Piperidinium-containing polymers

Abstract

The present invention provides a polymer having a piperidinium functionalization group. A hydroxide (anion) exchange membrane or a hydroxide (anion) exchange ionomer formed by the polymers shows excellent chemical stability, hydroxide conductivity, reduced water absorption, good solubility in a selected solvent, and excellent mechanical properties. And improved mechanical properties when modulating the polymer structure, the combination and ratio of various aromatic and ketone units.

Description

Technical Field

[0001] Anion exchange polymers and their crosslinking forms capable of forming anion exchange membranes (AEMs) and ionomers (AEIs) are provided for use in anion exchange membrane devices including fuel cells (FCs), electrolyzers (ELs), and electrodialyzers. Background Technology

[0002] Proton exchange membrane fuel cells (PEMFCs) are considered clean and efficient power sources. (Steele et al., Nature 2001, 414, 345). However, the high cost and unsatisfactory durability of catalysts are major obstacles to the large-scale commercialization of PEMFCs. (Borup et al., Chem Rev 2007, 107, 3904). By switching the polymer electrolyte from “acidic” to “alkaline” conditions, HEMFCs can work with non-precious metal catalysts, and more durable catalysts are expected. Other less expensive fuel cell components are also possible, such as metal bipolar plates. (Varcoe et al., Fuel Cells 2005, 5, 187; Gu et al., Angew Chem Int Edit 2009, 48, 6499; Gu et al., Chem Commun 2013, 49, 131).

[0003] Compared to Nafion, HEM inherently exhibits lower ionic conductivity under similar conditions because the mobility of OH- is lower than that of H+. (Hibbs et al., Chem Mater 2008, 20, 2566). HEM / HEI requires a larger ion exchange capacity (IEC) to achieve greater hydroxide conductivity. However, high IEC typically results in high water absorption (i.e., high swelling ratio), thus reducing the membrane's morphological stability and mechanical strength, especially after repeated wet-dry cycles. This highly swollen state when wet is a major cause of the reduced flexibility and brittleness of HEM when dry. Removing the trade-off between high hydroxide conductivity and low water absorption has become a major obstacle in designing high-performance HEM / HEI. (Pan et al., EnergEnviron Sci 2013, 6, 2912). Attempts have been made to reduce water absorption while maintaining acceptable hydroxide conductivity using chemical crosslinking, physical reinforcement, side-chain polymerization, and block copolymer structures. However, these techniques present challenging problems such as reduced mechanical flexibility, decreased alkali stability, and / or increased cost. (References: Gu et al., Chem Commun 2011, 47, 2856; Park et al., Electrochem Solid St 2012, 15, B27; Wang et al., Chemsuschem 2015, 8, 4229; Ran et al., Sci Rep-Uk 2014, 4; Tanaka et al., J Am Chem Soc 2011, 133, 10646). Furthermore, due to the limited available synthetic methods, almost all side-chain or block copolymer HEMs are based on flexible aliphatic polymer chains. Therefore, the membrane still cannot provide morphological stability (low swelling ratio) at high IEC and high temperatures. Wang et al., Chemsuschem 2015, 8, 4229; Ran et al., Sci Rep-Uk 2014, 4; Marino et al., Chemsuschem 2015, 8, 513; Li et al., M. Macromolecules 2015, 48, 6523.

[0004] Another obstacle to using HEMs is achieving mechanical flexibility and strength in an environmentally dry state. Most HEMs exhibit low mechanical strength and are very brittle in a fully dry state, especially after complete swelling. It is difficult to obtain and process the large-size films required for commercial use of HEMs. Without good mechanical properties, ionomers cannot form and maintain a sufficient three-phase structure in fuel cell electrodes at high temperatures (such as 80°C or above). (Li et al., J Am ChemSoc 2013, 135, 10124).

[0005] Recently, PEMFCs have been used as zero-emission power sources in commercially available vehicles, demonstrating long driving range and short refueling times—two preferred features recognized by consumers. However, PEMFCs use platinum electrocatalysts and are not yet cost-competitive with gasoline engines. Key approaches to reducing PEMFC costs include developing low-platinum-load, high-power-density membrane electrode assemblies (MEAs) and platinum group metal-free (PGM-free) cathode catalysts. A fundamentally different path for low-cost fuel cells is the transition from PEMFCs to hydroxide exchange membrane fuel cells (HEMFCs), which can operate with PGM-free anode and cathode catalysts due to their fundamental operating environment and are therefore potentially economically viable. However, to replace PEMFCs, HEMFCs must offer performance matching that of PEMFCs, which in turn requires highly active anode and cathode catalysts and highly chemically stable ionic conductivity.

[0006] A series of piperidinium-functionalized anion exchange polymers were prepared. Both crosslinked and non-crosslinked anion exchange membranes (hydrogen hydroxide exchange membranes) based on these anion exchange polymers exhibited excellent alkali stability. The mechanical strength, water absorption, swelling ratio, and conductivity of the membranes could be finely tuned by various aromatic monomers, ketone monomers, and combinations of crosslinking degrees and crosslinking agents in the polymer. Summary of the Invention

[0007] A first aspect of the invention relates to an anion exchange polymer comprising structural units of at least two of formula 1A, formula 2A, 2A-2, 3A, or 3A-2, and one of formula 4A, 5A, 5A-2, or 6A. The sum of the mole fractions of the structural units of formula 1A and 4A, 5A, 5A-2, or 6A is equal to the sum of the mole fractions of formulas 2A, 2A-2, 3A, and 3A-2 in the polymer, the mole fractions being calculated from the amount of monomer used in the polymerization reaction forming the polymer; and the molar ratio of the structural units of formula 1A to the structural units of formulas 4A, 5A, 5A-2, or 6A is from 0.01 to 100, the molar ratio being calculated from the amount of monomer used in the polymerization reaction; and the molar ratio between the structural units of formulas 2A, 2A-2, 3A, and 3A-2 is from 0.01 to 100, the molar ratio being calculated from the amount of monomer used in the polymerization reaction. The structural units of Equations 1A, 2A, 2A-2, 3A, 3A-2, 4A, 5A, 5A-2, and 6A have the following structures: ; ; ; ; ; ; ; ;

[0008] in: A - It is an anion; R 100 Independently alkyl, alkenyl, ynyl, or ;and R 130 R 140 R 150 R 160 and R 170 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and these alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with halides.

