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US-12617889-B1 - Polymers for use as anion exchange membranes

US12617889B1US 12617889 B1US12617889 B1US 12617889B1US-12617889-B1

Abstract

Polymers for use as an Anion Exchange Membranes (AEMs) and produce an alkaline stable AEM. The multinuclear aromatic and amine-functionalized acetal (ketal) come together to form a polymer with a hydrocarbon backbone that is stable to alkaline conditions. The use of an amine-functionalized acetal allows for the incorporation of a stable cation, dimethyl piperidinium, in the most stable confirmation while avoiding incorporation of a CF3 group with every cation. The amines within the amine-functionalized polyaromatic that results from this polymerization are quaternized to form the desired cationic groups to create an AEM that is mechanically robust, conductive, and stable.

Inventors

  • Michael K. Pagels
  • Cheyenne R. Peltier

Assignees

  • ENVISION ENERGY USA LTD.

Dates

Publication Date
20260505
Application Date
20250807

Claims (20)

  1. 1 . A polymer comprising a reaction product of a polymerization mixture, comprising: a multinuclear aromatic compound having a formula: and a cyclic-amine-functionalized acetal or ketal having a formula: or an amine-functionalized acetal or ketal having a formula: and a comonomer having a formula in any of a following group: wherein: R1 is each independently alkyl, aromatic, heteroaromatic, or hydrogen; R2 is nothing, methylene, alkyl, aromatic, heteroaromatic, amino, sulfide, sulfonyl, or ether linkages; R3 is hydrogen or methyl; R4 is alkyl, or covalently linked to R4 to form a ring; R5 is each independently hydrogen, alkyl, cyclic alkyl; R6 is each independently hydrogen, alkyl, cyclic alkyl or covalently linked to R5 to form a ring; R8 is hydrogen, alkyl, cyclic alkyl, aromatic, heteroaromatic; R9 is heteroaromatic; and x is an integer from 0 to 6.
  2. 2 . A polymer comprising a reaction product of an alkylating agent and the polymer of claim 1 comprising the reaction product of the polymerization mixture comprising: the cyclic-amine-functionalized acetal or ketal; or the amine-functionalized acetal or ketal.
  3. 3 . A polymer comprising a reaction product of a salt and the polymer of claim 2 , wherein the salt comprises sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, ammonium fluoride, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ammonium chloride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, ammonium bromide, sodium iodide, potassium iodide, calcium iodide, magnesium iodide, ammonium iodide, sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, ammonium nitrate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, sodium hexafluoroantimonate, potassium hexafluoroantimonate, calcium hexafluoroantimonate, magnesium hexafluoroantimonate, ammonium hexafluoroantimonate, sodium hexafluorophosphate, potassium hexafluorophosphate, calcium hexafluorophosphate, magnesium hexafluorophosphate, ammonium hexafluorophosphate, sodium cyanide, potassium cyanide, calcium cyanide, magnesium cyanide, ammonium cyanide, sodium acetate, potassium acetate, calcium acetate, magnesium acetate, ammonium acetate, sodium formate, potassium formate, calcium formate, magnesium formate, ammonium formate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, magnesium bicarbonate, ammonium bicarbonate, sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, ammonium sulfate, sodium bisulfate, potassium bisulfate, calcium bisulfate, magnesium bisulfate, ammonium bisulfate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, ammonium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, calcium hydrogen phosphate, magnesium hydrogen phosphate, ammonium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, magnesium dihydrogen phosphate, ammonium dihydrogen phosphate, sodium methanesulfonate, potassium methanesulfonate, calcium methanesulfonate, magnesium methanesulfonate, ammonium methanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, ammonium trifluoromethanesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, calcium p-toluenesulfonate, magnesium p-toluenesulfonate, ammonium p-toluenesulfonate, sodium nitrite, potassium nitrite, calcium nitrite, magnesium nitrite, ammonium nitrite, sodium chlorate, potassium chlorate, calcium chlorate, magnesium chlorate, ammonium chlorate, sodium bromate, potassium bromate, calcium bromate, magnesium bromate, ammonium bromate, sodium iodate, potassium iodate, calcium iodate, magnesium iodate, ammonium iodate, sodium bis(trifluoromethanesulfonyl)imide, potassium bis(trifluoromethanesulfonyl)imide, calcium bis(trifluoromethanesulfonyl)imide, magnesium bis(trifluoromethanesulfonyl)imide, or ammonium bis(trifluoromethanesulfonyl)imide.
