JP2020111662A - Polymer composition - Google Patents

Abstract

To provide a composition of an electron-donating polymer and an electron-attracting polymer, which can form a charge transfer complex.SOLUTION: A composition comprising an electron-donating polymer (D) and an electron-attracting polymer (A) is provided, in which the electron-donating polymer (D) comprises an electron-donating polymer (D1) having a structural unit represented by formula (1a): *-X1a-O-Y1a-O-Z1a-O-Y'1a-O-*, and the electron-attracting polymer (A) comprises an electron-attracting polymer (A1) having a structural unit represented by formula (4a) below. Symbols in the formulae are as described in the specification.SELECTED DRAWING: None

Description

The present invention relates to compositions comprising an electron donating polymer and an electron withdrawing polymer.

Many materials that form a charge transfer complex have been reported. For example, Non-Patent Document 1 reports a charge transfer complex using tetrathiafulvalene.p-chloranil and a derivative thereof. On the other hand, as a charge transfer complex of a polymer material, for example, Non-Patent Documents 2 and 3 report a charge transfer complex of a polymer polyimide and a low-molecular compound dihydroxynaphthalene. Further, Non-Patent Document 4 reports a polymer composition containing a charge transfer complex of an electron-withdrawing polymer and an electron-donating polymer.

Phys. Rev. B 43 (1991) 8224 Polymer Journal (2013) 45, 839-844 JOURNAL OF POLYMER SCIENCE, PART A POLYMER CHEMISTRY 2014, 52, 2991-2997 JOURNAL OF MEMBRANE SCIENCE 2018, 548, 223-231

As reported in Non-Patent Document 4, if a charge-transfer complex can be formed, a phase-separated electron-donating polymer and an electron-withdrawing polymer are suppressed, and a material (polymer composition) having improved strength is obtained. Expected to be obtained. The present invention has been made in view of such circumstances, and an object thereof is to provide a composition of an electron-donating polymer and an electron-withdrawing polymer capable of forming a charge transfer complex. ..

The present invention that can achieve the above object is as follows.
[1] A composition containing an electron-donating polymer (D) and an electron-withdrawing polymer (A),
The electron-donating polymer (D) has the formula (1a):
*-X ^1a -O-Y ^1a -O-Z ^1a -O-Y' ^1a -O-* (1a)
[In the formula, X ^1a represents the formula (2a) to the formula (2c):

[In the formula, * represents a bonding position. ]
Is a divalent group represented by
Y ^1a and Y′ ^1a each independently represent formula (3a) or formula (3b):

[In the formula, * represents a bonding position. ]
Is a divalent group represented by
Z ^1a has the formula (3c):

[Wherein, R ^{1 to} R ⁴ are each independently a C _1-3 alkyl group,
R ⁵ and R ⁶ are each independently a C _1-3 alkylene group,
* Indicates a binding position. ]
Is a divalent group represented by, and * indicates a bonding position. ]
An electron-donating polymer (D1) having a structural unit represented by
The electron-withdrawing polymer (A) has the formula (4a):

[In Formula, X ^<2a > is Formula (5a)-Formula (5c):

[In the formula, * represents a bonding position. ]
Is a tetravalent group represented by
Y ^2a is represented by formula (6a) to formula (9a):

[In formula, n1 is an integer of 1-4,
n2 to n10 are each independently an integer of 0 to 4,
R ^{1a to} R ^10a are each independently a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a hydroxy group, a halogen atom, or nitro. group, a formyl group, a cyano group, a sulfo group, a phenyl group which may be substituted with W ^1a, thienyl group which may be substituted with W ^1a or W ^1a with an optionally substituted furyl group,
W ^1a is a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group. Or a sulfo group,
When n1 to n10 are integers of 2 to 4, a plurality of R ^{1a to} R ^10a may be the same or different from each other,
At least one of n 1 R ^1a is a sulfo group,
At least one selected from the group consisting of n2 R ^2a and n3 R ^3a is a sulfo group,
At least one selected from the group consisting of n4 R ^4a , n5 R ^5a and n6 R ^6a is a sulfo group,
At least one selected from the group consisting of n7 R ^7a , n8 R ^8a , n9 R ^9a and n10 R ^10a is a sulfo group,
Z ^{1a to} Z ^6a each independently represent a single bond, a C _1-2 alkylene group which may be substituted with a halogen atom, a C _3-10 alkylene group, a sulfonyl group, a carbonyl group, *-CONH-*, *. -NHCO-*, *-C(R< ^11a >)(R< ^12a >)-*, or an oxy group,
R ^11a and R ^12a are each independently a C _1-3 alkyl group optionally substituted with a halogen atom, or R ^11a and R ^12a are bonded to each other, together with the carbon atom to which they are bonded, A C _3-6 hydrocarbon ring is formed, and * indicates a bonding position. ]
Is a divalent group represented by, and * indicates a bonding position. ]
A composition comprising an electron-withdrawing polymer (A1) having a structural unit represented by:

[2] The composition according to the above [1], wherein X ^1a is a divalent group represented by the formula (2a).
[3] The composition according to the above [1] or [2], wherein both Y ^1a and Y′ ^1a are a divalent group represented by the formula (3a).
[4] The composition according to any one of [1] to [3], wherein the electron-donating polymer (D1) has a glass transition temperature of 110° C. or lower.

[5] R ^{1a to} R ^10a are each independently a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a halogen atom, or nitro. group, a formyl group, a cyano group, a sulfo group, a phenyl group which may be substituted with W ^1a, thienyl group which may be substituted with W ^1a or W ^1a with an optionally substituted furyl group, And W ^1a is a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a halogen atom, a nitro group, a formyl group, a cyano group or a sulfo group. The composition according to any one of the above [1] to [4], which is a group.
[6] The composition according to any one of the above [1] to [5], wherein X ^2a is a tetravalent group represented by the formula (5a).
[7] The composition according to any one of the above [1] to [6], wherein Y ^2a is a divalent group represented by the formula (7a).

[8] The constitutional unit represented by the formula (4a) is represented by the formula (4a-1):

[Wherein, m1 and m2 are each independently an integer of 0 to 3, and * represents a bonding position. ]
The composition according to any one of the above [1] to [4], which is a structural unit represented by:

[9] The electron-withdrawing polymer (A1) has the formula (4a-1) as the structural unit represented by the formula (4a):

[Wherein, m1 and m2 are each independently an integer of 0 to 3, and * represents a bonding position. ]
And a structural unit represented by the formula (4b-1):

[In the formula, r1 and r2 are each independently an integer of 1 to 4, and * represents a bonding position. ]
The composition according to any one of [1] to [4], which has a structural unit represented by:

[10] The composition according to any one of the above [1] to [9], wherein the electron-donating polymer (D) and the electron-withdrawing polymer (A) form a charge transfer complex.

According to the present invention, a composition of an electron-donating polymer and an electron-withdrawing polymer capable of forming a charge transfer complex can be obtained.

It is a ¹ H NMR chart of the electron donating polymer (D1-1) obtained in Synthesis Example 1. It is the absorption spectrum by the ultraviolet-visible spectroscopy (UV-vis) of the film (Example 1) of the composition (I) measured in Test Example 1. It is the absorption spectrum by the ultraviolet-visible spectroscopy (UV-vis) of the film|membrane (Example 3) of the composition (III) measured in Test Example 3.

The composition of the present invention comprises an electron-donating polymer (D) and an electron-withdrawing polymer (A). The electron-donating polymer (D) may be used alone or in combination of two or more. Similarly, the electron-withdrawing polymer (A) may be used alone or in combination of two or more. Here, "electron-donating" means the property of a molecule or ion that can easily donate an electron to another molecule or ion. Further, "electron-withdrawing" means a property of a molecule or ion that can easily accept an electron from another molecule or ion. Hereinafter, the present invention will be described in order. The following examples and preferable descriptions can be combined as long as they do not contradict each other.

