US20220143592A1 - Anion exchange membranes and polymers for use in same - Google Patents

Anion exchange membranes and polymers for use in same Download PDF

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US20220143592A1
US20220143592A1 US17/347,805 US202117347805A US2022143592A1 US 20220143592 A1 US20220143592 A1 US 20220143592A1 US 202117347805 A US202117347805 A US 202117347805A US 2022143592 A1 US2022143592 A1 US 2022143592A1
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sebs
polymer
compound
alkyl chain
exchange membranes
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Chulsung Bae
Angela Dee Mohanty
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Rensselaer Polytechnic Institute
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C08F212/10—Styrene with nitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
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    • 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
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • 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
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/083—Alkaline fuel cells
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Alkaline exchange membranes or anion exchange membranes allow for the transportation of anions (e.g., OH ⁇ , Cl ⁇ , Br ⁇ ) from the cathode to the anode in an electrochemical reaction.
  • AEMs are a critical component of AEM fuel cells, where hydrogen and oxygen are used to generate electricity, with water as a byproduct.
  • AEMs are also used in water electrolysis, where water is split into hydrogen and oxygen using electricity.
  • hydroxide ions (OH ⁇ ) are transported through the AEM, along with water molecules.
  • AEMs may also be used, for example, in batteries, sensors, and as actuators.
  • AEMs are generally unsuitable for use in AEM fuel cells or water electrolysis.
  • Many commercially-available AEMs are based on polystyrene, which is generally considered a poor choice for AEM fuel cells or water electrolysis.
  • Other AEM materials contain an arylene ether linkage (—O—) in the mid-chain and a benzyltrimethyl ammonium group in the side-chain. This combination, however, has been found to be chemically unstable and to degrade easily under highly alkaline conditions.
  • the invention provides a polymer according to formula IX
  • x and y are mol % and n is 1-10.
  • the invention provides a polymer according to formula XII
  • x and y are mol % and n is 1-10.
  • the invention provides a polymer according to formula IV
  • each of R 1 and R 2 is, independently, a linear alkyl chain or a cyclic alkyl chain, and Z is selected from a group consisting of: a linear alkyl chain, a cyclic alkyl chain, and an alkylene ether chain.
  • the invention provides an anion exchange membrane comprising at least one polymer selected from a group consisting of:
  • each of R 1 and R 2 is, independently, a linear alkyl chain or a cyclic alkyl chain, and Z is selected from a group consisting of: a linear alkyl chain, a cyclic alkyl chain, and an alkylene ether chain;
  • x and y are mol and n is 1-10;
  • x and y are mol % and n is 1-10.
  • FIG. 1 shows chemical reactions included in an illustrative method of preparing a polymer according to an embodiment of the invention
  • FIG. 2 shows examples of various amine groups that may be incorporated into polymers according to various embodiments of the invention
  • FIG. 3 shows chemical reactions included in a method of preparing a polymer according to another embodiment of the invention.
  • FIG. 4 shows chemical reactions included in a method of preparing a polymer according to still another embodiment of the invention.
  • Embodiments of the invention include a new class of quaternized ammonium hydroxide-containing polymers prepared from a styrene-butadiene block copolymer (SEBS).
  • SEBS styrene-butadiene block copolymer
  • This new class of polymers may be used in alkaline exchange membranes (AEMs), lack an arylene ether linkage in the polymer main-chain, and can prepared with any of a number of quaternized ammonium groups in the polymer side-chains.
  • AEMs alkaline exchange membranes
  • FIG. 1 shows chemical reactions involved in a method of forming a quaternized ammonium hydroxide-containing polymer from an SEBS.
  • An iridium-catalyzed borylation is then performed using bis(pinacolato)diboron (B 2 Pin 2 ) to introduce a boronic ester group into the aromatic rings of the SEBS, yielding compound II.
  • B 2 Pin 2 bis(pinacolato)diboron
  • a palladium-catalyzed Suzuki coupling reaction is then carried out with an aryl bromide-containing amine to yield compound III.
