Oxidation-resistant polymers for use as anion exchange membranes and ionomers

Abstract

Hydroxide exchange membranes (HEMs) and hydroxide exchange ionomers (HEIs) are provided that include polymers with oxidation-resistant groups. The attachment of the oxidation-resistant groups to the polymer backbone allows for fine tuning of the membrane's mechanical properties and the incorporation of alkaline stable cations, such as imidazolium, phosphonium, and ammonium, providing enhanced stability to the polymer. HEMs / HEIs formed from these polymers exhibit superior chemical stability, anion conductivity, reduced water uptake, good solubility in selected solvents, and improved mechanical properties at ambient dry conditions compared to conventional HEMs / HEIs. HEMs exhibit enhanced stability in highly oxidizing environments.

Description

[Technical field]

[0001] (Government License Rights) This invention was made in part with Government support under Grant DE-EE0008438 awarded by the Office of Energy Efficiency and Renewable Energy of the United States Department of Energy. The Government has certain rights in this invention.

[0002] FIELD OF THEINVENTION Anion exchange membranes (AEM) and ionomers (AEI) are provided that have excellent oxidative stability and are for use in anion exchange membrane electrochemical devices, including anion exchange membrane fuel cells (AEMFC), anion exchange membrane electrolyzers (AEMEL), and flow batteries. More specifically, hydroxide exchange polymers capable of forming hydroxide-exchange membranes (HEM) and ionomers (HEI) for use in hydroxide exchange membrane fuel cells (HEMFC), hydroxide exchange membrane electrolyzers (HEMEL), and hydroxide exchange membrane flow batteries are provided. [Background technology]

[0003] Proton exchange membrane fuel cells (PEMFCs) are considered to be a clean and efficient power source. Steele et al., Nature 2001, 414, 345. However, the high cost and unsatisfactory durability of the catalysts are the main barriers to large-scale commercialization of PEMFCs. Borup et al., Chem Rev 2007, 107, 3904. By switching the polymer electrolyte from "acidic" to "basic" conditions, HEMFCs can function with non-precious metal catalysts, which are expected to be more durable. Other cheaper fuel cell components such as metal bipolar plates are also possible. 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. However, currently available HEM and HEI exhibit poor alkaline / chemical stability, poor hydroxide conductivity, high water absorption, and poor mechanical integrity under dry conditions, especially after wet-dry cycles.

[0004] The targeted durability of commercial automotive and stationary FC systems is 5000 and 40000 hours, with premature membrane failure mainly resulting from physical and chemical degradation (Walter Merida et al, Journal of Power Sources 2008, 184, 104; Borup et al. Chemical Reviews, 2007, 107, 3904). Chemical degradation, more specifically oxidative degradation, involving hydroxyl and hydroperoxy radicals, is the most challenging problem for FCs and ELs, as these oxidative radicals are generated during the operation of FCs and ELs and can cause the degradation of polymers that are supposed to be immune to oxidation (METisack, et al, J. Power Sources, 2004, 131, 41; RC McDonald, et al, ECS Trans. 2006, 1, 199). Perfluorinated PEMs have been found to have much higher oxidative stability compared to their hydrocarbon-based analogues. (R.C. McDonald, et al., In Handbook of Fuel Cells-Fundamentals, Technology and Application; John Wiley & Sons: New York, 2003; Vol. 3). As a result, hydrocarbon-based HEM / HEIs are more susceptible to oxidative degradation, and new chemistries are critically needed to improve the oxidation resistance of HEM / HEIs.

[0005] Another concern with current HEM / HEIs is their hydroxide conductivity. Compared to Nafion, HEMs have inherently 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. To achieve higher hydroxide conductivity, a higher ion-exchange capacity (IEC) is required for HEM / HEIs. However, high IEC usually results in membranes with high water uptake (high swelling ratio), which reduces the membrane's morphological stability and mechanical strength, especially after repeated wet-dry cycles. This highly swollen state in the wet state is the main reason for the reduced flexibility and brittleness of HEMs when dried. Eliminating the trade-off between high hydroxide conductivity and low water uptake is a major impediment in designing high-performance HEM / HEIs. Pan et al.,Energ Environ Sci 2013,6,2912. Chemical cross-linking, physical reinforcement, side chain polymerization, and block copolymer structures have been attempted to reduce water uptake while maintaining acceptable hydroxide conductivity, but these techniques result in difficult problems, such as reduced mechanical flexibility, reduced alkaline stability, and / or increased cost. 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. In addition, almost all side chain or block copolymer HEMs are based on flexible aliphatic polymer chains due to the limited synthesis methods available. As a result, the membranes still cannot provide morphological stability (low expansion ratio) at high IEC and high temperature.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.

[0006] A further obstacle to using HEMs is the achievement of mechanical flexibility and strength in ambient dry conditions. Most HEMs exhibit low mechanical strength and are very brittle in completely dry conditions, especially after full expansion. It is difficult to obtain and handle thin membranes of large sizes as required for commercial use of HEMs. Without good mechanical properties, ionomers cannot form and maintain a proper three-phase structure in fuel cell electrodes at high temperatures, such as above 80°C. Li et al., J Am Chem Soc 2013,135,10124.

[0007] Another highly desirable feature of the HEI is that the polymer is soluble in mixtures of low boiling alcohols and water, but insoluble in pure alcohol or water, so that the HEI can be easily incorporated into the electrocatalyst layer, but is not dissolved away by water or alcohol.

[0008] PEMFCs have recently been deployed as zero-emission power sources in commercially sold automobiles, demonstrating long driving ranges and short refueling times, two features favorable for customer acceptance. However, PEMFCs use platinum electrocatalysts and are not yet cost-competitive with gasoline engines. The main approaches to PEMFC cost reduction include the development of low platinum loading, high power density membrane electrode assemblies (MEAs), and platinum-group-metal-free (PGM-free) cathode catalysts. A fundamentally different route to low-cost fuel cells is to switch from PEMFCs to hydroxide exchange membrane fuel cells (HEMFCs), which, due to their basic operating environment, can operate with PGM-free anode and cathode catalysts and are therefore potentially economically viable. However, to replace PEMFCs, HEMFCs must offer performance that matches that of PEMFCs, which in turn requires highly active anode and cathode catalysts, as well as highly chemically stable, ionically conductive, and mechanically robust hydroxide exchange membranes (HEMs) / hydroxide exchange ionomers (HEIs) to establish efficient three-phase boundaries, thus dramatically improving catalyst particle utilization and reducing internal resistance.