<Group in chemical formula>
First, the groups and the like in the chemical formulas described in this specification will be described.
In the present specification, examples of the halogen atom include fluorine, chlorine, bromine and iodine.

In the present specification, examples of the C _1-3 alkyl group include a methyl group, an ethyl group, a propyl group and an isopropyl group.
In the present specification, examples of the C _1-10 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, Examples include neopentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.

In the present specification, examples of the C _1-10 alkoxy group include, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an isobutyl group. Examples thereof include a pentyloxy group, neopentyloxy group, tert-pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group and decyloxy group.

In the present specification, the C _1-2 alkylene group is a methylene group or an ethylene group.
In the present specification, examples of the C _1-3 alkylene group include a methylene group, an ethylene group, a trimethylene group and a 1-methylethylene group.
In the present specification, examples of the C _3-10 alkylene group include a trimethylene group, 1-methylethylene group, tetramethylene group, 1-methyltrimethylene group, 1,1-dimethylethylene group, pentamethylene group, 1- Methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-ethyltrimethylene group, hexamethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1- Examples include an ethyltetramethylene group, a 1,1,2-trimethyltrimethylene group, a 1,2,2-trimethyltrimethylene group, a 1-ethyl-1-methyltrimethylene group, and a 1-ethyl-2-methyltrimethylene group. To be

In the present specification, examples of the C _3-6 hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring.

<Electron donating polymer (D)>
In one embodiment of the present invention, the electron donating polymer (D) has the formula (1a):
*-X ^1a -O-Y ^1a -O-Z ^1a -O-Y' ^1a -O-* (1a)
[In the formula, X ^1a represents the formula (2a) to the formula (2c):

[In the formula, * represents a bonding position. ]
Is a divalent group represented by
Y ^1a and Y′ ^1a each independently represent formula (3a) or formula (3b):

[In the formula, * represents a bonding position. ]
Is a divalent group represented by
Z ^1a is represented by the formula (3c)

[Wherein, R ^{1 to} R ⁴ are each independently a C _1-3 alkyl group,
R ⁵ and R ⁶ are each independently a C _1-3 alkylene group,
* Indicates a binding position. ]
Is a divalent group represented by, and * indicates a bonding position. ]
The electron-donating polymer (D1) having a structural unit represented by In this embodiment, the electron donating polymer (D) preferably consists of the electron donating polymer (D1).

The above "structural unit represented by formula (1a)" may be abbreviated as "structural unit (1a)" below. The structural units and groups represented by other formulas may be similarly abbreviated. Since an electron is donated from the oxygen atom to X ^1a , it is considered that the structure of “—X ^1a —O—” in the structural unit (1a) imparts an electron donating property to the electron donating polymer (D1). To be

X ^1a in the electron-donating polymer (D1) may be a combination of at least two of the divalent group (2a), the divalent group (2b) and the divalent group (2c), or may be a single of these. X ^1a is preferably a divalent group (2a).

Both Y ^1a and Y′ ^1a in the electron donating polymer (D1) are preferably a divalent group (3a).

In Z ^1a (that is, the divalent group (3c)), R ^{1 to} R ⁴ may be the same or different from each other. R ^{1 to} R ⁴ are preferably the same as each other. In addition, R ⁵ and R ⁶ may be the same as or different from each other. R ⁵ and R ⁶ are preferably the same as each other.

R ^{1 to} R ⁴ are each independently preferably a methyl group, an ethyl group or a propyl group, and more preferably a methyl group or an ethyl group. It is further preferred that R ^{1 to} R ⁴ are both methyl groups.

R ⁵ and R ⁶ are each independently preferably a methylene group, an ethylene group or a trimethylene group. More preferably, both R ⁵ and R ⁶ are trimethylene groups.

The structural unit (1a) is preferably the formula (1a-1) to the formula (1a-3):

[In the formula, * represents a bonding position. ]
Or a structural unit represented by the formula (1a-1) is more preferable.

The weight average molecular weight (Mw) of the electron donating polymer (D1) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and further preferably 2,500 to 35,000. This Mw can be measured by gel permeation chromatography (GPC) using polystyrene as a standard, as described in Examples below. Mw of other polymers can be measured similarly.

In order to improve the amount of charge transfer complex formed in the composition of the present invention and to improve the orientation of sulfo groups in the composition due to the formation of the charge transfer complex, the glass transition temperature of the electron donating polymer (D1). (Tg) is preferably 110° C. or lower. This Tg is more preferably 80°C or lower, and further preferably 30°C or lower. This Tg can be measured using a differential scanning calorimeter, as described in Examples below. The improvement of the orientation of the sulfo group in the composition leads to the improvement of the proton conductivity of the fuel cell material and the improvement of the power generation characteristics of the fuel cell.

The electron donating polymer (D1) can be synthesized by a known reaction using a commercially available product as a starting material. Commercial products can be obtained from, for example, Shin-Etsu Chemical Co., Ltd., Tokyo Chemical Industry Co., Ltd., Fuji Film Wako Pure Chemical Industries, Ltd. For example, a divalent compound having an epoxy group (for example, 1,3-bis(3-glycidoxypropyl)tetramethyldisiloxane) and a divalent compound having a hydroxy group as described in Synthesis Examples below. By reacting with a compound (for example, 2,6-dihydroxynaphthalene), X ^1a is a divalent group (2a), Y ^1a and Y′ ^1a are divalent groups having a hydroxy group (3a), An electron donating polymer (D1) in which Z ^1a is a divalent group (3c) having a siloxane bond can be produced.

The reaction between the divalent compound having an epoxy group and the divalent compound having a hydroxy group for producing the electron donating polymer (D1) is usually performed in a solvent. Examples of the solvent include ketone solvents, such as cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. Preferred are cyclohexanone and acetone. The amount of the solvent is preferably 0.5 to 50 L, and more preferably 1 to 10 L with respect to 1 mol of the divalent compound having an epoxy group.

A catalyst may be used in the reaction. Examples of the catalyst include phosphines and imidazoles. Examples of the phosphines include triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine. Examples of the imidazoles include 2-methylimidazole. Of these, tris(2,6-dimethoxyphenyl)phosphine is preferred. When a catalyst is used, the amount thereof is preferably 0.0001 to 0.1 mmol, more preferably 0.001 to 0.015 mmol, relative to 1 mol of the divalent compound having an epoxy group.

The reaction temperature of the reaction is preferably 50 to 200°C, more preferably 100 to 180°C. When the reaction temperature is higher than the boiling point of the solvent, the reaction may be carried out in a sealed tube. The reaction time is preferably 20 to 250 hours, more preferably 30 to 150 hours.

After the reaction, the electron donating polymer (D1) in which Y ^1a and Y′ ^1a are a divalent group (3a) having a hydroxy group can be obtained by a known means such as precipitation, filtration and drying.

Further, it obtained as described ^{above, by Y 1a} and Y ^'1a oxidizes a divalent group (3a) electron donating polymer (D1) having a hydroxy group ^{(-OH), Y 1a} and Y 'one or both of ^1a can be manufactured a divalent group electron donating polymer is a (3b) (D1) having an oxo group (= O).

Oxidation of the hydroxy group can be carried out by using an addition compound of sulfur trioxide and a base. Examples of the compound include pyridine-sulfur trioxide complex and triethylamine-sulfur trioxide complex. Both the pyridine-sulfur trioxide complex and the triethylamine-sulfur trioxide complex are commercially available from, for example, Tokyo Chemical Industry. The amount of the compound is preferably 0.5 to 10 mol, and more preferably 1 to 1 mol of the hydroxy group in the electron-donating polymer (D1) in which Y ^1a and Y′ ^1a are divalent groups (3a). ~3 mol.

