EP4649102A1 - Reinforced anion exchnage membranes and methods of making same - Google Patents

Reinforced anion exchnage membranes and methods of making same

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Publication number
EP4649102A1
EP4649102A1 EP24742086.2A EP24742086A EP4649102A1 EP 4649102 A1 EP4649102 A1 EP 4649102A1 EP 24742086 A EP24742086 A EP 24742086A EP 4649102 A1 EP4649102 A1 EP 4649102A1
Authority
EP
European Patent Office
Prior art keywords
anion exchange
combinations
exchange membrane
group
reinforced
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24742086.2A
Other languages
German (de)
French (fr)
Inventor
Chulsung Bae
Jong Yeob Jeon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Orion Polymer Corp
Original Assignee
Orion Polymer Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/US2023/012399 external-priority patent/WO2023150341A2/en
Application filed by Orion Polymer Corp filed Critical Orion Polymer Corp
Publication of EP4649102A1 publication Critical patent/EP4649102A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2225—Synthetic macromolecular compounds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2287—After-treatment
    • C08J5/2293—After-treatment of fluorine-containing membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • AEMs are key components for electrochemical energy conversion devices such as fuel cells, electrolyzers, and flow batteries. The membranes transport anions between electrodes while preventing reactants from inter-mixing.
  • the membranes should have low ionic resistance, long-term durability, and good mechanical properties.
  • Conventional AEM materials include aryl ether containing polyaromatic electrolytes because of their beneficial mechanical properties.
  • the aryl ether group in the polymer provides flexibility into the rigid polyaromatic structure and this provides great strength to AEMs.
  • the aryl ether groups are not chemically stable under high pH conditions owing to aryl ether cleavage reactions of quaternized polyaromatics, and this deteriorates membrane long-term durability.
  • Other polymers have been developed for this purpose.
  • the present disclosure provides a reinforced anion exchange membrane prepared by impregnating an ionic polymer into a porous membrane substrate, wherein the impregnating polymer is an aryl ether-free polyaromatic polymer having a random copolymer architecture with two or more aromatic ring components.
  • the copolymer can be non-crosslinked or crosslinked. The latter can help to confine the polymer in the pores of the porous substrate, preventing polymer leaching.
  • the reinforced anion exchange membrane may be useful for electrochemical energy conversion devices, e.g., AEM fuel cells, AEM electrolyzers, and flow batteries.
  • the porous membrane substrates may be highly porous and thin films having a continuous porous structure from one side to the other side.
  • the porous substrates are hydrophobic, and do not swell in water.
  • the porous substrate is made from a material that preferably comprises high molecular weight polyethylene, ultrahigh molecular weight polyethylene, polytetrafluoroethylene, expanded polytetrafluoroethylene, polypropylene, and combinations thereof.
  • the porous membrane substrate is not greater than about 200 microns in thickness.
  • Some embodiments of the present disclosure include a novel method of making reinforced anion exchange membranes.
  • the method comprises reacting two or more aromatic compounds and a trifluoromethyl ketone compound under acidic condition to produce an aryl ether-free polyaromatic polymer having random copolymer architecture with two, or more aromatic ring components; reacting the polymer with an amine to form an ionic polymer; dissolving the ionic polymer in a solvent to make a polymeric solution; and impregnating a porous membrane substrate with the polymeric solution to form a reinforced anion exchange membrane BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG.1 shows an illustration of a method for a reinforced anion exchange membrane according to some embodiments of the invention DESCRIPTION
  • Some embodiments of the present disclosure include reinforced anion exchange membranes prepared by impregnating an ionic polymer into a porous membrane substrate, wherein the impregnating polymer is an aryl ether-free polyaromatic polymer based
  • the polymer can be non-crosslinked or crosslinked, the latter to confine the polymer in the pores of the porous membrane substrate preventing the reinforced anion exchange membrane from leaching of the impregnated copolymer during operation in water.
