# US 2026/0196545 A1 · Proton exchange membrane based on pvdf in the form of cryocrushed granules

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2026/0196545 A1
- Document ID: US20260196545A1
- Status: Published application
- Kind: A1
- Application number: 19/133,300
- Filed: 2023-11-28
- Published: 2026-07-09
- Earliest claimed: 2022-11-29
- Assignees: Arkema France
- Applicants: Arkema France
- Inventors: Samuel DEVISME; Helene MEHEUST; Anthony BONNET; Mauranne VASSY
- Web page: https://patentgrep.com/patent/US20260196545A1

## CPC

- H01M 8/1018: Polymeric electrolyte materials
- H01M 8/1039: halogenated, e.g. sulfonated polyvinylidene fluorides
- C08F 8/38: Sulfohalogenation
- C08J 3/28: Treatment by wave energy or particle radiation
- C08J 5/225: {containing fluorine}
- H01M 8/10: Fuel cells with solid electrolytes
- H01M 8/1058: characterised by a porous support having no ion-conducting properties
- H01M 8/1069: characterised by the manufacturing processes
- H01M 8/1088: Chemical modification, e.g. sulfonation
- C08F 2800/20: as weight or mass percentages
- C08F 2810/00: Chemical modification of a polymer
- C08J 2351/06: grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
- H01M 2008/1095: {Fuel cells with polymeric electrolytes}
- H01M 2300/0082: Organic polymers
- Y02E 60/50: Fuel cells
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention relates to a proton exchange membrane, to the process for preparing said membrane, and to the application of said membrane in fields requiring ion exchange, such as effluent purification and electrochemistry, or in energy fields. In particular, this membrane is used in the design of fuel cell membranes.

## Claims

### Claim 1

A material consisting of an irradiated PVDF in powder form to which at least one vinyl monomer is grafted, said irradiated and grafted PVDF bearing proton exchange sulfonate groups, characterized in that the tapped bulk density of said powder is greater than 0.4 g/ml, preferably between 0.5 and 1.2 g/ml.

### Claim 2 (depends on 1)

The material as claimed in claim 1, wherein said vinyl monomer is comprises a styrene monomer.

### Claim 3 (depends on 1)

The material as claimed in claim 1, wherein said vinyl monomer is comprises a nitrile monomer.

### Claim 4 (depends on 1, 2, 3)

The material of claim 1 as claimed in one of claims 1 to 3, wherein at least one vinyl monomer comprises said PVDF is grafted with a mixture of styrene and nitrile monomers, the styrene monomer/nitrile monomer molar ratio ranging from 0.7 to 1.3.

### Claim 5 (depends on 1, 2, 3, 4)

The material of claim 1 as claimed in one of claims 1 to 4, wherein the PVDF is selected from poly(vinylidene fluoride) homopolymers and copolymers of vinylidene difluoride with at least one comonomer selected from the group chosen from the list: vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, 1,1,3,3,3-pentafluoropropene, 1,2,3,3,3-pentafluoropropene, perfluoro (propyl vinyl ether), perfluoro(methyl vinyl ether), bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene, chlorotrifluoropropene, ethylene and mixtures thereof.

### Claim 6 (depends on 1, 2, 3, 4, 5)

The material of claim 1 as claimed in one of claims 1 to 5, wherein the PVDF is a vinylidene fluoride homopolymer.

### Claim 7 (depends on 1, 2, 3, 4, 5)

The material of claim 1 as claimed in one of claims 1 to 5, wherein the PVDF is a copolymer of vinylidene fluoride and hexafluoropropylene, having a weight percentage of hexafluoropropylene monomer units of from 1% to 35%, preferably from 2% to 23%, preferably from 4% to 20% by weight relative to the weight of the copolymer.

### Claim 8 (depends on 1, 2, 3, 4, 5)

The material of claim 1 as claimed in one of claims 1 to 5, wherein the PVDF is a heterogeneous thermoplastic copolymer and comprises two or more co-continuous phases, said co-continuous phases comprising:
a) from 25% to 50% by weight of a first co-continuous phase comprising 90% to 100% by weight of vinylidene fluoride monomer units and 0% to 10% by weight of units of at least one other fluorinated monomer, and
b) from more than 50% by weight to 75% by weight of a second co-continuous phase comprising from 65% to 95% by weight of vinylidene fluoride monomer units and one or more comonomers chosen selected from the group consisting of hexafluoropropylene and perfluoro (vinyl ether), to bring about the phase separation of the second co-continuous phase from the first co-continuous phase.