[0009] A second aspect of the invention relates to an anion exchange polymer comprising structural units of at least two of formula 1A, formula 2A, 2A-2, 3A, or 3A-2, and at least two of formula 4A, 5A, 5A-2, or 6A. The sum of the mole fractions of the structural units of formula 1A, 4A, 5A, 5A-2, and 6A is equal to the sum of the mole fractions of formula 2A, 2A-2, 3A, and 3A-2 in the polymer, the mole fractions being calculated from the amount of monomer used in the polymerization reaction forming the polymer; and the molar ratio of the structural unit of formula 1A to the sum of the mole fractions of formulas 4A, 5A, 5A-2, and 6A is from 0.01 to 100, the molar ratio being calculated from the amount of monomer used in the polymerization reaction; and the molar ratio between the structural units of formulas 2A, 2A-2, 3A, and 3A-2 is from 0.01 to 100, the molar ratio being calculated from the amount of monomer used in the polymerization reaction. The structural units of Equations 1A, 2A, 2A-2, 3A, 3A-2, 4A, 5A, 5A-2, and 6A have the following structures: ; ; ; ; ; ; ; ;

[0010] in: A - It is an anion; R 100 Independently alkyl, alkenyl, ynyl, or ;and R 130 R 140 R 150 R 160 and R 170 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and these alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with halides.

[0011] A third aspect of the invention relates to an anion exchange polymer comprising a reaction product of a polymerization mixture comprising: a piperidinone monomer of formula 1 or a salt or hydrate thereof, at least two of aromatic monomers of formula 2, 2-2, 3 or 3-2, and one of a ketone monomer of formula 4, 5 or 6.

[0012] Piperidone monomers or their salts or hydrates have the following formula: ; Aromatic monomers have the following formula: ; ; ;

[0013] Ketone monomers have the following formula: ; ; ; in: R 10 Independently alkyl, alkenyl, ynyl, or ;and R 130 R 140 R 150 R 160 and R 170 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and these alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with halides.

[0014] A fourth aspect of the invention relates to an anion exchange polymer comprising a reaction product of a polymerization mixture comprising: a piperidinone monomer of formula 1 or a salt or hydrate thereof, at least two of aromatic monomers of formula 2, 2-2, 3 or 3-2, and at least two of ketone monomers of formula 4, 5 or 6.

[0015] Piperidone monomers or their salts or hydrates have the following formula: ; Aromatic monomers have the following formula: ; ; ;

[0016] Ketone monomers have the following formula: ; ; ; in: R 10 Independently alkyl, alkenyl, ynyl, or ;and R 130 R 140 R 150 R 160 and R 170 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and these alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with halides.

[0017] The fifth aspect of the invention is a neutralized polymer comprising a reaction product of a base with a polymer of one of the third and fourth aspects of the invention.

[0018] The sixth aspect of the invention is an alkylated or alkylated polymer comprising a mixture of reaction products, the mixture comprising an alkylating agent and a neutralized polymer as described in the fifth aspect of the invention.

[0019] An anion exchange membrane is also provided, the construction and dimensions of which are optionally designed to be suitable for use in fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, demineralizers, water purifiers, wastewater treatment systems, ion exchangers or CO2 separators, and the anion exchange membrane contains any of the polymers described above.

[0020] It also provides anion exchange membrane fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, mineralizers, water purifiers, wastewater treatment systems, ion exchangers, or CO2 separators, and provides fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, mineralizers, water purifiers, wastewater treatment systems, ion exchangers, or CO2 separators containing any of the anion exchange polymers described above.

[0021] An enhanced electrolyte membrane is also provided, the construction and dimensions of which are optionally designed to be suitable for use in fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, demineralizers, water purifiers, wastewater treatment systems, ion exchangers, or CO2 separators. The membrane comprises a porous substrate impregnated with any of the polymers described above.

[0022] A method for preparing the anion exchange polymer as described above is provided. The method comprises: reacting a piperidinone monomer with an aromatic monomer and a ketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; reacting the acidified intermediate polymer with a base to form a neutralized polymer; alkylating the neutralized polymer in the presence of an organic solvent to form a piperidinium-functionalized polymer; and reacting the piperidinium-functionalized polymer with a halide ion, hydroxide ion, bicarbonate ion, or carbonate ion, or a combination thereof, to form an anion exchange polymer.

[0023] A method for preparing anion exchange membranes is provided. The method includes: reacting a piperidinone monomer with an aromatic monomer and a ketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; reacting the acidified intermediate polymer with a base to form a neutralized polymer; alkylating the neutralized polymer in the presence of an organic solvent to form a piperidinium-functionalized polymer; and reacting the piperidinium-functionalized polymer with a halide ion, hydroxide ion, bicarbonate ion, or carbonate ion, or a combination thereof, to form an anion exchange polymer. The anion exchange polymer is dissolved in a solvent to form a polymer suspension or solution; and the polymer suspension or solution is cast to form an anion exchange polymer membrane.

[0024] A method is provided for preparing a crosslinked anion exchange polymer comprising the anion exchange polymer described above. The method comprises: reacting a piperidinone monomer with an aromatic monomer and a ketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; reacting the acidified intermediate polymer with a base to form a neutral piperidinium-functionalized polymer; partially alkylating the neutral piperidinium-functionalized polymer with an alkylating agent to form a partially alkylated piperidinium-functionalized polymer having piperidinium groups available for crosslinking; reacting the partially alkylated piperidinium-functionalized polymer with a crosslinking agent to form a crosslinked polymer; exchanging the anion of the crosslinked polymer with a halide ion, hydroxide ion, bicarbonate ion, or carbonate ion, or a combination thereof, to form a crosslinked anion exchange polymer; and optionally, reacting the crosslinked anion exchange polymer with trimethylamine to alkylate the partially reacted crosslinking agent.

[0025] A method is provided for preparing a crosslinked anion exchange membrane comprising the anion exchange polymer described above. The method comprises: reacting a piperidinone monomer with an aromatic monomer and a ketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; reacting the acidified polymer with a base to form a neutral piperidinium-functionalized polymer; partially alkylating the neutral piperidinium-functionalized polymer with an alkylating agent, leaving a portion of the neutral piperidinium intact for crosslinking; exchanging the anion of the piperidinium-functionalized polymer with hydroxide ions, bicarbonate ions, or carbonate ions, or combinations thereof, to form an anion exchange polymer; dissolving the ion exchange polymer in a solvent to form a polymer suspension or solution; adding a crosslinking agent to the polymer suspension or solution and casting to form a crosslinked anion exchange polymer membrane; and optionally, reacting the crosslinked anion exchange polymer membrane with trimethylamine to alkylate a portion of the reacted crosslinking agent.

[0026] Other purposes and features will be apparent in part and will be noted in part below. Attached Figure Description

[0027] Figure 1A An exemplary hydroxide exchange membrane fuel cell is shown.

[0028] Figure 1B An exemplary hydroxide exchange membrane electrolyzer is shown.

[0029] Figure 2 The 1H NMR spectrum of P1-neutral-0.85 in CDCl3 was depicted.

[0030] Figure 3 The 1H NMR spectrum of P1-Me-0.85 in DMSO-d6 was depicted. Detailed Implementation

[0031] HEM / HEIs formed from poly(arylalkylene) polymers having various side-chain piperidinium functionalized groups and inherent hydroxide conduction channels have been discovered to simultaneously provide improved chemical stability, electrical conductivity, water absorption, good solubility in selected solvents, mechanical properties, and other properties related to HEM / HEI performance. Compared to conventional HEM / HEIs, HEM / HEIs formed from these polymers exhibit superior chemical stability, anionic conductivity, reduced water absorption, good solubility in selected solvents, and improved mechanical properties under ambient dry conditions. The HEMFCs of the present invention exhibit enhanced performance and durability at relatively high temperatures.