  • Various amine groups may be substituted for the boronic ester group in compound II, depending on the aryl bromide-containing amine employed.
  • R group of the aryl bromide-containing amine may be of formula V or formula VI below, wherein each of R.sub.1 and R.sub.2 is, independently, a linear alkyl chain or a cyclic alkyl chain, and Z is selected from a group consisting of: a linear alkyl (e.g., —(CH 2 ) n —) chain, a cyclic alkyl chain, and an alkylene ether chain (e.g., —(CH 2 CH 2 O) n —CH 2 CH 2 —).
  • a linear alkyl e.g., —(CH 2 ) n —
  • alkylene ether chain e.g., —(CH 2 CH 2 O) n —CH 2 CH 2 —
  • SEBS-QA quaternary ammonium-containing styrene block copolymer
  • any of a number of quaternary ammonium groups may be incorporated into the SEBS-QAs of the invention, some of which may be sterically hindered and chemically stable.
  • FIG. 2 shows five illustrative R groups and the resulting quaternary ammonium groups.
  • Illustrative quaternary ammonium groups include benzyltrimethylammonium (TMA), dimethylpiperazinium (DMP), benzyldicyclohexylmethylammonium (MCH), benzyldiisopropylmethylammonium (MiPr), trimethylhexylammonium (TMHA), and benzyldimethylhexylammonium (DMHA).
  • quaternary ammonium groups may similarly be employed, as will be recognized by one skilled in the art, and are within the scope of the invention.
  • suitable quaternary ammonium groups include, for example, alkyl-substituted imidazoliums and alkyl-substituted guadiniums.
  • Table 1 below shows comparative properties of SEBS-QAs according to embodiments of the invention.
  • SEBS-TMA 13 1.52 1.49 211 13 23 45 89 SEBS-DMP 13 1.39 1.20 249 10 13 19 33 SEBS-MCH 13 1.25 0.60 52 2 1 3 8 SEBS-MiPr 12.1 1.33 1.38 49 2 2 4 10 SEBS-TMHA 13 1.36 1.16 236 9 22 39 59 SEBS-DMHA 13 1.37 0.99 91 3 4 10 22
  • SEBS exhibits a nano-scale phase-separated morphology
  • SEBS-QAs of the invention will similarly exhibit nano-scale ion-transporting channels, allowing for the highly effective conduction of ions.
  • SEBS-based anion exchange membranes may be prepared without the use of an expensive transition metal catalyst such as iridium or palladium.
  • FIGS. 3 and 4 show examples of such methods.
  • n may be any integer value, although n is typically 1-10 (e.g., 5).
  • 6-bromohexanoic acid (compound 1) (0.50 g, 2.56 mmol), methanol (3.8 mL), and concentrated sulfuric acid (0.04 mL) are added to a 25 mL round bottom flask and the mixture stirred at 55° C. for 14 hours. Methanol is then evaporated, e.g., using a rotary evaporator, and the remaining product is diluted with ethyl acetate (15 mL), washed with NaHCO 3 (3 ⁇ 10 mL), and dried over Na 2 SO 4 .
  • the methyl 6-bromohexanoate ester (4.8 g, 23.0 mmol) and anhydrous THF (20 mL) are added to a 100 mL round bottom flask under nitrogen and cooled in an ice bath.
  • a mixture of methyl magnesium bromide [(CH 3 MgBr, 3 M in ether) 23 mL, 69 mmol] in anhydrous THF (10 mL) is then added to the flask, e.g., by syringe.
  • the ice bath is removed and the reaction mixture stirred at room temperature for 3 hours.
  • the reaction is then slowly quenched with saturated NH.sub.4Cl (10 mL), water (10 mL), and diethyl ether (20 mL).
  • tertiary alcohol (compound 3) is a colorless liquid (4.28 g, 92% yield). It should be noted that Grignard reagents or alkyllithium compounds other than methyl magnesium bromide can be used for preparation of similar tertiary alcohols.
