such as a nitro group and a nitrile group is preferred. It is also preferable to use these preferable elements alone, for example, all hydrogen atoms, all methyl groups, all fluorine and the like.

X in the general formula (4) independently represents an arylene group which may have a substituent, and Y independently represents a heteroatom alone or a carbon atom which may have a heteroatom having 6 carbon atoms. Represents an arylene group of 20 or more, and n
Each independently represents an integer of 0 to 5;

The expression "each independently" of X, Y and n means that all of the repeating units may be the same or all may be different. That is, for example, in the case of a polymer having m repeating units represented by the general formula (4), m X, Y or n
All may be the same, all may be different, or it may mean that some are the same and some are different.

As X in the general formula (4), specifically, for example, phenylene group, 4-methylphenylene group, 3
-Nitrophenylene group, 3-triphenylomethylphenylene group, naphthylene group, 5-methylnaphthylene group, 4-
Nitronaphthylene group and the like can be mentioned. Preferred are a phenylene group, a 3-nitrophenylene group, a 3-triphenylomethylphenylene group, a naphthylene group and a 4-nitronaphthylene group, and more preferred are a phenylene group and a 3-phenylnaphthylene group.
-A tritrifluoromethylphenylene group or a naphthylene group.

In the general formula (4), Y is
Specifically, oxygen, sulfur, selenium, NR (R is H or an alkyl group having 10 or less carbon atoms), phenylene group, 3-nitrophenylene group, 2,5-dimethoxyphenylene group,
Examples include a naphthylene group. Preferred are oxygen, phenylene, 3-nitrophenylene, and naphthylene, and more preferred are oxygen and phenylene.

The combination of X and Y is preferably a combination of a phenylene group and an electron donating group such as oxygen and naphthylene group, or a combination of an electron-withdrawing group such as 3-trifluoromethylphenylene group. Further, a group that can be used in both X and Y, such as a phenylene group and a naphthylene group, is also preferable when both X and Y are the same.

Further, n represents an integer of 0 to 5, and a preferable range depends on Y.

Specific examples of the polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I) include polyphenylquinoxaline (hereinafter abbreviated as “PPQ”) and poly-2,2 ′. -(P, p'-oxydiphenylene)-
6,6′-oxydi (3-phenylquinoxaline) (hereinafter abbreviated as “POPQ”) and the like, but are not limited thereto. See "JP
polymer Science: part A1, 5th
Vol., P. 1453, 1967 ".

The quinoxaline structure of the polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I) has a nuclear magnetic resonance spectrum (hereinafter abbreviated as “NMR”) and an infrared spectrum (hereinafter abbreviated as “NMR”). Abbreviated as “IR”), elemental analysis,
It can be analyzed and identified by a method such as mass spectrometry (hereinafter abbreviated as “MS”).

Specifically, for example, a polymer having a quinoxaline structure represented by the general formula (1) is separated from the proton conductive polymer solid electrolyte of the present invention (I) by a method such as neutralization and washing. , And thermogravimetric analysis-mass spectrometry (hereinafter, referred to as
Abbreviated as "TG-MS". ) To identify the quinoxaline skeleton from the structure of the decomposition product, determine the composition ratio of the elements by elemental analysis,
The quinoxaline structure can be identified by a method such as identification of the binding state by R and IR. See "J. Poly
mer Science: part A1, Volume 5, 1
453, 1967 ".

The molecular weight of the polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I) can be determined, for example, by gel permeation chromatography (hereinafter, “GPC”).
Abbreviated. ) Can be measured by liquid chromatography. Specifically, for example, it is common to dissolve in a solvent such as hexaisopropanol and measure by GPC. For example, “J. Polymer Science”
e: part B: Polymer Physics,
38, 1348, 2000 "or" Chem.
issue Letters, p. 1049, 1999
The year is described.

The molecular weight of the polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I) is not particularly limited. Generally, durability against insertion and release of protons,
A higher one is preferred from the point of strength when formed into a film.
Specifically, the weight average molecular weight measured by absolute molecular weight measurement by GPC is preferably 5,000 or more, more preferably 10,000 or more.

The polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I) preferably has a small amount of a low molecular weight compound. Specifically, 10% in the weight average molecular weight in the absolute molecular weight measurement by the light scattering method described above.
The content of the low-molecular-weight compound having a molecular weight of less than 00 is preferably 5% by mass or less, more preferably 1% by mass or less, based on the whole polymer.

At this time, the measurement of the amount of the low molecular weight substance can be specifically performed by using, for example, the above-described method such as GPC.

Next, the "B) acidic compound in the proton conductive polymer solid electrolyte of the present invention (I) will be described.

As the "B) acidic compound" in the proton-conductive polymer solid electrolyte of the present invention (I), any compound can be used as long as it separates and releases a proton. Any inorganic or organic acid may be used, and a polymer capable of releasing protons may be used. These may be used alone,
Two or more types may be used in combination.

Specific examples of the inorganic acid include sulfuric acid and nitric acid. Further, specific examples of the organic acid include acetic acid, fluorinated acetic acid, propionic acid, fluorinated propionic acid, butyric acid, butyric fluoric acid, acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, Examples thereof include fluorinated styrene sulfonic acid, vinyl sulfonic acid, and vinyl phosphoric acid.

The term “fluorination” such as “fluorinated acetic acid” as used herein refers to an organic acid in which at least one or more hydrogen atoms have been replaced by fluorine. Specifically, trifluoroacetic acid, heptafluoropropionic acid,
Hexafluorostyrene sulfonic acid and the like can be mentioned.

The “B) acidic compound” of the present invention (I) is preferably an “acid type polymer” which is a polymer capable of releasing protons. The term "acid-type polymer" as used herein means a polymer in which a proton-releasing group is bonded to the side chain, main chain, and / or terminal of the polymer. Specifically, it refers to polystyrene sulfonic acid, polyphosphoric acid, polyacrylic acid, and fluorides thereof.

Examples of compounds which can be used as "B) acidic compound" in the present invention (I) include carboxylic acid polymers, sulfonic acid polymers and phosphoric acid polymers. Specific examples include polyacrylic acid, polymethacrylic acid, polystyrenesulfonic acid, polyvinylsulfonic acid, polyphosphoric acid, polyvinylphosphoric acid, and fluorides thereof. Preferred are polystyrenesulfonic acid, polyvinylsulfonic acid, polyphosphoric acid, polyvinylphosphoric acid and fluorides thereof, and more preferred are polystyrenesulfonic acid, polyvinylsulfonic acid, polyvinylphosphoric acid and fluorides thereof. These may be used alone or in combination of two or more.

The molecular weight of the acid type polymer can be measured by a method such as GPC. Specifically, the acid-type polymer can be made into a solution state such as an aqueous solution and measured by GPC.

The preferred molecular weight of the acid type polymer which can be used as the “B) acidic compound of the present invention (I) is not particularly limited, but preferably the weight average molecular weight measured by GPC described above is preferably 500-100,000
0, more preferably from 1,000 to 10,000
00 range.

Next, the proton conductive polymer solid electrolyte of the present invention (I) will be described. The proton conductive solid polymer electrolyte of the present invention (I) is characterized by containing: A) a polymer having a quinoxaline structure represented by the general formula (1); and B) an acidic compound.

General formula (1)

Embedded image

(Wherein at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the others are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid Group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, alkyl group having 1 to 20 carbon atoms which may have a substituent, carbon atom 2 which may have a substituent
Represents an alkenyl group having 20 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent. )

In the proton conductive polymer solid electrolyte of the present invention (I), the ratio of A) the polymer having a quinoxaline structure represented by the general formula (1) and B) the acidic compound is not particularly limited. Preferably, from the viewpoint of proton conductivity and thermal stability, the amount of the anion of the acidic compound in the molar ratio of A) to the amount of nitrogen in the polymer having a quinoxaline structure represented by the general formula (1) in a molar ratio. The amount of nitrogen in the polymer having a quinoxaline structure: the amount of anion of the acidic compound = 1: 20 to 20: 1 (mole: mole), more preferably the amount of nitrogen in the polymer having a quinoxaline structure: The amount of the anion of the acidic compound is in the range of 1:10 to 10: 1 (mole: mole).

In the proton conductive polymer solid electrolyte of the present invention (I), the ratio of A) a polymer having a quinoxaline structure represented by the general formula (1) and B) an acidic compound is determined by elemental analysis, thermal analysis, or the like. Can be measured. Specifically, for example, there can be mentioned a method of measuring the ratio of the element of nitrogen and an acid component by elemental analysis, and a method of measuring the volatile weight of an acidic component by TG.