[0032] A first aspect of the invention relates to an anion exchange polymer comprising structural units of at least two of formulas 1A, 2A, 2A-2, 3A, and 3A-2, and one of formulas 4A, 5A, 5A-2, and 6A. The sum of the mole fractions of the structural units of formula 1A and 4A, 5A, 5A-2, or 6A is equal to the sum of the mole fractions of formulas 2A, 2A-2, 3A, and 3A-2 in the polymer, the mole fractions being calculated from the amount of monomer used in the polymerization reaction forming the polymer; and the molar ratio of the structural units of formula 1A to the structural units of formulas 4A, 5A, 5A-2, or 6A is from 0.01 to 100, the molar ratio being calculated from the amount of monomer used in the polymerization reaction; and the molar ratio between the structural units of formulas 2A, 2A-2, 3A, and 3A-2 is from 0.01 to 100, the molar ratio being calculated from the amount of monomer used in the polymerization reaction. The structural units of Equations 1A, 2A, 2A-2, 3A, 3A-2, 4A, 5A, 5A-2, and 6A have the following structures: ; ; ; ; ; ; ; ;

[0033] in: A - It is an anion; R 130 R 140 R 150 R 160 and R 170 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and these alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with halides; R 100 Independently alkyl, alkenyl, ynyl, or .

[0034] A second aspect of the invention relates to an anion exchange polymer comprising structural units of at least two of formulas 1A, 2A, 2A-2, 3A, and 3A-2, and at least two of formulas 4A, 5A, 5A-2, and 6A. The sum of the mole fractions of the structural units of formulas 1A, 4A, 5A, 5A-2, and 6A is equal to the sum of the mole fractions of formulas 2A, 2A-2, 3A, and 3A-2 in the polymer, the mole fractions being calculated from the amount of monomer used in the polymerization reaction forming the polymer; and the molar ratio of the structural unit of formula 1A to the sum of the mole fractions of formulas 4A, 5A, 5A-2, and 6A is from 0.01 to 100, the molar ratio being calculated from the amount of monomer used in the polymerization reaction; and the molar ratio between the structural units of formulas 2A, 2A-2, 3A, and 3A-2 is from 0.01 to 100, the molar ratio being calculated from the amount of monomer used in the polymerization reaction. The structural units of Equations 1A, 2A, 2A-2, 3A, 3A-2, 4A, 5A, 5A-2, and 6A have the following structures: ; ; ; ; ; ; ; ;

[0035] in: A - It is an anion; R 130 R 140 R 150 R 160 and R 170 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and these alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with halides; R 100 Independently alkyl, alkenyl, ynyl, or .

[0036] A third aspect of the invention relates to an anion exchange polymer comprising a reaction product of a polymerization mixture comprising: a piperidinone monomer of formula 1 or a salt or hydrate thereof, at least two of aromatic monomers of formulas 2, 2-2, 3, and 3-2, and one of ketone monomers of formulas 4, 5, and 6.

[0037] Piperidone monomers or their salts or hydrates have the following formula: ; Aromatic monomers have the following formula: ; ; ;

[0038] Ketone monomers have the following formula: ; ; ; in: R 130 R 140 R 150 R 160 and R 170 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and these alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with halides; R 10 Independently alkyl, alkenyl, ynyl, or

[0039] A fourth aspect of the invention relates to an anion exchange polymer comprising a reaction product of a polymerization mixture comprising: a piperidinone monomer of formula 1 or a salt or hydrate thereof, at least two of aromatic monomers of formulas 2, 2-2, 3, and 3-2, and at least two of ketone monomers of formulas 4, 5, and 6.

[0040] Piperidone monomers or their salts or hydrates have the following formula: ; Aromatic monomers have the following formula: ; ; ;

[0041] Ketone monomers have the following formula: ; ; ; in: R 130 R 140 R 150 R 160 and R 170Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and these alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with halides; R 10 Independently alkyl, alkenyl, ynyl, or .

[0042] A fifth aspect of the invention is a polymer comprising a second reaction product of a second polymerization mixture comprising: a base, an alkylating agent, and an intermediate polymer; wherein the intermediate polymer comprises a first reaction product of a first polymerization mixture comprising: a piperidinone monomer having formula (1) or a salt or hydrate thereof; at least two aromatic monomers having formulas 2, 2-2, 3, and 3-2; and one of ketone monomers having formulas 4, 5, and 6. (That is, the first polymerization mixture comprises monomers of the third aspect of the invention).

[0043] A sixth aspect of the invention is a polymer comprising a second reaction product of a second polymerization mixture comprising: a base, an alkylating agent, and an intermediate polymer; wherein the intermediate polymer comprises a first reaction product of a first polymerization mixture comprising: a piperidinone monomer having formula (1) or a salt or hydrate thereof; at least two aromatic monomers having formulas 2, 2-2, 3, and 3-2; and at least two ketone monomers having formulas 4, 5, and 6. (That is, the first polymerization mixture comprises monomers of the fourth aspect of the invention).

[0044] A seventh aspect of the invention is a neutralized polymer comprising a reaction product of a base and a polymer of one of the third and fourth aspects of the invention. Another alkylated polymer is provided, comprising a reaction product of an alkylating agent and a neutralized polymer. Yet another polymer comprises a reaction product of a base and an alkylated polymer.

[0045] An anion exchange membrane is also provided, the construction and dimensions of which are optionally designed to be suitable for use in fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, demineralizers, water purifiers, wastewater treatment systems, ion exchangers or CO2 separators, and the anion exchange membrane contains any of the anion exchange polymers described above.

[0046] It also provides anion exchange membrane fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, mineralizers, water purifiers, wastewater treatment systems, ion exchangers, or CO2 separators, and provides fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, mineralizers, water purifiers, wastewater treatment systems, ion exchangers, or CO2 separators containing any of the anion exchange polymers described above.

[0047] An enhanced electrolyte membrane is also provided, the construction and dimensions of which are optionally designed to be suitable for use in fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, demineralizers, water purifiers, wastewater treatment systems, ion exchangers, or CO2 separators. The membrane comprises a porous substrate impregnated with any of the anion exchange polymers described above.

[0048] A method for preparing the anion exchange polymer as described above is provided. The method comprises: reacting a piperidinone monomer with an aromatic monomer and a ketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; reacting the acidified intermediate polymer with a base to form a neutralized polymer; alkylating the neutralized intermediate polymer in the presence of an organic solvent to form a piperidinium-functionalized polymer; and reacting the piperidinium-functionalized polymer with a halide ion, hydroxide ion, bicarbonate ion, or carbonate ion, or a combination thereof, to form an anion exchange polymer.

