# US 2014/0154610 A1 · Aromatic copolymer having proton conductive group and uses thereof

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- Number: US 2014/0154610 A1
- Document ID: US20140154610A1
- Status: Published application
- Kind: A1
- Application number: 14/235,656
- Filed: 2012-07-27
- Published: 2014-06-05
- Earliest claimed: 2011-07-29
- Assignees: Jsr Corporation
- Inventors: Takuya Murakami; Toshiaki Kadota; Yoshitaka Yamakawa
- Web page: https://patentgrep.com/patent/US20140154610A1

## CPC

- H01M 8/1023: having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
- C08G 61/12: Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G 61/126: {with a five-membered ring containing one sulfur atom in the ring}
- C08G 65/4006: {(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)}
- 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 8/1025: having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
- H01M 8/1027: having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
- C08G 2261/1428: containing acyl groups
- C08G 2261/143: Side-chains containing nitrogen
- C08G 2261/1452: containing sulfonyl or sulfonate-groups
- C08G 2261/312: Non-condensed aromatic systems, e.g. benzene
- C08G 2261/344: containing heteroatoms
- C08G 2261/412: Yamamoto reactions
- C08G 2261/516: ion-conductive
- H01M 2008/1095: {Fuel cells with polymeric electrolytes}
- Y02E 60/50: Fuel cells
- 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

## Abstract

An aromatic copolymer comprises a hydrophilic segment (A) and a hydrophobic segment (B), wherein the hydrophilic segment (A) comprises a structural unit (1) having a proton conductive group, and the hydrophobic segment (B) comprises at least one structural unit selected from the group consisting of a structural unit (2) and a structural unit (3), wherein the structural unit (2) is a divalent structural unit having an aromatic ring and no proton conductive groups and having two bonding sites at the para-position of one ring included in the aromatic ring, and the structural unit (3) is a divalent structural unit having a benzene ring and is a structural unit different from the structural unit (2), the hydrophobic segment (B) in its entirety contained in the aromatic copolymer including both the structural unit (2) and the structural unit (3).

## Claims

### Claim 1

An aromatic copolymer comprising a hydrophilic segment (A) and a hydrophobic segment (B), wherein
the hydrophilic segment (A) comprises a structural unit (1) having a proton conductive group, and
the hydrophobic segment (B) comprises at least one structural unit selected from the group consisting of a structural unit (2) and a structural unit (3),
wherein the structural unit (2) is a divalent structural unit having an aromatic ring and no proton conductive groups and having two bonding sites at the para-position of one ring included in the aromatic ring, and
the structural unit (3) is a divalent structural unit having a benzene ring and is a structural unit different from the structural unit (2),
the hydrophobic segment (B) in its entirety contained in the aromatic copolymer comprising both the structural unit (2) and the structural unit (3).

### Claim 2 (depends on 1)

The aromatic copolymer of claim 1, wherein the structural unit (2) is represented by formula (2),
wherein a replaceable carbon atom constituting an aromatic ring may be replaced with a nitrogen atom,
R21 is independently a halogen atom, a hydroxyl group, a nitro group, a nitrile group or R22-E- where E is a direct bond, —O—, —S—, —CO—, —SO2—, —CONH—, —COO—, —CF2—, —CH2—, —C(CF3)2—, or —C(CH3)2—, and R22 is an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a halogenated aryl group or a nitrogen-containing heterocyclic ring, wherein a hydrogen atom of these groups may be replaced with at least one group selected from the group consisting of a hydroxyl group, a nitro group, a nitrile group and R22-E-, and multiple R21 s may be bonded to one another to form a ring structure,
c1 and c2 are each independently an integer of 0, or 1 or greater,
d is an integer of 1 or greater, and
e is independently an integer of 0 to (2c1+2c2+4).

### Claim 3 (depends on 1)

The aromatic copolymer of claim 1, wherein the structural unit (3) is at least one structural unit selected from the group consisting of a structural unit represented by formula (3a) and a structural unit represented by formula (3b),
wherein a replaceable carbon atom constituting an aromatic ring may be replaced with a nitrogen atom,
R31 is independently a halogen atom, a hydroxyl group, a nitro group, a nitrile group, a proton conductive group, or R22-E- where E is a direct bond, —O—, —S—, —CO—, —SO2—, —CONH—, —COO—, —CF2—, —CH2—, —C(CF3)2—, or —C(CH3)2—, and R22 is an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, a halogenated aryl group or a nitrogen-containing heterocyclic ring, wherein a hydrogen atom of these groups may be replaced with at least one group selected from the group consisting of a hydroxyl group, a nitro group, a nitrile group and R22-E-, and multiple R31s may be bonded to one another to form a ring structure,
f is an integer of 0, or 1 or greater, and
g is an integer of 0 to (2f+4); and
wherein A and D are each independently a direct bond, —O—, —S—, —CO—, —SO2—, —SO—, —CONH—, —COO—, —(CF2)i— where i is an integer of 1 to 10, —(CH2)j— where j is an integer of 1 to 10, —CR′2— where R′ is an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a halogenated hydrocarbon group, a cyclohexylidene group, or a fluorenyl idene group,
B is independently an oxygen atom or a sulfur atom,
R1 to R16 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a nitrite group, a proton conductive group, or R22-E- where E and R22 are each independently defined as in formula (3a); and multiple groups of R1 to R16 may be bonded to one another to form a ring structure,
s and t are each independently an integer of 0 to 4, and
r is an integer of 0, or 1 or greater.