[0009] HEM / HEIs are typically composed of organic cations tethered to a polymer backbone, with OH- being the charge-balancing anion. So far, almost all HEM / HEIs are non-fluorinated and have hydrocarbon-based cationic groups (e.g., benzyltrimethylammonium) and polymer backbones (e.g., polysulfones), which have poor alkaline / oxidative stability, resulting in HEMFCs and HEMELs with durability of less than 1000 hours (John Varcoe et al, J. Mater. Chem. A, 2018, 6, 15404; BS Pivovar, et al. J Electrochem Soc, 2019, 166, 637). Fluorinated HEM / HEIs have not been available so far due to the difficulty and high cost of synthesis. Herein, a novel approach is provided by covalently tethering an oxidation resistant group (ORG) to HEM / HEI, which utilizes existing HEM / HEI platforms and allows for maximum preservation of original membrane properties. Radical scavengers such as organic nitroxides are ORGs that are known to trap and quench radicals. (Hanns Fischer et al, J Am Chem Soc 2001, 123, 2849; SR Powell et al, Proc. Natl. Acad. Sci. USA 1991, 88, 4680). Once HEM / HEI are covalently tethered with such radical scavengers, they are insensitive to hydroxyls and hydroperoxyls generated in FCs and ELs, ensuring durable HEMFCs and HEMELs. Unlike cerium oxide, which is physically mixed and blended in PEMFCs, radical scavengers chemically bound to HEM / HEI will not wash away / dissolve during device operation, providing HEM / HEI with permanent oxidation resistance. (Vijay Ramani et al, Electrochem. Solid-State Lett, 2008, 11, B113; Fernando H Garzon et al, J. Electrochem. Soc. 2011, 158, B1175).Another approach to improving the oxidation resistance of HEM / HEI is to physically blend the HEM / HEI with ORG containing small molecules, oligomers and polymers, optionally covalently linking the ORG containing molecules to the HEM / HEI backbone after blending. Summary of the Invention

[0010] In a first aspect of the present invention, a polymer for improved oxidation resistance is provided. The polymer has the formula (1A ORG ) and / or (2A ORG ) structural units of the formulae (3A) and (4A ORG ) and (5A ORG and at least one structural unit of the formula (1A ORG ), (2A ORG ), (3A), (4A ORG ) and (5A ORG The structural unit of ) has the following structure:

[0011] [ka] having During the ceremony, A is aryl; n1 is 1, 2, 3, or 4; n2 is 0, 1, 2, 3 or 4; R1, R 13 , and R 18 are each independently alkylene, alkenylene, alkynylene, or arylene, the alkylene, alkenylene, alkynylene, or arylene being optionally substituted with a halide, or R 13 does not exist, R2 and R 19 are each independently -NH2, -NHR3, -NR3R4, -NO, -NS, or a nitrogen-containing heterocycle, wherein the nitrogen of the heterocycle has an oxygen, sulfur, or hydrogen substituent; R3 and R4 are each independently an alkyl, alkenyl, alkynyl, or aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R5, R6, R7, R8, R9, R 10 , R 11 , and R 12 are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; and R6 and R9 are optionally linked to form a 5-membered ring, optionally substituted with a halide or an alkyl; R 16 and R 17 is independently alkylene optionally substituted with halide or alkyl; Z is independently hydrogen, hydroxyl, oxygen, or sulfur.

[0012] In a second aspect of the present invention, there is also provided another polymer exhibiting improved oxidation resistance. The polymer comprises: (i) The following formula (1 ORG )

[0013] [ka] and / or The following formula (2 ORG )

[0014] [ka] and (ii) at least one aromatic monomer, The following formula (3)

[0015] [ka] or The following formula (4ORG )

[0016] [ka] or A compound having a nitrogen-containing substituent and having the following formula (5 ORG )

[0017] [ka] and wherein the reaction product of a polymerization mixture includes at least one aromatic monomer, the aryl monomer having the formula: During the ceremony, A, n1, n2, R1~R 13 , R 16 ~R 19 and Z is as defined above, R 14 and R 15 is each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide.

[0018] As a third aspect of the present invention, there is provided yet another polymer for providing improved oxidation resistance. The polymer has the formula (4A ORG ) and / or (5A ORG ) structural units of the formula (1A ORG ), (2A ORG and at least one of the formula (1A), (6A), (7A), (8A) and (9A), ORG ), (2A ORG ), (4A ORG ), (5A ORG ) are as described above, and the structural units of the formulae (6A), (7A), (8A) and (9A) have the following structures:

[0019] [ka] having During the ceremony, A, R1 to R4, R 16 ~R 19 and Z is as defined above, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; n is 1, 2, 3, 4, 5, 6, 7 or 8; q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; Q is N or P; Each R 20 is independently hydrogen, hydroxyl, halide, alkyl, alkenyl, alkynyl, or aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with halide; Each R 21 is independently an alkyl, alkenyl, or alkynyl, or a substituent of formula (8A-1);

[0020] [ka] The alkyl, alkenyl, or alkynyl is optionally substituted with a halide; R 22 is a halide, or a quaternary ammonium or phosphonium group, or a nitrogen-containing heterocyclic group, or a salt thereof, the quaternary ammonium or phosphonium group having the formula (9A-1):

[0021] [ka] the nitrogen-containing heterocyclic group is an optionally substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, quinoline, piperidine, pyrrolidine, pyrazolidine, imidazolidine, azepane, isoxazole, isoxazoline, oxazole, oxazoline, oxadiazole, oxatriazole, dioxazole, oxazine, oxadiazine, isoxazolidine, morpholine, thiazole, isothiazole, oxathiazole, oxathiazine, or caprolactam, each substituent being independently alkyl, alkenyl, alkynyl, aryl, or aralkyl; R 23 , R 24 , R 25 , R 26 , and R 27 are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R 28 and R 29 are each independently alkylene; R 30 , R 31 , R 32 , R 33 , and R 34 are each independently alkyl, alkenyl, or alkynyl; X - is an anion.

[0022] As a fourth aspect of the present invention, yet another polymer for improved oxidation resistance is provided. The polymer comprises: (i) The following formula (4 ORG ) and / or A compound having a nitrogen-containing substituent and having the following formula (5 ORG ), and (ii) the following monomer: The above formula (1 ORG ), The above formula (2 ORG ) a trifluoromethyl ketone monomer having the formula A piperidone monomer having the formula (6), or a salt or hydrate thereof:

[0023] [ka] An azoniaspiro salt monomer having the formula (7):

[0024] [ka] A trifluoromethyl ketone monomer having the formula (8):

[0025] [ka] The reaction product of a polymerization mixture comprising at least one halogenated trifluoromethyl ketone monomer having formula (9):

[0026] [ka] In the formula, A, m, n, q, Q, R1 to R4, R 16 ~R 34 , X - and Z is as defined above.

[0027] In a fifth aspect of the present invention, there is provided another polymer for improving oxidation resistance. The polymer is represented by the formula (6A ORG ) and (3A) structural units,

[0028] [ka] During the ceremony, n1, n2, Q, R5~R 13 , R 20 and X - is as defined above, n3 and n5 are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; n4 is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; R 59 -(CH2)n3-[Q(R 60 )(R 61 )-(CH2) n4 ] n5 -R 62 or -[(CH2) n3 -O] n5 -R 62 and R 60 and R 61 are each independently alkyl, alkenyl, or alkynyl; R 62 is a nitrogen-containing heterocycle, where the nitrogen of the heterocycle has an oxygen, sulfur, or hydrogen substituent.