[0049] A method for preparing anion exchange membranes is provided. The method includes: reacting a piperidinone monomer with an aromatic monomer and a ketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; reacting the acidified intermediate polymer with a base to form a neutralized polymer; alkylating the neutralized intermediate polymer in the presence of an organic solvent to form a piperidinium-functionalized polymer; and reacting the piperidinium-functionalized polymer with a halide ion, hydroxide ion, bicarbonate ion, or carbonate ion, or a combination thereof, to form an anion exchange polymer. The anion exchange polymer is dissolved in a solvent to form a polymer suspension or solution; and the polymer suspension or solution is cast to form an anion exchange polymer membrane.

[0050] A method is provided for preparing a crosslinked anion exchange polymer comprising the anion exchange polymer described above. The method comprises: reacting a piperidinone monomer with an aromatic monomer and a ketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; reacting the acidified intermediate polymer with a base to form a neutral piperidinium-functionalized polymer; partially alkylating the neutral piperidinium-functionalized polymer with an alkylating agent to form a partially alkylated piperidinium-functionalized polymer having piperidinium groups available for crosslinking; reacting the partially alkylated piperidinium-functionalized polymer with a crosslinking agent to form a crosslinked polymer; exchanging the anion of the crosslinked polymer with a halide ion, hydroxide ion, bicarbonate ion, or carbonate ion, or a combination thereof, to form a crosslinked anion exchange polymer; and optionally, reacting the crosslinked anion exchange polymer with trimethylamine to alkylate the partially reacted crosslinking agent.

[0051] A method is provided for preparing a crosslinked anion exchange membrane comprising the anion exchange polymer described above. The method comprises: reacting a piperidinone monomer with an aromatic monomer and a ketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; reacting the acidified polymer with a base to form a neutral piperidinium-functionalized polymer; partially alkylating the neutral piperidinium-functionalized polymer with an alkylating agent, leaving a portion of the neutral piperidinium intact for crosslinking; exchanging the anion of the piperidinium-functionalized polymer with hydroxide ions, bicarbonate ions, or carbonate ions, or combinations thereof, to form an anion exchange polymer; dissolving the ion exchange polymer in a solvent to form a polymer suspension or solution; adding a crosslinking agent to the polymer suspension or solution and casting to form a crosslinked anion exchange polymer membrane; and optionally, reacting the crosslinked anion exchange polymer membrane with trimethylamine to alkylate a portion of the reacted crosslinking agent.

[0052] Salts of piperidone monomers may include hydrochloride, hydrofluoride, hydrobromide, hydroiodide, trifluoroacetate, acetate, trifluoromethanesulfonate, methanesulfonate, sulfate, nitrate, tetrafluoroborate, hexafluorophosphate, formate, benzenesulfonate, toluenesulfonate, perchlorate or benzoate, or any hydrate of the salt, or any combination thereof.

[0053] Salts of piperidinone monomers may include N-methyl-4-piperidinone hydrofluoric acid, N-methyl-4-piperidinone hydrochloride, N-methyl-4-piperidinone hydrobromide, N-methyl-4-piperidinone hydroiodide, N-methyl-4-piperidinone trifluoroacetate, N-methyl-4-piperidinone tetrafluoroborate, N-methyl-4-piperidinone hexafluorophosphate, N-methyl-4-piperidinone acetate, N-methyl-4-piperidinone trifluoromethanesulfonate, N-methyl-4-piperidinone methanesulfonate, N-methyl-4-piperidinone formate, N-methyl-4-piperidinone benzenesulfonate, N-methyl-4-piperidinone toluenesulfonate, N-methyl-4-piperidinone sulfate, N-methyl-4-piperidinone nitrate, N-methyl-4-piperidinone perchlorate, N-methyl-4-piperidinone benzoate, or any hydrate of such salts, or any combination thereof.

[0054] Anion A of structural unit 1A or 5A-2 - It may include halide ions, carbonate ions, bicarbonate ions, hydroxide ions, trifluoroacetate ions, acetate ions, trifluoromethanesulfonate ions, methanesulfonate ions, sulfate ions, nitrate ions, tetrafluoroborate ions, hexafluorophosphate ions, formate ions, benzenesulfonate ions, toluenesulfonate ions, perchlorate ions, or benzoate ions, or any combination thereof.

[0055] The polymerization catalyst used in any of the methods described herein may include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, heptafluorobutyric acid, or combinations thereof.

[0056] Each organic solvent used in any of the above methods may be independently selected from polar aprotic solvents (e.g., dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylacetamide, or dimethylformamide) or other suitable solvents, including but not limited to dichloromethane, trifluoroacetic acid, trifluoromethanesulfonic acid, chloroform, 1,1,2,2-tetrachloroethane, dimethylacetamide, or combinations thereof.

[0057] The solvent in the dissolution step of any of the above methods may include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, pentanol, hexanol, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, chloroform, ethyl lactate, tetrahydrofuran, 2-methyltetrahydrofuran, water, phenol, acetone, or combinations thereof.

[0058] The crosslinking agent used for the cast crosslinked film in the methods described herein may include 1,6-dibromohexane, 1,4-dibromobutane, 1,8-dibromooctane, 1,4-dibromoheptane, 1,7-dibromoheptane, 1,10-dibromodecane, 1,12-dibromododecane, 1,6-diiodohexane, 1,4-diiodobutane, 1,10-diiododecane, 1,5-diiodopentane, 1,8-diiodooctane, α,α'-dichloro-p-xylene, 4,4'-bis(chloromethyl)-1,1'-biphenyl, cationic crosslinking agents of formula (7) as described below, or any combination thereof.

[0059] The crosslinking agent used for casting crosslinked films in the methods described herein may include a cationic crosslinking agent of formula (7):

[0060] in: A is an anion; q is an integer between 1 and 100; R 21 R 22 R 23 R 24 R 25 and R 26 Each can be independently alkyl or aryl; X and Y are each independently Cl, Br, or I; and Z can be either N or P.

[0061] The base used in any of the above methods may include a hydroxide-containing base, such as sodium hydroxide or potassium hydroxide; a bicarbonate-containing base, such as sodium bicarbonate or potassium bicarbonate; or a carbonate-containing base, such as sodium carbonate or potassium carbonate.

[0062] Alkylating agents used in any of the methods described herein may include methyl iodine, iodoethane, 1-iodopropane, 1-iodobutane, 1-iodopentane, 1-iodohexane, methyl bromide, bromoethane, 1-bromopropane, methyl chloride, chloroethane, 1-chloropropane, methyl fluorosulfonate, methyl trifluoromethanesulfonate, or combinations thereof.

[0063] An enhanced electrolyte membrane, such as an enhanced anion exchange membrane, is also provided to increase the mechanical robustness of the anion exchange membrane, thereby achieving stability through repeated wet and dry cycling. This enhanced membrane comprises a porous substrate impregnated with any anion exchange polymer as described herein. Methods for preparing the enhanced membrane are well known to those skilled in the art, such as those disclosed in U.S. Patents RE37,656 and RE37,701, the descriptions of enhanced membrane synthesis and materials in which are incorporated herein by reference.