The proton conductivity of the proton conductive solid polymer electrolyte of the present invention (I) is not particularly limited. The preferred range varies depending on the performance required for an electrochemical device prepared using the proton-conductive polymer solid electrolyte. In general, it may be 0.1 mS / cm or more at 25 ° C. and 1 mS / cm or more at 80 ° C. It is preferably 1 mS / cm or more at 25 ° C and 10 mS / cm at 80 ° C.
S / cm or more. As a method for measuring the proton conductivity, an AC impedance method can be used. Specifically, a method in which a proton conductive polymer solid electrolyte sample processed into a membrane or the like is sandwiched between inert electrodes such as platinum, an alternating current is applied to the sample, and measurement is performed based on the frequency dependence of impedance. it can. The details are described in “Electrochemical Measurement Method” (edited by the Electrochemical Society, published on November 15, 1984, 1st edition, 1st edition).

Next, the present invention (II) will be described.
The present invention (II) is a method for producing the proton conductive solid polymer electrolyte of the present invention (I).

The production method of the polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I) is not particularly limited, but the following production methods A, B and C are specifically described. Examples can be given.

<Production Method A> As a first example of the method for producing a polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I), a quinoxaline represented by the general formula (1) It can be obtained by polymerizing a compound having at least one of R ^{1 to} R ⁶ of the compound having a skeleton, which is a polymerizable functional group such as a vinyl group, by radical polymerization or the like.

If a compound having a quinoxaline skeleton represented by the general formula (1) can be provided with a polymerizable functional group by this method, the functional group may be polymerized.
Material design is easy, and polymers can be obtained relatively easily. For example, Photochem. Photobio
l. 54, No. 1, p. 7, 1991, there is a description of the polymerization of styrylquinoxaline. However, in this method, it is difficult to provide only a specific functional group, and the chemical stability of the functional group portion of the obtained polymer may be a problem.

The compound having a quinoxaline skeleton provided with such a polymerizable functional group is represented by, for example, the general formula (5).

Formula (5)

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(In the formula, R ^{31 to} R ³⁷ may have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent. Good C1-C20 alkyl group, C2-C20 alkenyl group which may have a substituent, C2-C20 which may have a substituent
Represents an alkynyl group or an aryl group which may have a substituent, X each independently represents an arylene group which may have a substituent, and Y each independently represents a hetero atom alone or has a hetero atom. Represents an arylene group having 4 to 20 carbon atoms, and n represents an integer of 0 to 5. )

Specific examples thereof include 5-vinylquinoxaline, 2-styrylquinoxaline, 5- (meth) acryloylquinoxaline, and derivatives of these substituents.

<Production Method B> As a second example of the method for producing the polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I), a quinoxaline represented by the general formula (1) A method in which at least two of R ^{1 to} R ⁶ of the compound having a skeleton are halogen atoms such as a bromo group and the like are subjected to dehalogenation polymerization using a metal catalyst such as Cu or Ni.

If a halogen can be imparted to the compound having the quinoxaline skeleton represented by the general formula (1) by this method, dehalogenation polymerization may be performed, so that material design is easy and the polymer can be used. Can be obtained relatively easily. For example, JP-A-9-3171 discloses an example in which various dihalide derivatives such as quinoxaline are polymerized with a nickel (0) -valent catalyst such as bis (1,5-cyclooctadiene) nickel.

However, in this method, it is difficult to introduce a halogen into a specific portion of the quinoxaline skeleton, and the dehalogenation catalyst is relatively expensive, which may cause a problem in production cost. Further, in the polymer after polymerization, there is a high possibility that a metal residue or a halogen residue of the catalyst remains as an impurity, which may affect the chemical stability of the polymer.

Examples of such halogen-substituted quinoxaline compounds include 2,6-dibromoquinoxaline and 2,5-dibromoquinoxaline.
Dibromoquinoxaline and their substituent derivatives.

<Production Method C> As a third example of the production method of the polymer having a quinoxaline structure represented by the general formula (1) of the present invention (I), a tetramine derivative and bisbenzyl and / or a derivative thereof are used. A method of dehydration polycondensation may be mentioned. For example, J. Polymer Scie
nce: part A1, vol. 5, p. 1453, 196
It is described in 7 years that various quinoxaline-based polymers are polymerized by dehydration polycondensation.

As a method for producing a polymer having a quinoxaline skeleton represented by the general formula (1) of the present invention (I), this method is simple in a polymerization step, high in yield and high in molecular weight. Is preferred. However, there is a disadvantage that the design diversity of the compounds is slightly inferior to those of Production Method A and Production Method B.

Hereinafter, the production method C, which is considered to be the most preferable production method for producing the polymer having a quinoxaline skeleton represented by the general formula (1) of the present invention (I), ie, various tetramines and bisbenzyl and / or bisbenzyl derivatives Will be described in more detail.

<Tetramine Derivative> Tetramine, one of the compounds used in Production Method C, is represented by the general formula (6).

General formula (6)

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(In the formula, R ^{38 to} R ⁴³ may have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent. Good C1-C20 alkyl group, C2-C20 alkenyl group which may have a substituent, C2-C20 which may have a substituent
Represents an alkynyl group or an aryl group which may have a substituent. Z independently represents a heteroatom alone or an aryl group which may have a heteroatom and has 4 to 20 carbon atoms, and m represents an integer of 0 to 5. )

Specific examples thereof include 3,3-diaminobenzidine represented by the general formula (7) and derivatives thereof represented by the general formula (7):

Embedded image

Alternatively, 3 represented by the general formula (8)
3 ′, 4,4′-tetraaminodiphenyl ether and derivatives thereof General formula (8)

Embedded image And the like.

<Bisbenzyl and / or bisbenzyl derivative> Another compound used in Production method C, bisbenzyl and / or bisbenzyl derivative, is represented by the general formula (9).

General formula (9)

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(In the formula, R ^{44 to} R ⁵⁷ may have a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, or a substituent. Good C1-C20 alkyl group, C2-C20 alkenyl group which may have a substituent, C2-C20 which may have a substituent
Represents an alkynyl group or an aryl group which may have a substituent. )

Specific examples thereof include 1,4-bisbenzyl (para-form), 1,3-bisbenzyl (meta-form) represented by the general formula (10) or (11), and substituted compounds thereof. Can be mentioned.

General formula (10)

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General formula (11)

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<Dehydration Polycondensation Conditions> The conditions for dehydration polycondensation in Production Method C will be described. The reaction temperature is not particularly limited. The preferred reaction temperature varies depending on the type of the monomer used and the solvent and cannot be unconditionally limited, but is generally around the reflux temperature of the solvent used.

The reaction time is not particularly limited. The preferred reaction time varies depending on the type of the monomer used and the solvent and cannot be limited unconditionally, but generally requires at least about 10 hours to polymerize from dehydration polycondensation. The preferred range is from 25 hours to 100 hours, and particularly preferably from 30 hours to 70 hours.

The solvent to be used is not particularly limited as long as the monomer to be used easily dissolves and does not react. For example, N, N-dimethylformamide (hereinafter, referred to as N, N-dimethylformamide)
Also referred to as “DMF”. ), A nitrogen-containing polar solvent such as N-methylpyrrolidone, tetrahydrofuran, 1,2-dimethoxyethane, triethylene glycol dimethyl ether,
Ethers such as tetraethylene glycol dimethyl ether; For example, when the solvent is N, N-dimethylformamide, the reaction is preferably performed at 130 ° C. or more and 150 ° C. or less.

The concentration of the monomer in the solvent at the time of polymerization is as follows:
The total mass of bisbenzyl and / or the bisbenzyl derivative and tetramine is preferably from 5% by mass to 40% by mass, particularly preferably from 8% by mass to 30% by mass. If the monomer concentration is too low, polymerization does not proceed easily, and the molecular weight does not increase. If the monomer concentration is too high, the viscosity of the polymerization solution will increase, making it difficult to mix, and the polymer may precipitate at an early stage and the molecular weight may not be easily elongated.

Next, the addition of an acidic compound to a polymer having a quinoxaline structure will be described. The term “addition” as used herein means that the compound of the present invention binds to the polymer having a quinoxaline structure by various reactions. For example, "adding" indicates that an acid is bonded to a nitrogen atom in a highly basic quinoxaline by an acid-base reaction. In addition, "adding" means that an acid is bonded to a nitrogen atom or a phosphorus atom in a side chain of a polymer having a quinoxaline structure by an acid-base reaction. The term “addition” also means that an acid reacts with an unsaturated bond such as a phenyl group in a polymer having a quinoxaline structure to form a covalent bond.