### Claim 9 (depends on 2, 4, 5, 6, 7, 8)

The material of claim 2 as claimed in one of claims 2 and 4 to 8, wherein said styrene monomer is chosen selected from the group: α-methylstyrene, α-fluorostyrene, α-bromostyrene, α-methoxystyrene, vinyl pentafluorostyrene, and α,β,β-trifluorostyrene and combinations thereof.

### Claim 10 (depends on 3, 4, 5, 6, 7, 8, 9)

The material of claim 3 as claimed in one of claims 3 to 9, wherein said nitrile monomer is chosen selected from the group: acrylonitrile, 2-methyl-2-butenenitrile, 2-methylene glutaronitrile, and methylacrylonitrile and combinations thereof.

### Claim 11 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10)

The material of claim 1 as claimed in one of claims 1 to 10, wherein said PVDF is grafted with α-methylstyrene and 2-methylene glutaronitrile and is functionalized with chlorosulfonic acid.

### Claim 12 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11)

The material of claim 1 as claimed in one of claims 1 to 11, wherein said powder results from ground PVDF granules having a particle size defined by a Dv50 of less than or equal to 120 μm, preferably of between 30 and 80 micrometers.

### Claim 13 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12)

A process for preparing the material of claim 1 as claimed in one of claims 1 to 12, said process comprising the grafting of an irradiated PVDF powder with at least one vinyl monomer chosen selected from styrene monomers, and nitrile monomers, or with a mixture of styrene and nitrile monomers, followed by a post-treatment of the PVDF powder thus irradiated and grafted, by sulfonation.

### Claim 14 (depends on 13)

The process of claim 13 as claimed in claim 13, comprising the following steps:
exposing said PVDF powder to ionizing radiation chosen from electron beams, gamma rays, or X-rays;
exposing the irradiated powder to at least one vinyl monomer chosen selected from styrene monomers, and nitrile monomers, or to a mixture of styrene and nitrile monomer, said styrene monomer being chosen selected from the group: α-methylstyrene, α-fluorostyrene, α-bromostyrene, α-methoxystyrene, vinyl pentafluorostyrene, and α,β,β-trifluorostyrene and combinations thereof, and wherein said nitrile monomer being chosen selected from the group: acrylonitrile, 2-methyl-2-butenenitrile, 2-methylene glutaronitrile, and methylacrylonitrile and combinations thereof;
subjecting the grafted PVDF powder to a post-functionalization reaction with chlorosulfonic acid, followed by hydrolysis in water or an alkaline solution.

### Claim 15 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12)

A process for producing a proton exchange polymer electrolyte membrane from the PVDF material of claim 1 as claimed in any one of claims 1 to 12, said process comprising converting the PVDF powder into film form.

### Claim 16 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12)

A process for producing a proton exchange polymer electrolyte membrane from a mixture of comprising the PVDF material of claim 1 as claimed in any one of claims 1 to 12 and another polymer chosen selected from: polymethyl methacrylate and copolymers thereof, fluoropolymers, polyurethanes, and polyesters, and combinations thereof; said process comprising converting said mixture into film form.

### Claim 17 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12)

A proton exchange polymer electrolyte membrane, said membrane consisting of a film obtained from the PVDF material of claim 1 as claimed in any one of claims 1 to 12.

### Claim 18 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12)

A proton exchange polymer composite membrane, said membrane consisting of a porous support impregnated with the PVDF material of claim 1 as claimed in any one of claims 1 to 12 by the solvent and/or aqueous route, said porous support being a polymer chosen selected from: polymethyl methacrylate and copolymers thereof, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), fluoropolymers, polyurethanes, polyesters, poly(vinylidene fluoride) (PVDF), polysulfone (PSU), polyethersulfone (PESU), polyimide (PI), and the family of the polyaryletherketones (PAEK), such as PEEK or PEKK and combinations thereof.

### Claim 19 (depends on 17, 18)

The membrane of claim 17 as claimed in one of claims 17 and 18, having an ion exchange capacity (IEC) of greater than 0.65 mmol/g, preferably of greater than 0.7 mmol/g, as measured by titration with a 0.05 M KOH solution.

### Claim 20 (depends on 17, 18, 19)

A fuel cell comprising the membrane of claim 17 a membrane as defined in one of claims 17 to 19.