  4. 4 . The polymer of claim 1 , wherein R1 is each independently alkyl, aromatic, heteroaromatic, or hydrogen; and R2 is nothing, methylene, alkyl, aromatic, heteroaromatic, amino, sulfide, sulfonyl, or ether linkages, wherein: the aromatic or heteroaromatic groups of R1 or R2 comprise one or more fused ring structures including naphthalene, anthracene, fluorene, carbazole, B dibenzothiophene, and derivatives thereof.
  5. 5 . The polymer of claim 1 , wherein the cyclic-amine-functionalized acetal or B ketal comprises 4-(2,2-diethoxyethyl)piperidine, 4-(2,2-diethoxypropyl)piperidine, 4-(dimethoxymethyl)piperidine, 4-(1,3-dioxolan-2-yl)-1-methylpiperidine, 4-(dimethoxymethyl)-1,1-dimethylpiperidin-1-ium, 3-(dimethoxymethyl)-6-azaspiro[5.5]undecan-6-ium; the amine-functionalized acetal or ketal comprises 2,2-diethoxyethan-1-amine,2,2-diethoxypropan-1-amine, 2,2-diethoxy-N-methylpropan-1-amine, 2,2-diethoxy-N-methylethan-1-amine, 2,2-diethoxy-N,N-dimethylpropan-1-amine, 2,2-diethoxy-N,N-dimethylethan-1-amine, 3,3-diethoxypropan-1-amine, 4,4-diethoxybutan-1-amine, 4,4-diethoxy-N,N,N-trimethylbutan-1-aminium; the multinuclear aromatic compound comprises biphenyl, propane-2,2-diyldibenzene, diphenylmethane, diphenylsulfane, sulfonyldibenzene, oxydibenzene; the comonomer comprises trifluoroacetone, trifluoroacetaldehyde, piperidin-4-one, indoline-2,3-dione, isonicotinaldehyde, 1-(pyridin-4-yl)ethan-1-one, 1-methylpiperidin-4-one, 1-propylindoline-2,3-dione, cyclohexane-1,2-dione, oxalaldehyde, 1H-imidazole-5-carbaldehyde.
  6. 6 . An anion exchange polymer (AEM), wherein the AEM comprising: a first repeating unit of formula one: or, a second repeating unit of formula two: wherein: R1 is each independently alkyl, aromatic, heteroaromatic, polycyclic aromatic, or hydrogen; R2 is nothing, methylene, alkyl, aromatic, heteroaromatic, polycyclic aromatic, amino, sulfide, sulfonyl, or ether linkages; R3 is hydrogen or methyl; R5 is hydrogen, C 1 -C 20 alkyl, and C 5 -C 10 cycloalkyl; R6 is hydrogen, C 1 -C 20 alkyl, and C 5 -C 10 cycloalkyl, or covalently linked to R5 to form a ring; R7 is hydrogen, C 1 -C 20 alkyl, and C 5 -C 10 cycloalkyl; R10 is each independently hydrogen or derived from polymerization products of comonomer; R11 is each independently hydrogen or derived from polymerization products of comonomer; y is an integer from 0 to 6, and optionally comprises a linear, branched, or cyclic hydrocarbons; n is an integer corresponding to 1 to less than 100 mole % of a total repeating units in the polymer; and X − is an anion.
  7. 7 . The AEM of claim 6 , wherein R10 is derived from polymerization products of comonomer, wherein the comonomer comprises electron deficient ketone or aldehyde compounds, wherein the electron deficient ketone or aldehyde compounds comprises trifluoroacetone, trifluoroacetaldehyde, piperidin-4-one, indoline-2,3-dione, isonicotinaldehyde, 1-(pyridin-4-yl)ethan-1-one, 1-methylpiperidin-4-one, 1-propylindoline-2,3-dione, cyclohexane-1,2-dione, oxalaldehyde, or 1H-imidazole-5-carbaldehyde.
  8. 8 . The AEM of claim 6 , wherein R11 is derived from polymerization products of comonomer, wherein the comonomer comprises electron deficient ketone or aldehyde compounds, wherein the electron deficient ketone or aldehyde compounds comprises trifluoroacetone, trifluoroacetaldehyde, piperidin-4-one, indoline-2,3-dione, isonicotinaldehyde, 1-(pyridin-4-yl)ethan-1-one, 1-methylpiperidin-4-one, 1-propylindoline-2,3-dione, cyclohexane-1,2-dione, oxalaldehyde, or 1H-imidazole-5-carbaldehyde.
