# US 2014/0193742 A1 · Block copolymer, manufacturing method therefor, and polymer electrolyte material, molded polymer electrolyte, and solid-polymer fuel cell using said block copolymer

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- Number: US 2014/0193742 A1
- Document ID: US20140193742A1
- Status: Published application
- Kind: A1
- Application number: 14/187,243
- Filed: 2012-08-23
- Published: 2014-07-10
- Earliest claimed: 2011-08-23
- Assignees: Toray Industries, Inc.
- Inventors: Daisuke Izuhara; Hiroaki Umeda; Emi Amano; Tomoyuki Kunita
- Web page: https://patentgrep.com/patent/US20140193742A1

## CPC

- H01M 8/1025: having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
- C08G 65/4012: {Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones}
- C08G 65/4025: {(I) or (II) containing fluorine other than as leaving group (X)}
- C08G 65/4037: {in ring structure, e.g. pyridine group}
- C08G 65/405: {in ring structure, e.g. phenolphtalein}
- C08G 65/4056: {(I) or (II) containing sulfur (as the sulfone group C08G75/23)}
- C08G 65/48: Polymers modified by chemical after-treatment
- C08J 5/2256: {based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation}
- H01B 1/122: {Ionic conductors}
- H01M 8/0289: Means for holding the electrolyte (solid polymer electrolytes H01M8/1018)
- H01M 8/1083: {Starting from polymer melts other than monomer melts}
- C08G 2650/40: containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
- C08J 2371/12: Polyphenylene oxides
- H01M 2300/0082: Organic polymers
- Y02E 60/50: Fuel cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

To provide: a block copolymer that exhibits excellent proton conductivity even under low-humidification conditions, exhibits excellent mechanical strength and chemical stability, and when used in a polymer electrolyte fuel cell, allows high output and excellent physical durability; a polymer electrolyte material; and a polymer electrolyte form article and a polymer electrolyte fuel cell, using the same. The block copolymer of the present invention includes each one or more of: a segment (A1) containing an ionic group; a segment (A2) not containing an ionic group; and a linker moiety connecting the segments. The segment (A1) containing an ionic group comprises a constituent unit represented by a specific structure. The polymer electrolyte material, the polymer electrolyte form article, and the polymer electrolyte fuel cell according to the present invention are manufactured by using the above block copolymer.

## Claims

### Claim 1

A block copolymer including each one or more of: a segment (A1) containing an ionic group; a segment (A2) not containing an ionic group; and a linker moiety connecting the segments, wherein the segment (A1) containing an ionic group comprises a constituent unit represented by a general formula (S1) described below,
where, in the general formula (S1), Ar1 to Ar4 are each an arbitrary divalent arylene group; Ar1 and/or Ar2 contains an ionic group, and Ar3 and Ar4 can each contain or not contain an ionic group; Ar1 to Ar4 may each be arbitrarily substituted, and in Ar1 to Ar4, two or more kinds of arylene groups can be used independently of each other; and the symbol * signifies a bond moiety with the general formula (S1) or with other constituent unit.

### Claim 2 (depends on 1)

The block copolymer according to claim 1, wherein the segment (A2) not containing an ionic group comprises a constituent unit represented by a general formula (S2) described below,
where, in the general formula (S2), Ar5 to Ar8 are each an arbitrary divalent arylene group, which Ar5 to Ar8 can each be arbitrarily substituted, and do not contain an ionic group; in Ar5 to Ar8, two or more kinds of arylene groups can be used independently of each other; and the symbol * signifies a bond moiety with the general formula (S2) or with other constituent unit.

### Claim 3 (depends on 1)

The block copolymer according to claim 1, wherein the ionic group is a sulfonic acid group.

### Claim 4 (depends on 1)

The block copolymer according to claim 1, wherein the ion-exchange capacity is in a range of 1.5 to 3.5 meq/g.

### Claim 5 (depends on 1)

The block copolymer according to claim 1, wherein the molar composition ratio of the segment (A1) containing an ionic group to the segment (A2) not containing an ionic group, A1/A2, is 0.2 or larger and 5 or smaller.

### Claim 6 (depends on 2)

The block copolymer according to claim 2, wherein the constituent unit represented by the general formula (S2) is expressed by the formula (S3) described below.

### Claim 7 (depends on 1)

The block copolymer according to claim 1, wherein the constituent unit represented by the general formula (S1) is expressed by the formula (S4) described below,
where, in the formula (S4), M1 and M2 are each a hydrogen atom, a metal cation, or an ammonium cation; and M1 and M2 may each be represented by two or more kinds of groups.