The proton conductive polymer solid electrolyte of the present invention (I) is characterized by containing A) a polymer having a quinoxaline structure represented by the general formula (1), and B) an acidic compound. .

Formula (1)

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(Wherein, at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the others are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid Group, carboxylic acid ester group, sulfonic acid group, sulfonic acid ester group, alkyl group having 1 to 20 carbon atoms which may have a substituent, carbon atom 2 which may have a substituent
Represents an alkenyl group having 20 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent. )

In the proton-conductive polymer solid electrolyte of the present invention (I), there is no particular limitation on the method of adding B) an acidic compound to the polymer having a quinoxaline structure represented by the general formula (1) in the solid electrolyte. . For example, an acid can be added onto nitrogen by an acid-base reaction between the nitrogen of the quinoxaline skeleton and the acid. As a method of adding, a method of immersing a powdery or film-like polymer in an acid solution may be mentioned. However, a low molecular acid compound such as sulfuric acid is easily impregnated and added to the PPQ film by this method, but a polymer such as polystyrene sulfonic acid has a problem that it is difficult to impregnate the inside of the film. Further, a polymer having an unsubstituted quinoxaline skeleton is generally hydrophobic,
It is necessary to control the wettability by changing the acid solution to an aqueous solution, a non-aqueous solution, or the like.

For efficiently adding the polymer acid, the following two methods can be exemplified. (A) a method of synthesizing a polymer having a quinoxaline skeleton in a medium in which a polymeric acid is present; (b) immersing and impregnating a polymer having a quinoxaline skeleton in a solution of an acidic compound having a polymerizable functional group; Method for polymerizing compounds

As the method (a), for example, various tetramines represented by the general formula (6) and bisbenzyl and / or bisbenzyl derivatives represented by the general formula (9) are dissolved in a solution of polystyrene sulfonic acid. The above-mentioned method of dehydration polycondensation can be exemplified.

General formula (6)

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General formula (9)

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In the method (b), a polymer having a quinoxaline skeleton is immersed and impregnated in an aqueous solution of a styrenesulfonic acid monomer, for example, as an acidic compound having a polymerizable functional group, and styrenesulfonic acid is added to nitrogen of the quinoxaline. After that, a method of polymerizing styrene sulfonic acid can be exemplified.

The polymerization of styrene sulfonic acid exemplified here can be carried out under general radical polymerization conditions.
That is, after adding a light and / or thermal polymerization initiator, polymerization can be performed by heating, irradiating ultraviolet light, or irradiating an electron beam. Examples of such acidic compounds having a polymerizable functional group include derivatives such as vinylsulfonic acid, vinylphosphoric acid, acrylic acid, and fluorides thereof.

Next, the present invention (III) will be described. The present invention (III) is a proton-conductive polymer solid electrolyte membrane comprising the proton-conductive polymer solid electrolyte of the present invention (I).

The proton-conductive polymer solid electrolyte membrane of the present invention (III) may be any membrane-like material containing the proton-conductive polymer solid electrolyte of the present invention (I).

The thickness of the proton conductive polymer solid electrolyte membrane of the present invention (III) is not particularly limited, but is usually 5 μm.
Not less than 200 μm and preferably not less than 10 μm and 80 μm
The following are particularly preferred. The thickness of the film can be measured by using a dial gauge.

In general, when the proton conductive polymer solid electrolyte membrane of the present invention (III) is used in various devices, it is also important that the thickness of the membrane is small. Accordingly, the preferable range of the thickness of a single film depends on the area of the film, but is usually preferably in the range of ± 10%, and particularly preferably in the range of ± 5% with respect to the average thickness.

Further, the strength of the film is not particularly limited.
00kg / cm ² or more is preferable, 500 kg / cm ² or more is particularly preferable. The tensile strength in this case is defined by JIS
Standard: A value measured according to JK7127.

[0211] A reinforcing agent can be added to the proton conductive polymer solid electrolyte membrane of the present invention (III) for the purpose of improving the strength of the membrane as far as the physical properties are not impaired. Addition of a reinforcing agent increases the strength of the membrane,
Alternatively, it is possible to improve the storage stability of the film and to improve the handleability thereof, thereby improving the productivity of various devices.

The reinforcing agent to be added is preferably non-electroconductive, electrochemically stable, heat resistant, and acid / alkali resistant. Specifically, for example, oxide particles such as alumina, polyolefin fibers such as polypropylene, Teflon (E.I.
And the like.

Particularly, it is preferable to add oxide fine particles, because not only the strength of the film, but also the stability of the film is improved and the liquid retention property is increased. As the oxide fine particles, those having a larger specific surface area are preferable. In general,
Those having a BET specific surface area of 10 m ² / g or more are preferable,
More preferably, the BET specific surface area is 50 m ² / g or more.

The size of the oxide fine particles (primary particles when agglomerated to form secondary particles) is determined according to the general formula of the present invention.
There is no particular limitation as long as it can be mixed with the polymer having a quinoxaline skeleton represented by (1), but those having a maximum particle size of 10 μm or less are preferred. More preferably, the maximum diameter is 0.001.
It is a fine particle of μm to 1 μm.

Further, various shapes such as a sphere, an egg, a cube, a rectangular parallelepiped, a cylinder or a rod can be used.

Specific examples of such oxide fine particles include alumina-based fine particles such as α, β, and γ-alumina, silica-based fine particles, titania-based fine particles, magnesia-based fine particles, and the like.
And ion-conductive or non-conductive oxide fine particles such as composite oxide fine particles thereof. Among these,
Alumina-based particles and silica-based particles are preferable because of their excellent stability. In particular, the surface of the alumina-based fine particles has a high affinity for anions, and particularly has an effect of reducing proton binding and promoting proton transfer. Specific examples of the alumina-based fine particles include α, β, and γ-type Al ₂ O ₃ fine particles and alumina-based composite oxide fine particles of these and other metals obtained by various production methods such as a solid phase method and a gas phase method. Is mentioned. Among them, aluminum oxide C (trade name, manufactured by Degussa Co., Ltd.) having a large specific surface area and a large surface activity, and gamma-type Al ₂ O ₃ fine particles of UA-5805 (manufactured by Showa Denko KK) are suitable. Specific examples of the silica-based fine particles include Aerosil (trade name; manufactured by Degussa) having a large specific surface area and a large surface activity, colloidal silica, and the like.

The preferable amount of the reinforcing agent added is in the range of 0.1% by mass to 50% by mass, particularly preferably in the range of 1% by mass to 30% by mass, per unit mass of the solid polymer electrolyte membrane. If the amount of the reinforcing agent is 0.1% or less, it is difficult to exhibit a sufficient effect. If it exceeds 50% by mass, the ionic conductivity of the membrane may be reduced, which is not preferable.

The amount of the reinforcing agent contained in the proton conductive polymer solid electrolyte membrane of the present invention (III) can be measured by a method such as residual weight in thermogravimetric analysis or elemental analysis.

Next, the present invention (IV) will be described.
The present invention (IV) is a method for producing the proton conductive polymer solid electrolyte membrane of the present invention (III).

The method for producing the proton-conductive polymer solid electrolyte membrane of the present invention (IV) can be carried out by any method as long as the substance containing the proton-conductive polymer solid electrolyte of the present invention (I) can be formed into a film. But it doesn't matter.

Specifically, for example, a conventionally known method in which a polymer is dissolved in a soluble solvent and then a film is formed by casting. For example, Polymer Collection, 1987
Year, Vol. 44, no. 4,317 pages, JP-A-9-2
No. 45818, etc.

In the case of a polymer having a softening point, a general-purpose thermoplastic resin film forming method of pressurizing and heating with a heated roll press, extruder or the like can be used. For example, it is described in Japanese Patent Application Laid-Open No. 2-142063.

Further, there is a method in which a polymerizable compound having a quinoxaline structure represented by the general formula (1) or a monomer solution is cast on a support, or the monomer solution is mixed with a reinforcing agent, and then polymerized. This method is particularly useful when preparing a composite film with another support or reinforcing agent.

Generally, the film obtained by the casting method is
It is suitable for producing a thin film having a thickness of about 5 μm to 10 μm, but the film obtained by this method is generally weak in strength. In addition, the variation in thickness tends to increase.
Therefore, strength and thickness can be improved by using a heat and pressure molding method such as a roll press in combination, which is preferable.