  • the reinforced anion exchange membrane may be useful for electrochemical energy conversion devices, e.g., AEM fuel cells, AEM electrolyzers, and flow batteries.
  • the impregnated membranes of the present disclosure provide significantly improved mechanical (e.g. tensile) strength, chemical durability, and water management characteristics when compared to impregnated membranes that are currently available.
  • the impregnated ionic polymer has the following formula I: ... random copolymers, wherein Arn is 2 to 20, wherein each of a1, a2, a3, ... and an is, independently, 1 to 1,000,000, wherein R1, R2, R3, ... and Rn, wherein Rn is 2 to 20, include
  • A’ includes N, an alkyl group, or combinations thereof;
  • X includes a halide, e.g., Br;
  • FG’ includes NR 2 + X – , NR 2 + OH – ;
  • R is an alkyl group, e.g., CH 3 or CH 2 CH 3 ;
  • m is from 0 to 20;
  • R includes an alkyl group, e.g., CH3 or CH2CH3, a halide, e.g., F, or combinations thereof;
  • R' includes H, an alkyl group, e.g., CH 3 or CH 2 CH 3 , or combinations thereof;
  • X includes a halide;
  • A includes S, O, NH, SO 2 , an alkyl group, e.g., CH 2 or CH 2 CH 3 , or combinations thereof; and n is from 0 to 20.
  • the ionic polymer having two or more aromatic rings components is contained in the pores of a porous membrane substrate.
  • the porous substrates may be highly porous and thin films having a continuous porous structure from one side to the other side.
  • the porous substrates are hydrophobic, and it doesn’t swell in water.
  • the porous substrate preferably comprises a material selected from high molecular weight polyethylene, ultrahigh molecular weight polyethylene, polytetrafluoroethylene, expanded polytetrafluoroethylene, or polypropylene.
  • the porous substrate is preferably not greater than about 200 microns in thickness, more preferably less than about 50 microns.
  • the porous substrate has porosity greater than 30%, preferably greater than 70%.
  • Preferred substrate membranes have a pore size of from 0.05 micron to 1.0 microns.
  • the pore-filled reinforced membrane contains the ionic polymer greater than 30 wt.%, preferably greater than 70 wt.%.
  • Some embodiments of the present disclosure include novel methods of making the reinforced anion exchange membranes. The method comprises reacting two or more aromatic compounds and a trifluoromethyl ketone compound under acidic conditions to produce aryl ether-free polyaromatic based on random copolymer architecture with two or more aromatic ring components; reacting the polyaromatic with an amine to form an ionic polymer; dissolving the ionic polymer in a solvent to make a polymeric solution; and impregnating a porous membrane substrate with the polymeric solution to form a reinforced anion exchange membrane.
  • the R1, R2, R3, ... or Rn are partially crosslinked by a crosslinking agent selected from a group consisting of: multi- amines or combinations thereof, wherein R include H, an alkyl group, such as for example, CH3 or CH2CH3, or combinations thereof; and n is from 0 to 20.