  • Preparation of the polymer according to the embodiment in FIG. 3 begins with an SEBS copolymer (compound VII; 0.50 g, 2.07 mmol styrene units), to which is added compound 3 (1.29 g, 6.22 mmol) in, e.g., a 20 mL vial.
  • the vial is then evacuated and purged with nitrogen.
  • FIG. 4 also shows the reactions involved in preparing an SEBS-based polymer without use of a transition metal catalyst according to another embodiment of the invention.
  • the method begins with an SEBS co-polymer (compound VII; 29.9 mol % styrene units).
  • Anhydrous dichloromethane (15 mL) is added, e.g., by syringe.
  • the flask After stirring to dissolve the polymer, the flask is cooled in an ice bath and AlCl.sub.3 powder (0.93 g, 6.96 mmol) is added all at once. The mixture is then stirred in an ice bath for 45 minutes and at room temperature for 12 hours. The reaction mixture is then poured into methanol to precipitate the polymer, which is filtered, redissolved in chloroform, and precipitated in methanol to yield the SEBS-acylBr polymer of compound X. After vacuum drying at room temperature for 6 hours, 0.38 g of the polymer of compound X was obtained, in which 100% of the styrene units were reacted (i.e., the polymer contained 29.9 mol % acyl-bromide).
  • the ketone of the SEBS-acylBr of compound X may then be reduced to yield the SEBS-alkBr of compound XI.
  • SEBS-acylBr of compound X (0.38 g, 0.91 mmol ketone) is added to a 100 mL round bottom flask, which is evacuated and purged with nitrogen. Anhydrous dichloromethane (19 mL) is added and the solution stirred until the polymer is dissolved.
  • Triethylsilane (Et 3 SiH; 0.58 mL, 3.64 mmol) and trifluoroacetic acid (0.56 mL, 7.28 mmol) are added, e.g., by syringe, and the mixture stirred in a 45° C. oil bath. After 14 hours, the reaction is poured into methanol to precipitate the polymer, which is filtered, redissolved in chloroform, and precipitated in methanol to yield the SEBS-alkBr of compound XI. After vacuum drying at room temperature for 6 hours, 0.30 g of the polymer of compound XI was obtained in which 100% of the ketone was reduced.
  • SEBS-alkBr of compound XI may then be aminated to yield the SEBS-alkTMA of compound XII.
  • SEBS-alkBr compound XI; 0.15 g
  • toluene 3 mL
  • the thin SEBS-alkBr film (approximately 30-40 m thick) is removed from the plate by immersion in water, immersed in aqueous trimethylamine (45 wt % in water) and heated to 50° C. for 48 hours. After 48 hours, the film is rinsed with water and ion exchanged to hydroxide form by immersion in 1 M NaOH at room temperature for 48 hours, yielding the SEBS-alkTMA polymer of compound XII.
  • Polymers according to embodiments of the invention may be employed in any number of contexts, including, for example, as fuel cell alkaline exchange membranes, fuel cell ionomers, electrolysis alkaline exchange membranes, as actuators, and in any number of battery applications, as will be apparent to one skilled in the art.

Abstract

Embodiments of the invention relate generally to anion exchange membranes and, more particularly, to anion exchange membranes comprising a styrene block copolymer and methods for their manufacture. In one embodiment, the invention provides a polymer according to formula IV, wherein x and y are mol %, QA is or each of R1 and R2 is, independently, a linear alkyl chain or a cyclic alkyl chain, and Z is selected from a group consisting of: a linear alkyl chain, a cyclic alkyl chain, and an alkylene ether chain.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a continuation of U.S. patent application Ser. No. 16/696,186, filed Nov. 26, 2019, which is a continuation of U.S. patent application Ser. No. 16/351,989, filed Mar. 13, 2019, which is a continuation of U.S. patent application Ser. No. 15/326,538, filed Jan. 16, 2017, which is a national stage filing of International Patent Application No. PCT/US2015/041487, filed Jul. 22, 2015, which claims the benefit of U.S. Provisional Patent Application No. 62/027,497, filed Jul. 22, 2014, which are hereby incorporated herein as though set forth in their entireties.