A reinforcing agent can be added to the proton-conductive polymer solid electrolyte membrane of the present invention (III), but the method of adding is not particularly limited. For example, a method of forming a film after adding a reinforcing agent while heating and melting a polymer before film formation, a method of adding a reinforcing agent to a polymer solution before casting film formation, and forming a film can be exemplified. Further, there is also a method in which a reinforcing agent is first stretched in the form of a film on a support, and the above-described polymer melt or polymer solution is applied thereon to form a film.

Next, the present invention (V) and the present invention (VI) will be described. The present invention (V) comprises the proton-conductive polymer solid electrolyte of the present invention (I) and / or the present invention (III)
The present invention (VI) is a method for producing an electrochemical device according to the present invention (V).

The proton conductive polymer solid electrolyte of the present invention (I) and / or the proton conductive polymer solid electrolyte membrane of the present invention (III) can be used as an electrolyte for various electrochemical devices. Specific examples of the element include, for example, batteries such as secondary batteries and fuel cells, electric double layer capacitors,
Electrochromic elements and the like can be mentioned,
However, it is not limited to these.

Hereinafter, as examples of various electrochemical devices, a secondary battery, a fuel cell, and an electrochromic device will be described with respect to specific structures and manufacturing methods thereof.

<Structure and Manufacturing Method of Secondary Battery> As an example of the electrochemical device of the present invention (V), the concept of the structure of a proton transfer secondary battery is shown in a sheet type as shown in FIG.
Basically, the secondary battery has a laminated structure of a positive electrode / a proton conductive polymer solid electrolyte membrane / anode. Regarding these secondary batteries and a method of manufacturing the same, see JP-A-11-1
26610 and JP-A-11-144732.

For the negative electrode, a conductive auxiliary such as carbon black and Teflon (E.I. Dupont de Nemours and Co.) are used for a polymer capable of doping n-type protons represented by polypyridine and its derivatives.
Add a binder such as (Company registered trademark).
What is molded into a plate having a thickness of about 1 mm to 1 mm can be used. For molding, for example, a press machine or a heat press machine can be used. Electrodes may have various sizes depending on the shape, capacity, etc. of the proton transfer secondary battery.

Specific examples of other materials capable of n-type proton doping include polypyrimidine and derivatives thereof,
Examples thereof include nitrogen-containing aromatic polymers such as polyquinoline and derivatives thereof, quinone polymers such as polyquinone and polyanthraquinone and derivatives thereof, polyphenylene, polyphenylenevinylene and derivatives thereof.

For the positive electrode, a conductive polymer such as carbon black and a conductive auxiliary such as carbon black and Teflon (registered trademark of E.I. Add a binder like
A sheet molded into a plate having a thickness of about 0.1 mm to 1 mm can be used. For molding, for example, a press machine or a heat press machine can be used. Electrodes may have various sizes depending on the shape, capacity, etc. of the proton transfer secondary battery.

Examples of other materials capable of p-type proton doping include amine-containing aromatic nitrogen-based polymers such as polyindole, polyisoindole, polypyrrole and derivatives thereof, and sulfur-containing polymers such as polythiophene and derivatives. Examples thereof include aromatic polymers, oxygen-containing aromatic polymers such as polyfuran and derivatives.

The above positive electrode and negative electrode are laminated via the proton conductive polymer solid electrolyte membrane of the present invention, and the entire laminate is housed in a battery outer package such as an aluminum laminate or a polyolefin resin, and then a polyolefin resin, an epoxy resin By sealing with an insulating resin such as this, a proton transfer secondary battery as one type of the present invention (V) can be manufactured. More details are described in JP-A-11-126610 and JP-A-11-144732.

The structure of the proton transfer type secondary battery of the present invention (V) is not limited to the sheet type shown in FIG. 1, but may be any shape such as a chip type, coin type, square type and cylindrical type. It goes without saying that the size is not particularly limited, and that various sizes can be manufactured.

<Structure of Fuel Cell and Manufacturing Method Thereof> FIG. 2 shows the concept of the structure of a fuel cell as an example of the electrochemical device of the present invention (V). Basically, a single cell has a laminated structure of separator / porous support + cathode catalyst / proton conductive polymer solid electrolyte membrane / anode catalyst + porous support / separator. Regarding the configuration of the fuel cell and the method of manufacturing the same, see "Development and Practical Use of Polymer Electrolyte Fuel Cell" (edited by the Technical Information Association, 1999, first edition), JP-A-7-22034, JP-A-7-22034 -326
No. 363 publication. Various members are used depending on the size of the fuel cell.

[0237] The "separator" here is a conductive material that connects the single cells in series, and the gas supply holes must be formed in the catalyst layer, and the workability is required. Since acid resistance is required, a conductive carbon material is used. Specifically, for example, a graphite sheet or a composite sheet of graphite and various resins is used.

The catalyst layer generally comprises a catalyst and a porous support. Platinum is usually used as a catalyst in a layer where electric charges such as hydrogen are reacted with oxygen at the air electrode and charge is taken out, and in order to increase efficiency, platinum is thinly coated on porous carbon. You. The porous support serves to fix the catalyst and needs strength, but gas diffusion is also important, and a conductive carbon porous sheet such as a carbon fiber sheet is usually used. The contact between the catalyst layer and the proton conductive polymer solid electrolyte membrane is important for battery characteristics, and the membrane and the catalyst layer are laminated by heating and pressing at a temperature higher than the softening point of the membrane.

A fuel cell can be manufactured by bonding separators on both sides of the catalyst layer / polymer solid electrolyte membrane laminate as a fuel electrode and an air electrode and packaging them. The obtained fuel cell operates as a cell by supplying fuel from the fuel electrode. Further, by stacking the unit cells at the separator portion, a stacked fuel cell pack can be manufactured.

The structure of the solid polymer electrolyte fuel cell of the present invention (V) is not limited to the sheet type shown in FIG. 2, but may be any shape such as a chip type, a coin type, a square type, a cylindrical type and the like. It goes without saying that there is no particular limitation, and that various sizes can be manufactured.

<Structure of Electrochromic Element and Manufacturing Method Thereof> FIG. 3 shows the structure of an electrochromic element as an example of the electrochemical element of the present invention (V). Basically, it has a laminated structure of a transparent electrode / color changing electrode material / proton conductive polymer solid electrolyte membrane / counter electrode material / electrode. Regarding the electrochromic element and its manufacturing method, see “Polymer” (1989, No. 38, p. 970),
JP-A-3-231229, JP-A-7-15205
No. 0 publication.

The color change of the electrochromic device occurs by a redox reaction of the material. When a proton-conductive polymer solid electrolyte membrane is used as the electrolyte, a material that undergoes a good reversible oxidation-reduction reaction due to the transfer of protons or counter anions and changes color is used. This is called “discoloring pole material”
That.

Specific examples of such materials include metal oxides such as tungsten oxide and iridium oxide, conductive polymers such as polyaniline and polypyrrole, and redox organic substances such as viologen and viologen polymers. Can be mentioned. These materials are formed into a thickness of about 0.1 μm to 1 μm on a transparent electrode by a casting method or a vapor deposition method and used as a color changing electrode.

As the counter electrode material, a material capable of compensating for the oxidation-reduction reaction of the discoloring electrode material and causing a good reversible oxidation-reduction by transfer of a proton or counter anion is used. In this case, no color change is required. Specific examples of such materials include various metal oxides and conductive polymers. These counter electrode materials are also used as electrodes by forming a film having a thickness of about 0.1 μm to 1 μm on the electrode by a casting method or a vapor deposition method.

As the transparent electrode, a material in which ITO, tin oxide, or the like is formed on a glass substrate by sputtering or the like, or a material in which gold is thinly deposited can be used.

The proton conducting polymer solid electrolyte of the present invention (I) or the proton conducting polymer solid electrolyte membrane of the present invention (III) is cut into a desired size, and the above-mentioned discoloration electrode and counter electrode are provided on both sides thereof. Are bonded to each other so that they do not come into contact with each other, and in some cases, a proton conductive electrolyte such as an acid is added and sealed, as shown in FIG.
The electrochromic device of the present invention (V) can be manufactured.

The configuration of the electrochromic device of the present invention (V) is not limited to the sheet type shown in FIG. 3, but may be a chip type, coin type, square type, etc., and the size is also particularly limited. It goes without saying that various sizes can be manufactured.

[0248]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to typical examples. These are merely examples for explanation, and the present invention is not limited to these.