For the oxidation of hydroxy groups with the pyridine-sulfur trioxide complex it is preferred to use triethylamine. The amount of triethylamine is preferably 2 to 10 mol, and more preferably 4 to 8 mol with respect to 1 mol of the hydroxy group in the electron donating polymer (D1) in which Y ^1a and Y′ ^1a are divalent groups (3a). is there.

The oxidation is usually performed in a solvent. The solvent is not particularly limited as long as it does not inhibit the progress of the reaction, for example, dimethyl sulfoxide, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, diethyl ether, 1,2-dimethoxyethane, 1,4-dioxane and the like. Are listed. Of these, dimethyl sulfoxide and dichloromethane are preferable. These solvents may be used alone or in combination of two or more.

The oxidation temperature is preferably −30° C. to 80° C., more preferably −10° C. to 50° C., and the time is preferably 1 to 24 hours, more preferably 6 to 18 hours.

After the oxidation, the electron-donating polymer (D1) in which one or both of Y ^1a and Y′ ^1a is a divalent group (3b) having an oxo group is obtained by a known means such as precipitation, filtration and drying. be able to.

Oxidation of the hydroxy group can be carried out by using a highly active nitroxyl radical type alcohol oxidation catalyst such as 2-azaadamantane-N-oxyl, 1-methyl-2-azaadamantane-N-oxyl and an oxidizing agent. .. The oxidation catalyst can be obtained, for example, from Fuji Film Wako Pure Chemical Industries, Ltd. or Sigma-Aldrich Japan. The amount of the oxidation catalyst is preferably 0.001 to 0.5 mol, based on 1 mol of the hydroxy group in the electron donating polymer (D1) in which Y ^1a and Y′ ^1a are divalent groups (3a). It is preferably 0.005 to 0.1 mol.

Examples of the oxidant used in combination with the highly active nitroxyl radical type alcohol oxidation catalyst include sodium hypochlorite and (diacetoxyiodo)benzene. The oxidizing agent can be obtained from, for example, Tokyo Chemical Industry Co., Ltd., Fuji Film Wako Pure Chemical Industries, Ltd., Sigma-Aldrich Japan Co. When using sodium hypochlorite, for example, known reaction conditions such as J. Org. Chem. 1987, 52, 2559 2562., J. Org. Chem. 1997, 62, 20, 6974-6977. By means of the means, an electron-donating polymer (D1) can be obtained in which one or both of Y ^1a and Y′ ^1a is a divalent group (3b) having an oxo group.

The amount of the electron-donating polymer (D) in the composition of the present invention is preferably 1 to 10,000 parts by weight, more preferably 10 to 1, based on 100 parts by weight of the electron-withdrawing polymer (A). It is 500 parts by weight, more preferably 20 to 900 parts by weight, and most preferably 50 to 500 parts by weight.

<Electron-withdrawing polymer (A)>
The electron-withdrawing polymer (A) has the formula (4a):

［式中、Ｘ^２ａは、式（５ａ）〜式（５ｃ）：

[In Formula, X ^<2a > is Formula (5a)-Formula (5c):

[In the formula, * represents a bonding position. ]
Is a tetravalent group represented by
Y ^2a is represented by formula (6a) to formula (9a):

[In formula, n1 is an integer of 1-4,
n2 to n10 are each independently an integer of 0 to 4,
R ^{1a to} R ^10a are each independently a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a hydroxy group, a halogen atom, or nitro. group, a formyl group, a cyano group, a sulfo group, a phenyl group which may be substituted with W ^1a, thienyl group which may be substituted with W ^1a or W ^1a with an optionally substituted furyl group,
W ^1a is a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group. Or a sulfo group,
When n1 to n10 are integers of 2 to 4, a plurality of R ^{1a to} R ^10a may be the same or different from each other,
At least one of n 1 R ^1a is a sulfo group,
At least one selected from the group consisting of n2 R ^2a and n3 R ^3a is a sulfo group,
At least one selected from the group consisting of n4 R ^4a , n5 R ^5a and n6 R ^6a is a sulfo group,
At least one selected from the group consisting of n7 R ^7a , n8 R ^8a , n9 R ^9a and n10 R ^10a is a sulfo group,
Z ^{1a to} Z ^6a each independently represent a single bond, a C _1-2 alkylene group which may be substituted with a halogen atom, a C _3-10 alkylene group, a sulfonyl group, a carbonyl group, *-CONH-*, *. -NHCO-*, *-C(R< ^11a >)(R< ^12a >)-*, or an oxy group,
R ^11a and R ^12a are each independently a C _1-3 alkyl group optionally substituted with a halogen atom, or R ^11a and R ^12a are bonded to each other, together with the carbon atom to which they are bonded, A C _3-6 hydrocarbon ring is formed, and * indicates a bonding position. ]
Is a divalent group represented by, and * indicates a bonding position. ]
The electron-withdrawing polymer (A1) having a structural unit represented by The electron-withdrawing polymer (A) preferably consists of the electron-withdrawing polymer (A1). It is considered that the imide structure in the structural unit (4a) imparts electron withdrawing property to the polymer (A).

The composition of the present invention has an ion exchange capacity due to the sulfo group in the electron-withdrawing polymer (A). In the present invention, by using the above-mentioned electron-donating polymer (D), it is possible to suppress the reduction of the ion exchange capacity of the composition even if it is heat treated.

In the above formula, n2 being 0 means that R ^2a does not exist. In addition, when n2 is an integer of 2 to 4, the plurality of R ^2a may be the same or different from each other. The same applies to other groups.

In the divalent group (7a), n2 and n3 are each independently an integer of 1 to 4, at least one of n2 R ^2a is a sulfo group, and at least one of n3 R ^3a is It is preferably a sulfo group.

In the divalent group (8a), n4 to n6 are each independently an integer of 1 to ⁴ , at least one of n4 R ^4a is a sulfo group, and at least one of n5 R ^5a is a sulfo group. Group, and at least one of n6 R ^6a 's is preferably a sulfo group.

In the divalent group (9a), n7 to n10 are each independently an integer of 1 to 4, at least one of n7 R ^7a is a sulfo group, and at least one of n8 R ^8a is a sulfo group. It is preferable that at least one of n 9 R ^9a is a sulfo group, and at least one of n 10 R ^10a is a sulfo group.

R ^{1a to} R ^10a each independently represent a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a halogen atom, a nitro group, or formyl. group, a cyano group, a sulfo group, a phenyl group which may be substituted with W ^1a, thienyl group which may be substituted with W ^1a or W ^1a with an optionally substituted furyl group, and W ^1a Is a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a halogen atom, a nitro group, a formyl group, a cyano group or a sulfo group. It is preferable.

X ^2a is preferably a tetravalent group (5a). Y ^2a is preferably a divalent group (7a). The structural unit (4a) is preferably the formula (4a-1):

[Wherein, m1 and m2 are each independently an integer of 0 to 3, and * represents a bonding position. ]
Is a structural unit represented by.

Both m1 and m2 are preferably 0. That is, the structural unit (4a-1) preferably has the formula (4a-11):

[In the formula, * represents a bonding position. ]
Is a structural unit represented by.