  9. 9 . The AEM of claim 6 , wherein the anion is selected from a group consisting of fluoride, chloride, bromide, iodide, nitrate, hydroxide, hexafluoroantimonate, hexafluorophosphate, cyanide, acetate, formate, carbonate, bicarbonate, sulfate, bisulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, methane sulfonate (mesylate), trifluoromethanesulfonate (triflate), p-toluenesulfonate (tosylate), nitrite, chlorate, bromate, iodate, and bis(trifluoromethanesulfonyl)imide (bistriflimide).
  10. 10 . A prepolymer, wherein the prepolymer comprising: a first repeating unit of formula one: or, a second repeating unit of formula two: wherein: R1 is each independently alkyl, aromatic, heteroaromatic, polycyclic aromatic, or hydrogen; R2 is nothing, methylene, alkyl, aromatic, heteroaromatic, polycyclic aromatic, amino, sulfide, sulfonyl, or ether linkages; R3 is hydrogen or methyl; R5 is hydrogen, C 1 -C 20 alkyl, and C 5 -C 10 cycloalkyl; R6 is hydrogen, C 1 -C 20 alkyl, and C 5 -C 10 cycloalkyl, or covalently linked to R5 to form a ring; R10 is each independently hydrogen or derived from polymerization products of comonomer; R11 is each independently hydrogen or derived from polymerization products of comonomer; y is an integer from 0 to 6, and optionally comprises a linear, branched, or cyclic hydrocarbons; n is an integer corresponding to 1 to less than 100 mole % of a total repeating units in the prepolymer.
  11. 11 . The prepolymer of claim 10 , wherein R10 is derived from polymerization products of comonomer, wherein the comonomer comprises electron deficient ketone or aldehyde compounds, wherein the electron deficient ketone or aldehyde compounds comprises trifluoroacetone, trifluoroacetaldehyde, piperidin-4-one, indoline-2,3-dione, isonicotinaldehyde, 1-(pyridin-4-yl)ethan-1-one, 1-methylpiperidin-4-one, 1-propylindoline-2,3-dione, cyclohexane-1,2-dione, oxalaldehyde, or 1H-imidazole-5-carbaldehyde.
  12. 12 . The prepolymer of claim 10 , wherein R11 is derived from polymerization products of comonomer, wherein the comonomer comprises electron deficient ketone or aldehyde compounds, wherein the electron deficient ketone or aldehyde compounds comprises trifluoroacetone, trifluoroacetaldehyde, piperidin-4-one, indoline-2,3-dione, isonicotinaldehyde, 1-(pyridin-4-yl)ethan-1-one, 1-methylpiperidin-4-one, 1-propylindoline-2,3-dione, cyclohexane-1,2-dione, oxalaldehyde, or 1H-imidazole-5-carbaldehyde.
  13. 13 . A method of making the polymer of claim 3 , the method comprising: reacting the multinuclear aromatic compound, the cyclic-amine-functionalized acetal or ketal or the amine-functionalized acetal or ketal, and an optional comonomer in a presence of first solvent and a polymerization catalyst to form an amine-functionalized acetal or ketal intermediate polymer; precipitating the amine-functionalized acetal or ketal intermediate polymer using aqueous solvent to form a solid amine-functionalized acetal or ketal intermediate polymer; dissolving the solid amine-functionalized acetal or ketal intermediate polymer in second solvent; alkylating the amine-functionalized acetal or ketal intermediate polymer using an alkylating agent in the presence of a second solvent to form quaternized-amine-functionalized acetal or ketal intermediate polymer; and reacting the quaternized-amine-functionalized acetal or ketal intermediate polymer with salt to form the polymer.
  14. 14 . A method of making an anion exchange polymer membrane comprising the polymer of claim 6 , the method comprising: reacting multinuclear aromatic compound, cyclic-amine-functionalized acetal or ketal or amine-functionalized acetal or ketal, and an optional comonomer in a presence of first solvent and a polymerization catalyst to form an amine-functionalized acetal or ketal intermediate polymer; precipitating the amine-functionalized acetal or ketal intermediate polymer using precipitation solvent to form a solid amine-functionalized acetal or ketal intermediate polymer; dissolving the solid amine-functionalized acetal or ketal intermediate polymer in second solvent; alkylating the amine-functionalized acetal or ketal intermediate polymer using an alkylating agent in the presence of a second solvent to form quaternized-amine-functionalized acetal or ketal intermediate polymer; reacting the quaternized-amine-functionalized acetal or ketal intermediate polymer with salt to form a polymer solution; precipitating a quaternized-amine-functionalized acetal or ketal functionalized polymer from the polymer solution using precipitation solvent to a dried polymer powder; and casting a final polymer product solution to form an anion exchange polymer membrane.