Example 1 Polyphenylquinoxaline ( hereinafter referred to as polyphenylquinoxaline)
Below, it is abbreviated as “PPQ”. ) Was carried out according to the following scheme (1). Scheme (1)

[0250]

Embedded image

That is, DMF (water content: 200 ppm) 600
1L glass four-necked flask (4 cm long)
With stirring and a cooling pipe), 41.52 g of 1,4-bisbenzyl (hereinafter abbreviated as “BBZ”) (Mw 342.4, manufactured by Showa Denko, GC purity 98%), 3,3-diaminobenzidine (Hereinafter abbreviated as “DABZ”).
214.3, Aldrich LC purity 98%) 25.9
8 g, and the mixture was stirred for 30 minutes under a nitrogen atmosphere at room temperature.
Z and DABZ were completely dissolved. Thereafter, the temperature was raised to 130 ° C. for 1 hour in a nitrogen atmosphere, and the reaction was carried out at 130 ° C. with stirring for 40 hours.

The obtained yellow precipitate was filtered, washed with methanol, dried, and dried under vacuum at 120 ° C. for 12 hours to obtain 54.03 g of PPQ powder.

From the elemental analysis value and IR spectrum of this powder, it was estimated that the structure was as intended. The absolute absolute weight average molecular weight by light scattering from GPC using hexafluoroisopropanol (hereinafter abbreviated as “HFIP”) as an eluent was 51,000.

Example 2 Production of PPQ Film A 5% by mass HFIP solution of the PPQ powder produced in Example 1 was prepared. After forming this with a screen printing machine,
HFIP is volatilized slowly at normal pressure, average film thickness 50μ
m was produced. Tensile strength of this film (JIS: JK7127, sample width 1
0 mm) was 750 kg / cm ² . Thermogravimetric analysis of the film in air indicated that weight loss occurred around 530 ° C., suggesting that there was some change in PPQ itself.

Example 3 Production of PPQ Film Added with Sulfuric Acid The PPQ film produced in Example 2 was immersed in a 40% sulfuric acid aqueous solution to add sulfuric acid, and left at 50 ° C. for 10 hours. changed. From the elemental analysis of CHNS, it was estimated that one sulfate ion was added to about three N atoms of PPQ.

The ionic conductivity of the film measured by an AC impedance method under 90% humidification was 3.0 mS / cm at 25 ° C. and 35 mS / cm at 80 ° C.
Tensile strength of this film (JIS: JK712
7, sample width 10 mm) was slightly reduced at 720 kg / cm ² compared to before sulfuric acid addition.

When the thermogravimetric analysis of the film in air was carried out, the weight decreased at about 180 ° C., which was considered to be the desorption of sulfate ion, and the weight decreased at about 510 ° C., which seemed to be a change in PPQ itself. .

Example 4: PPQ film added with polyphosphoric acid
In order to add polyphosphoric acid to the PPQ film produced in Example 2, 50% polyphosphoric acid (weight average molecular weight 800
0) When it was left at 80 ° C. for 20 hours in an aqueous solution, it turned yellow-red. From the elemental analysis of CHNP, it was estimated that one phosphate ion in polyphosphoric acid was added to about four N atoms of PPQ. The ionic conductivity of this film under 90% humidification was measured by the AC impedance method.
/ Cm. Tensile strength of this film (JIS
Standard: JK7127, sample width 10mm) is 830k
g / cm 2, the concentration slightly increased before the addition of polyphosphoric acid.

The film was subjected to thermogravimetric analysis in air. As a result, a change in PPQ itself and a decrease in mass due to desorption of polyphosphoric acid were observed at around 510 ° C.

Example 5: P added with polystyrenesulfonic acid
Production of PQ Film To add polystyrene sulfonic acid to the PPQ film produced in Example 2, 2% at 80 ° C. in a 30% aqueous solution of polystyrene sulfonic acid (weight average molecular weight 12000).
When left for 0 hours, it turned yellow-red. From the elemental analysis of CHNS, it was estimated that one sulfonic acid ion in polystyrene sulfonic acid was added to about 5 N atoms of PPQ. The ionic conductivity of this film under 90% humidification was measured by the AC impedance method.
It was 1.0 mS / cm at 5 ° C and 23 mS / cm at 80 ° C. Tensile strength of this film (JIS: JK
7127, sample width 10 mm) is 1000 kg / cm ²
Increased before the addition of polystyrenesulfonic acid.

When the thermogravimetric analysis of the film in air was carried out, there was a decrease in mass at around 200 ° C., which was thought to be due to the desorption of sulfonic acid ions, and at around 500 ° C., there was a decrease in mass thought to be due to the change in PPQ itself. there were.

Example 6: Acid having various polymerizable functional groups
Production of PPQ film to which compound was added and polymerization thereof The PPQ film produced in Example 2 was left in an aqueous acidic compound solution having various polymerizable functional groups shown in Table 1 at 30 ° C. for 20 hours in the same manner as in Example 3. As a result, the PPQ film in each solution turned yellow-red. From the elemental analysis of CHNSP, it was estimated that one anion in each of the various acids was added to about three N atoms of PPQ.
When the ionic conductivity of these films under 90% humidification was measured by the AC impedance method, the results were as shown in Table 1. In addition, film tensile strength (JIS standard: JK712
7, sample width 10 mm) were as shown in Table 1. In addition, the thermogravimetric analysis of this film in air was as shown in Table 1.

The acidic compound having a polymerizable functional group was polymerized by leaving the PPQ film to which the acidic compound having a polymerizable functional group was added at a temperature shown in Table 1 for 2 hours in a nitrogen atmosphere. When the ionic conductivity, tensile strength, and thermogravimetric analysis of these films under 90% humidification were performed in the same manner as before the polymerization, the results shown in Table 1 were obtained.

[0264]

[Table 1]

Example 7: Polyphenylquinoxaline A
The synthesis of ter (hereinafter abbreviated as “PPQE” ) was carried out according to the following scheme (2). Scheme (2)

[0266]

Embedded image

That is, DABZ25.9 used in Example 1
Instead of 8 g, 3,3 ′, 4,4′-tetraaminodiphenyl ether (hereinafter abbreviated as “TADE”) (M
(w 230.27, LC purity 98%) In the same manner as in Example 1 except that 27.92 g was used, 55.83 g of yellow PPQE powder was obtained.

The powder obtained from the elemental analysis value and IR spectrum of this powder was presumed to have the desired structure. Further, the absolute molecular weight (weight average) determined by light scattering from GPC using HFIP as an eluent was 48,000.

Example 8 Production of PPQE Film A 5% by mass HFIP solution of the PPQE powder produced in Example 7 was prepared. After this was formed into a film by a screen printing machine, HFIP was slowly volatilized at normal temperature / normal pressure to obtain an average film thickness of 50 μm.
m was produced. Tensile strength of this film (JIS standard: JK7127, sample width 1)
0 mm) was 1050 kg / cm ² . Thermogravimetric analysis of this film in air indicated that weight loss occurred around 460 ° C., suggesting that there was some change in PPQE itself.

Example 9: P added with p-styrenesulfonic acid
Production of PQ Film and Its Polymer The PPQ film produced in Example 8 was immersed in a 20% aqueous solution of p-styrenesulfonic acid and left at 80 ° C. for 20 hours. From the elemental analysis of CHNS, it was estimated that about one parastyrene sulfonic acid ion was added to about three N atoms of PPQE. When the ionic conductivity of this film under a 90% humidification was measured by an AC impedance method, it was 3.0 mS / c at 25 ° C.
m and 50 mS / cm at 80 ° C. The tensile strength (JIS standard: JK7127, sample width 10 mm) of this film was 980 kg / cm ^2, which was slightly decreased from that before the acid addition. The thermogravimetric analysis of this film in air showed that there was a mass loss at around 240 ° C., which was thought to be due to desorption of p-styrenesulfonate ions, and at around 450 ° C., there was a mass loss which was considered to be a change in PPQE itself. .

This PP to which parastyrene sulfonic acid has been added
The QE film was left under a nitrogen atmosphere at 120 ° C. for 2 hours to polymerize p-styrenesulfonic acid.
The ionic conductivity of this film under 90% humidification was 2.8 mS / cm at 25 ° C and 70 mS / cm at 80 ° C.
Tensile strength of this film (JIS standard: JK712
7, sample width 10 mm) was 1250 kg / cm ² , which was higher than before polymerization and before acid addition.

Example 10: Polymethoxyphenyl quinoki
Synthesis of sarin (hereinafter abbreviated as “PPQOM” ) was carried out according to the following scheme (3). Scheme (3)

[0273]

Embedded image

That is, BBZ 41.52 used in Example 1
g, a BBZ methoxy compound (hereinafter referred to as “BBZO”).
M ”. ) (Mw 404.41, LC purity 98%)
In the same manner as in Example 1 except that 49.04 g was used,
60.33 g of a yellow-red PPQOM powder was obtained.