    • STATEMENT REGARDING FEDERALLY-SPONSORED RESEARCH OR DEVELOPMENT
  • This invention was made with government support under grant number DMR1261331 awarded by the National Science Foundation. The government has certain rights in the invention.
    • BACKGROUND
  • Alkaline exchange membranes or anion exchange membranes (AEMs) allow for the transportation of anions (e.g., OH−, Cl−, Br−) from the cathode to the anode in an electrochemical reaction. AEMs are a critical component of AEM fuel cells, where hydrogen and oxygen are used to generate electricity, with water as a byproduct. AEMs are also used in water electrolysis, where water is split into hydrogen and oxygen using electricity. In both AEM fuel cells and water electrolysis, hydroxide ions (OH−) are transported through the AEM, along with water molecules. AEMs may also be used, for example, in batteries, sensors, and as actuators.
  • Known AEMs are generally unsuitable for use in AEM fuel cells or water electrolysis. Many commercially-available AEMs are based on polystyrene, which is generally considered a poor choice for AEM fuel cells or water electrolysis. Other AEM materials contain an arylene ether linkage (—O—) in the mid-chain and a benzyltrimethyl ammonium group in the side-chain. This combination, however, has been found to be chemically unstable and to degrade easily under highly alkaline conditions.
    • BRIEF DESCRIPTION OF THE INVENTION
  • In one embodiment, the invention provides a polymer according to formula IX
  • Figure US20220143592A1-20220512-C00001
  • wherein x and y are mol % and n is 1-10.
  • In another embodiment, the invention provides a polymer according to formula XII
  • Figure US20220143592A1-20220512-C00002
  • wherein x and y are mol % and n is 1-10.
  • In still another embodiment, the invention provides a polymer according to formula IV
  • Figure US20220143592A1-20220512-C00003
  • wherein x and y are mol % and n is 1-10, QA is
  • Figure US20220143592A1-20220512-C00004
  • each of R1 and R2 is, independently, a linear alkyl chain or a cyclic alkyl chain, and Z is selected from a group consisting of: a linear alkyl chain, a cyclic alkyl chain, and an alkylene ether chain.
  • In yet another embodiment, the invention provides an anion exchange membrane comprising at least one polymer selected from a group consisting of:
  • a polymer of formula IV
  • Figure US20220143592A1-20220512-C00005
  • wherein x and y are mol % and n is 1-10, QA is
  • Figure US20220143592A1-20220512-C00006
  • each of R1 and R2 is, independently, a linear alkyl chain or a cyclic alkyl chain, and Z is selected from a group consisting of: a linear alkyl chain, a cyclic alkyl chain, and an alkylene ether chain;
  • a polymer of compound IX
  • Figure US20220143592A1-20220512-C00007
  • wherein x and y are mol and n is 1-10; and
  • a polymer of compound XII
  • Figure US20220143592A1-20220512-C00008
  • wherein x and y are mol % and n is 1-10.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • These and other features of this invention will be more readily understood from the following detailed description of the various aspects of the invention taken in conjunction with the accompanying drawings that depict various embodiments of the invention, in which:
  • FIG. 1 shows chemical reactions included in an illustrative method of preparing a polymer according to an embodiment of the invention;
  • FIG. 2 shows examples of various amine groups that may be incorporated into polymers according to various embodiments of the invention;
  • FIG. 3 shows chemical reactions included in a method of preparing a polymer according to another embodiment of the invention; and
  • FIG. 4 shows chemical reactions included in a method of preparing a polymer according to still another embodiment of the invention.
    •
  • It is noted that the drawings of the invention are not to scale. The drawings are intended to depict only typical aspects of the invention, and therefore should not be considered as limiting the scope of the invention.