[0029] In an eighth aspect of the present invention, there is provided another polymer for improving oxidation resistance, the polymer comprising: (i) a polymer having the formula (10),

[0030] [ka] (ii) The following formula (11 ORG ),

[0031] [ka] During the ceremony,

[0032] [ka] represents a polymer backbone comprising at least one polyaryletherketone (PAEK) derivative, polysulfone (PSU) derivative, polystyrene (PS) derivative, poly(p-phenylene oxide) derivative, styrene-ethylene-butylene-styrene (SEBS) derivative, polyethylene derivative, poly(norbornene) derivative, or poly(arylalkylene) derivative structural unit; m1, m2, and m6 are each independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; m3, m4, m5, and m7 are each independently 0, 1, 2, 3, or 4; R 35 , R 36 , R 37 , R 40 , R 41 , R 42 , and R 43 are each independently alkylene, arylene, alkenylene, alkynylene, ether, thioether, keto, amino, ammonium, or piperidinyl, wherein the alkylene, arylene, alkenylene, or alkynylene is optionally substituted with a halide; R 38 is a halide, mesylate, tosylate, azide, alkenyl, or alkynyl; R 39 is an amine, a phosphine, a thiol, a hydroxyl, an alkenyl, or an alkynyl, or R 38 is an amine, a phosphine, a thiol, a hydroxyl, an alkenyl, or an alkynyl; R 39 is a halide, mesylate, tosylate, azide, alkenyl, or alkynyl; R 44 But -NH2, -NHR 45 , -NR 45 R 46 , -NO, -NS, or a nitrogen-containing heterocycle, the nitrogen of the heterocycle having an oxygen, sulfur, or hydrogen substituent; R45 and R 46 is each independently an alkyl, alkenyl, alkynyl, or aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; The PAEK derivative structural unit has the formula:

[0033] [ka] having The PSU derivative structural unit has the following formula:

[0034] [ka] having The PS derivative structural unit has the following formula:

[0035] [ka] having The poly(p-phenylene oxide) derivative structural unit has the following formula:

[0036] [ka] having The SEBS derivative structural unit has the following formula:

[0037] [ka] having The polyethylene derivative structural unit has the following formula:

[0038] [ka] having The poly(norbornene) derivative structural unit has the formula:

[0039] [ka] having The poly(aryl alkylene) structural unit has the formula:

[0040] [ka] has.

[0041] In a ninth aspect of the present invention, there is provided yet another polymer for improving oxidation resistance, the polymer comprising: (i) a polymer having a backbone that contains a nitrogen-containing heterocyclic ring or a nitrogen-containing heterocyclic ring attached to an aryl or heterocyclic ring; or A polymer comprising at least two of the structural units of the above formulae (3A), (6A), (7A), (8A) and (9A), wherein m, n, n1, n2, n3, n4, n5, q, Q, R5 to R 13 , R 20 ~R 34 , and X - is as defined above, and (ii) Formula (12 ORG ),

[0042] [ka] During the ceremony, m8 and m10 are each independently 0, 1, 2, 3, or 4; m9 is independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; R 47 is a halide, mesylate, tosylate, azide, alkenyl, or alkynyl; R 48 , R 49 , R 50 , and R 51are each independently alkylene, arylene, alkenylene, alkynylene, ether, thioether, keto, amino, ammonium, or piperidinyl, wherein the alkylene, arylene, alkenylene, or alkynylene is optionally substituted with a halide; R 52 But -NH2, -NHR 53 , -NR 53 R 54 , -NO, -NS, or a nitrogen-containing heterocycle, the nitrogen of the heterocycle having an oxygen, sulfur, or hydrogen substituent; R 53 and R 54 is each independently an alkyl, alkenyl, alkynyl, or aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide.

[0043] Other objects and features will be in part apparent and in part pointed out hereinafter. [Brief description of the drawings]

[0044] [Figure 1A] 1 illustrates an exemplary hydroxide exchange membrane fuel cell. [Figure 1B] 1 illustrates an exemplary hydroxide exchange membrane electrolyzer. [Diagram 2] 1H NMR spectrum of MQN-TMPH in CDCl3. [Diagram 3] 1H NMR spectrum of PAP-MQN-TMPH in DMSO-d6. [Figure 4] Water uptake of PAP-MQN-TMPH compared to PAP-TP-85 and PAP-MQN is shown. [Diagram 5] 1 shows the swelling ratio of PAP-MQN-TMPH compared to PAP-TP-85 and PAP-MQN. [Figure 6] DMA of PAP-MQN-TMPH is shown. [Figure 7A] 1 shows the through plane conductivity of PAP-MQN-TMPH in the HCO3- and Cl- forms. [Figure 7B] 1H NMR of PAP-MQN after immersion in Fenton's reagent for 72 hours. [Figure 7C] 1 shows HNMR of PAP-MQN-TMPH before testing and after immersion in Fenton's reagent for 72 hours. [Figure 7D] 1 shows the H NMR of TP85 after immersion in Fenton's reagent. [Figure 8] 1H NMR of S6 in CDCl3 and PFu-BP-C2-50 in DMSO, respectively. [Figure 9] 1H NMR of S6 in CDCl3 and PFu-BP-C2-50 in DMSO, respectively. [Figure 10A] 1 shows the membranes PPO-C2-TEMPO and PPO-TMA after immersion in Fenton's reagent for 65 hours. [Figure 10B] 1 shows the water uptake of PFu-TEMPO-40 and PFu-TEMPO-50 after immersion in Fenton's reagent. [Figure 10C] 1 shows the conductivity of PFu-TEMPO-40 and PFu-TEMPO-50 after immersion in Fenton's reagent. [Figure 10D] 1H NMR of PPO-C2-TEMPO, PATF-TP-Br, and PATF-TP-C2-TEMPO-0.9 in DMSO-d6, respectively. [Figure 11] 1H NMR of PPO-C2-TEMPO, PATF-TP-Br, and PATF-TP-C2-TEMPO-0.9 in DMSO-d6, respectively. [Figure 12] 1H NMR of PPO-C2-TEMPO, PATF-TP-Br, and PATF-TP-C2-TEMPO-0.9 in DMSO-d6, respectively. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0045] It has been discovered that HEM / HEI polymers with ORG and inherent hydroxide conducting channels simultaneously provide improved chemical stability, conductivity, water uptake, good solubility in selected solvents, mechanical properties, and other attributes related to HEM / HEI performance. The attachment of ORG to the polymer backbone allows for fine tuning of the membrane mechanical properties and the incorporation of alkaline stable cations such as imidazolium, phosphonium, and ammonium, providing improved stability to the polymer. HEM / HEIs formed from these polymers exhibit superior chemical stability, anion conductivity, reduced water uptake, good solubility in selected solvents, and improved mechanical properties at ambient dry conditions compared to conventional HEM / HEIs. The HEMs of the present invention exhibit improved stability in highly oxidizing environments.

[0046] In a first aspect of the present invention, a polymer for improved oxidation resistance is provided. The polymer has the formula (1A ORG ) and / or (2A ORG ) structural units of the formulae (3A) and (4A ORG ) and (5A ORG and at least one structural unit of the formula (1A ORG ), (2A ORG ), (3A), (4A ORG ) and (5A ORG The structural unit of A has the above-mentioned structure, and A, n1, n2, R1 to R 13 , R 16 ~R 19 and Z is as defined above.

[0047] The polymer of formula (1A ORG ) and (2A ORG The sum of the mole fractions of structural units of the formulae (3A), (4A ORG ), and (5A ORG The molar fraction of the structural units of the formulae (3A), (4A) in the polymer may be approximately equal to the sum of the molar fractions of the structural units of the formulae (3A), (4A) ORG ), and (5A ORG The sum of the molar fraction of structural units of formulae 1A and 2A in the polymer relative to the sum of the molar fraction of structural units of formulae 1A and 2A) may be about 0.01 to 1.