The electron-withdrawing polymer (A1) may be a polymer composed of one type of structural unit (4a) or a polymer composed of two or more types of structural unit (4a). The electron-withdrawing polymer (A1) is composed of one or more structural units (4a) and one or more other structural units (that is, a structural unit different from the structural unit (4a)). The polymer may be

As another structural unit, for example, formula (4b):

［式中、Ｘ^２ｂは、式（５ａ）〜式（５ｃ）：

[In Formula, X ^<2b > is Formula (5a)-Formula (5c):

［式中、＊は、結合位置を示す。］
のいずれかで表される４価の基であり、
Ｙ^２ｂは、式（６ｂ）〜式（９ｂ）：

[In the formula, * represents a bonding position. ]
Is a tetravalent group represented by
Y ^2b is represented by formula (6b) to formula (9b):

[In the formula, p1 to p10 are each independently an integer of 0 to 4,
R ^{1b to} R ^10b are each independently a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a hydroxy group, a halogen atom, or nitro. group, a formyl group, a cyano group, a phenyl group which may be substituted with W ^1b, thienyl group which may be substituted with W ^1b or W ^1b with an optionally substituted furyl group,
W ^1b is a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a hydroxy group, a halogen atom, a nitro group, a formyl group or a cyano group. And
When p1 to p10 are integers of 2 to 4, a plurality of R ^{1b to} R ^10b may be the same or different from each other,
Z ^{1b to} Z ^6b each independently represent a single bond, a C _1-2 alkylene group which may be substituted with a halogen atom, a C _3-10 alkylene group, a sulfonyl group, a carbonyl group, *-CONH-*, *. -NHCO-*, *-C(R< ^11b >)(R< ^12b >)-*, or an oxy group,
R ^11b and R ^12b are each independently a C _1-3 alkyl group optionally substituted with a halogen atom, or R ^11b and R ^12b are bonded to each other, together with the carbon atom to which they are bonded, A C _3-6 hydrocarbon ring is formed, and * indicates a bonding position. ]
Is a divalent group represented by, and * indicates a bonding position. ]
The structural unit represented by

R ^{1b to} R ^10b each independently represent a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a halogen atom, a nitro group, or formyl. group, a cyano group, a W phenyl group which may be substituted by ^1b, thienyl group which may be substituted with W ^1b or an optionally substituted furyl group in W ^1b,, and W ^1b is halogen It is preferably a C _1-10 alkyl group optionally substituted with an atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a halogen atom, a nitro group, a formyl group or a cyano group.

X ^2b is preferably a tetravalent group (5a). Y ^2b is preferably formula (10) to formula (15):

[Wherein, r1 to r3 are each independently an integer of 1 to 4,
k1 is an integer of 1 to 4,
R ^1c is a fluorine atom or a trifluoromethyl group, and when k1 is an integer of 2 to 4, a plurality of R ^1c may be the same or different from each other,
k2-k5 are each independently an integer of 0-4,
R ^2c is a nitro group or a trifluoromethyl group, and when k2 is an integer of 2 to 4, a plurality of R ^2c may be the same or different from each other,
R ^3c and R ^4c are both chlorine atoms,
R ^5c is a nitro group or a trifluoromethyl group, and when k 5 is an integer of 2 to 4, a plurality of R ^5c's may be the same or different from each other,
k6 and k7 are each independently an integer of 0 to 4,
R ^6c is a C _1-3 alkyl group optionally substituted with a halogen atom, and when k ⁶ is an integer of 2 to 4, a plurality of R ^{6c s} may be the same or different from each other,
R ^7c is a C _1-3 alkyl group optionally substituted with a halogen atom, and when k ⁷ is an integer of 2 to 4, a plurality of R ^{7c s} may be the same or different from each other,
k8 and k9 are each independently an integer of 0 to 4,
R ^8c is a C _1-3 alkyl group optionally substituted with a halogen atom, and when k ⁸ is an integer of 2 to 4, a plurality of R ^8c's may be the same or different from each other,
R ^9c is a C _1-3 alkyl group which may be substituted with a halogen atom, and when k 9 is an integer of 2 to 4, a plurality of R ^9c may be the same or different from each other, and * Indicates a binding position. ]
Is a divalent group represented by any of the above.

Examples of preferable structural unit (4b) include structural units represented by any of the following formulas (4b-1) to (4b-7) (the definition of the group in the formula is as described above). is there).

Among the above-mentioned ones, the structural unit (4b-1) is preferable. In the structural unit (4b-1), both r1 and r2 are preferably 4. That is, the structural unit (4b-1) preferably has the formula (4b-11):

[In the formula, * represents a bonding position. ]
Is a structural unit represented by.

In one embodiment of the present invention, the amount of the structural unit (4a) in the electron-withdrawing polymer (A1) is 80 per 100 mol of the total of the structural unit (4a) and the other structural unit (for example, the structural unit (4b)). -100 mol, more preferably 90-100 mol. The electron-withdrawing polymer (A1) is more preferably a polymer composed of one or more structural units (4a).

In one aspect of the present invention, the structural unit (4a) is preferably the structural unit (4a-1). In this aspect, the structural unit (4a-1) may be only one type or two or more types. In this aspect, the structural unit (4a-1) is preferably one type, and more preferably the structural unit (4a-11).

In one embodiment of the present invention, the electron-withdrawing polymer (A1) preferably has the structural unit (4a-1) as the structural unit (4a) and the structural unit (4b-1) as another structural unit. .. In this aspect, the structural unit (4a-1) and the structural unit (4b-1) may each be only one kind or two or more kinds. In this aspect, the structural unit (4a-1) is preferably one type, and more preferably the structural unit (4a-11). In this aspect, the structural unit (4b-1) is preferably one type, and more preferably the structural unit (4b-11).

When the electron-withdrawing polymer (A1) has the structural unit (4a-1) and the structural unit (4b-1), the number and the constitution of the structural unit (4a-1) (preferably the structural unit (4a-11)). The ratio with the number of units (4b-1) (preferably the structural unit (4b-11)) (the number of structural units (4a-1)/the number of structural units (4b-1)) is preferably 0.1. /99.9 to 99.9/0.1, more preferably 1/99 to 99/1, and further preferably 30/70 to 95/5.

The weight average molecular weight (Mw) of the electron-withdrawing polymer (A1) is preferably 5,000 to 1,000,000, more preferably 8,000 to 900,000, and further preferably 10,000 to 150,000. Is.

The electron-withdrawing polymer (A1) can be synthesized by a known reaction using a commercially available product as a starting material. Commercially available products can be obtained from, for example, Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., and the like. For example, a tetracarboxylic dianhydride (for example, naphthalene-1,4,5,8-tetracarboxylic dianhydride) and a diamine (for example, 4,4′-diamino) as described in Synthesis Examples below. The electron-withdrawing polymer (A1) can be produced by the reaction with −2,2′-biphenyldisulfonic acid. In addition, a compound obtained by introducing a substituent into a commercially available product by a known reaction may be used as a starting material.

The electron-withdrawing polymer described above is, for example, Macromolecules, 2002, 35, 9022-9028, Macromol. Chem. Phys. 2016, 217, 654-663, or Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 41. , 3901-3907 (2003).

The amount of tetracarboxylic dianhydride in the above reaction is preferably 0.98 to 1.02 mol, and more preferably 0.99 to 1.01 mol, based on 1 mol of diamine.

The method for producing the electron-withdrawing polymer (A1) includes a dissolving step, a polymerizing step, and a modifying step as necessary.

The dissolving step is a step of heating a mixture of diamine (0.1 mM to 5 M), a tertiary amine (0.1 mM to 20 M) and an organic solvent to dissolve the diamine in the organic solvent. The tertiary amine is used to dissolve a diamine having an acidic group in an organic solvent. The temperature for heating the mixture is not particularly limited, but by setting the temperature to about 20 to 160° C., the diamine can be easily and uniformly dissolved in the solvent.

The tertiary amine is not particularly limited, and examples thereof include trimethylamine, triethylamine, tripropylamine, N-ethyl-N-methylbutylamine, tributylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, and triethylamine. Ribenzylamine, diazabicycloundecene and the like can be mentioned. Of these, triethylamine is preferable. These tertiary amines may be used alone or in combination of two or more.

As the organic solvent, those having a high boiling point and a high polarity are preferable, and for example, phenol, m-cresol, m-chlorophenol, p-chlorophenol, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidinone. , N-cyclohexyl-2-pyrrolidinone and the like. Among them, m-cresol, dimethyl sulfoxide and N-methyl-2pyrrolidinone are preferable. These organic solvents may be used alone or in combination of two or more.
In addition, in this specification, "m-" represents "meta" and "p-" represents "para."