    • DETAILED DESCRIPTION OF THE INVENTION
  • Embodiments of the invention include a new class of quaternized ammonium hydroxide-containing polymers prepared from a styrene-butadiene block copolymer (SEBS). This new class of polymers may be used in alkaline exchange membranes (AEMs), lack an arylene ether linkage in the polymer main-chain, and can prepared with any of a number of quaternized ammonium groups in the polymer side-chains.
  • FIG. 1 shows chemical reactions involved in a method of forming a quaternized ammonium hydroxide-containing polymer from an SEBS. An SEBS, compound I, is employed where x and y are mol % of each repeating unit and 2x+y=100. For example, in some embodiments of the invention, x is 15 and y is 70. Other values are possible, of course, as will be recognized by one skilled in the art. An iridium-catalyzed borylation is then performed using bis(pinacolato)diboron (B2Pin2) to introduce a boronic ester group into the aromatic rings of the SEBS, yielding compound II.
  • A palladium-catalyzed Suzuki coupling reaction is then carried out with an aryl bromide-containing amine to yield compound III. Various amine groups may be substituted for the boronic ester group in compound II, depending on the aryl bromide-containing amine employed. For example, the R group of the aryl bromide-containing amine may be of formula V or formula VI below, wherein each of R.sub.1 and R.sub.2 is, independently, a linear alkyl chain or a cyclic alkyl chain, and Z is selected from a group consisting of: a linear alkyl (e.g., —(CH2)n—) chain, a cyclic alkyl chain, and an alkylene ether chain (e.g., —(CH2CH2O)n—CH2CH2—).
  • Figure US20220143592A1-20220512-C00009
  • The resulting polymer is then cast into a film, followed by methylation of the amine groups in the polymer and an ion exchange reaction to form compound IV, a quaternary ammonium-containing styrene block copolymer (SEBS-QA) according to one embodiment of the invention. Applicants have found the SEBS-QAs of the invention to be chemically stable and suitable for use in AEMs, even in highly alkaline environments.
  • Any of a number of quaternary ammonium groups may be incorporated into the SEBS-QAs of the invention, some of which may be sterically hindered and chemically stable. FIG. 2 shows five illustrative R groups and the resulting quaternary ammonium groups. Illustrative quaternary ammonium groups include benzyltrimethylammonium (TMA), dimethylpiperazinium (DMP), benzyldicyclohexylmethylammonium (MCH), benzyldiisopropylmethylammonium (MiPr), trimethylhexylammonium (TMHA), and benzyldimethylhexylammonium (DMHA). Other quaternary ammonium groups may similarly be employed, as will be recognized by one skilled in the art, and are within the scope of the invention. Other suitable quaternary ammonium groups include, for example, alkyl-substituted imidazoliums and alkyl-substituted guadiniums.
  • Table 1 below shows comparative properties of SEBS-QAs according to embodiments of the invention.
  • TABLE 1
    Representative Data of SEBS-QA.
    Cl− HCO3 − OH— σ
    Mol % of Theor. IEC Expt. IEC WU σ at 30° C. σ at 30° C. (mS/cm)
    Sample amine (meq/g) (meq/g) (%) (mS/cm) (mS/cm) 30° C. 60° C.
    SEBS-TMA 13 1.52 1.49 211 13 23 45 89
    SEBS-DMP 13 1.39 1.20 249 10 13 19 33
    SEBS-MCH 13 1.25 0.60 52 2 1 3 8
    SEBS-MiPr 12.1 1.33 1.38 49 2 2 4 10
    SEBS-TMHA 13 1.36 1.16 236 9 22 39 59
    SEBS-DMHA 13 1.37 0.99 91 3 4 10 22
  • The results in Table 1 show that these SEBS-QAs have high anion conductivity (Cl−, HCO3 −, OH−), which allows them to be used in a solid electrolyte membrane (in this case AEM) and as an ionomer in the electrodes in electrochemical devices.