[0048] Formula (1A ORG ) and (2A ORG The sum of the mole fractions of structural units of formula (3A), (4A ORG ), and (5A ORG The molar ratio of the structural units of formula (1A) to the sum of the molar fractions of the structural units of formula (1A) may be about 0.95:1 to about 1.4:1. ORG ) and (2A ORG The sum of the mole fractions of structural units of formula (3A), (4A ORG ), and (5A ORG ) may have a ratio of about 0.01 to 1 to the sum of the molar fractions of the structural units.

[0049] Formula (1A ORG ) and (2A ORG The sum of the mole fractions of structural units of formula (3A), (4A ORG ), and (5A ORG ) may have a molar ratio of about 1:1 to about 1.2:1 relative to the sum of the molar fractions of the structural units.

[0050] Structural unit (2A ORG ) is expressed as follows:

[0051] [ka] may have:

[0052] For example, (2A ORG ) may be any of the following structural units:

[0053] [ka] In the formula, n is 1 to 12.

[0054] In the structural unit (3A), R 13 When is alkyl, examples of representative structural units include:

[0055] [ka] Examples include:

[0056] Structural unit (4A ORG ) is expressed by the formula (4A ORG -1) and / or (4A ORG -2) and / or (4A ORG -3)

[0057] [ka] The compound may include a structural unit having the following structure:

[0058] The following is (4A ORG ) Structural unit

[0059] [ka] This is an example.

[0060] The polymer may further comprise at least one of the structural units (6A), (7A), (8A) or (9A) described above, and m, n, q, Q, R 20 ~R 34 and X - is as defined above.

[0061] An example of structural unit (7A) is:

[0062] [ka] It is.

[0063] As a further aspect of the invention, any of the structural units (3A), (6A), (7A), (8A) and / or (9A) described above can be modified with any of the ORG groups described herein. Example 19 is an example of such a modification of structural unit (9A).

[0064] Below is an example of a (3A) structural unit modified to include an ORG substituent:

[0065] [ka] In the formula, Z is hydrogen, oxygen, or sulfur.

[0066] Preferably, X in any of the structural units, monomers, or polymers described herein - The anions are halides, BF4 - , PF6 - , CO3 2- or HCO3.

[0067] The nitrogen-containing heterocyclic group or nitrogen-containing heterocycle in any of the structural units, monomers, or polymers described herein may be an optionally substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, quinoline, piperidine, pyrrolidine, pyrazolidine, imidazolidine, azepane, isoxazole, isoxazoline, oxazole, oxazoline, oxadiazole, oxatriazole, dioxazole, oxazine, oxadiazine, isoxazolidine, morpholine, thiazole, isothiazole, oxathiazole, oxathiazine, or caprolactam, where each substituent is independently alkyl, alkenyl, alkynyl, aryl, or aralkyl.

[0068] The nitrogen-containing heterocyclic group may be unsaturated, such as pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, or quinoline, and any substitutable positions of the heterocycle may be independently substituted with alkyl (e.g., methyl, ethyl, propyl, n-butyl) or aryl groups (e.g., phenyl with alkyl substituents).

[0069] Alternatively, the nitrogen-containing heterocycle may be saturated, for example, the nitrogen-containing heterocycle may be 2,2,6,6-tetramethylpiperidine.

[0070] The nitrogen-containing heterocyclic group may include an imidazolium group having the formula (9A-2):

[0071] [ka] In the formula, R 55 , R 56 , R 57 and R 58 are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, the alkyl, alkenyl, alkynyl, or aryl being optionally substituted with a halide; X - is as described above. Preferably, R 55 is 2,4,6-alkylphenyl, R 56 , R 57 and R 58 are each independently C1 to C6 alkyl. An example of an imidazole as a nitrogen-containing heterocycle is represented by the following formula:

[0072] [ka] The compound is 1-butyl-2-mesityl-4,5-dimethyl-1H-imidazole-imidazole having the formula:

[0073] As a second aspect of the invention, there is also provided a polymer that exhibits improved oxidation resistance. Whereas the polymer of the first aspect of the invention is defined in terms of the structural units within the polymer, the polymer of the second aspect of the invention defines the polymer in terms of the monomers used in making the polymer. The polymer may be (i) The above formula (1 ORG ), and / or Formula(2 ORG ) and (ii) at least one aromatic monomer, a phenyl-based monomer having the formula (3), ORGor a nitrogen-containing substituent and having the formula (5 ORG ), wherein A, n1, n2, R1-R2 are each independently an integer of 1 to 10, and R2 is an integer of 1 to 10. 19 and Z is as defined above.

[0074] Trifluoromethyl ketone monomer (2 ORG ) is expressed by the formula (2 ORG -1)

[0075] [ka]

[0043]

[0076] Nitrogen Heterocycle-Aryl Monomers (4 ORG ) is expressed by the formula (4 ORG -1)

[0077] [ka] and optionally comprising an isoindoline monomer having the formula: wherein the dibenzo ring is optionally present and Z is as defined above.

[0078] Nitrogen Heterocycle-Aryl Monomers (4 ORG ) is expressed by the formula (4 ORG -2)

[0079] [ka] and optionally comprising a benzo[de]isoquinoline monomer having the formula: In the formula, Z is as defined above.

[0080] (4 ORG ) Examples of monomers are provided below.

[0081] [ka]

[0082] The polymerization mixture may further comprise at least one of the following monomers: a piperidone monomer having formula (6), or a salt or hydrate thereof, an azoniaspirosalt monomer having formula (7), a trifluoromethyl ketone monomer having formula (8), or a halogenated trifluoromethyl ketone monomer having formula (9), all as described above.

[0083] Any of the structural units (3), (6), (7), (8) and / or (9) can be modified with any of the ORG groups described herein.

[0084] (3 ORG An example of a (3) monomer that has been modified to become a (4) monomer is provided below.

[0085] [ka]

[0086] In a third aspect of the present invention, there is provided a polymer for providing improved oxidation resistance. The polymer has the formula (4A ORG ) and / or (5A ORG ) structural units of the formula (1A ORG ), (2A ORG and at least one of the formula (1A), (6A), (7A), (8A) and (9A), ORG ), (2A ORG ), (4A ORG ), (5A ORG ), (6A), (7A), (8A) and (9A) have the above-mentioned structures, and A, m, n, q, Q, R1 to R4, R 16 ~R 34 , X - and Z is as defined above.

[0087] The polymer of formula (1A ORG ), (2A ORGThe sum of the mole fractions of structural units of formula (4A), (6A), (7A), (8A) and (9A) in the polymer is ORG ) and (5A ORG ) in the polymer, ORG ) and (5A ORG ) in the polymer relative to the sum of the mole fractions of structural units of the formula (1A ORG ), (2A ORG The sum of the molar fractions of the structural units (6A), (7A), (8A) and (9A) may be about 0.01 to 1.