In the polymerization step, tetracarboxylic acid dianhydride (0.1 mM to 5 M) was added to the solution of diamine obtained in the dissolution step, and the resulting mixture was heated in the presence of an organic acid (0.01 mM to 20 M). And then polymerize. The organic acid acts as a catalyst for polymerization and ring closure reaction, and promotes formation of polyamic acid and formation of imide ring by ring closure thereof.

The organic acid is preferably a compound having a high boiling point and high solubility in the above organic solvent, and examples thereof include benzoic acid, methylbenzoic acid, dimethylbenzoic acid, salicylic acid and the like. Among them, benzoic acid is preferable. The organic acid has only to be present in the polymerization step and may be added in the stage of the dissolution step. The amount of the organic acid added is not particularly limited, but when benzoic acid is used as the organic acid, the amount thereof is preferably about 1 to 6 mol per 1 mol of tetracarboxylic acid dianhydride. The temperature for heating the reaction mixture is at least 40°C or higher. By setting this temperature to preferably 100 to 190° C., more preferably 140 to 180° C., the polymerization reaction proceeds efficiently, and a polyimide which is a high molecular weight electron-withdrawing polymer can be obtained.

The modification step is a step of correcting structural defects in the polyimide obtained in the polymerization step. The structural defect is a defect based on an unclosed ring portion (amic acid) in polyimide. In the reforming step, the reaction mixture after the polymerization step is heated at a temperature higher than the temperature of the polymerization step to perform a dehydration reaction and imidize the unclosed ring portion. This temperature is preferably at least 150°C or higher, more preferably 190 to 220°C. In this modification step, the ring closure reaction proceeds efficiently, and a polyimide having no structural defect can be obtained.

After the above step, the electron-withdrawing polymer (A1) can be obtained by a known means such as precipitation, filtration, dialysis and drying.

<Charge transfer complex>
In the composition of the present invention, it is preferable that the electron-donating polymer (D) and the electron-withdrawing polymer (A) form a charge transfer complex. As a result, a composition in which the electron-donating polymer (D) and the electron-withdrawing polymer (A) are sufficiently mixed and phase separation is suppressed can be obtained.

Here, the "charge transfer complex" means an intermolecular compound formed between two types of neutral molecules by a charge transfer force. The fact that the electron-donating polymer (D) and the electron-withdrawing polymer (A) form a charge transfer complex means that Nature, 375(6529), 303-305 (1995) and Polym. J. (2013), As described in 45, 839-844, it can be confirmed that the UV-vis absorption spectrum of the composition has a peak or a shoulder near 530 nm.

<Film produced from the composition of the present invention>
Membranes can be produced by preparing a solution of the composition of the invention and then evaporating the solvent from this solution. The method for preparing the solution of the composition of the present invention is not particularly limited. For example, the solution of the composition may be prepared by sequentially or simultaneously adding the electron-donating polymer (D) and the electron-withdrawing polymer (A) to the solvent and heating them appropriately. Alternatively, the solution of the composition may be prepared by separately preparing a solution of the electron-donating polymer (D) and a solution of the electron-withdrawing polymer (A), and mixing the obtained solutions.

As a solvent for preparing a solution of the composition, for example, water, methanol, ethanol, trifluoroethanol, 1-propanol, 2-propanol, 2-methyl-2-butanol, ethylene glycol, benzyl alcohol, cyclohexane, benzene. , Nitrobenzene, chloroform, carbon tetrachloride, diethyl ether, tetrahydrofuran, isoxazole, 1,4-dioxane, cyclopentyl methyl ether, acetone, acetonitrile, nitromethane, dimethyl sulfoxide, N,N-dimethylformamide, sulfolane, 1,3-propane. Sulton is mentioned. These solvents may be used alone or in combination of two or more. Among these, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, benzyl alcohol, cyclohexane, benzene, nitrobenzene, chloroform, carbon tetrachloride, diethyl ether, tetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, acetone. , Acetonitrile, nitromethane, dimethylsulfoxide, N,N-dimethylformamide, sulfolane, and 1,3-propanesultone are preferable, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, and dimethylsulfoxide are more preferable, and dimethylsulfoxide is More preferable.

In the solution containing the electron-donating polymer (D) and the electron-withdrawing polymer (A), the total concentration of the electron-donating polymer (D) and the electron-withdrawing polymer (A) is preferably based on the whole solution. Is 0.1 to 90% by weight, more preferably 0.5 to 10% by weight.

The method of distilling the solvent from the solution of the composition is not particularly limited, and the solvent may be distilled by a known means (for example, heat drying, vacuum drying, etc.). The thickness of the film can be adjusted by adjusting the charged amounts of the electron-donating polymer (D) and the electron-withdrawing polymer (A) and the area of the petri dish used when the solvent is distilled off. The thickness of the film produced from the composition of the present invention is preferably 0.01 to 200 μm, more preferably 0.1 to 100 μm, still more preferably 0.3 to 60 μm.

Evaporation of the solvent from the solution of the composition of the present invention may be performed in an air atmosphere or an inert gas (for example, nitrogen, argon) atmosphere. Further, this solvent distillation may be carried out under normal pressure, or may be carried out under reduced pressure using a vacuum dryer or a vacuum pump.

The temperature for distilling off the solvent is preferably -10 to 200°C, more preferably 40 to 160°C, and further preferably 50 to 130°C. The solvent may be distilled off at a constant temperature, or the temperature may be changed in multiple steps. The time for distilling off the solvent is preferably 0.5 to 300 hours, more preferably 1 to 160 hours, and further preferably 2 to 150 hours.

The conditions for producing a film from the composition of the present invention (for example, the type of the solvent described above, the concentration of the polymer in the solution, and the atmosphere, pressure, temperature and time for distilling the solvent) can be appropriately selected. ..

It is preferable to heat-treat the film of the composition of the present invention obtained as described above. This heat treatment can increase the amount of charge transfer complex formed in the film. The heat treatment is preferably performed in an inert gas (for example, nitrogen, argon) atmosphere. The heat treatment temperature is preferably 40 to 200° C., more preferably 60 to 180° C., further preferably 70 to 160° C., and the time thereof is preferably 0.01 to 200 hours, more preferably 0.5 to It is 160 hours, more preferably 1 to 80 hours.

Membranes made from the compositions of the invention (ie, membranes containing the compositions of the invention) can be used in a variety of applications. Examples of uses of the membrane containing the composition of the present invention include an electrolyte membrane of a fuel cell, an electrolyte coating membrane on an electrode catalyst in a catalyst layer, a gas permeation suppression membrane, and the like. Among these, the electrolyte membrane of the fuel cell and the electrolyte coating membrane on the electrode catalyst are preferable, and the electrolyte membrane of the fuel cell is more preferable. The thickness of the electrolyte membrane of the fuel cell containing the composition of the present invention is preferably 0.1 to 200 μm, more preferably 2 to 50 μm, and further preferably 5 to 20 μm. The thickness of the electrolyte coating film on the electrode catalyst in the catalyst layer of the fuel cell containing the composition of the present invention is preferably 1 to 100 nm, more preferably 2 to 50 nm, further preferably 5 to 30 nm.

The synthesis examples and examples of the present invention will be described more specifically below, but the present invention is not limited thereto. The analyzers and conditions used in the synthesis examples and examples are as follows.