It was estimated from the elemental analysis value and IR spectrum of this powder that the desired PPQOM was obtained. In addition, the absolute molecular weight (weight average) by light scattering from GPC using HFIP as an eluent was 38,000.

Example 11: Production of PPQOM film 5% by mass HFI of PPQOM powder produced in Example 10
A P solution was prepared. After forming this with a screen printer,
HFIP is volatilized slowly at normal temperature / normal pressure, and the average film thickness is 5
A 0 μm uniform yellow film was produced. The tensile strength (JIS standard: JK7127, sample width 10 mm) of this film was 780 kg / cm ² . Thermogravimetric analysis of this film in air showed a two-stage mass reduction around 380 ° C. and around 500 ° C., suggesting that there was some change in PPQOM itself.

Example 12: PPQ added with vinyl sulfonic acid
Production of OM Film and Its Polymer The PPQOM film produced in Example 11 was immersed in a 20% aqueous solution of vinyl sulfonic acid and left at 80 ° C. for 20 hours to turn red. From the elemental analysis of CHNS, it was estimated that one parastyrene sulfonic acid ion was added to about three N-atoms of PPQOM. When the ionic conductivity of this film under a 90% humidification was measured by an AC impedance method, it was 3.2 mS / c at 25 ° C.
m and 43 mS / cm at 80 ° C. The tensile strength (JIS standard: JK7127, sample width 10 mm) of this film was 720 kg / cm ^2, which was slightly decreased from that before acid addition. A thermogravimetric analysis of the film in air showed that the mass decreased at around 190 ° C., which was considered to be the desorption of parastyrene sulfonic acid ions, and that at around 370 ° C. and around 500 ° C., the mass of PPQOM seemed to change. There was a decrease.

This vinyl sulfonic acid-added PPQOM
The film was left under a nitrogen atmosphere at 120 ° C. for 3 hours to polymerize vinyl sulfonic acid. The ionic conductivity of this film under 90% humidification is 2.3 mS at 25 ° C.
/ Cm, 60 mS / cm at 80 ° C. The tensile strength (JIS standard: JK7127, sample width 10 mm) of this film was 830 kg / cm ² , which was higher than before polymerization or before acid addition.

Example 13: Polypyridine-2,5-dii
(Hereinafter abbreviated as “Ppy”) electrode production Synth. Metals ( 25 103 1988)
Ppy powder was obtained by the Ni (0) method (the weight average molecular weight of the HFIP solution was 1800 in terms of polystyrene).
0).

A mass ratio of the Ppy powder, acetylene black (hereinafter abbreviated as “AB”) (manufactured by Denki Kagaku Kogyo) and polyvinylidene fluoride (hereinafter abbreviated as “PVDF”) (manufactured by Kureha): 70:25: An excess of N-methylpyrrolidone (hereinafter abbreviated as “NMP”) was added to the mixture of No. 5 to obtain a gel electrode composition. After applying this composition,
Ton pressure was applied to produce several Ppy electrodes of 1 × 1 cm and 500 μm in thickness. The average weight of these electrodes was 40 mg.

Example 14: Polyaniline (hereinafter referred to as "PA
n ”. ) Production of electrode According to the method described in JP-A-62-108459, aniline is oxidatively polymerized in 1N hydrochloric acid using ammonium persulfate as an oxidizing agent, and then neutralized with an aqueous ammonia solution to obtain a dark purple base-type PAn powder, 100 g. Got. From the elemental analysis and IR, it was presumed that the present PAn had almost the desired structure. From the result of GPC in NMP, the molecular weight (in terms of PMMA) of PAn was about 120,000 in weight average.

This PAn powder, AB (manufactured by Denki Kagaku), V
85 of GCF (manufactured by Showa Denko) and PVDF (manufactured by Kuraray)
Excess NMP was added to the 7: 1: 7 mixture to obtain a gel composition. This composition was applied to a conductive film current collector 1 cm ×
After coating on 1 cm, press-molded for 1 ton and vacuum-dried at 80 ° C. for 8 hours to obtain a 0.5 mm thick PAn.
Several electrodes (average 38 mg) were prepared.

Example 15: Production of secondary battery The PAn electrode produced in Example 14 and the PPQ / p-styrene sulfonic acid polymer membrane produced in Example 6 (50 μm,
1.2 cm × 1.2 cm). The Ppy electrode manufactured in Example 13 was overlapped, and the same conductive film (1 cm × 1 cm) as used in Example 14 was further stacked as a current collector. After these laminates were pressed and brought into close contact with each other, both ends were fixed with a polyimide tape (Kapton tape).
Then, attach the platinum foil as a lead wire to the conductive film collector on the positive and negative electrode sides with silver paste, put this laminate inside the aluminum laminate outer package, and place it outside so as not to short-circuit the two platinum lead wires. I took it out. Then, a 20% aqueous sulfuric acid solution is injected into the exterior body as an electrolytic solution, and while the excess sulfuric acid aqueous solution is extracted under reduced pressure, the exterior body is brought into close contact with the interior of the exterior body, and then sealed by heat fusion to form a Ppy / PAn secondary battery.
(Each of n = 3, a total of 18 pieces). FIG. 1 shows the battery configuration inside the outer package.

The battery was operated at 25 ° C. and an operating voltage of 0 to 0.8.
When the battery was charged and discharged at V and currents of 2 mA and 10 mA, the maximum discharge capacities were 1.5 mAh and 1.2 mAh. When the battery was discharged at 0 ° C. and −10 ° C. at 2 mA, the values were 1.4 mAh and 1.0 mAh. Also, 10
When the charge / discharge cycle was repeated at mA, the capacity after 200 cycles was 1.5 mAh.

Example 16: Production of fuel cell A platinum catalyst and a porous conductive carbon were formed on both sides of the PPQ / vinyl sulfonic acid polymer membrane (50 μm, 1.2 cm × 1.2 cm) produced in Example 6 by a conventional method. Electrode (1cm × 1
cm) to produce a fuel cell laminate. By creating a hydrogen supply chamber and an air chamber on both sides of this laminate and supplying hydrogen to the hydrogen supply electrode, 80 ° C.
An electromotive force of 0.8 V was obtained at 200 mA. Also, 1A
Was 0.5V.

Example 17: Tungsten trioxide (hereinafter referred to as "tungsten trioxide")
Abbreviated as “WO ³ ”. ) Manufacturing of electrochromic layer Indium tin oxide manufactured by Matsuzaki Vacuum Co., Ltd.
Abbreviated as "ITO". ) 1.2cm x 1.2cm glass
The end of the cut piece was covered, and the exposed part of ITO was 1 cm.
On the electrode having a size of 1 cm, WO ³ was vacuum-deposited by a resistance heating method. The thickness of the obtained film was about 1500 ° and the density was about 5 g / cc.

Example 18: Electrochromic device
Production : ITO glass 1.2cm x 1.2c manufactured by Matsuzaki Vacuum Co., Ltd.
Using a 1 M aqueous hydrochloric acid solution containing 0.5 M aniline as an electrolytic solution, an electro-polymerized polyaniline (hereinafter, referred to as about 5000 ° C.) by a potential scanning method in a range of −0.2 to 0.8 V vs SCE.
Abbreviated as "PAn". ) A film was formed on ITO glass.

The PAn / ITO electrode was applied to the PPQ / p-styrene sulfonic acid polymer film (50 μm) prepared in Example 6.
m, 1.2 cm × 1.2 cm). Next, the WO ³ / ITO electrodes manufactured in Example 17 were overlapped, and these laminates were pressed and adhered to each other, and then both ends were fixed with a polyimide tape (Kapton tape). Then, a 20% aqueous sulfuric acid solution is injected into the exterior body as an electrolytic solution, and while the excess sulfuric acid aqueous solution is extracted under reduced pressure, the interior of the exterior body is brought into close contact, and the entire electrode end is sealed with an epoxy resin, and WO ³ / P
A PQ film / PAn-based electrochromic device was manufactured.

When the electrochromic device was repeatedly subjected to color development / decoloring driving with an injection electric quantity of 6 mC, it was found that the electrochromic device had a dark blue color.
/ Showed pale blue electrochromism. The response speed was 100 msec. Further, under these conditions, the
No change was found in the color tone and the response speed even after repeated times.

[0290]

As described above, a proton conductive polymer solid electrolyte comprising: A) a polymer having a quinoxaline structure represented by the general formula (1); and B) an acidic compound. Since the electrolyte membrane composed of the electrolyte has a quinoxaline skeleton having high proton affinity, it has higher strength, heat resistance, and acid resistance than the conventional high proton conductive polymer solid electrolyte and the electrolyte membrane composed of the electrolyte. It is clear that the redox resistance is excellent.