[0064] The construction and dimensions of any polymer membrane-enhanced ion exchange membrane, including those of the present invention, may optionally be designed to be suitable for use in fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, demineralizers, water purifiers, wastewater treatment systems, ion exchangers, or CO2 separators.

[0065] The porous substrate of the enhanced electrolyte membrane may include a membrane made of polytetrafluoroethylene, polypropylene, polyethylene, poly(ether) ketone, polyaryletherketone, imidazole-linked poly(arylalkylene), imidazole-onium-linked poly(arylalkylene), polysulfone, perfluoroalkoxyalkane or fluorinated ethylene propylene polymer, and the membrane may optionally be a dimensionally stable membrane.

[0066] The porous substrate of the reinforced electrolyte membrane may have at least one of the following: The porous substrate has a porous microstructure of polymer fibrils; By impregnating the porous substrate with the polymer, the internal volume of the substrate is substantially closed. The porous substrate comprises a microstructure of nodes interconnected by fibrils; The porous substrate has a thickness of about 1 micrometer to about 100 micrometers; The film is prepared by repeatedly impregnating the substrate with the polymer; or The membrane is prepared by the following steps: wetting the porous substrate in a liquid to form a wetted substrate; dissolving the polymer in a solvent to form a homogeneous solution or suspension; The solution or suspension is applied to the wetted substrate to form an enhanced film; and the film is dried.

[0067] The porous substrate may have a thickness of about 1 micrometer to about 10 micrometers, 15 micrometers, 20 micrometers, 25 micrometers, 30 micrometers, 35 micrometers, 40 micrometers, 45 micrometers, 50 micrometers, 55 micrometers, 60 micrometers, 65 micrometers, 70 micrometers, 75 micrometers, 80 micrometers, 85 micrometers, 90 micrometers, 95 micrometers, or 100 micrometers. Preferably, the porous substrate has a thickness of about 5 micrometers to about 30 micrometers, or about 7 micrometers to about 20 micrometers.

[0068] Example The following non-limiting embodiments are provided to further illustrate the present invention.

[0069] Example 1 Non-crosslinked poly(arylpiperidinium) membranes were prepared from N-methyl-4-piperidinone, p-terphenyl, biphenyl, and 2,2,2-trifluoroacetophenone. (Referred to as P1-Ax, where x is the molar ratio of N-methyl-4-piperidinone to the sum of 2,2,2-trifluoroacetophenone and N-methyl-4-piperidinone, and is from 0.01 to 0.99.) P1-Ax was prepared by three main steps: (1) synthesis of piperidine-functionalized polymers, (2) synthesis of piperidinium-functionalized polymers, and (3) membrane casting and hydroxide ion exchange. The reaction scheme is shown below: (1) Synthesis of piperidine-functionalized polymer P1-neutral-0.85 (i.e., x=0.85). In a 100 mL three-necked flask equipped with a top-mounted mechanical stirrer, N-methyl-4-piperidinone (0.962 g, 8.5 mmol), 2,2,2-trifluoroacetophenone (0.262 g, 1.5 mmol), p-terphenyl (1.152 g, 5 mmol), and biphenyl (0.771 g, 5 mmol) were suspended in dichloromethane (10 mL). Trifluoromethanesulfonic acid (TFSA) (10 mL) was then added dropwise over 30 minutes. The reaction was then continued at 0 °C for 12 hours. The resulting viscous solution was slowly poured into ethanol. The pale yellow fibrous solid was filtered, washed with water, and immersed in 1 M KOH at room temperature for 12 hours. Finally, the white fibrous product was filtered, washed with water, and completely dried under vacuum at 60 °C. The polymer yield was close to 100%.

[0070] (2) Synthesis of piperidinium-functionalized polymer P1-Me-0.85 In a 50 mL single-necked flask equipped with a magnetic rod, the piperidine-functionalized polymer (1.0 g) was dissolved in 1-methyl-2-pyrrolidone (10 mL). Methyl iodine (0.5 mL) was rapidly added to the mixture. The solution was stirred at room temperature for 12 hours. The resulting viscous yellow solution was added dropwise to diethyl ether. The yellow solid was filtered, washed with diethyl ether, and completely dried under vacuum at 60 °C. The yield of polymer P1-Me-0.85 was almost 100%.

[0071] (3) Membrane casting and hydroxide exchange A membrane was prepared by dissolving 1.0 g of P1-Me-0.85 polymer in 10 mL of NMP and casting it on a transparent glass plate at 80 °C for 8 hours. The membrane (iodide form) was then peeled off from the glass plate in contact with deionized (DI) water. A hydroxide form membrane was obtained by ion exchange in 1 M KOH at 60 °C for 24 hours, followed by washing the membrane in DI water under argon atmosphere and immersion for 48 hours to remove residual KOH.

[0072] Other P1-Ax membranes were prepared by using different molar ratios of N-methyl-4-piperidinone with 2,2,2-trifluoroacetophenone and / or different molar ratios of biphenyl with p-terphenyl.

[0073]

[0074] n is an integer from 1 to 1,000,000; x = 0.01 to 0.99; A - OH- anion - HCO3 - Cl - CO3 2- P1-neutral-0.85 was obtained in a yield close to 98%. 1 HNMR (CDCl3; δ, ppm): 7.20–7.68 (Ar1-H and Ar2-H, protons on the aromatic ring), 2.61 (H1, H2), 2.31 (H3) (see [reference]). Figure 2 ).

[0075] P1-neutral-0.85 in DMSO-d6 was obtained in a yield close to 97%. 1 ¹H NMR (DMSO-d6; δ, ppm): 7.14–7.80 (Ar1-H and Ar2-H, protons on the aromatic ring), 3.35 (H2), 3.14 (H3), 2.85 (H1) (see [reference]). Figure 3 ).

[0076] Example 2: Crosslinked polymers based on P1-neutral-xpiperidine functionalized polymers .

[0077] A crosslinked poly(arylpiperidinium) named P1-Ax(a)-XL (where x is the molar ratio of N-methyl-4-piperidinone to the sum of 2,2,2-trifluoroacetophenone and N-methyl-4-piperidinone, and is from 0.01 to 0.99, and a is the ratio of partial quaternization) was prepared from a P1-neutral-x piperidinium-functionalized polymer. P1-Ax(a)-XL was prepared by two main steps: (1) synthesis of the partially alkylated piperidinium-functionalized polymer P1-Ax(a), and (2) crosslinking of P1-Ax(a) to obtain P1-Ax(a)-XL. The reaction scheme is shown below: (1) Synthesis of partially alkylated piperidinium functionalized polymer P1-A-0.85 (0.75) (i.e., x = 0.85, a = 0.75） In a 50 mL single-necked flask equipped with a magnetic rod, P1-neutral-0.85 (1.0 g) was dissolved in 1-methyl-2-pyrrolidone (10 mL). Methyl iodine (0.23 g) was rapidly added to the mixture to partially alkylate the piperidine. The solution was stirred at room temperature for 12 hours. The resulting viscous yellow solution was added dropwise to diethyl ether. The yellow solid was filtered, washed with diethyl ether, ion-exchanged with 1 M sodium bicarbonate, and completely dried under vacuum at 60 °C. The yield of polymer P1-A-0.85 (0.75) was almost 100%.