¹ H NMR:
The chemical shift value of the proton nuclear magnetic resonance ( ¹ H NMR) of the polymer was determined by using Bruker AV-400 (400 MHz) or Bruker AVANCE III (600 MHz) as a measuring instrument, and using heavy dimethyl sulfoxide as a heavy solvent. (DMSO-d ₆ ) or deuterated chloroform (CDCl ₃ -d) was used, and the chemical shift was shown as a δ value (ppm) when tetramethylsilane was used as an internal standard (0.0 ppm).
In the description of NMR spectrum, "s" is singlet, "brs" is broad singlet, "d" is doublet, "t" is triplet, "dd" is double doublet, "m" is multiplet, and "br" is broad. , "J" means coupling constant, and "Hz" means hertz.
“DMSO-d ₆ ”means deuterated dimethyl sulfoxide and “CDCl ₃ -d” means deuterated chloroform.
The method of adding trifluoroacetic acid to the heavy solvent to be measured and clarifying the peak of NMR was performed according to the sample to be measured.

Glass-transition temperature:
The glass transition temperature of the polymer was measured using a differential scanning calorimeter NETZSC DSC 204 Fi Phoenix manufactured by Netti under a nitrogen flow of 10 mL/min, a heating rate of 10° C./min and an analytical range of −100 to 200° C. It was measured at.

GPC:
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC) under analysis conditions A and converted using a calibration curve of standard polystyrene.
<Analysis condition A>
Column: Tosoh TSK guard column Super AW-H, Tosoh TSK gel super AW 3000 and Tosoh TSK gel super AW 5000 columns are connected in series in this order. did.
Column temperature: 40°C
Detector: JASCO's differential refractive index detector RI-2031 and UV-visible detector UV-2075
Eluent: chloroform Flow rate: 1.0 mL/min

UV-vis:
Ultraviolet-visible spectroscopy (UV-vis) of the composition is measured by UV-Vis near-infrared spectrophotometer V-650 manufactured by JASCO Corporation, integrating sphere unit ISV-722 manufactured by JASCO Corporation and JASCO Corporation. This was carried out by mounting a sample holder made by SSH-506.

Ion exchange capacity:
The theoretical ion exchange capacity (theoretical IEC) was calculated as the amount (mmol) of sulfo groups contained per polymer or composition (1 g).
The ion exchange capacity (IEC) by titration was calculated as follows. First, a polymer or composition film cut into a size of 1×1 cm ² was immersed in 10 mL of a sodium chloride aqueous solution (concentration: 15% by weight) for 1 day, and then phenolphthalein as an indicator and a sodium hydroxide aqueous solution. (Concentration: 0.001 mol/L) was used for titration until the pH of the aqueous sodium chloride solution reached 7. From the amount of the aqueous sodium hydroxide solution used until the pH reaches 7, the following formula:
Ion exchange capacity (IEC) by titration (mmol/g)
= [Amount (L) of sodium hydroxide aqueous solution used until reaching pH 7] x [concentration of sodium hydroxide aqueous solution (mol/L)] x [1/1000]/[dry weight of membrane (g)]
The ion exchange capacity (IEC) by titration was calculated by.

Fuel cell power generation test:
A membrane electrode assembly (Membrane Electrode Assembly, hereinafter abbreviated as "MEA") was prepared from an electrolyte membrane, a catalyst ink and a gas diffusion layer.
The catalyst ink is a platinum-supported carbon electrode catalyst (manufactured by Tanaka Kikinzoku Kogyo KK, platinum content: 46.2% by weight, product name "TEC10E50E"), ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), deionized water, and Nafion dispersion. It was prepared using a solution (manufactured by Wako Pure Chemical Industries, Ltd., product name “5% Nafion Dispersion Solution DE521 CS type”).
For the gas diffusion layer, hydrophobic carbon paper (manufactured by Toray Industries, Inc., product name “EC-TP1-060T”) was used.

After irradiating the catalyst ink with ultrasonic waves for 30 minutes with a homogenizer UH-600 manufactured by SMT Co., Ltd., the catalyst ink was applied to both surfaces of the electrolyte membrane using a spray coating device V8H manufactured by Nordson. In this test, the membrane prepared from the composition of the electron-donating polymer (D) and the electron-withdrawing polymer (A) was used as the electrolyte membrane. The coating conditions were 0.3 mg of platinum per cm ^{2 of} the electrolyte membrane, and Nafion ratio (wt %) (=[Nafion solid content (weight)/[electrode catalyst (weight) + Nafion solid content (weight)]]]× 100) was 28% by weight.

Next, a gas diffusion layer (hereinafter abbreviated as “GDL”) is arranged on both sides of a catalyst coating film (Catalyst Coated Membrane, hereinafter abbreviated as “CCM”) which is an electrolyte film coated with a catalyst ink. After that, a single cell having an electrode area of 1 cm ² (JARI standard cell manufactured by FC Development Co., Ltd.) was assembled, and CCM and GDL were pressure-bonded to produce MEA. The produced MEA was placed in a single cell (JARI standard cell manufactured by FC Development Co., Ltd.) having an electrode area of 1 cm ² .

Using a fuel cell evaluation system (AutoPEM, manufactured by Toyo Technica), evaluation was performed at a temperature of 40° C., a relative humidity of 100%, hydrogen of 100 mL/min and an air gas flow at atmospheric pressure, and current density and voltage were measured. Cell resistance and open circuit voltage (hereinafter abbreviated as “OCV”) were measured by a four-terminal method using SI 1287 electrochemical interface impedance analyzer manufactured by Solartron. Note that OCV is a potential when no voltage or current is applied to the single cell.

Synthesis Example 1: Synthesis of electron donating polymer (D1-1) After replacing the inside of the reaction vessel with nitrogen, 1,3-bis(3-glycidoxypropyl)tetramethyldisiloxane) (9.66 g, 26) .64 mmol), 2,6-dihydroxynaphthalene (4.27 g, 26.64 mmol), tris(2,6-dimethoxyphenyl)phosphine (44.2 mg, 0.10 mmol) and cyclohexanone (24 mL), in that order, in a reaction vessel. Added to. The reaction mixture was then stirred at 150° C. for 96 hours. After completion of the reaction, the reaction mixture was added dropwise to methanol to obtain a yellow oily crude product. This crude product was dissolved in chloroform, this solution was added dropwise to methanol to wash the crude product, and then the solvent was dried under reduced pressure to obtain the compound of formula (1a-1):

An electron-donating polymer (D1-1) having a structural unit represented by the following was obtained as a yellow oil (3.25 g, yield 23%).

¹ H NMR (600 MHz, DMSO-d ₆ +CF ₃ CO ₂ H)
δ: 7.66 (2H), 7.21 (2H), 7.09 (2H), 4.02 (2H), 3.95 (4H), 3.45 (4H), 3.34 (4H). , 1.48 (4H), 0,44 (4H), -0.02 (12H).
FIG. 1 shows a ¹ H NMR chart of the electron donating polymer (D1-1).

GPC:
Weight average molecular weight (Mw)=2.8×10,000
Number average molecular weight (Mn)=1.8×10,000
Molecular weight distribution (Mw/Mn)=1.5
Glass transition temperature (°C) = 12.5°C

Synthesis Example 2: Synthesis of electron-withdrawing polymer (A1-1) After replacing the inside of the reaction vessel with nitrogen, 4,4′-diamino-2,2′-biphenyldisulfonic acid (10.33 g, 30.0 mmol) ), m-cresol (75 mL), and triethylamine (7.59 g, 75.0 mmol) were sequentially added to the reaction vessel. The reaction mixture is then stirred at 140-145° C. to dissolve the solids and then naphthalene-1,4,5,8-tetracarboxylic dianhydride (8.21 g, 30.6 mmol) therein. , And benzoic acid (7.33 g, 60.0 mmol) were added, and the mixture was stirred at 180 to 185° C. for 20 hours and further stirred at 190 to 195° C. for 5 hours to carry out the reaction. After completion of the reaction, the reaction mixture was added dropwise to a mixed solvent of methanol and concentrated hydrochloric acid (methanol:concentrated hydrochloric acid=5:1 (volume ratio)) to deposit a precipitate, and the precipitate was collected by filtration.