Further, the electrochemical element containing the electrolyte and / or the electrolyte membrane in its structure is excellent in durability, reliability, high-speed current characteristics and response speed, and is particularly suitable for batteries such as secondary batteries and fuel cells, and capacitors. It is clear that the electrochromic device is superior to the conventional device.

[0292]

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an example of a sheet-type battery shown as an example of a proton transfer battery of the present invention.

FIG. 2 is a schematic sectional view of an embodiment, which is shown as an example of the fuel cell of the present invention.

FIG. 3 is a schematic cross-sectional view of an example of a sheet-type electrochromic device shown as an example of the electrochromic device of the present invention.

[Explanation of symbols]

1 positive electrode 2 Proton conductive polymer solid electrolyte + separator 3 Negative electrode 4 Current collector sheet 5 Lead wire 6 Exterior body 7 Fuel electrode separator 8. Fuel electrode catalyst layer 9 Proton conductive polymer solid electrolyte membrane 10 Air electrode catalyst layer 11 Air electrode separator 12 Glass 13 Transparent conductive film 14 Electrochromic layer 15 Proton conductive polymer solid electrolyte + separator 16 Counter electrode layer 17 Insulating film spacer 18 Insulating resin sealant 19 Lead wire

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/02 C08L 101/02 H01B 13/00 H01B 13/00 Z H01G 9/025 H01M 8/02 P H01M 8/02 8/10 8/10 10/40 B 10/40 H01G 9/00 301G F-term (reference) 4J002 BC12X BG01X BG07W BJ00W CE00W CH06W CM02W DF036 DG046 DH026 EF036 EF046 EV236 EW046 FD20X FD206 GQ00 4J032 BA12 BB 5G301 CA30 CD01 5H026 AA06 BB00 CX05 EE11 EE17 EE18 HH00 HH01 HH03 HH05 5H029 AJ03 AJ07 AK06 AK16 AL06 AL16 AM16 BJ04 BJ06 (54) [Title of the Invention] Proton conductive polymer solid electrolyte, method for producing the electrolyte, and method for producing the electrolyte Electrolyte membrane, method for producing the electrolyte membrane, the electrolyte and / or an electrochemical element using the electrolyte membrane, and the electrolyte membrane Manufacturing method of the gas-chemical element

Claims (39)