### Claim 8 (depends on 1)

The block copolymer according to claim 1, wherein the number-average molecular weight of the segment (A1) containing an ionic group and the segment (A2) not containing an ionic group is 5,000 or larger and 50,000 or smaller.

### Claim 9 (depends on 1)

The block copolymer according to claim 1, wherein the linker moiety connecting the segments is represented by any of the general formulae (L1) to (L7),
where, in the general formula (L1), X is an electron-withdrawing group selected from the group consisting of H, NO2, CN, CF3, Cl, Br, and I; in the general formula (L2), Y is an electron-withdrawing group selected from the group consisting of NO2, CN, CF3, Cl, Br, and I; in the general formula (L3), Z is an electron-withdrawing group selected from the group consisting of NO2, CN, CF3, Cl, Br, and I; in the general formula (L5), R is an arbitrary organic group; in the general formula (L6), Ar is an arbitrary arylene group; and in the general formula (L7), E is oxygen or sulfur; the general formulae (L1) to (L7) can each be further substituted with an electron-withdrawing group, and in the general formulae (L1) to (L7), two or more kinds of X to Z, R, Ar, and E can be used independently of each other; and the symbol * signifies a bond moiety between any of the general formulae (L1) to (L7) and other segment.

### Claim 10 (depends on 2)

A method of manufacturing the block copolymer according to claim 2, comprising at least the steps of (1) and (2) described below:
(1) introducing a linker moiety through a reaction between a linker compound and —OM group at both terminals of a segment (A1) or a segment (A2): the segment (A1) containing a constituent unit represented by the general formula (S1) described below and/or a constituent unit serving as a precursor of the constituent unit represented by the general formula (S1), and having —OM group (M is a hydrogen atom, a metal cation, or an ammonium cation) at both terminals thereof, and further containing an ionic group; the segment (A2) containing a constituent unit represented by the general formula (S2) described below and/or a constituent unit serving as a precursor of the constituent unit represented by the general formula (S2), and having —OM group (M is a hydrogen atom, a metal cation, or an ammonium cation) at both terminals thereof, and further not containing an ionic group,
(2) manufacturing a block copolymer or a precursor of the block copolymer through polymerization of linker moieties at both terminals of the segment, to which the linker moiety synthesized in the step (1) is introduced, with the —OM groups at both terminals of another segment,
where, in the general formula (S1), Ar1 to Ar4 are each an arbitrary divalent arylene group; Ar1 and/or Ar2 contains an ionic group; Ar3 and Ar4 can each contain or not contain an ionic group; Ar1 to Ar4 can each be arbitrarily substituted, in Ar1 to Ar4, two or more kinds of arylene groups can be used independently of each other; and the symbol * signifies a bond moiety with the general formula (S1) or with other constituent unit,
where, in the general formula (S2), Ar5 to Ar8 are each an arbitrary divalent arylene group; Ar5 to Ar8 can each be arbitrarily substituted, and do not contain an ionic group; in Ar5 to Ar8, two or more kinds of arylene groups can be used independently of each other; and the symbol * signifies a bond moiety with the general formula (S2) or with other constituent unit.

### Claim 11 (depends on 10)

The method of manufacturing the block copolymer according to claim 10, wherein there is used at least one kind of linker compound selected from general formulae (M1) to (M7) described below,
where, in the general formulae (M1) to (M7), W is Cl or F; in the general formula (M1), X is an electron-withdrawing group selected from the group consisting of H, NO2, CN, CF3, Cl, Br, and I; in the general formula (M2), Y is an electron-withdrawing group selected from the group consisting of NO2, CN, CF3, Cl, Br, and I; in the general formula (M3), Z is an electron-withdrawing group selected from the group consisting of NO2, CN, CF3, Cl, Br, and I; in the general formula (M5), R is an arbitrary organic group; in the general formula (M6), Ar is an arbitrary arylene group; and in the general formula (M7), E is oxygen or sulfur; the general formulae (M1) to (M7) can each further be substituted with an electron-withdrawing group, and in the general formulae (M1) to (M7), two or more kinds of X to Z, R, Ar, and E can be used independently of each other.

### Claim 12 (depends on 10)

The method of manufacturing the block copolymer according to claim 10, wherein there is used at least one kind of linker compound selected from the group consisting of formulae (M1-1), (M1-2), (M1-8), (M2-1), (M2-2), (M2-3), (M5-1), M5-4), and (M7-2) described below,

### Claim 13 (depends on 1)

A polymer electrolyte material including the block copolymer according to claim 1.

### Claim 14 (depends on 13)

A polymer electrolyte form article including the polymer electrolyte material according to claim 13.

### Claim 15 (depends on 13)

A polymer electrolyte fuel cell including the polymer electrolyte material according to claim 13.