  • Because SEBS exhibits a nano-scale phase-separated morphology, the SEBS-QAs of the invention will similarly exhibit nano-scale ion-transporting channels, allowing for the highly effective conduction of ions.
  • According to other embodiments of the invention, SEBS-based anion exchange membranes may be prepared without the use of an expensive transition metal catalyst such as iridium or palladium. FIGS. 3 and 4 show examples of such methods.
  • The inset within FIG. 3 shows the reactions involved in the esterification of 6-bromohexanoic acid and its subsequent methylation to a tertiary alcohol, which may be used in preparation of a polymer according to the invention. At each stage within the inset, n may be any integer value, although n is typically 1-10 (e.g., 5).
  • Referring now to the inset of FIG. 3, 6-bromohexanoic acid (compound 1) (0.50 g, 2.56 mmol), methanol (3.8 mL), and concentrated sulfuric acid (0.04 mL) are added to a 25 mL round bottom flask and the mixture stirred at 55° C. for 14 hours. Methanol is then evaporated, e.g., using a rotary evaporator, and the remaining product is diluted with ethyl acetate (15 mL), washed with NaHCO3 (3×10 mL), and dried over Na2SO4. Ethyl acetate is then removed, e.g., with rotary evaporation, and the product is vacuum dried, yielding the methyl 6-bromohexanoate ester (compound 2). It should be noted that alcohols other than methanol (e.g., ethanol, propanol) can be used for preparation of similar ester compounds.
  • The methyl 6-bromohexanoate ester (4.8 g, 23.0 mmol) and anhydrous THF (20 mL) are added to a 100 mL round bottom flask under nitrogen and cooled in an ice bath. A mixture of methyl magnesium bromide [(CH3MgBr, 3 M in ether) 23 mL, 69 mmol] in anhydrous THF (10 mL) is then added to the flask, e.g., by syringe. The ice bath is removed and the reaction mixture stirred at room temperature for 3 hours. The reaction is then slowly quenched with saturated NH.sub.4Cl (10 mL), water (10 mL), and diethyl ether (20 mL). The resulting product is then extracted with diethyl ether (3×15 mL), dried over MgSO4, and concentrated, e.g., using a rotary evaporator. The resulting tertiary alcohol (compound 3) is a colorless liquid (4.28 g, 92% yield). It should be noted that Grignard reagents or alkyllithium compounds other than methyl magnesium bromide can be used for preparation of similar tertiary alcohols.
  • Preparation of the polymer according to the embodiment in FIG. 3 begins with an SEBS copolymer (compound VII; 0.50 g, 2.07 mmol styrene units), to which is added compound 3 (1.29 g, 6.22 mmol) in, e.g., a 20 mL vial. The vial is then evacuated and purged with nitrogen.
  • Anhydrous dichloromethane (5 mL) is added, e.g. by syringe, and the polymer stirred until dissolved. The vial is then cooled in an ice bath and trifluoromethanesulfonic acid (0.55 mL, 6.22 mmol) is added. The reaction is stirred in the ice bath for one hour, after which the reaction is poured into methanol to precipitate the polymer.
  • The polymer is then filtered, redissolved in chloroform, and precipitated in methanol, yielding the SEBS-alkBr polymer of compound VIII after isolation and vacuum drying at room temperature for 6 hours. In practice, Applicants found 59.3% of the styrene units of compound VIII to be reacted (17.7 mol % alkyl-bromide and 12.2 mol % unfunctionalized styrene units). Molecular weights measured by GPC at 30° C. with THF as the eluent were SEBS-Mn=106,315 g/mol (PDI=1.04) and SEBS-alkBr-Mn=60,228 g/mol (PDI=2.07). Viscosities measured in toluene at 30° C. were SEBS=0.82 dL/g and SEBS-alkBR=0.68 dL/g.