[0088] Formula (1A ORG ), (2A ORG The sum of the mole fractions of structural units of formula (4A), (6A), (7A), (8A) and (9A) in the polymer ORG ) and (5A ORG The molar ratio of the structural units of formula (1A) to the sum of the molar fractions of the structural units of formula (1A) may be about 0.95:1 to about 1.4:1. ORG ), (2A ORG The sum of the mole fractions of structural units of formula (4A), (6A), (7A), (8A) and (9A) ORG ) and (5A ORG ) may have a ratio of about 0.01 to 1 to the sum of the molar fractions of the structural units.

[0089] Formula (1A ORG ), (2A ORG The sum of the mole fractions of structural units of formula (4A), (6A), (7A), (8A) and (9A) in the polymer ORG ) and (5A ORG ) may have a molar ratio of about 1:1 to about 1.2:1 relative to the sum of the molar fractions of the structural units.

[0090] Structural unit (2A ORG ) is expressed by the above formula (2A ORG -1).

[0091] Structural unit (4A ORG ) is expressed by the above formula (4A ORG -1), (4A ORG -2), or (4AORG -3).

[0092] The polymer may further comprise structural units of formula (3A) above. Examples of (3) monomers are:

[0093] [ka] It is.

[0094] In a fourth aspect of the invention, a polymer for improved oxidation resistance is provided. Whereas the polymer of the third aspect of the invention is defined in terms of the structural units within the polymer, the polymer of the fourth aspect of the invention defines the polymer in terms of the monomers used in making the polymer. The polymer comprises: (i) The following formula (4 ORG ) and / or A compound having a nitrogen-containing substituent and having the following formula (5 ORG ), and (ii) the following monomer: Formula(1 ORG ), Formula(2 ORG ) a trifluoromethyl ketone monomer having the formula A piperidone monomer having the formula (6), or a salt or hydrate thereof: An azoniaspiro salt monomer having the formula (7): a trifluoromethyl ketone monomer having the formula (8): The reaction product of a polymerization mixture comprising at least one halogenated trifluoromethyl ketone monomer having formula (9): In the formula, A, m, n, q, Q, R1 to R4, R 16 ~R 34 , X - and Z is as defined above.

[0095] Trifluoromethyl ketone monomer (2 ORG ) is expressed by the above formula (2 ORG-1).

[0096] Nitrogen Heterocycle-Aryl Monomers (4 ORG ) is expressed by the formula (4 ORG -1), or an isoindoline monomer having the formula (4 ORG -2), or the benzo[de]isoquinoline monomer having the formula (4 ORG -3) may be included.

[0097] The polymer is made up of n1, n2, and R5 to R 15 The phenyl-based monomer may further comprise a phenyl-based monomer having the above formula (3), wherein

[0098] In a fifth aspect of the present invention, a polymer for improved oxidation resistance is provided. The polymer is of formula (6A) further modified to include an ORG substituent. ORG ) structural units and n1, n2, n3, n4, n5, Q, R5~R 13 , R 20 , R 59 ~R 62 and X - and a structural unit of formula (3A) above, wherein is as defined above. Examples 1 and 13-15 include polymers according to the fifth aspect of the invention.

[0099] R 59 may be an ORG substituent such as a hexenyl TMPH ether, MQN-TMPH, or MQN-TMPH-C2 group.

[0100] The polymer of the fifth aspect of the present invention has the formula (1A ORG ), (2A ORG ), (4A ORG ), (5A ORG ), (6A), (7A), (8A) or (9A).

[0101] A sixth aspect of the present invention is a polymer comprising the reaction product of any one of the polymers described above in the first, second, third, fourth or fifth aspects of the present invention comprising structural units (6A) and / or (9A) (or monomers (6) and / or (9) as starting materials) with a quaternizing agent.

[0102] The quaternizing agent may include a trialkylamine, such as trimethylamine, or an MQN compound, such as MQN-TMPH or MQN-TMPH-C2, having the following formula:

[0103] [ka] Examples 2, 4, 6, 8, 10 and 12 comprise polymers according to the sixth aspect of the invention.

[0104] A seventh aspect of the invention is an anion exchange polymer comprising the reaction product of a quaternized polymer of the sixth aspect of the invention with a base. Examples 2, 4, 6, 8, 10 and 12 comprise a polymer of the seventh aspect of the invention.

[0105] Preferably, the base comprises 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.

[0106] Representative anion exchange polymers according to the seventh aspect of the present invention include the following, in which x is 0.01-1 and y is 0.01-1.

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] Representative polymers having an ORG that does not have ion exchange capacity (for example, the polymer represented by the formula (1) ORG ) or (2 ORG Examples of the structural unit of ) include the following, in which n=5 to 10,000.

[0111] [ka]

[0112] In an eighth aspect of the present invention, there is provided a polymer for improving oxidation resistance, the polymer comprising: (i) a polymer having the above formula (10), and (ii) The following formula (11 ORG ) wherein:

[0113] [ka] m1 to m7, and R 35 ~R 46 The present invention also includes the reaction product of a mixture comprising a compound wherein

[0114] The following are further preferred examples of polymers of formula (10):

[0115] [ka]

[0116] For example, m7 is 1, m5 and m6 are 0, and R 43 is an amine or hydroxyl, and R 44 is a 2,2,6,6-piperidine nitrogen-containing heterocycle, and the nitrogen of the heterocycle has an oxygen or hydrogen substituent, (11 ORG ) monomer has the following formula:

[0117] [ka] has.

[0118] An example of polymer (10) is where m4 is 1, m3 is 2, m2 is 0, and m1 is 1, and R 37 is alkyl, and R 38 are halides.

[0119] Another example is when m7 is 1, m5 is 1, m6 is 0, and R 43 and R 40 is alkylene, and R 39 is an amine and R 44 When is a 2,2,6,6-piperidine nitrogen-containing heterocycle and the nitrogen of the heterocycle has a hydrogen substituent, (11 ORG ) monomer has the following formula:

[0120] [ka] has.

[0121] Another example is when m7 is 1, m5 is 1, m6 is 1, and R 40 , R 41 and R 43 is alkylene, R is ammonium, and R 39 is an amine and R 44 When is a 2,2,6,6-piperidine nitrogen-containing heterocycle and the nitrogen of the heterocycle has a hydrogen substituent, (11 ORG ) monomer has the following formula:

[0122] [ka] has.

[0123] Another example is when m7 is 1, m5 is 1, m6 is 1, and R 40 , R 41 and R 43 is alkylene, and R42 is the ether, and R 39 is an amine and R 44 is a 2,2,6,6-piperidine nitrogen-containing heterocycle, and the nitrogen of the heterocycle has an oxygen or hydrogen substituent, (11 ORG ) monomer has the following formula:

[0124] [ka] wherein n is 1 to 12.

[0125] The mole fraction of structural units of formula 10 in the polymer is ORG ) in the polymer, ORG ) to the mole fraction of structural units of formula 10 in the polymer may be about 0.01 to 1.

[0126] The sum of the mole fractions of structural units of formula 10 in the polymer is expressed as the sum of the mole fractions of structural units of formula (11 ORG The molar ratio of the structural unit of formula (11) to the molar fraction of the structural unit of formula (11) may be from about 0.95:1 to about 1.4:1. ORG The ratio of the molar fraction of the structural units of formula 10 to the molar fraction of the structural units of formula 12 may be about 0.01 to 1.