[0078] (2) Film casting P1-A-0.85(0.75)-XL (i.e., x=0.85, a=0.75) A crosslinked membrane was prepared by dissolving P1-A-0.85 (0.75) polymer (10.0 g) and 1,6-dibromohexane (0.51 g) in a solvent (100 mL) and casting on a transparent glass plate at 80 °C for 8 hours. The membrane was then peeled off from the glass plate in contact with deionized (DI) water. Residual KOH was removed by ion exchange in 1 M KOH at 60 °C for 24 hours, followed by washing the membrane in DI water under argon atmosphere and immersion for 48 hours to obtain a membrane in hydroxide form.

[0079]

[0080]

[0081] n is an integer from 10 to 1,000,000; x = 0.01 to 0.99; a = 0.01 to 0.99; c = 1 to 20; A - OH- anion - HCO3 - Cl - CO3 2- B - OH- anion - HCO3 - Cl - I - CO3 2- Example 3 A polymer was prepared from a mixture of biphenyl, p-terphenyl, N-methyl-4-piperidinone, 2,2,2-trifluoroacetophenone, and indigo. The synthesis of the polymer was similar to the procedure described in Example 1. The reaction scheme is shown below.

[0082]

[0083] n is an integer from 10 to 1,000,000; x = 0.01 to 0.99, y = 0.01 to 0.99 A - OH- anion - HCO3 - Cl - CO3 2- Example 4 A crosslinked membrane based on the P2-neutral-x polymer was prepared in a manner similar to that of Example 2.

[0084]

[0085]

[0086] n is an integer from 10 to 1,000,000. x = 0.01 to 0.99; y = 0.01 - 0.99; a = 0.01 to 0.99; c = 1 to 20 A - OH- anion - HCO3 - Cl - CO3 2- B - OH- anion - HCO3 - Cl - CO3 2- definition As used herein, the term "suitable substituent" is intended to refer to a chemically acceptable functional group that preferably does not negate the activity of the compounds of the present invention. Such suitable substituents include, but are not limited to, halide groups, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroarylalkyl groups, arylalkoxy or heteroarylalkoxy groups, HO-(C=O)- groups, heterocyclic groups, cycloalkyl groups, amino groups, alkylamino and dialkylamino groups, carbamoyl groups, alkyl carbonyl groups, alkoxy carbonyl groups, alkylamino carbonyl groups, dialkylamino carbonyl groups, aryl carbonyl groups, aryloxy carbonyl groups, alkylsulfonyl groups, and arylsulfonyl groups. Those skilled in the art will understand that many substituents can be replaced by other substituents.

[0087] As used herein, the term "alkyl" refers to a straight-chain, branched, or cyclic hydrocarbon group, preferably having 1 to 32 carbon atoms (i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbon atoms), and more preferably having 1 to 18 carbon atoms. Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Alkyl groups may be unsubstituted or substituted with one or more suitable substituents.

[0088] As used herein, the term "alkenyl" refers to a straight-chain, branched, or cyclic hydrocarbon group, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbon atoms, more preferably having 1 to 18 carbon atoms, and having one or more carbon-carbon double bonds. Alkenyl groups include, but are not limited to, vinyl, 1-propenyl, 2-propenyl (allyl), isopropenyl, 2-methyl-1-propenyl, 1-butenyl, and 2-butenyl. Alkenyl groups may be unsubstituted or substituted with one or more suitable substituents, as defined above.

[0089] As used herein, the term "alkynyl" refers to a straight-chain, branched, or cyclic hydrocarbon group, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbon atoms, more preferably having 1 to 18 carbon atoms, and having one or more carbon-carbon triple bonds. Alynyl groups include, but are not limited to, ethynyl, propynyl, and butynyl. Alynyl groups may be unsubstituted or substituted with one or more suitable substituents, as defined above.

[0090] The term "aryl" or "aromatic," as used alone or as part of another group (e.g., aralkyl), means a monocyclic, bicyclic, or tricyclic aromatic group, such as phenyl, naphthyl, tetrahydronaphthyl, indanyl, etc., optionally substituted with one or more suitable substituents, preferably one to five suitable substituents, as defined above. The term "aryl" also includes heteroaryl.

[0091] "Arylalkyl" or "aryl group" refers to an aryl group attached to the parent molecule via an alkylene group. The number of carbon atoms in the aryl group and the alkylene group is chosen such that there are a total of about 6 to about 18 carbon atoms in the arylalkyl group. A preferred arylalkyl group is benzyl.

[0092] As used herein, the term "cycloalkyl" refers to a monocyclic, bicyclic, or tricyclic carbocyclic group (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclopentenyl, cyclohexenyl, bicyclic [2.2.1]heptyl, bicyclic [3.2.1]octyl, and bicyclic [5.2.0]nonyl, etc.); optionally containing one or two double bonds. The cycloalkyl group may be unsubstituted or substituted with one or more suitable substituents, preferably one to five suitable substituents, as defined above.

[0093] The term "-ene," used as a suffix as part of another group, indicates a divalent group, wherein a hydrogen atom is removed from each of the two terminal carbons of the group, or, if the group is cyclic, from each of the two distinct carbon atoms in the ring. For example, alkylene indicates a divalent alkyl group, such as ethylene (-CH2CH2-) or isopropylene (–CH(CH3)CH2–). For clarity, adding the suffix "-ene" is not intended to change the definition of the primary term other than indicating a divalent group. Therefore, continuing with the example above, alkylene indicates an optionally substituted straight-chain saturated divalent hydrocarbon group.

[0094] As used in this article, the term "hydrocarbon" describes a compound or group consisting only of the elements carbon and hydrogen.

[0095] As used herein, the term "polycyclic" describes a compound or group having two or more hydrocarbon rings, which may be substituted with heteroatoms such as nitrogen or oxygen. Polycyclic compounds can be aromatic or non-aromatic.

[0096] The term “substituted” means that in the group under discussion, at least one hydrogen atom bonded to a carbon atom is replaced by one or more substituents, such as hydroxyl (-OH), alkylthio, phosphino, amide (-CON(RA)(RB), where RA and RB are independently hydrogen, alkyl, or aryl), amino (-N(RA)(RB), where RA and RB are independently hydrogen, alkyl, or aryl), halide (fluorine, chlorine, bromine, or iodine), silyl, nitro (-NO2), ether (-ORA, where RA is alkyl or aryl), ester (-OC(O)RA, where RA is alkyl or aryl), ketone (-C(O)RA, where RA is alkyl or aryl), heterocycle, etc. When the term “substituted” is introduced or follows a list of possible substituents, the term is intended to apply to each member of the group. That is, the phrase “optionally substituted alkyl or aryl” should be interpreted as “optionally substituted alkyl or optional substituted aryl.” Similarly, the phrase “optionally fluorinated alkyl or aryl” should be interpreted as “optionally fluorinated alkyl or optionally fluorinated aryl”.