### Claim 4 (depends on 1)

The aromatic copolymer of claim 1, wherein the hydrophobic segment (B) comprises the structural unit (2) and the structural unit (3), and the structural unit (3) is a structural unit represented by the formula (3a).

### Claim 5 (depends on 1)

The aromatic copolymer of claim 1, wherein the structural unit (1) is a divalent structural unit having a proton conductive group and an aromatic ring and having two bonding sites, wherein the two bonding sites are bonded to one aromatic ring, or one of the two bonding sites is bonded to one aromatic ring (a) and the other bonding site is bonded to an aromatic ring (b) that is bonded to the aromatic ring (a) via a single bond or via at least one aromatic ring.

### Claim 6 (depends on 1)

The aromatic copolymer of claim 1, wherein the structural unit (1) is represented by formula (1),
wherein Ar11, Ar12 and Ar13 are each independently a benzene ring, a condensed aromatic ring, or an aromatic group having a nitrogen-containing heterocyclic ring, which may be substituted by a halogen atom, a C1-20 monovalent hydrocarbon group or a C1-20 monovalent halogenated hydrocarbon group,
Y and Z are each independently a direct bond, —O—, —S—, —CO—, —SO2—, —SO—, —(CH2)u—, —(CF2)u— where u is an integer of 1 to 10, —C(CH3)2—, or —C(CF3)2—,
R17 is independently a direct bond, —O(CH2)p—, —O(CF2)p—, —(CH2)p— or —(CF2)p— where p is an integer of 1 to 12,
R18 and R19 are each independently a hydrogen atom or a protective group, wherein at least one of all R18s and R19s which are contained in the structural unit (1) is a hydrogen atom,
x1 is independently an integer of 0 to 6,
x2 is an integer of 1 to 7,
a is 0 or 1, and
b is an integer of 0 to 20.

### Claim 7 (depends on 1)

The aromatic copolymer of claim 1, wherein the hydrophobic segment (B) is a segment in which the structural unit (2) is randomly copolymerized with the structural unit (3).

### Claim 8 (depends on 1)

The aromatic copolymer of claim 1, comprising the structural unit (2) in an amount of 33 to 99 wt %, provided that a total content of the structural units (2) and (3) is 100 wt %.

### Claim 9 (depends on 1)

A polymer electrolyte membrane comprising the aromatic copolymer of claim 1.

### Claim 10 (depends on 9)

A membrane-electrode assembly comprising a gas diffusion layer, a catalyst layer, the polymer electrolyte membrane of claim 9, a catalyst layer and a gas diffusion layer that are laminated in this order.

### Claim 11 (depends on 10)

A polymer electrolyte fuel cell comprising the membrane-electrode assembly of claim 10.

### Claim 12 (depends on 2)

The aromatic copolymer of claim 2, wherein the hydrophobic segment (B) comprises the structural unit (2) and the structural unit (3), and the structural unit (3) is a structural unit represented by the formula (3a).

### Claim 13 (depends on 3)

The aromatic copolymer of claim 3, wherein the hydrophobic segment (B) comprises the structural unit (2) and the structural unit (3), and the structural unit (3) is a structural unit represented by the formula (3a).

### Claim 14 (depends on 2)

The aromatic copolymer of claim 2, wherein the hydrophobic segment (B) is a segment in which the structural unit (2) is randomly copolymerized with the structural unit (3).

### Claim 15 (depends on 3)

The aromatic copolymer of claim 3, wherein the hydrophobic segment (B) is a segment in which the structural unit (2) is randomly copolymerized with the structural unit (3).

### Claim 16 (depends on 4)

The aromatic copolymer of claim 4, wherein the hydrophobic segment (B) is a segment in which the structural unit (2) is randomly copolymerized with the structural unit (3).

### Claim 17 (depends on 5)

The aromatic copolymer of claim 5, wherein the hydrophobic segment (B) is a segment in which the structural unit (2) is randomly copolymerized with the structural unit (3).

### Claim 18 (depends on 6)

The aromatic copolymer of claim 6, wherein the hydrophobic segment (B) is a segment in which the structural unit (2) is randomly copolymerized with the structural unit (3).

### Claim 19 (depends on 2)

The aromatic copolymer of claim 2, comprising the structural unit (2) in an amount of 33 to 99 wt %, provided that a total content of the structural units (2) and (3) is 100 wt %.

### Claim 20 (depends on 3)

The aromatic copolymer of claim 3, comprising the structural unit (2) in an amount of 33 to 99 wt %, provided that a total content of the structural units (2) and (3) is 100 wt %.

### Claim 21 (depends on 4)

The aromatic copolymer of claim 4, comprising the structural unit (2) in an amount of 33 to 99 wt %, provided that a total content of the structural units (2) and (3) is 100 wt %.

### Claim 22 (depends on 5)

The aromatic copolymer of claim 5, comprising the structural unit (2) in an amount of 33 to 99 wt %, provided that a total content of the structural units (2) and (3) is 100 wt %.

### Claim 23 (depends on 6)

The aromatic copolymer of claim 6, comprising the structural unit (2) in an amount of 33 to 99 wt %, provided that a total content of the structural units (2) and (3) is 100 wt %.