[0127] The mole fraction of structural units of formula (10) in the polymer is ORG ) may have a molar fraction of structural units of about 1:1 to about 1.2:1.

[0128] Preferably, in the eighth aspect of the present invention, m1, m2, m3, m4 and m6 are 0, m5 is 1, and R 40 is alkylene optionally substituted with halide; R 44 is a nitrogen-containing heterocycle, the nitrogen of the heterocycle having an oxygen, sulfur, or hydrogen substituent; R 39 is an amine.

[0129] In another preferred polymer, R38 is an amine, a tertiary phosphine, a thiol, a hydroxyl, an alkenyl or an alkynyl; R 39 is a halide, mesylate, tosylate, azide, alkenyl, or alkynyl; The PAEK derivative structural unit has the formula:

[0130] [ka] having The PSU derivative structural unit has the following formula:

[0131] [ka] having The PS derivative structural unit has the following formula:

[0132] [ka] having The poly(p-phenylene oxide) derivative structural unit has the following formula:

[0133] [ka] having The SEBS derivative structural unit has the following formula:

[0134] [ka] having The polyethylene derivative structural unit has the following formula:

[0135] [ka] having The poly(aryl alkylene) structural unit has the formula:

[0136] [ka] where Ar is aryl.

[0137] Preferably, m1 to m4 are 0, m6 is 0 or 1, m5 and m7 are 1, and R 41 , R 42 , and R 43 is alkylene optionally substituted with halide; R 41 is ammonium, and R 44 is a nitrogen-containing heterocycle, the nitrogen of the heterocycle having an oxygen, sulfur, or hydrogen substituent; R 39 are halides.

[0138] Another example is when m4 is 1, m3 is 2, m2 is 0, and m1 is 1, then R 37 is alkyl, and R 38 are halides.

[0139] The following is an example of such a polymer (10):

[0140] [ka]

[0141] The following are examples of compounds for use in the polymers described herein: ORG ) monomer.

[0142] [ka]

[0143] In a ninth aspect of the present invention, there is provided another polymer for improving oxidation resistance, the polymer comprising: (i) a polymer having a backbone that contains a nitrogen-containing heterocyclic ring or a nitrogen-containing heterocyclic ring attached to an aryl or heterocyclic ring; or A polymer comprising at least two of the structural units of the above formulae (3A), (6A), (7A), (8A) and (9A), wherein m, n, n1, n2, n3, n4, n5, q, Q, R5 to R 13 , R 20 ~R 34 , and X - is as defined above, and (ii) Formula (12 ORG ),

[0144] [ka] m8~m10, and R 47 ~R 54 is as defined above. The following is (12 ORG ) is an example.

[0145] [ka]

[0146] An example of a polymer having a backbone containing a nitrogen-containing heterocyclic ring attached to an aryl or heterocycle is as follows:

[0147] [ka]

[0148] An example of a polymer comprising at least two of the structural units of formulae (3A), (6A), (7A), (8A) and (9A) is a polymer comprising three structural units, such as a polymer comprising structural units of formulae (3A), (6A) and (8A) as follows:

[0149] [ka] In the formula, Ar is a structural unit of the formula (3A), and x is an integer of 0 to 0.99.

[0150] The polymer of the ninth aspect of the invention may comprise two of the structural units such as those of formulae (3A) and (6A), (3A) and (7A), (3A) and (8A), (3A) and (9A), (6A) and (7A), (6A) and (8A), (6A) and (9A), (7A) and (8A), (7A) and (9A), or (8A) and (9A).

[0151] The polymer of the ninth aspect of the present invention may comprise three of the structural units such as those of formulae (3A), (6A), and (7A), (3A), (6A) and (8A), (3A), (6A) and (9A), (3A), (7A) and (8A), (3A), (7A) and (9A), (3A), (8A) and (9A), (6A), (7A) and (8A), (6A), (7A) and (9A), (7A), (8A) and (9A), and (8A), (6A) and (9A).

[0152] The polymer of the ninth aspect of the invention may comprise four of the structural units such as those of formulae (3A), (6A), (7A) and (8A), (3A), (6A), (7A) and (9A), (3A), (6A), (8A) and (9A), (3A), (7A), (8A) and (9A), and (6A), (7A), (8A) and (9A).

[0153] The polymer of the ninth aspect of the invention may comprise five of the structural units.

[0154] The tenth aspect of the present invention is a method for preparing an anion exchange polymer membrane comprising the anion exchange polymer of the seventh aspect of the present invention. The method includes: reacting an ORG monomer having a trifluoromethylketone group, optionally a trifluoromethylketone monomer, and an aromatic monomer in the presence of an organic solvent and a polymerization catalyst to form a cationically functionalized polymer; dissolving the cationically functionalized polymer in a solvent to form a polymer solution; casting the polymer solution to form a polymer membrane; and exchanging the anion of the polymer membrane with hydroxide ion, bicarbonate ion, or carbonate ion, or a combination thereof, to form an anion exchange polymer membrane.

[0155] For example, an ORG monomer, such as a trifluoromethylketone monomer having a pendant TEMPO derivative, an optional trifluoromethylketone monomer, such as piperidone, 2,2,2-trifluoroacetophenone or 1,1,1-trifluoroacetone, and an aromatic monomer, such as benzene, biphenyl, p-terphenyl, m-terphenyl or p-quaterphenyl, may be placed in a stirred vessel and dissolved or dispersed in an organic solvent. A polymerization catalyst in a solvent may then be added dropwise at -78 to 60°C over a period of up to 60 minutes. The reaction is then continued at this temperature for about 1 to about 120 hours. The resulting solution is slowly poured into an aqueous ethanol solution. The resulting solid is filtered, washed with water, and immersed in 1M K2CO3 at room temperature for about 1 to 48 hours. The product is then filtered, washed with water, and thoroughly dried under high vacuum. The polymer is then reacted with a quaternizing agent, such as methyl iodide, to quaternize the piperidine ring. The cation-functionalized polymer is then subjected to anion exchange, for example, in 1 M KOH at about 20-100° C. for about 12-48 hours for hydroxide exchange, followed by washing and immersion in deionized water for about 12-48 hours in an oxygen-free atmosphere to remove residual KOH.

[0156] The eleventh aspect of the present invention is a method for preparing anion exchange polymer membrane comprising the anion exchange polymer of the seventh aspect of the present invention and an ORG-containing polymer that does not have anion exchange capacity.The method includes: reacting an ORG monomer having trifluoromethylketone group, optionally trifluoromethylketone monomer, and aromatic monomer in the presence of organic solvent and polymerization catalyst to form an ORG-containing polymer; dissolving the ORG-containing polymer together with HEM having ORG in a solvent to form a polymer solution; casting the polymer solution to form a polymer membrane; and exchanging the anion of the polymer membrane with hydroxide ion, bicarbonate ion, or carbonate ion, or a combination thereof, to form an anion exchange polymer membrane.

