# US 2019/0169420 A1 · Block copolymer, multilayer structure, solid polymer film, fuel cell, production method for multilayer structure, and production method for multilayer structure containing inorganic nanoparticles

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- Number: US 2019/0169420 A1
- Document ID: US20190169420A1
- Status: Published application
- Kind: A1
- Application number: 16/321,083
- Filed: 2017-08-01
- Published: 2019-06-06
- Earliest claimed: 2016-08-05
- Assignees: Japan Science and Technology Agency
- Applicants: Japan Science and Technology Agency
- Inventors: Hiroshi YABU
- Web page: https://patentgrep.com/patent/US20190169420A1

## CPC

- C08F 212/22: {Oxygen}
- C08F 8/12: Hydrolysis
- C08F 212/24: {Phenols or alcohols}
- C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent}
- C08J 7/043: Improving the adhesiveness of the coatings per se, e.g. forming primers (adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50)
- C08J 7/06: with compositions not containing macromolecular substances
- C08L 53/005: {Modified block copolymers}
- H01M 8/02: Details (electrodes H01M4/86 - H01M4/98)
- H01M 8/0228: in the form of layered or coated products
- H01M 8/10: Fuel cells with solid electrolytes
- H01M 8/1004: characterised by membrane-electrode assemblies [MEA] (H01M8/12 takes precedence)
- H01M 8/1025: having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
- H01M 8/103: having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
- H01M 8/1053: consisting of layers of polymers with at least one layer being ionically conductive
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C08F 299/022: {from polycondensates with side or terminal unsaturations}
- C08F 2438/03: Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
- C08J 2323/02: not modified by chemical after treatment
- C08J 2325/06: Polystyrene
- C09D 153/00: Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- H01M 8/0221: Organic resins; Organic polymers
- H01M 2008/1095: {Fuel cells with polymeric electrolytes}
- Y02E 60/50: Fuel cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED 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)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- 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

The problem addressed by the present invention is to provide a block copolymer that can be used in a neutral solvent atmosphere and can produce a solid polymer membrane including nanoparticles. The problem is solved by a block copolymer represented by formula (1) below. wherein in the formula, R1 represents a C1-20 linear, branched, or cyclic alkyl group, C6-20 aryl group, or C7-20 aralkyl group; R2 represents a group having a functional group having an acid dissociation constant pKa of from 0.5 to 7; R3, R4, and R5 each show H or a C1-20 linear, branched, or cyclic alkyl group; R6, R7, and R8 each represent a hydrogen, hydroxyl group, nitro group, carboxy group, or carbonyl group; X represents an amide or ester, but may not be included; Y represents an amide or ester, but may not be included; p represents an integer of 1-10, but may not be included; n represents an integer of 3-1000; m represents an integer of 3-1000; and t represents an integer of 3-1000, but n may not be included; the arrangement of n, m, and t is arbitrary, but n and m are adjacent when n is included.

## Claims

### Claim at position 1

1: A block copolymer represented by formula (1) below.
wherein in the formula, R1 represents a C1-20 linear, branched, or cyclic alkyl group, C6-20 aryl group, or C7-20 aralkyl group; R2 represents a group having a functional group having an acid dissociation constant pKa of from 0.5 to 7; R3, R4, and R5 each show H or a C1-20 linear, branched, or cyclic alkyl group; R6, R7, and R8 each represent a hydrogen, hydroxyl group, nitro group, carboxy group, or carbonyl group; X represents an amide or ester, but may not be included; Y represents an amide or ester, but may not be included; p represents an integer of 1-10, but may not be included; n represents an integer of 3-1000; m represents an integer of 3-1000; and t represents an integer of 3-1000, but n may not be included; the arrangement of n, m, and t is arbitrary, but n and m are adjacent when n is included.

### Claim at position 2 (depends on 1)

2: The block copolymer according to claim 1, wherein m, n, and t are such that m+n/m+n+t=0.2-0.8.

### Claim at position 3 (depends on 1)

3: The block copolymer according to claim 1, wherein n is included.

### Claim at position 4 (depends on 1)

4: A multilayered structure wherein the hydrophilic segments represented by m and n and the hydrophobic segment represented by t of the block copolymer according to claim 1 have a microlayer-separated layer structure.

### Claim at position 5 (depends on 4)

5: The multilayered structure according to claim 4, wherein a thickness of the multilayered structure is from 20 nm to 500 nm.

### Claim at position 6 (depends on 4)

6: The multilayered structure according to claim 4, wherein the microlayers having hydrophilic segments include inorganic nanoparticles.

### Claim at position 7 (depends on 6)

7: The multilayered structure according to claim 6, wherein the hydrophilic segments include a catechol group and quinone.

### Claim at position 8 (depends on 6)

8: A solid polymer membrane for a separator of a fuel cell including the multilayered structure according to claim 6.