  • the copolymer has a degree of crosslinking of from 0% to 100%, or any subranges therebetween. The crosslinking reaction takes place in the pores of the porous substrate to confine the copolymer in the pores preventing the reinforced anion exchange membrane from leaching of the impregnated copolymer during operations.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

High performing anion exchange membranes having high mechanical properties and novel process for their manufacture are described herein. The membranes are useful for application of fuel cells or electrolyzers due to their low ionic resistance and high durability in alkaline conditions. The membranes are made by preparing an ionic polymer with two or more aromatic monomers and a trifluoromethyl ketone compound: and impregnating a porous membrane substrate with the ionic polymer. The novel process for the reinforced anion exchange membranes allows the membranes significantly thinner and more dimensionally stable in water than prior art commercial membranes

Description

REINFORCED ANION EXCHNAGE MEMBRANES AND METHODS OF MAKING SAME BACKGROUND 1. Field of the Disclosure The present disclosure provides an anion exchange membrane that is reinforced with a porous polymer support. More particularly, the present disclosure provides an anion exchange membrane that is impregnated with an aryl ether-free polyaromatic polymer having a random copolymer architecture with two or more aromatic ring components. 2. Discussion of the Related Art Anion exchange membranes (AEMs) are key components for electrochemical energy conversion devices such as fuel cells, electrolyzers, and flow batteries. The membranes transport anions between electrodes while preventing reactants from inter-mixing. For better performance of the devices, the membranes should have low ionic resistance, long-term durability, and good mechanical properties. Conventional AEM materials include aryl ether containing polyaromatic electrolytes because of their beneficial mechanical properties. The aryl ether group in the polymer provides flexibility into the rigid polyaromatic structure and this provides great strength to AEMs. However, the aryl ether groups are not chemically stable under high pH conditions owing to aryl ether cleavage reactions of quaternized polyaromatics, and this deteriorates membrane long-term durability. Other polymers have been developed for this purpose. (US 10,435,504, US11,040,339) Regarding ionic resistance of AEMs, membranes with higher ion exchange capacity (IEC) usually show higher anion conductivity and low ionic resistance. However, the high IEC can also cause flooding in the membrane, deteriorating its mechanical properties in high relative humidity conditions. Because of this problem with desirable property trade-offs, a lot of reinforcement methods have been developed for ion exchange membranes to possess good mechanical properties and high IEC, simultaneously. The reinforcement methods include forming composite membranes with additive fillers, pore-filled membranes, and crosslinking with additives or between polymers in the pores of support. SUMMARY The present disclosure provides a reinforced anion exchange membrane prepared by impregnating an ionic polymer into a porous membrane substrate, wherein the impregnating polymer is an aryl ether-free polyaromatic polymer having a random copolymer architecture with two or more aromatic ring components. The copolymer can be non-crosslinked or crosslinked. The latter can help to confine the polymer in the pores of the porous substrate, preventing polymer leaching. The reinforced anion exchange membrane may be useful for electrochemical energy conversion devices, e.g., AEM fuel cells, AEM electrolyzers, and flow batteries. Membranes impregnated with random copolymers using two or more different aromatic monomers employed for the aryl ether group-free quaternized polyaromatics do not currently exist. In some embodiments, the porous membrane substrates may be highly porous and thin films having a continuous porous structure from one side to the other side. The porous substrates are hydrophobic, and do not swell in water. The porous substrate is made from a material that preferably comprises high molecular weight polyethylene, ultrahigh molecular weight polyethylene, polytetrafluoroethylene, expanded polytetrafluoroethylene, polypropylene, and combinations thereof. The porous membrane substrate is not greater than about 200 microns in thickness. Some embodiments of the present disclosure include a novel method of making reinforced anion exchange membranes. The method comprises reacting two or more aromatic compounds and a trifluoromethyl ketone compound under acidic condition to produce an aryl ether-free polyaromatic polymer having random copolymer architecture with two, or more aromatic ring components; reacting the polymer with an amine to form