[0097] The term "linked" refers to the binding of the group in question to a specified polymer backbone. For example, an imidazolium-linked poly(arylalkylene) polymer is a polymer having imidazolium groups bound to the poly(arylalkylene) polymer backbone.

[0098] When describing elements of the invention or its preferred embodiments, the articles “a,” “an,” “the,” and “the” are intended to indicate the presence of one or more elements. The terms “comprising,” “including,” and “having” are intended to be inclusive and mean that additional elements may be present in addition to those listed.

[0099] Based on the above, it can be seen that several objectives of the present invention have been achieved and other advantageous results have been obtained.

[0100] Since various changes can be made to the above-described products and methods without departing from the scope of the invention, all contents contained in the above specification and shown in the accompanying drawings should be interpreted as illustrative rather than restrictive.

Claims

1. An anion exchange polymer, said anion exchange polymer comprising: Structural units of at least two of Equations 1A, 2A, 2A-2, 3A, and 3A-2, and one of Equations 4A, 5A, 5A-2, and 6A; or Structural units of at least two of Equations 1A, 2A, 2A-2, 3A and 3A-2, and at least two of Equations 4A, 5A, 5A-2 and 6A; in: The sum of the mole fractions of structural units of formulas 1A, 4A, 5A, 5A-2, and 6A is equal to the sum of the mole fractions of formulas 2A, 2A-2, 3A, and 3A-2 in the polymer, the mole fractions being calculated from the amount of monomer used in the polymerization reaction forming the polymer; and the molar ratio of structural units of formula 1A to structural units of formulas 4A, 5A, 5A-2, or 6A is from 0.01 to 100, the molar ratio being calculated from the amount of monomer used in the polymerization reaction; and the molar ratio between structural units of formulas 2A, 2A-2, 3A, and 3A-2 is from 0.01 to 100, the molar ratio being calculated from the amount of monomer used in the polymerization reaction; and The structural units of Equations 1A, 2A, 2A-2, 3A, 3A-2, 4A, 5A, 5A-2, and 6A have the following structures: ； ； ； ； ； ； ； ； in: A - It is an anion; R 100 Independently alkyl, alkenyl, ynyl, or ;and R 130 R 140 R 150 R 160 and R 170 Each of the groups is independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, and the alkyl, alkenyl, alkynyl, or aryl group may optionally be substituted with a halide.

2. An anion exchange polymer comprising a reaction product of a polymerization mixture, the polymerization mixture comprising: The piperidinone monomer of formula 1 or its salt or hydrate, at least two of the aromatic monomers of formulas 2, 2-2, 3 and 3-2, and one of the ketone monomers of formulas 4, 5 and 6; or The piperidinone monomer of Formula 1 or its salt or hydrate, at least two of the aromatic monomers of Formulas 2, 2-2, 3 and 3-2, and at least two of the ketone monomers of Formulas 4, 5 and 6; in: (i) The piperidinone monomer or its salt or hydrate has the following formula: ； (ii) The aromatic monomers have the following formula: ； ； ； (iii) The ketone monomer has the following formula: ； ； ； in: R 10 Independently alkyl, alkenyl, ynyl, or ;and R 130 R 140 R 150 R 160 and R 170 Each of the groups is independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, and the alkyl, alkenyl, alkynyl, or aryl group may optionally be substituted with a halide.

3. A polymer comprising a reaction product of a base and the polymer according to claim 2.

4. A polymer comprising an alkylating agent and a reaction product of the polymer according to claim 3.

5. A partially alkylated polymer, said partially alkylated polymer comprising an alkylating agent and a reaction product of the polymer according to claim 3.

6. A crosslinked polymer comprising a crosslinking agent and a reaction product of the polymer according to claim 5.

7. A polymer comprising the reaction product of the polymer according to any one of claims 1, 4, 5 and 6 with a solution of a halide ion, hydroxide ion, bicarbonate ion or carbonate ion or a combination thereof.

8. The polymer according to any one of claims 4 to 6, wherein the alkylating agent comprises methyl iodine, iodoethane, 1-iodopropane, 1-iodobutane, 1-iodopentane, 1-iodohexane, methyl bromide, bromoethane, 1-bromopropane, methyl chloride, chloroethane, 1-chloropropane, methyl fluorosulfonate, methyl trifluoromethanesulfonate, or combinations thereof.

9. The polymer according to claim 1, wherein A - Including halide ions, carbonate ions, bicarbonate ions, hydroxide ions, trifluoroacetate ions, acetate ions, trifluoromethanesulfonate ions, methanesulfonate ions, sulfate ions, nitrate ions, tetrafluoroborate ions, hexafluorophosphate ions, formate ions, benzenesulfonate ions, toluenesulfonate ions, perchlorate ions, or benzoate ions, or any combination thereof.

10. The polymer according to any one of claims 2 to 6, wherein in the ketone monomer, R 10 Each is independently alkyl, alkenyl, or alkynyl, and the alkyl, alkenyl, or alkynyl group is optionally substituted with fluorine.

11. The polymer according to any one of claims 2 to 6, wherein in the ketone monomer, R 10 Each can be independently methyl, ethyl, propyl, butyl, pentyl, or hexyl.

12. The polymer according to any one of claims 2 to 6, wherein in the ketone monomer, R 10 Independently And R 130 R 140 R 150 R 160 and R 170 Each of the groups is independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, and the alkyl, alkenyl, alkynyl, or aryl group may optionally be substituted with a halide.

13. The polymer according to any one of claims 2 to 6, wherein the salt of the piperidinone monomer comprises N-methyl-4-piperidinone hydrofluoric acid, N-methyl-4-piperidinone hydrochloride, N-methyl-4-piperidinone hydrobromide, N-methyl-4-piperidinone hydroiodide, N-methyl-4-piperidinone trifluoroacetate, N-methyl-4-piperidinone tetrafluoroborate, N-methyl-4-piperidinone hexafluorophosphate, N-methyl-4-piperidinone ethyl... Salts, N-methyl-4-piperidinone trifluoromethanesulfonate, N-methyl-4-piperidinone methanesulfonate, N-methyl-4-piperidinone carboxylate, N-methyl-4-piperidinone benzenesulfonate, N-methyl-4-piperidinone toluenesulfonate, N-methyl-4-piperidinone sulfate, N-methyl-4-piperidinone nitrate, N-methyl-4-piperidinone perchlorate, N-methyl-4-piperidinone benzoate, or any hydrate of said salts, or any combination thereof.