[0157] For example, ORG monomers, such as trifluoromethyl ketone monomers with pendant TEMPO derivatives, and aromatic monomers, such as benzene, biphenyl, p-terphenyl, m-terphenyl, or p-quaterphenyl, may be placed in a stirred vessel and dissolved or dispersed in an organic solvent. A polymerization catalyst in a solvent may then be added dropwise at -78 to 60°C over a period of up to 60 minutes. The reaction is then continued at this temperature for about 1 to about 120 hours. The resulting solution is slowly poured into an aqueous ethanol solution. The resulting solid is filtered, washed with water, and immersed in 1M K2CO3 at room temperature for about 1 to 48 hours. The product is then filtered, washed with water, and thoroughly dried under high vacuum to obtain a dry ORG-containing polymer that does not have anion exchange capacity.

[0158] An eleventh aspect of the present invention is an anion exchange membrane, optionally configured and sized to be suitable for use in a fuel cell, an electrolyzer, an electrodialyzer, a solar hydrogen generator, a flow battery, a desalination device, a sensor, a demineralizer, a water purifier, a wastewater treatment system, an ion exchanger, or a CO2 separator, comprising the anion exchange polymer of the seventh aspect of the present invention.

[0159] The anion exchange polymer may be made into a reinforced hydroxide exchange membrane as described below. Such a reinforced hydroxide exchange membrane may be prepared by a method including wetting a porous substrate in a liquid to form a wet substrate, dissolving a polymer in a solvent to form a homogeneous solution, applying the solution onto the wet substrate to form a reinforced membrane, drying the reinforced membrane, and exchanging the anions of the reinforced membrane with hydroxide ions to form a reinforced hydroxide exchange polymer membrane. The solution may be applied to the wet substrate by any known membrane forming technique, such as casting, spraying, or doctor knife application.

[0160] The resulting reinforced membrane can be impregnated multiple times with ORG-containing polymer, if desired, by rewetting the reinforced membrane and repeating the dissolving, casting and drying steps.

[0161] The polymerization catalyst used in forming the polymer may include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, heptafluorobutyric acid, or combinations thereof.

[0162] Each of the organic solvents used in any of the above-mentioned methods can be independently selected from polar aprotic solvents (e.g., dimethylsulfoxide, 1-methyl-2-pyrrolidinone, 1-methyl-2-pyrrolidone, 1-methyl-2-pyrrolidone, or dimethylformamide) or other suitable solvents, including, but not limited to, methylene chloride, trifluoroacetic acid, trifluoromethanesulfonic acid, chloroform, 1,1,2,2-tetrachloroethane, dimethylacetamide, or combinations thereof.

[0163] The solvent in the dissolution step may include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, pentanol, hexanol, dimethylsulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, chloroform, ethyl lactate, tetrahydrofuran, 2-methyltetrahydrofuran, water, phenol, acetone, or combinations thereof.

[0164] The liquid used to wet the porous substrate can be a low boiling point solvent such as a lower alcohol (e.g., methanol, ethanol, propanol, isopropanol) and / or water. Preferably, the liquid is absolute ethanol.

[0165] Additional aspects of the invention are described below.

[0166] Anion exchange membranes, such as hydroxide exchange membranes, are also provided, which are 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, and comprise any of the ORG-containing polymers described in the present invention.

[0167] Reinforced electrolyte membranes, such as reinforced hydroxide exchange membranes, are also provided to increase the mechanical robustness of anion exchange membranes for stability through multiple wet and dry cycles (relative humidity cycles) in fuel cells. The membranes are 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, and include a porous substrate impregnated with any of the ORG-containing polymers described in the present invention. Methods for preparing reinforced membranes are well known to those skilled in the art, such as those disclosed in U.S. Patents RE37,656 and RE37,701, which are incorporated herein by reference for the description of the synthesis and materials of the reinforced membranes.

[0168] The porous substrate can include a membrane made of polytetrafluoroethylene, polypropylene, polyethylene, poly(etherketone), polyaryletherketone, containing ORG anchored with imidazolium, containing ORG anchored with imidazole, polysulfone, perfluoroalkoxyalkane, or fluorinated ethylenepropylene polymer, or other porous polymers known in the art, such as the dimensionally stable membranes manufactured by Giner for use in preparing reinforced membranes for fuel cells.Such porous substrates are commercially available, for example, from WL Gore & Associates.

[0169] The porous substrate may have a porous microstructure of polymer fibrils. Such substrates composed of polytetrafluoroethylene are commercially available. The porous substrate may include a microstructure of nodes interconnected by fibrils.

[0170] The interior volume of the porous substrate may be made substantially occlusive by impregnation with an ORG-containing polymer as described herein.

[0171] The porous substrate may have a thickness of from about 1 micron to about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100 microns. Preferably, the porous substrate has a thickness of from about 5 microns to about 30 microns, or from about 7 microns to about 20 microns.

[0172] Also provided is an anion exchange membrane fuel cell, an electrolyzer, an electrolytic dialyzer, a solar hydrogen generator, a flow battery, a desalination device, a sensor, a demineralizer, a water purifier, a wastewater treatment system, an ion exchanger, or a CO2 separator, wherein the fuel cell, the electrolyzer, the electrolytic dialyzer, the solar hydrogen generator, a flow battery, a desalination device, a sensor, a demineralizer, a water purifier, a wastewater treatment system, an ion exchanger, or a CO2 separator comprises an anion exchange polymer.

[0173] The ORG-containing polymers can be used in HEMFCs, such as a typical fuel cell 10 as shown in FIG. 1A. FIG. 1A shows a typical fuel cell 10 having an anode portion 12 (shown on the left) and a cathode portion 14 (shown on the right) separated by an electrolyte membrane 16. The electrolyte membrane 16 can be any membrane containing any of the ORG-containing polymers described herein, and can be a reinforced membrane. Support members are not shown. The anode portion performs an anode half-reaction that oxidizes a fuel to release electrons to an external circuit and produce an oxidation product. The cathode portion performs a cathode half-reaction that reduces an oxidant consuming electrons from the external circuit. Gas diffusion layers (GDLs) 18 and 20 function to distribute the fuel 22 and oxidant 24 uniformly across the respective catalyst layers 26 and 28. Charge neutrality is maintained by the flow of ions from the anode to the cathode for positive ions and from the cathode to the anode for negative ions. The electrolyte membrane is typically selected to be as thin as possible while maintaining the structural integrity of the membrane, so the dimensions shown are not representative.

[0174] In the illustrated hydroxide exchange membrane fuel cell (HEMFC), the anode half reaction consumes fuel and OH- ions and produces wastewater (and carbon dioxide in the case of carbon-containing fuels). The cathode half reaction consumes an oxidant and produces OH- ions, which flow through the electrolyte membrane from the cathode to the anode. The fuel is limited only by the oxidation capacity of the anode catalyst and typically includes hydrogen gas, methanol, ethanol, ethylene glycol, and glycerol. Preferably, the fuel is H2 or methanol. The catalyst is typically platinum (Pt), silver (Ag), or one or more transition metals, such as Ni. In the case of a PEMFC, the anode half reaction consumes fuel and produces H+ ions and electrons. The cathode half reaction consumes oxygen, H+ ions, and electrons to produce wastewater, and the H+ ions (protons) flow through the electrolyte membrane from the anode to the cathode.