an ionic polymer; dissolving the ionic polymer in a solvent to make a polymeric solution; and impregnating a porous membrane substrate with the polymeric solution to form a reinforced anion exchange membrane BRIEF DESCRIPTION OF THE DRAWINGS FIG.1 shows an illustration of a method for a reinforced anion exchange membrane according to some embodiments of the invention DESCRIPTION Some embodiments of the present disclosure include reinforced anion exchange membranes prepared by impregnating an ionic polymer into a porous membrane substrate, wherein the impregnating polymer is an aryl ether-free polyaromatic polymer based on random copolymer architecture with two or more aromatic ring components. The polymer can be non-crosslinked or crosslinked, the latter to confine the polymer in the pores of the porous membrane substrate preventing the reinforced anion exchange membrane from leaching of the impregnated copolymer during operation in water. The reinforced anion exchange membrane may be useful for electrochemical energy conversion devices, e.g., AEM fuel cells, AEM electrolyzers, and flow batteries. The impregnated membranes of the present disclosure provide significantly improved mechanical (e.g. tensile) strength, chemical durability, and water management characteristics when compared to impregnated membranes that are currently available. In some embodiments, the impregnated ionic polymer has the following formula I: … random copolymers, wherein Arn is 2 to 20, wherein each of a1, a2, a3, … and an is, independently, 1 to 1,000,000, wherein R1, R2, R3, … and Rn, wherein Rn is 2 to 20, include
, or com natons tereo, weren ncues , , , 2, an a y group, or com natons tereof; A’ includes N, an alkyl group, or combinations thereof; X includes a halide, e.g., Br; FG includes NR3 + X–, NR3 + OH–, OH, NR2, SO3H, P(=O)(OH)2, CO2H, SO3 – M+, P(=O)(O–)22M+, CO2 – M+(M = Li, Na, K), linear multi-quaternary ammonium groups, branched multi-quaternary ammonium groups, or combinations thereof; FG’ includes NR2 + X–, NR2 + OH–; R is an alkyl group, e.g., CH3 or CH2CH3; m is from 0 to 20; and n is from 0 to 20. In one embodiment, a “random copolymer” is one that is composed of two or more different monomers with a completely random sequence of repeat units. In some embodiments, Ar1, Ar2, Ar3, … and Arn can be
, or combinations thereof, wherein R includes an alkyl group, e.g., CH3 or CH2CH3, a halide, e.g., F, or combinations thereof; R' includes H, an alkyl group, e.g., CH3 or CH2CH3, or combinations thereof; X includes a halide; A includes S, O, NH, SO2, an alkyl group, e.g., CH2 or CH2CH3, or combinations thereof; and n is from 0 to 20. The ionic polymer having two or more aromatic rings components is contained in the pores of a porous membrane substrate. In some embodiments, the porous substrates may be highly porous and thin films having a continuous porous structure from one side to the other side. The porous substrates are hydrophobic, and it doesn’t swell in water. The porous substrate preferably comprises a material selected from high molecular weight polyethylene, ultrahigh molecular weight polyethylene, polytetrafluoroethylene, expanded polytetrafluoroethylene, or polypropylene. The porous substrate is preferably not greater than about 200 microns in thickness, more preferably less than about 50 microns. In some embodiments, the porous substrate has porosity greater than 30%, preferably greater than 70%. Preferred substrate membranes have a pore size of from 0.05 micron to 1.0 microns. In some embodiments, the pore-filled reinforced membrane contains the ionic polymer greater than 30 wt.%, preferably greater than 70 wt.%. Some embodiments of the present disclosure include novel methods of making the reinforced anion exchange membranes. The method comprises reacting two or more aromatic compounds and a trifluoromethyl ketone compound under acidic conditions to produce aryl ether-free polyaromatic based on random copolymer architecture with two or more aromatic ring components; reacting the polyaromatic with an amine to form an ionic polymer; dissolving the ionic polymer in a solvent to make a polymeric solution; and impregnating a porous membrane substrate with the polymeric solution to form a reinforced anion exchange membrane. In some embodiments, the R1, R2, R3, … or Rn are partially crosslinked by a crosslinking agent selected from a group consisting of: multi- amines or combinations thereof, wherein R include H, an alkyl group, such as for example, CH3 or CH2CH3, or combinations thereof; and n is from 0 to 20. In some embodiments the copolymer has a degree of crosslinking of from 0% to 100%, or any subranges therebetween. The crosslinking reaction takes place in the pores of the porous substrate to confine the copolymer in the pores preventing the reinforced anion exchange membrane from leaching of the impregnated copolymer during operations.