  • Next, 0.15 g of compound VIII is dissolved in toluene (3 mL), filtered, cast onto a Teflon plate, and dried under a gentle flow of air at 80° C. The thin SEBS-alkBr film (approximately 30-40 m thick) is then removed from the plate by immersion in water and immersed in aqueous trimethylamine (45 wt % in water) and heated to 50° C. for 48 hours. The film is then ion exchanged to hydroxide form by immersion in 1 M NaOH at room temperature for 48 hours, yielding compound IX of FIG. 3.
  • FIG. 4 also shows the reactions involved in preparing an SEBS-based polymer without use of a transition metal catalyst according to another embodiment of the invention. Again, the method begins with an SEBS co-polymer (compound VII; 29.9 mol % styrene units). Compound VII (0.30 g, 4.64 mmol styrene units) and 6-bromohexanoyl chloride (compound 4; 1.49 g, 6.96 mmol, n=5) are added to a 100 mL round bottom flask under nitrogen. Anhydrous dichloromethane (15 mL) is added, e.g., by syringe.
  • After stirring to dissolve the polymer, the flask is cooled in an ice bath and AlCl.sub.3 powder (0.93 g, 6.96 mmol) is added all at once. The mixture is then stirred in an ice bath for 45 minutes and at room temperature for 12 hours. The reaction mixture is then poured into methanol to precipitate the polymer, which is filtered, redissolved in chloroform, and precipitated in methanol to yield the SEBS-acylBr polymer of compound X. After vacuum drying at room temperature for 6 hours, 0.38 g of the polymer of compound X was obtained, in which 100% of the styrene units were reacted (i.e., the polymer contained 29.9 mol % acyl-bromide).
  • The ketone of the SEBS-acylBr of compound X may then be reduced to yield the SEBS-alkBr of compound XI. To do so, SEBS-acylBr of compound X (0.38 g, 0.91 mmol ketone) is added to a 100 mL round bottom flask, which is evacuated and purged with nitrogen. Anhydrous dichloromethane (19 mL) is added and the solution stirred until the polymer is dissolved. Triethylsilane (Et3SiH; 0.58 mL, 3.64 mmol) and trifluoroacetic acid (0.56 mL, 7.28 mmol) are added, e.g., by syringe, and the mixture stirred in a 45° C. oil bath. After 14 hours, the reaction is poured into methanol to precipitate the polymer, which is filtered, redissolved in chloroform, and precipitated in methanol to yield the SEBS-alkBr of compound XI. After vacuum drying at room temperature for 6 hours, 0.30 g of the polymer of compound XI was obtained in which 100% of the ketone was reduced.
  • The SEBS-alkBr of compound XI may then be aminated to yield the SEBS-alkTMA of compound XII. To do so, SEBS-alkBr (compound XI; 0.15 g) is dissolved in toluene (3 mL), filtered, cast onto a Teflon plate, and dried under a gentle flow of air at 80° C. The thin SEBS-alkBr film (approximately 30-40 m thick) is removed from the plate by immersion in water, immersed in aqueous trimethylamine (45 wt % in water) and heated to 50° C. for 48 hours. After 48 hours, the film is rinsed with water and ion exchanged to hydroxide form by immersion in 1 M NaOH at room temperature for 48 hours, yielding the SEBS-alkTMA polymer of compound XII.
  • Polymers according to embodiments of the invention may be employed in any number of contexts, including, for example, as fuel cell alkaline exchange membranes, fuel cell ionomers, electrolysis alkaline exchange membranes, as actuators, and in any number of battery applications, as will be apparent to one skilled in the art.
  • One skilled in the art will also recognize, of course, that various changes, additions, or modifications of or to the methods described above may be made without substantively altering the compounds obtained or their characteristics. Such changes, additions, and modifications are therefore intended to be within the scope of the invention.
  • This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any related or incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.

Claims (2)

What is claimed is:
1. A polymer according to formula IX
Figure US20220143592A1-20220512-C00010
wherein x and y are mol % and n is 1-10.
2.-12. (canceled)
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