### Claim at position 9 (depends on 8)

9: A fuel cell including the solid polymer membrane according to claim 8, an anode electrode, and a cathode electrode.

### Claim at position 10

10: A method for producing a multilayered structure including
a step that dissolves a block copolymer represented by formula (1) below in an organic solvent to prepare a block copolymer solution,
a casting step that casts the block copolymer solution,
a multilayered structure production step that produces the multilayered structure in which hydrophilic segments represented by m and n and hydrophobic segment represented by t of the block copolymer are microlayer-separated by evaporating off the solvent of the cast block copolymer solution.
wherein in the formula, R1 represents a C1-20 linear, branched, or cyclic alkyl group, C6-20 aryl group, or C7-20 aralkyl group; R2 represents a group having a functional group having an acid dissociation constant pKa of from 0.5 to 7; R3, R4, and R5 each show H or a C1-20 linear, branched, or cyclic alkyl group; R6, R7, and R8 each represent a hydrogen, hydroxyl group, nitro group, carboxy group, or carbonyl group; X represents an amide or ester, but may not be included; Y represents an amide or ester, but may not be included; p represents an integer of 1-10, but may not be included; n represents an integer of 3-1000; m represents an integer of 3-1000; and t represents an integer of 3-1000, but n may not be included; the arrangement of n, m, and t is arbitrary, but n and m are adjacent when n is included.

### Claim at position 11 (depends on 10)

11: The method for producing the multilayered structure according to claim 10, wherein n is included.

### Claim at position 12 (depends on 10)

12: A method for producing a multilayered structure including inorganic nanoparticles that includes
an immersion step for immersing a multilayered structure produced by the production method according to claim 10 in a solution that includes an inorganic ion,
an inorganic nanoparticle production step in which the inorganic ion is reduced by the catechol groups of segments represented by m of the multilayered structure and inorganic nanoparticles are produced in microlayers that include segments represented by m.

### Claim at position 13

13: A block copolymer including
a hydrophilic segment including a catechol group,
a hydrophobic segment including a substitution more hydrophobic than the hydrophilic segment including a catechol group,
and,
included as needed, a hydrophilic segment including a functional group having an acid dissociation constant pKa of from 0.5 to 7,
in which the hydrophilic segment including the functional group having an acid dissociation constant pKa of from 0.5 to 7, when included, is adjacent to the hydrophilic segment including the catechol group.

### Claim at position 14 (depends on 13)

14: The block copolymer according to claim 13, wherein the hydrophilic segment including the functional group having the acid dissociation constant pKa of from 0.5 to 7 is included.

### Claim at position 15 (depends on 13)

15: A multilayered structure in which the hydrophilic segments and hydrophobic segments of the block copolymer according to claim 13 have a microlayer-separated layer structure.

### Claim at position 16 (depends on 15)

16: The multilayered structure according to claim 15, wherein a thickness of the multilayered structure is from 20 nm to 500 nm.

### Claim at position 17 (depends on 15)

17: The multilayered structure according to claim 15, wherein microlayers having hydrophilic segments include inorganic nanoparticles.

### Claim at position 18 (depends on 17)

18: The multilayered structure according to claim 17, wherein the hydrophilic segments include a catechol group and quinone.

### Claim at position 19 (depends on 15)

19: A solid polymer membrane for a separator of a fuel cell including the multilayered structure according to claim 15.

### Claim at position 20 (depends on 19)

20: A fuel cell including the solid polymer membrane according to claim 19, an anode electrode, and a cathode electrode.

### Claim at position 21 (depends on 3)

21: The block copolymer according to claim 3, wherein the acid dissociation constant pKa is from 0.5 to 4 and R2 does not include a catechol group.

### Claim at position 22 (depends on 21)

22: A multilayered structure wherein the hydrophilic segments represented by m and n and the hydrophobic segment represented by t of the block copolymer according to claim 21 have a microlayer-separated layer structure.

### Claim at position 23 (depends on 22)

23: The multilayered structure according to claim 22, wherein the microlayers having hydrophilic segments include inorganic nanoparticles.

### Claim at position 24 (depends on 23)

24: A solid polymer membrane for a separator of a fuel cell including the multilayered structure according to claim 23.

### Claim at position 25 (depends on 24)

25: A fuel cell including the solid polymer membrane according to claim 24, an anode electrode, and a cathode electrode.

### Claim at position 26 (depends on 11)

26: The method for producing the multilayered structure according to claim 11, wherein the acid dissociation constant pKa is from 0.5 to 4 and R2 does not include a catechol group.

### Claim at position 27 (depends on 26)

27: A method for producing a multilayered structure including inorganic nanoparticles that includes
an immersion step for immersing a multilayered structure produced by the production method according to claim 26 in a solution that includes an inorganic ion,
an inorganic nanoparticle production step in which the inorganic ion is reduced by the catechol groups of segments represented by m of the multilayered structure and inorganic nanoparticles are produced in microlayers that include segments represented by m.