Claims

CLAIMS 1. A method of making a reinforced anion exchange membrane, comprising: reacting two or more aromatic compounds and a trifluoromethyl ketone compound under acidic condition to produce a precursor copolymer; reacting the precursor copolymer with an amine to form an ionic polymer; dissolving the ionic polymer in a solvent to make a polymeric solution; and impregnating a porous membrane substrate with the polymeric solution to form a reinforced anion exchange membrane. 2. The method of claim 1, wherein the aromatic compounds are selected from the group consisting of: , and combinations thereof, wherein R includes an alkyl group, e.g., CH3 or CH2CH3, a halide, e.g., F, or combinations thereof; R' includes H, an alkyl group, e.g., CH3 or CH2CH3, or combinations thereof; X includes a halide; A includes S, O, NH, SO2, an alkyl group, e.g., CH2 or CH2CH3, and combinations thereof; and n is from 0 to 20. 3. The method of claim 1, wherein the trifluoromethyl ketone compound is selected from the group consisting of: O (CH 2 ) n CH 3 F3C F3C F3C , n X n n , , thereof; A’ includes N, an alkyl group, or combinations thereof; X includes a halide, e.g., Br; and n is from 0 to 20. 4. The method of claim 1, wherein the amine is selected from the group consisting of: trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, tripentylamine, trihexylamine, N,N-diisopropylmethylamine, N-isopropyl-N-methyl-tert-butylamine, N- methylpiperidine, N-methylpyrrolidine, 1-ethylpyrrolidine, 1-butylpyrrolidine, 1,2,2,6,6- pentamethylpiperidine, diamines, multi-amines and combinations thereof. 5. The method of claim 1, wherein the solvent is selected from a group consisting of toluene, tetrahydrofuran, dichloromethane, chloroform, chlorobenzene, 1,2-dichlorobenzene, 1,3- dichlorobenzene, nitrobenzene, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N- methyl-2-pyrrolidone, methanol, ethanol, 1-propanol, 2-propanol, or combinations thereof 6. The method of claim 1, wherein the porous membrane substrate comprises a polymer selected from a group consisting of high molecular weight polyethylene, ultrahigh molecular weight polyethylene, polytetrafluoroethylene, expanded polytetrafluoroethylene, polypropylene or combinations thereof.
7. The method of claim 1, wherein thickness of the porous membrane substrate is less than about 200 microns. 8. The method of claim 1, wherein thickness of the porous membrane substrate is about 10 - 50 microns. 9. The method of claim 1, wherein the ionic copolymer is according to Formula I: wherein Ar1, Arn are different aryl groups to form random copolymers, and are selected from the group consisting of: a halide, or combinations thereof, wherein n is 2 to 20, wherein each of a1, … and an is, independently, 10 to 1,000,000, wherein each of R1, … and Rn is independently: from 0 to 20, wherein FG is selected from the group consisting of NR3+ X–, NR3+ OH–, OH, NR2, SO3H, P(=O)(OH)2, CO2H, SO3– M+, P(=O)(O–)22M+, CO2– M+(M = Li, Na, K), linear multi-quaternary ammonium groups, branched multi-quaternary ammonium groups, crosslinked multi-quaternary ammonium groups, and combinations thereof, and R is an alkyl group, and X is a halide.