  15. 15 . The method of claim 14 , wherein the polymerization catalyst comprises trifluoromethanesulfonic acid, fluorosulfuric acid, magic acid, fluoroantimonic acid, methanesulfonic acid, fluoroboric acid, or bistriflimidic acid.
  16. 16 . The method of claim 14 , wherein the alkylating agent comprises methyl iodide, iodoethane, 1-iodopropane, 1-iodobutane, 1-iodopentane, 1-iodohexane, methyl bromide, ethyl bromide, n-propyl bromide, n-butyl bromide, 1-bromopentane, 1-bromohexane, methyl chloride, ethyl chloride, n-propyl chloride, n-butyl chloride, 1-chloropentane, 1-chlorohexane or a combination thereof.
  17. 17 . The method of claim 14 , wherein the first solvent comprises dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, or nitrobenzene.
  18. 18 . The method of claim 14 , wherein the salt comprises sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, ammonium fluoride, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ammonium chloride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, ammonium bromide, sodium iodide, potassium iodide, calcium iodide, magnesium iodide, ammonium iodide, sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, ammonium nitrate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, sodium hexafluoroantimonate, potassium hexafluoroantimonate, calcium hexafluoroantimonate, magnesium hexafluoroantimonate, ammonium hexafluoroantimonate, sodium hexafluorophosphate, potassium hexafluorophosphate, calcium hexafluorophosphate, magnesium hexafluorophosphate, ammonium hexafluorophosphate, sodium cyanide, potassium cyanide, calcium cyanide, magnesium cyanide, ammonium cyanide, sodium acetate, potassium acetate, calcium acetate, magnesium acetate, ammonium acetate, sodium formate, potassium formate, calcium formate, magnesium formate, ammonium formate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, magnesium bicarbonate, ammonium bicarbonate, sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, ammonium sulfate, sodium bisulfate, potassium bisulfate, calcium bisulfate, magnesium bisulfate, ammonium bisulfate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, ammonium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, calcium hydrogen phosphate, magnesium hydrogen phosphate, ammonium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, magnesium dihydrogen phosphate, ammonium dihydrogen phosphate, sodium methanesulfonate, potassium methanesulfonate, calcium methanesulfonate, magnesium methanesulfonate, ammonium methanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, ammonium trifluoromethanesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, calcium p-toluenesulfonate, magnesium p-toluenesulfonate, ammonium p-toluenesulfonate, sodium nitrite, potassium nitrite, calcium nitrite, magnesium nitrite, ammonium nitrite, sodium chlorate, potassium chlorate, calcium chlorate, magnesium chlorate, ammonium chlorate, sodium bromate, potassium bromate, calcium bromate, magnesium bromate, ammonium bromate, sodium iodate, potassium iodate, calcium iodate, magnesium iodate, ammonium iodate, sodium bis(trifluoromethanesulfonyl)imide, potassium bis(trifluoromethanesulfonyl)imide, calcium bis(trifluoromethanesulfonyl)imide, magnesium bis(trifluoromethanesulfonyl)imide, or ammonium bis(trifluoromethanesulfonyl)imide.
  19. 19 . The method of claim 14 , wherein the precipitation solvent independently comprises water, methanol, hexane, chloroform, tetrahydrofuran, isopropanol, ethanol, acetone, or mixtures thereof.
  20. 20 . The method of claim 14 , wherein the second solvent independently comprises tetrahydrofuran, dichloromethane, chloroform, N,N-dimethylformamide, dimethyl sulfoxide chloroform, 1,1,2-trichloroethylene, benzene, toluene, chlorobenzene, bromobenzene, N-methyl pyrrolidone, N,N-dimethylacetamide, or acetonitrile.