Dimethyl sulfoxide was added to the obtained precipitate and heated to 100 to 110° C., and the obtained dimethyl sulfoxide solution was added dropwise to a mixed solvent of methanol and concentrated hydrochloric acid (methanol:concentrated hydrochloric acid=5:1 (volume ratio)). Then, a precipitate was deposited and collected by filtration. The operations of adding dimethyl sulfoxide to the obtained precipitate, preparing a dimethyl sulfoxide solution, dropping the dimethyl sulfoxide solution into the mixed solvent, and collecting the deposited precipitate by filtration were repeated.

Dimethyl sulfoxide was added to the obtained precipitate and heated to 100 to 110° C., and the obtained dimethyl sulfoxide solution was treated with a dialysis membrane (Spectra/Por 7, MWCO(Daltons) 3500, Spectrum with a molecular weight cut off of 3,500). It dialyzed for 4 days using the laboratory company. After completion of dialysis, the solution is dried and the structural unit represented by formula (4a-11):

The electron-withdrawing polymer (A1-1) was obtained as a blackish brown solid (12.5 g, yield 70%).

¹ H NMR (500 MHz, DMSO-d ₆ ).
δ: 9.09-8.51 (br), 8.04 (s), 7.76 (brs), 7.62-7.25 (m).
GPC:
Weight average molecular weight (Mw)=1.3×100,000
Number average molecular weight (Mn)=5.9×1,000
Molecular weight distribution (Mw/Mn)=21
Ion exchange capacity:
Theoretical ion exchange capacity (theoretical IEC)=3.47 (mmol/g)
Ion exchange capacity (IEC) by titration=3.47 (mmol/g)

Synthesis Example 3: Synthesis of electron-withdrawing polymer (A1-2) After replacing the inside of the reaction vessel with nitrogen, 4,4′-diamino-2,2′-biphenyldisulfonic acid (4.14 g, 12.0 mmol) ), 4,4′-Diaminooctafluorobiphenyl (0.44 g, 1.3 mmol), m-cresol (38 g), and triethylamine (3.38 g, 33.4 mmol) were sequentially added to the reaction vessel. The reaction mixture is then stirred at 140-145° C. to dissolve the solids, after which naphthalene-1,4,5,8-tetracarboxylic dianhydride (3.65 g, 13.6 mmol). , And benzoic acid (3.27 g, 26.8 mol) were added. Then, the reaction mixture was stirred at 170 to 175° C. for 27 hours to carry out the reaction. After the reaction was completed, the reaction mixture was added dropwise to a mixed solvent of methanol and concentrated hydrochloric acid (methanol:concentrated hydrochloric acid=5:1 (volume ratio)) to deposit a precipitate, which was then collected by filtration to obtain The obtained precipitate was added to dimethyl sulfoxide, heated to 100 to 110° C., and dissolved to obtain a dimethyl sulfoxide solution.

Next, the obtained dimethyl sulfoxide solution was added dropwise to a mixed solvent of methanol and concentrated hydrochloric acid (methanol:concentrated hydrochloric acid=5:1 (volume ratio)) to deposit a precipitate, which was collected by filtration. Dimethyl sulfoxide was added to the precipitate and heated to 100 to 110° C. to dissolve it, and then the dimethyl sulfoxide solution was added dropwise to methanol to precipitate the precipitate, which was collected by filtration. Dimethyl sulfoxide was added to the precipitate, and the precipitate was heated to 100 to 110° C. to dissolve it. , Manufactured by Spectrum Laboratory Co., Ltd.) and dialyzed for 4 days. After the completion of dialysis, the solution is freeze-dried and the structural unit represented by the formula (4a-11) and the structural unit represented by the formula (4b-11):

The electron-withdrawing polymer (A1-2), which is a random copolymer having ##STR3## was obtained as a black-brown solid (5.4 g, yield 70%). The number of structural units (4a-11)/the number of structural units (4b-11) in the electron-withdrawing polymer (A1-2) calculated from the charged amount of the raw materials was 9/1.

¹ H NMR (400 MHz, DMSO-d ₆ ).
δ: 8.81 (brs), 8.06 (s), 7.78 (brs), 7.43 (brs).
GPC:
Weight average molecular weight (Mw)=7.5×10,000
Number average molecular weight (Mn)=1.6×10,000
Molecular weight distribution (Mw/Mn)=4.7
IEC:
Theoretical ion exchange capacity (IEC)=3.13 (meq/g)

Synthetic Example 4: Synthesis of electron donating polymer (D1-2) In the same manner as in Synthetic Example 1 except that the raw material 2,6-dihydroxynaphthalene was changed to 1,5-dihydroxynaphthalene, the compound of formula (1a-2) :

An electron-donating polymer (D1-2) having a structural unit represented by was obtained as a yellow oil (1.5 g, yield 11%).

GPC:
Weight average molecular weight (Mw)=2.3×10,000
Number average molecular weight (Mn)=1.1×10,000
Molecular weight distribution (Mw/Mn)=2.1

Synthesis Example 5: Synthesis of electron donating polymer (D1-3) Formula (1a-3) was carried out in the same manner as in Synthesis Example 1 except that 2,6-dihydroxynaphthalene as a raw material was changed to 2,3-dihydroxynaphthalene. :

An electron donating polymer (D1-3) having a structural unit represented by was synthesized. It was confirmed that the electron-donating polymer (D1-3) was obtained by analyzing the reaction solution with GPC.

GPC:
Weight average molecular weight (Mw)=7.2×1,000
Number average molecular weight (Mn)=3.4×1,000
Molecular weight distribution (Mw/Mn)=2.1

Example 1: Production of film of composition (I) of electron-donating polymer (D1-1) and electron-withdrawing polymer (A1-1) Electron-donating polymer (D1-1) (95.1 mg), electron The attracting polymer (A1-1) (104.9 mg) and dimethylsulfoxide (3 mL) were sequentially placed in a reaction vessel, the polymer was dissolved in dimethylsulfoxide, and the obtained mixture was mixed with polytetrafluoro having an inner diameter of 3 cm. It was added to an ethylene petri dish. The amount of the structural unit (1a-1) in the electron donating polymer (D1-1) used was 182 mmol, and the structural unit (4a-11) in the electron withdrawing polymer (A1-1) used. Was 182 mmol.

Next, the petri dish containing the mixture was placed in a vacuum drier, and dried at 50° C. under a reduced pressure of 500 hPa for 12 hours and then at 65° C. under a reduced pressure of 0 hPa for 24 hours to remove dimethyl sulfoxide. A film of the composition (I) of the electron-donating polymer (D1-1) and the electron-withdrawing polymer (A1-1) was obtained (dark brown, film thickness: 60 μm).

Example 2: Production of film of composition (II) of electron-donating polymer (D1-1) and electron-withdrawing polymer (A1-2) Electron-donating polymer (D1-1) (49.2 mg), electron The attracting polymer (A1-2) (107.6 mg) and dimethylsulfoxide (1.6 mL) were sequentially placed in a reaction vessel, the polymer was dissolved in dimethylsulfoxide, and then the resulting mixture had an inner diameter of 1.7 cm. Was added to a petri dish made of polytetrafluoroethylene. The amount of the structural unit (1a-1) in the electron donating polymer (D1-1) used was 94.1 mmol, and the structural unit (4a- in the electron withdrawing polymer (A1-2) used. The total amount of 11) and the structural unit (4b-11) was 187.2 mmol.

Next, the petri dish containing the mixture was placed in a vacuum dryer, and the pressure reduction degree was reduced from atmospheric pressure to 800 hPa at 60° C. over 30 minutes, and then at 60° C., the pressure reduction degree was changed from 800 hPa to 0 hPa for 800 minutes. Then, the mixture is decompressed and further dried at 60° C. under a reduced pressure of 0 hPa for 24 hours to remove dimethyl sulfoxide, and thus the composition of the electron-donating polymer (D1-1) and the electron-withdrawing polymer (A1-2). A film of the product (II) was obtained (dark brown, film thickness: 43 μm).