10. A reinforced anion exchange membrane, comprising: a porous membrane substrate; and an ionic polymer according to Formula I, impregnated into pores of the porous membrane substrate … are groups to random copolymers, wherein Arn is 2 to 20, wherein each of a1, a2, a3, … and an is, independently, 1 to 1,000,000, wherein R1, R2, R3, … and Rn, wherein Rn is 2 to 20, include , thereof; A’ includes N, an alkyl group, or combinations thereof; X includes a halide, e.g., Br; FG includes NR3+ X–, NR3+ OH–, OH, NR2, SO3H, P(=O)(OH)2, CO2H, SO3– M+, P(=O)(O–)22M+, CO2– M+(M = Li, Na, K), linear multi-quaternary ammonium groups, branched multi- quaternary ammonium groups, or combinations thereof; FG’ includes NR2+ X–, NR2+ OH–; R is an alkyl group, e.g., CH3 or CH2CH3; m is from 0 to 20; and n is from 0 to 20. 11. The reinforced anion exchange membrane of claim 9, wherein Ar1, Ar2, Ar3, … and Arn is independently selected from the group consisting of:
, and comb nat ons t ereo , w ere n nc udes an a y group, e.g., C 3 or CH2CH3, a halide, e.g., F, or combinations thereof; R' includes H, an alkyl group, e.g., CH3 or CH2CH3, or combinations thereof; X includes a halide; A includes S, O, NH, SO2, an alkyl group, e.g., CH2 or CH2CH3, and combinations thereof; and n is from 0 to 20. 12. The reinforced anion exchange membrane of claim 9, wherein the porous membrane substrate comprises a polymer selected from the group consisting of: high molecular weight polyethylene, ultrahigh molecular weight polyethylene, polytetrafluoroethylene, polypropylene or combinations thereof. 13. The reinforced anion exchange membrane of claim 9, wherein thickness of the reinforced anion exchange membrane is less than or equal to about 200 microns.
14. The reinforced anion exchange membrane of claim 9, wherein thickness of the reinforced anion exchange membrane is about 10 - 50 microns. 15. The reinforced anion exchange membrane of claim 9, wherein the reinforced anion exchange membrane has an ion exchange capacity of from about 0.5 to about 5.0 mequiv./g. 16. The reinforced anion exchange membrane of claim 9, wherein a portion of R1, R2, R3, … and Rn is crosslinked by a diamine selected from the group consisting of: multi-amines or combinations thereof, wherein R include H, an alkyl group, e.g., CH3 or CH2CH3, and combinations thereof; and n is from 0 to 20. 17. A reinforced anion exchange membrane, comprising: a porous membrane substrate; and an ionic polymer according to Formula II, impregnated into pores of the porous membrane substrate wherein m and n is 1 to 1,000,000. 18. The reinforced anion exchange membrane of claim 16, wherein the porous membrane substrate comprises a polymer selected from the groups consisting of high molecular weight polyethylene, ultrahigh molecular weight polyethylene, polytetrafluoroethylene, polypropylene or combinations thereof.
19. The reinforced anion exchange membrane of claim 16, wherein thickness of the reinforced anion exchange membrane is less than or equal to about 200 microns. 20. The reinforced anion exchange membrane of claim 16, wherein thickness of the reinforced anion exchange membrane is about 10 - 50 microns. 21. The reinforced anion exchange membrane of claim 16, wherein the reinforced anion exchange membrane has an ion exchange capacity of from about 0.5 to about 5.0 mequiv./g. 22. The reinforced anion exchange membrane of claim 1, wherein the ionic copolymer is according to Formula I: wherein Ar1, Arn are different aryl groups to form random copolymers, and are selected from the group consisting of: a halide, or combinations thereof, wherein n is 2 to 20, wherein each of a1, … and an is, independently, 10 to 1,000,000, wherein each of R1, … and Rn is independently: x FG wherein x is from 0 to 20, wherein FG is selected from the group consisting of NR3 + X–, NR3 + OH–, OH, NR2, SO3H, P(=O)(OH)2, CO2H, SO3 – M+, P(=O)(O–)22M+, CO2 – M+(M = Li, Na, K), linear multi-quaternary ammonium groups, branched multi-quaternary ammonium groups, crosslinked multi-quaternary ammonium groups, and combinations thereof, and R is an alkyl group, and X is a halide.
EP24742086.2A 2023-01-13 2024-01-12 Reinforced anion exchnage membranes and methods of making same Pending EP4649102A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US202363438983P 2023-01-13 2023-01-13
PCT/US2023/012399 WO2023150341A2 (en) 2022-02-07 2023-02-06 Quaternized polyaromatics for use in electrochemical devices
US18/164,980 US12024576B2 (en) 2022-02-07 2023-02-06 Quaternized polyaromatics for use in electrochemical devices
US202363307532P 2023-02-07 2023-02-07
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