Description

FIELD OF THE INVENTION The present invention generally relates to the field of anion exchange membranes (AEMs). In particular, the present invention is directed to polymers for use as an anion exchange membranes. BACKGROUND Anion Exchange Membranes (AEMs) are semi-permeable membranes that facilitate the selective transport of anions, typically hydroxide ions (OH−), while blocking the passage of cations. AEMs generally consist of a polymeric backbone functionalized with positively charged groups that enable anion conduction through electrostatic interactions. In traditional polyaromatic AEMs, cations such as piperidinium are typically introduced either by direct attachment to the aromatic rings or by incorporating fluorinated groups like trifluoromethyl (CF3). These approaches increase synthetic complexity, may require environmentally regulated fluorinated materials, and can reduce chemical stability. Additionally, polymer systems using piperidone monomers often adopt strained, non-ideal conformations that promote chemical degradation, lower ionic conductivity, and compromise long-term durability under alkaline conditions. SUMMARY OF THE DISCLOSURE In an aspect, a polymer comprising a reaction product of a polymerization mixture, including: a multinuclear aromatic compound having a formula: and a cyclic-amine-functionalized acetal or ketal having a formula: or an amine-functionalized acetal or ketal having a formula: and optionally, a comonomer having a formula in any of a following groups: wherein: R1 is each independently alkyl, aromatic, heteroaromatic, or hydrogen;R2 is nothing, methylene, alkyl, aromatic, heteroaromatic, amino, sulfide, sulfonyl, or ether linkages;R3 is hydrogen or methyl or trifluoromethyl;R4 is alkyl, or covalently linked to R4 to form a ring;R5 is each independently hydrogen, alky, cyclic alkyl;R6 is each independently hydrogen, alky, cyclic alkyl or covalently linked to R5 to form a ring;R8 is hydrogen, alkyl, cyclic alkyl, aromatic, heteroaromatic;R9 is heteroaromatic; andx is an integer from 0 to 6. In another aspect, an anion exchange polymer including: a first repeating unit of formula one: a second repeating unit of formula two: wherein: R1 is each independently alkyl, aromatic, heteroaromatic, polycyclic aromatic, or hydrogen;R2 is nothing, methylene, alkyl, aromatic, heteroaromatic, polycyclic aromatic, amino, sulfide, sulfonyl, or ether linkages;R3 is hydrogen or methyl, or trifluoromethyl;R5 is hydrogen, C1-C20 alkyl, and C5-C10 cycloalkyl;R6 is hydrogen, C1-C20 alkyl, and C5-C10 cycloalkyl, or covalently linked to R5 to form a ring;R7 is hydrogen, C1-C20 alkyl, and C5-C10 cycloalkyl;R10 is each independently derived from polymerization products of comonomer;R11 is each independently derived from polymerization products of comonomer;y is an integer from 0 to 6, and optionally comprises a linear, branched, or cyclic hydrocarbons;n is an integer corresponding to 1 to 100 mole % of a total repeating units in the polymer; andX− is an anion. A method of making a polymer as described above is provided, the method including: reacting the multinuclear aromatic compound, the cyclic-amine-functionalized acetal or ketal or the amine-functionalized acetal or ketal, and an optional comonomer in a presence of first solvent and a polymerization catalyst to form an amine-functionalized acetal or ketal intermediate polymer; precipitating the amine-functionalized acetal or ketal intermediate polymer using aqueous solvent to form a solid amine-functionalized acetal or ketal intermediate polymer; dissolving the solid amine-functionalized acetal or ketal intermediate polymer in second solvent; alkylating the amine-functionalized acetal or ketal intermediate polymer using an alkylating agent in the presence of a second solvent to form quaternized-amine-functionalized acetal or ketal intermediate polymer; and reacting the quaternized-amine-functionalized acetal or ketal intermediate polymer with salt to form the polymer. A method of making an hydroxide exchange polymer membrane including an hydroxide exchange polymer as described above is also provided, the method including: reacting the multinuclear aromatic compound, the cyclic-amine-functionalized acetal or ketal or the amine-functionalized acetal or ketal, and an optional comonomer in a presence of first solvent and a polymerization catalyst to form an amine-functionalized acetal or ketal intermediate polymer; precipitating the amine-functionalized acetal or ketal intermediate polymer using precipitation solvent to form a solid amine-functionalized acetal or ketal intermediate polymer; dissolving the solid amine-functionalized acetal or ketal intermediate polymer in second solvent; alkylating the amine-functionalized acetal or ketal intermediate polymer using an alkylating agent in the presence of a second solvent to form quaternized-amine-functionalized acetal or ketal intermediate polymer; reacting the quaternized-amine-functionalized aceta