Example 3: Production of film of composition (III) of electron-donating polymer (D1-1) and electron-withdrawing polymer (A1-2) Electron-donating polymer (D1-1) (104.4 mg), electron The attracting polymer (A1-2) (114.8 mg) and dimethylsulfoxide (4 mL) were sequentially placed in a reaction vessel, the polymer was dissolved in dimethylsulfoxide, and the resulting mixture was mixed with a polymer having an inner diameter of 1.7 cm. It was added to a petri dish made of tetrafluoroethylene. The amount of the structural unit (1a-1) in the electron donating polymer (D1-1) used was 199.7 mmol, and the structural unit (4a- in the electron withdrawing polymer (A1-2) used. The total amount of 11) and the structural unit (4b-11) was 199.7 mmol.

Next, the petri dish containing the mixture was placed in a vacuum drier, the temperature was raised from 25° C. to 60° C., the pressure reduction degree was reduced from atmospheric pressure to 800 hPa over 30 minutes, and then at 60° C. Decompression degree was reduced from 800 hPa to 0 hPa over 150 minutes, further dried under reduced pressure at 0 °Pa at 60 °C for 3 hours, and further heated at 60 °C to 100 °C at reduced pressure of 0 hPa to obtain dimethyl sulfoxide. Was removed to obtain a film of the composition (III) of the electron-donating polymer (D1-1) and the electron-withdrawing polymer (A1-2) (dark brown, film thickness: 25 μm).

Test Example 1: Confirmation of Charge Transfer Complex The absorption spectrum of the film of the composition (I) obtained in Example 1 was measured by ultraviolet-visible spectroscopy (UV-vis). This absorption spectrum is shown in FIG.

As shown in FIG. 2, the absorption spectrum of the film of the composition (I) had a shoulder near 530 nm. This shoulder is an absorption by a charge transfer complex (see Nature, 375(6529), 303-305 (1995) and Polym. J. (2013), 45, 839-844). Therefore, from this result, it was confirmed that the film of the composition (I) formed a charge transfer complex.

Test Example 2: Fuel Cell Power Generation Test A fuel cell power generation test was performed as described above using the composition (I) film (film thickness: 60 μm) produced in the same manner as in Example 1 as an electrolyte membrane. It was Table 1 shows the results of the voltage and the current density in the power generation test. The OCV of the single cell produced by using the film of the composition (I) as an electrolyte film was 0.562V.

Test Example 3: Confirmation of charge transfer complex The absorption spectrum of the film of the composition (III) obtained in Example 3 was measured by ultraviolet-visible spectroscopy (UV-vis). This absorption spectrum is shown in FIG.

As shown in FIG. 3, the absorption spectrum of the film of the composition (III) has a shoulder in the vicinity of 530 nm, and the film may form a charge transfer complex like the film of the composition (I). confirmed.

The composition of the present invention is useful, for example, as an electrolyte material (for example, an electrolyte membrane) of a fuel cell.

Claims (10)

A composition comprising an electron-donating polymer (D) and an electron-withdrawing polymer (A),
The electron-donating polymer (D) has the formula (1a):
*-X ^1a -O-Y ^1a -O-Z ^1a -O-Y' ^1a -O-* (1a)
[In the formula, X ^1a represents the formula (2a) to the formula (2c):

[In the formula, * represents a bonding position. ]
Is a divalent group represented by
Y ^1a and Y′ ^1a each independently represent formula (3a) or formula (3b):

[In the formula, * represents a bonding position. ]
Is a divalent group represented by
Z ^1a has the formula (3c):

[Wherein, R ^{1 to} R ⁴ are each independently a C _1-3 alkyl group,
R ⁵ and R ⁶ are each independently a C _1-3 alkylene group,
* Indicates a binding position. ]
Is a divalent group represented by, and * indicates a bonding position. ]
An electron-donating polymer (D1) having a structural unit represented by
The electron-withdrawing polymer (A) has the formula (4a):

[In Formula, X ^<2a > is Formula (5a)-Formula (5c):

[In the formula, * represents a bonding position. ]
Is a tetravalent group represented by
Y ^2a is represented by formula (6a) to formula (9a):

[In formula, n1 is an integer of 1-4,
n2 to n10 are each independently an integer of 0 to 4,
R ^{1a to} R ^10a are each independently a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a hydroxy group, a halogen atom, or nitro. group, a formyl group, a cyano group, a sulfo group, a phenyl group which may be substituted with W ^1a, thienyl group which may be substituted with W ^1a or W ^1a with an optionally substituted furyl group,
W ^1a is a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a hydroxy group, a halogen atom, a nitro group, a formyl group, a cyano group. Or a sulfo group,
When n1 to n10 are integers of 2 to 4, a plurality of R ^{1a to} R ^10a may be the same or different from each other,
At least one of n 1 R ^1a is a sulfo group,
At least one selected from the group consisting of n2 R ^2a and n3 R ^3a is a sulfo group,
At least one selected from the group consisting of n4 R ^4a , n5 R ^5a and n6 R ^6a is a sulfo group,
At least one selected from the group consisting of n7 R ^7a , n8 R ^8a , n9 R ^9a and n10 R ^10a is a sulfo group,
Z ^{1a to} Z ^6a each independently represent a single bond, a C _1-2 alkylene group optionally substituted with a halogen atom, a C _3-10 alkylene group, a sulfonyl group, a carbonyl group, *-CONH-*, *. -NHCO-*, *-C(R< ^11a >)(R< ^12a >)-*, or an oxy group,
R ^11a and R ^12a are each independently a C _1-3 alkyl group optionally substituted with a halogen atom, or R ^11a and R ^12a are bonded to each other, together with the carbon atom to which they are bonded, A C _3-6 hydrocarbon ring is formed, and * indicates a bonding position. ]
Is a divalent group represented by, and * indicates a bonding position. ]
A composition comprising an electron-withdrawing polymer (A1) having a structural unit represented by: The composition according to claim 1, wherein X ^1a is a divalent group represented by formula (2a). The composition according to claim 1, wherein Y ^1a and Y′ ^1a are both divalent groups represented by the formula (3a). The composition according to claim 1, wherein the electron-donating polymer (D1) has a glass transition temperature of 110° C. or lower. R ^{1a to} R ^10a each independently represent a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a halogen atom, a nitro group, or formyl. group, a cyano group, a sulfo group, a phenyl group which may be substituted with W ^1a, thienyl group which may be substituted with W ^1a or W ^1a with an optionally substituted furyl group, and W ^1a Is a C _1-10 alkyl group optionally substituted with a halogen atom, a C _1-10 alkoxy group optionally substituted with a halogen atom, a halogen atom, a nitro group, a formyl group, a cyano group or a sulfo group. The composition according to any one of claims 1 to 4. X ^2a is a tetravalent group represented by formula (5a), The composition according to any one of claims 1 to 5. The composition according to any one of claims 1 to 6, wherein Y ^2a is a divalent group represented by formula (7a). The structural unit represented by formula (4a) is represented by formula (4a-1):

[Wherein, m1 and m2 are each independently an integer of 0 to 3, and * represents a bonding position. ]
The composition according to any one of claims 1 to 4, which is a structural unit represented by: The electron-withdrawing polymer (A1) has the formula (4a-1) as the constitutional unit represented by the formula (4a):

[Wherein, m1 and m2 are each independently an integer of 0 to 3, and * represents a bonding position. ]
And a structural unit represented by the formula (4b-1):

[In the formula, r1 and r2 are each independently an integer of 1 to 4, and * represents a bonding position. ]
The composition according to claim 1, which has a structural unit represented by: The composition according to any one of claims 1 to 9, wherein the electron-donating polymer (D) and the electron-withdrawing polymer (A) form a charge transfer complex.

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