[Claims] 1. A proton conductive solid polymer electrolyte comprising: A) a polymer having a quinoxaline structure represented by the general formula (1); and B) an acidic compound. General formula (1) (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) 2. A proton conductive solid polymer electrolyte comprising: A) a polymer having a quinoxaline structure represented by the general formula (1) in a side chain; and B) an acidic compound. General formula (1) (Wherein at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the others are each independently a hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) 3. A proton-conductive polymer solid electrolyte comprising: A) a polymer containing a quinoxaline structure represented by the general formula (2) as a part of a repeating unit; and B) an acidic compound. General formula (2) (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) 4. A) a polymer containing a quinoxaline structure represented by the general formula (1) in a side chain and a quinoxaline structure represented by the general formula (2) as a part of a repeating unit; and B) an acid A proton conductive polymer solid electrolyte comprising a compound. General formula (1) (Wherein at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the others are each independently a hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) General formula (2) (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) 5. A) The quinoxaline structure represented by the general formula (2) is a quinoxaline structure represented by the general formula (3). Proton conductive polymer solid electrolyte. General formula (3) (Wherein, R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) 6. The method according to claim 3, wherein A) the quinoxaline structure represented by the general formula (2) is a quinoxaline structure represented by the general formula (4). Proton conductive polymer solid electrolyte. General formula (4) (Wherein, R ^{15 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent, X each independently represents an aryl group which may have a substituent, and Y each independently has a hetero atom or a hetero atom. A good carbon number represents an aryl group which may have a substituent of 4 or more and 20 or less, and n represents an integer of 0-5. ) 7. B) The acidic compound is sulfuric acid, nitric acid, acetic acid,
The proton conductivity according to claim 1, wherein the proton conductivity is at least one or more selected from the group consisting of fluorinated acetic acid, propionic acid, fluorinated propionic acid, butyric acid, and fluorinated butyric acid. 8. Molecular solid electrolyte. 8. The proton conductive polymer solid electrolyte according to claim 1, wherein B) the acidic compound is an acid type monomer. 9. The acid type monomer is at least one selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid. The proton conductive polymer solid electrolyte according to claim 8, wherein: 10. The proton conductive polymer solid electrolyte according to claim 1, wherein B) the acidic compound is an acid type polymer. 11. The acid type polymer is a carboxylic acid type polymer,
The proton conductive polymer solid electrolyte according to claim 10, wherein the solid electrolyte is at least one selected from the group consisting of a sulfonic acid polymer and a phosphoric acid polymer. 12. The method for producing a proton conductive solid polymer electrolyte according to claim 1, comprising the following steps. Step A) Step of mixing a polymer having a quinoxaline structure represented by the general formula (1) and B) an acidic compound to obtain a proton conductive polymer solid electrolyte General formula (1) (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) 13. The proton conductive solid polymer electrolyte according to claim 1, comprising the following first step and second step: Production method. First step A) A polymer having a quinoxaline structure represented by the general formula (1) and B) Acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl Mixing a acidic compound having at least one or more polymerizable functional groups selected from the group consisting of sulfonic acid and vinyl phosphoric acid to obtain a composition for producing a proton-conductive polymer solid electrolyte, a second step, and a first step. Step of polymerizing an acidic compound contained in the composition for producing a proton-conductive polymer solid electrolyte to obtain a proton-conductive polymer solid electrolyte, general formula (1): (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) 14. The proton conductive polymer solid electrolyte according to claim 1, comprising the following first step and second step: Production method. First step A) A polymer having a quinoxaline structure represented by the general formula (1) in a side chain, and B) Acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfone Mixing an acidic compound having at least one or more polymerizable functional groups selected from the group consisting of acid, vinyl sulfonic acid and vinyl phosphoric acid to obtain a composition for producing a proton conductive polymer solid electrolyte Step of polymerizing an acidic compound contained in the composition for producing a proton-conductive polymer solid electrolyte obtained in the step to obtain a proton-conductive polymer solid electrolyte, general formula (1): (Wherein at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the others are each independently a hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) 15. The proton conductive polymer solid electrolyte according to claim 1, comprising the following first step and second step: Production method. First step A) A polymer containing a quinoxaline structure represented by the general formula (2) as a part of a repeating unit and B) Acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, hydrofluoric acid, Mixing a acidic compound having at least one or more polymerizable functional groups selected from the group consisting of hydrogenated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid to obtain a composition for producing a proton conductive polymer solid electrolyte. Step of obtaining a proton-conductive polymer solid electrolyte by polymerizing an acidic compound contained in the composition for producing a proton-conductive polymer solid electrolyte obtained in the first step, to obtain a proton-conductive polymer solid electrolyte. (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) 16. The proton conductive polymer solid electrolyte according to claim 1, comprising the following first step and second step: Production method. First step A) a polymer containing a quinoxaline structure represented by the general formula (1) in a side chain and a quinoxaline structure represented by the general formula (2) as a part of a repeating unit, and B) acrylic acid; Mixing an acidic compound having at least one or more polymerizable functional groups selected from the group consisting of fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid and vinyl phosphoric acid A step of obtaining a composition for producing a proton-conductive polymer solid electrolyte, a second step, polymerizing an acidic compound contained in the composition for producing a proton-conductive polymer solid electrolyte obtained in the first step, and obtaining a high proton-conductivity. Step of obtaining molecular solid electrolyte General formula (1) (Wherein at least one of R ^{1 to} R ⁶ is a group bonded to the main chain of the polymer, and the others are each independently a hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) General formula (2) (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) 17. The method for producing a proton-conductive polymer solid electrolyte according to claim 1, comprising the following first step and second step. First step A) Step of mixing a polymerizable compound having a quinoxaline structure represented by the general formula (1) and B) an acidic compound to obtain a composition for producing a proton-conductive polymer solid electrolyte. Step of polymerizing a polymerizable compound contained in the composition for producing a proton-conductive polymer solid electrolyte obtained in the step to obtain a proton-conductive polymer solid electrolyte, general formula (1): (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) 18. The method for producing a proton conductive polymer solid electrolyte according to claim 1, comprising the following first step and second step. First step A) Step of mixing a polymerizable compound having a quinoxaline structure represented by the general formula (1) and B) an acid-type polymer to obtain a composition for producing a proton-conductive polymer solid electrolyte. Step of polymerizing a polymerizable compound contained in the composition for producing a proton-conductive polymer solid electrolyte obtained in the first step to obtain a proton-conductive polymer solid electrolyte General formula (1) (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) 19. A proton conductive polymer solid electrolyte membrane comprising the proton conductive polymer solid electrolyte according to claim 1. Description: 20. The proton conductive polymer solid electrolyte membrane according to claim 19, wherein the thickness of the membrane is in a range of 5 μm to 200 μm. 21. The proton conductive polymer solid electrolyte membrane according to claim 19, wherein a non-electron conductive reinforcing agent is added. 22. The proton conductive polymer solid electrolyte membrane according to claim 21, wherein the non-electron conductive reinforcing agent is an oxide particle. 23. The proton conductive polymer solid electrolyte membrane according to claim 22, wherein the oxide particles are oxides of at least one element selected from Al, Si and Ti. 24. The oxide particles having a particle diameter of 0.001 μm
The proton conductive polymer solid electrolyte membrane according to any one of claims 22 and 23, wherein the thickness is in a range of 10 to 10 µm. 25. The method for producing a proton-conductive polymer solid electrolyte membrane according to claim 19, comprising the following first step and second step. First step A step of applying a solution of at least one of any of the polymers represented by the following (a) to (d) to a substrate and then distilling off the solvent to obtain a polymer film (a): Polymer containing quinoxaline structure represented by general formula (1) (b) Polymer containing quinoxaline structure represented by general formula (2) as a part of repeating unit (c) Represented by general formula (3) (D) a polymer containing a quinoxaline structure as a part of a repeating unit represented by the general formula (4): (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) General formula (2) (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) General formula (3) (Wherein, R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) General formula (4) (Wherein, R ^{15 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent, X each independently represents an aryl group which may have a substituent, Y is each independently a heteroatom alone, Represents an aryl group having 4 to 20 carbon atoms, and n represents an integer of 0 to 5. 2) Step B) a step of adding an acidic compound to the polymer membrane obtained in the first step to obtain a proton conductive polymer solid electrolyte membrane 26. The method for producing a proton conductive solid polymer electrolyte membrane according to claim 19, comprising the following first to third steps. First step A step of obtaining a polymer film by applying a solution of at least one of the polymers represented by the following (a) to (d) to a base material and then distilling off the solvent. Polymer containing quinoxaline structure represented by general formula (1) (b) Polymer containing quinoxaline structure represented by general formula (2) as a part of repeating unit (c) Represented by general formula (3) (D) a polymer containing a quinoxaline structure as a part of a repeating unit represented by the following general formula (1): (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) General formula (2) (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) General formula (3) (Wherein, R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) General formula (4) (Wherein, R ^{15 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent, X each independently represents an aryl group which may have a substituent, Y is each independently a heteroatom alone, Represents an aryl group having 4 to 20 carbon atoms, and n represents an integer of 0 to 5. Step 2) Step of adding an acid-type monomer to the polymer membrane obtained in Step 1 to obtain a proton-conductive polymer solid electrolyte precursor membrane Step 3 Step 3 Proton-conductive polymer solid obtained in Step 2 Step of polymerizing an acid-type monomer contained in an electrolyte precursor membrane to obtain a proton-conductive polymer solid electrolyte membrane 27. The acid-type monomer is at least one selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid, and vinyl phosphoric acid. The method for producing a proton conductive polymer solid electrolyte membrane according to claim 26, wherein the acidic compound has a polymerizable functional group. 28. The method for producing a proton conductive polymer solid electrolyte membrane according to claim 19, comprising the following first step and second step. First step A) At least one polymer of any polymer represented by the following (a) to (d) (a) Polymer containing quinoxaline structure represented by general formula (1) ( b) A polymer containing the quinoxaline structure represented by the general formula (2) as a part of the repeating unit (c) A polymer (d) containing the quinoxaline structure represented by the general formula (3) as a part of the repeating unit A polymer containing a quinoxaline structure represented by the general formula (4) as a part of a repeating unit. (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) General formula (2) (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) General formula (3) (Wherein, R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) General formula (4) (Wherein, R ^{15 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent, X each independently represents an aryl group which may have a substituent, Y is each independently a heteroatom alone, Represents an aryl group having 4 to 20 carbon atoms, and n represents an integer of 0 to 5. ) And B) Step of Obtaining a Composition for Producing a Proton Conducting Polymer Solid Electrolyte Membrane Containing an Acidic Compound Second Step The composition for producing a proton conducting polymer solid electrolyte membrane obtained in the first step is pressurized and / or Or a step of obtaining a proton conductive polymer solid electrolyte membrane by heat molding 29. The method for producing a proton conductive polymer solid electrolyte membrane according to claim 19, comprising the following first step and second step. First step A) At least one polymer of any polymer represented by the following (a) to (d) (a) Polymer containing quinoxaline structure represented by general formula (1) ( b) A polymer containing the quinoxaline structure represented by the general formula (2) as a part of the repeating unit (c) A polymer (d) containing the quinoxaline structure represented by the general formula (3) as a part of the repeating unit A polymer containing a quinoxaline structure represented by the general formula (4) as a part of a repeating unit. (In the formula, at least one of R ^{1 to} R ⁶ is a group that binds to the main chain of the polymer and / or at least two are groups that form the main chain of the polymer, and the others are each independently Hydrogen atom,
A halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, an alkyl group having 1 to 20 carbon atoms, which may have a substituent, having a substituent An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group optionally having a substituent. ) General formula (2) (Wherein, R ^{7 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) General formula (3) (Wherein, R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent. ) General formula (4) (Wherein, R ^{15 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group,
An alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and 2 to 2 carbon atoms which may have a substituent Carbon number 20
Represents an alkynyl group or an aryl group which may have a substituent, X each independently represents an aryl group which may have a substituent, Y is each independently a heteroatom alone, Represents an aryl group having 4 to 20 carbon atoms, and n represents an integer of 0 to 5. ) And B) Step of Obtaining a Composition for Producing a Proton-Conducting Polymer Solid Electrolyte Membrane Containing an Acid-Type Monomer Second Step To obtain a proton conductive polymer solid electrolyte membrane by pressurizing and heating while polymerizing 30. The acid-type monomer is at least one selected from the group consisting of acrylic acid, fluorinated acrylic acid, methacrylic acid, fluorinated methacrylic acid, styrene sulfonic acid, fluorinated styrene sulfonic acid, vinyl sulfonic acid, and vinyl phosphoric acid. 30. The method according to claim 29, wherein the acidic compound has a polymerizable functional group. 31. The proton conductive polymer solid electrolyte according to any one of claims 1 to 11 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 19 to 24. An electrochemical device characterized by being used. 32. The proton conductive solid polymer electrolyte according to claim 1 and / or the proton conductive solid polymer electrolyte membrane according to claim 19 to 24. A battery characterized by being used. 33. The proton conductive solid polymer electrolyte according to any one of claims 1 to 11 and / or the proton conductive solid polymer electrolyte membrane according to any one of claims 19 to 24. A fuel cell characterized by being used. 34. The proton conductive polymer solid electrolyte according to claim 1 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 19 to 24. An electric double layer capacitor characterized by being used. 35. The proton conductive polymer solid electrolyte according to claim 1 and / or the proton conductive polymer solid electrolyte membrane according to claim 19 to 24. An electrochromic device characterized by being used. 36. The method according to claim 1, wherein the positive electrode and the negative electrode are provided between the positive electrode and the negative electrode.
A method for producing a battery, comprising: installing the proton conductive polymer solid electrolyte according to any one of claims 1 and / or the proton conductive polymer solid electrolyte membrane according to any one of claims 19 to 24. . 37. The proton conductive solid polymer electrolyte according to claim 1, and / or the proton according to claim 19, between the fuel electrode and the air electrode. A method for manufacturing a fuel cell, comprising providing a conductive polymer solid electrolyte membrane. 38. The proton conductive polymer solid electrolyte according to claim 1, and / or the proton according to claim 19, between two polarizable electrodes. A method for manufacturing an electric double layer capacitor, comprising installing a conductive polymer solid electrolyte membrane. 39. The proton conducting solid polymer electrolyte according to claim 1, and / or the proton conducting catalyst according to claim 19, between the discoloring electrode and the counter electrode. A method for producing an electrochromic device, comprising providing a conductive polymer solid electrolyte membrane.