14. A method for preparing anion exchange polymer according to any one of claims 2 to 13, the method comprising: In the presence of an organic solvent and a polymerization catalyst, the piperidinone monomer is reacted with the aromatic monomer and the ketone monomer to form an acidified intermediate polymer. The acidified intermediate polymer is reacted with a base to form a neutralized polymer; The neutralized polymer is alkylated in the presence of an organic solvent to form a piperidinium-functionalized polymer; and The piperidinium-functionalized polymer is reacted with halide ions, hydroxide ions, bicarbonate ions, or carbonate ions, or combinations thereof, to form the anion exchange polymer.

15. A method for preparing an anion exchange membrane from the anion exchange polymer according to any one of claims 2 to 13, the method comprising: In the presence of an organic solvent and a polymerization catalyst, the piperidinone monomer is reacted with the aromatic monomer and the ketone monomer to form an acidified intermediate polymer. The acidified intermediate polymer is reacted with a base to form a neutralized polymer; The neutralized polymer is alkylated in the presence of an organic solvent to form a piperidinium-functionalized polymer; The piperidinium-functionalized polymer is reacted with halide ions, hydroxide ions, bicarbonate ions, or carbonate ions, or combinations thereof, to form the anion exchange polymer. The anion exchange polymer is dissolved in a solvent to form a polymer suspension or solution; The polymer suspension or solution is cast to form the anion exchange polymer membrane.

16. A method for preparing a crosslinked anion exchange polymer comprising any one of claims 2 to 13, the method comprising: In the presence of an organic solvent and a polymerization catalyst, the piperidinone monomer is reacted with the aromatic monomer and the ketone monomer to form an acidified intermediate polymer. The acidified intermediate polymer is reacted with a base to form a neutral piperidine-functionalized polymer; The neutral piperidine-functionalized polymer is partially alkylated with an alkylating agent to form a partially alkylated piperidinium-functionalized polymer having piperidine groups that can be used for crosslinking; The partially alkylated piperidinium-functionalized polymer is reacted with a crosslinking agent to form a crosslinked polymer; Optionally, the crosslinked polymer is reacted with trimethylamine to alkylate the partially reacted crosslinking agent; and The crosslinked polymer is reacted with halide ions, hydroxide ions, bicarbonate ions, or carbonate ions, or combinations thereof.

17. A method for preparing a crosslinked anion exchange membrane comprising the anion exchange polymer according to any one of claims 2 to 13, the method comprising: In the presence of an organic solvent and a polymerization catalyst, the piperidinone monomer is reacted with the aromatic monomer and the ketone monomer to form an acidified intermediate polymer. The acidified polymer is reacted with a base to form a neutral piperidine-functionalized polymer; The neutral piperidine-functionalized polymer is partially alkylated using an alkylating agent, so that some of the neutral piperidine remains intact for crosslinking; The partially alkylated piperidinium-functionalized polymer is reacted with halide ions, hydroxide ions, bicarbonate ions, or carbonate ions, or combinations thereof, to form the anion exchange polymer. The anion exchange polymer is dissolved in a solvent to form a polymer suspension or solution; A crosslinking agent is added to the polymer suspension or solution and cast to form a crosslinked anion exchange polymer membrane; as well as Optionally, the cross-linked anion exchange polymer membrane is reacted with trimethylamine to alkylate the partially reacted cross-linking agent.

18. The method according to any one of claims 14 to 17, wherein the polymerization catalyst comprises trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, heptafluorobutyric acid, or combinations thereof.

19. The method according to any one of claims 3 and 14 to 17, wherein the base comprises sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, or combinations thereof.

20. The method according to any one of claims 14 to 17, wherein the organic solvent comprises dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dichloromethane, trifluoroacetic acid, trifluoromethanesulfonic acid, chloroform, 1,1,2,2-tetrachloroethane, dimethylacetamide, or combinations thereof.

21. The method according to claim 15 or 17, wherein the membrane is cast in the presence of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, pentanol, hexanol, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, chloroform, ethyl lactate, tetrahydrofuran, 2-methyltetrahydrofuran, water, phenol, acetone, or combinations thereof.

22. The method according to any one of claims 6 and 16 to 20, wherein the crosslinking agent comprises 1,4-dibromobutane, 1,6-dibromohexane, 1,8-dibromooctane, 1,4-dibromoheptane, 1,7-dibromoheptane, 1,10-dibromodecane, 1,12-dibromododecane, 1,6-diiodohexane, 1,4-diiodobutane, 1,10-diiododecane, 1,5-diiodopentane, 1,8-diiodooctane, α,α'-dichloro-p-xylene, 4,4'-bis(chloromethyl)-1,1'-biphenyl, a cationic crosslinking agent of formula 7, or any combination thereof, wherein the cationic crosslinking agent has the following formula: in: A is an anion; q is an integer between 1 and 100; R 21 R 22 R 23 R 24 R 25 and R 26 Each is independently alkyl or aryl; X and Y are each independently Cl, Br, or I; and Z can be either N or P.

23. An anion exchange membrane, the anion exchange membrane being constructed and sized to be suitable for use in fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, water demineralization, ultrapure water production, wastewater treatment, ion exchangers, or CO2 separators, and comprising a polymer according to any one of claims 1 to 7.

24. An anion exchange membrane fuel cell, electrolyzer, electrodialyzer, solar hydrogen generator, flow battery, desalination device, sensor, water demineralization device, ultrapure water production device, wastewater treatment device, ion exchanger, or CO2 separator, comprising the polymer according to any one of claims 1 to 7.

25. An enhanced ion exchange membrane or electrolyte membrane, the enhanced ion exchange membrane or electrolyte membrane being optionally configured and sized to be suitable for use in fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, demineralizers, water purifiers, wastewater treatment systems, ion exchangers, or CO2 separators, said enhanced membrane comprising a porous substrate impregnated with a polymer according to any one of claims 1 to 7.

26. The membrane of claim 25, wherein the porous substrate comprises a membrane made of polytetrafluoroethylene, polypropylene, polyethylene, poly(ether) ketone, polyaryletherketone, imidazole-linked poly(arylalkylene), imidazole-onium-linked poly(arylalkylene), polysulfone, perfluoroalkoxyalkane, or fluorinated ethylene propylene polymer, and the membrane is optionally a dimensionally stable membrane.

27. The membrane according to claim 25 or 26, wherein: The porous substrate has a porous microstructure of polymer fibrils; By impregnating the porous substrate with the polymer, the internal volume of the substrate is substantially closed. The porous substrate comprises a microstructure of nodes interconnected by fibrils; The porous substrate has a thickness of about 1 micrometer to about 100 micrometers; The film is prepared by repeatedly impregnating the substrate with the polymer; or The membrane is prepared by the following steps: The porous substrate is wetted in a liquid to form a wetted substrate; The polymer is dissolved in a solvent to form a homogeneous solution or suspension; The solution or suspension is applied to the wetted substrate to form the reinforced film; as well as The membrane is dried.

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