[0175] Thus, it can be seen how electrolyte membranes made from ORG-containing polymers significantly improve fuel cell performance. First, higher fuel cell efficiency requires lower internal resistance, and therefore electrolyte membranes with higher ionic conductivity (reduced ionic resistance) are preferred. Second, higher power requires higher fuel cell current, and therefore electrolyte membranes with higher ionic current carrying capacity are preferred. A practical electrolyte membrane should also resist chemical degradation, be mechanically stable in the fuel cell environment, and be easily manufactured.

[0176] The ORG-containing polymers can be used in HEMEL, such as the electrolyzer 30 shown in FIG. 1B. FIG. 1B shows the electrolyzer 30 having an anode portion 32 (shown on the left) and a cathode portion 34 (shown on the right) separated by an electrolyte membrane 36. The electrolyte membrane 36 can be any membrane containing any of the ORG-containing polymers described herein, and can be a reinforced membrane. Support members are not shown. The anode portion performs an anode half-reaction that oxidizes ions and releases electrons to an external circuit to produce an oxidation product. The cathode portion performs a cathode half-reaction that reduces an oxidant consuming electrons from the external circuit. Gas diffusion layers (GDLs) 38 and 40 function to distribute the oxidant 42 and fuel 44 uniformly across the respective catalyst layers 46 and 48. Charge neutrality is maintained by the flow of ions from the anode to the cathode for positive ions and from the cathode to the anode for negative ions. The electrolyte membrane is typically selected to be as thin as possible while maintaining the structural integrity of the membrane, so the dimensions shown are not representative.

[0177] In the illustrated hydroxide exchange membrane fuel cell (HEMFC), the anode half-reaction consumes OH- ions and produces hydrogen. The cathode half-reaction consumes water to produce hydrogen and OH- ions, which flow through the electrolytic membrane from the cathode to the anode. The fuel is limited only by the oxidation capacity of the cathode catalyst and typically includes hydrogen gas, methanol, ethanol, ethylene glycol, and glycerol. Preferably, the fuel is H2 or methanol. The catalyst is typically platinum (Pt), silver (Ag), or one or more transition metals, such as Ni.

[0178] Thus, it can be seen how electrolyte membranes made from ORG-containing polymers significantly improve electrolyzer performance. First, higher electrolyzer efficiency requires lower internal resistance, and therefore electrolyte membranes with higher ionic conductivity (reduced ionic resistance) are preferred. Second, higher fuel production requires higher electrolyzer current, and therefore electrolyte membranes with higher ionic current carrying capacity are preferred. A practical electrolyte membrane should also resist chemical degradation, be mechanically stable in the electrolyzer environment, and be easily manufactured.

[0179] The primary application of ORG containing polymers is for energy conversion such as use in anion exchange membranes, hydroxide exchange membranes, anion exchange membrane fuel cells, and hydroxide exchange membrane fuel cells, however, anion / hydroxide exchange ionomers and membranes can be used for many other purposes such as fuel cells (e.g. hydrogen / alcohol / ammonia fuel cells), electrolyzers (e.g. water / carbon dioxide / ammonia electrolyzers), electrodialyzers, ion exchangers, solar hydrogen generators, desalination (e.g. sea / brackish water desalination), demineralizers (e.g. water demineralizers), water purifiers (e.g. ultrapure water production), wastewater treatment systems, concentration of electrolyte solutions in food, drug, chemical and biotechnology fields, electrolysis (e.g. chlor-alkali production and H2 / O2 production), energy storage (e.g. supercapacitors, metal air batteries and redox flow batteries), sensors (e.g. pH / RH sensors), and other applications where anion conducting ionomers are advantageous.

[0180] Also provided is a reinforced electrolyte membrane, optionally configured and sized to be suitable for use in a fuel cell, an electrolyzer, an electrodialyzer, a solar hydrogen generator, a flow battery, a desalination device, a sensor, a demineralizer, a water purifier, a wastewater treatment system, an ion exchanger, or a CO2 separator. The membrane includes a porous substrate impregnated with an anion exchange polymer.

[0181] Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention as defined in the appended claims. EXAMPLES

[0182] Example 1 The oxidation-resistant HEM is based on the Menshutkin reaction of poly(aryl piperidone) polymer (PAP) with 2,2,6,6-tetramethylpiperidine multiple quaternary ammonium side chains (MQN-TMPH) according to the fifth aspect of the present invention. Poly(aryl piperidone) polymer with 2,2,6,6-tetramethylpiperidine multiple quaternary ammonium side chains (PAP-MQN-TMPH) was synthesized by three main steps: (1) Menshutkin reaction of an alkyl dihalide (e.g., 1,6-dibromohexane (below) or 1,6-diiodohexane) with an aminated piperidine monomer (e.g., an alkyl piperidine amine such as 2,2,6,6-tetramethylpiperidin-4-amine, or an alkyl piperidine alkyl amine such as N,N,2,2,6,6-hexamethylpiperidin-4-amine (below)) to prepare MQN-TMPH, (2) quaternization of PAP with MQN-TMPH, and (3) membrane casting and hydroxide ion exchange. The reaction scheme is shown below.

[0183] [ka]

[0184] (1) Synthesis of MQN-TMPH. To a 200 ml solution of 1,6-dibromohexane (15.4 ml, 0.100 mol, 10 equiv.) in THF, a mixture of diethyl ether (50 ml) and N,N-2,2,6,6-tetramethylpiperidine-4-dimethylamine (2 g, 0.01 equiv.) was added dropwise. After addition, the mixture was stirred for 16 h. A white solid slowly formed. The white precipitate was filtered and washed with cold diethyl ether. After drying under high vacuum, MQN-TMPH (4.37 g, 95% yield) was obtained as a white or pale yellow powder. 1H NMR (400MHz, CDCl3) (Figure 2), δ(ppm)=1.38-1.61(m,16H),1.76-1.86(m,4H),1.86-1. 94(p,2H),2.04,2.07(d,2H),3.36(s,6H),3.39(s,1H),3.45(t,2H),3.67(t,2H).

[0185] (2) Synthesis of PAP-MQN-TMPH. A mixture of 10 ml of N-methyl-4-piperidone (NMP), 1 g of PAP-TP-85-N polymer (prepared as described in Example 10 of WO 2019 / 068051) and 1.28 g of MQN-TMPH (1.2 equivalents) was stirred at 40° C. for 120 hours. The reaction mixture progresses through a solid-liquid mixture to a clear yellow solution, then ends up with a pale yellow NMP solution containing the crude PAP-MQN-TEMPH product as a pale yellow powder or small particles. The resulting NMP slurry was added with 10 ml of acetone, filtered, washed with 3×10 mL of acetone, and dried overnight at 80° C. to obtain the final PAP-MQN-TMPH polymer (2 g, 90% yield, 100% quaternization yield). 1H NMR (400MHz, DMSO-D6) (Figure 3), δ (ppm) = 7.79-7.16 (Ar, 12.75H), 3.99, 3.10, 3.03, 2.22, 2.19, 1.87, 1.68, 1.41, 1.31.

[0186] (3) Membrane Casting. 2 g of PAP-MQN-TMPH was dissolved in 10 ml of DMSO at 80°C. The yellow DMSO solution was filtered through a small piece of medical cotton. The filtered polymer solution was deposited on a clean glass plate and cast into a thin film using a Mayer bar. The film on the glass plate was immediately transferred to a 40°C oven to remove most of the DMSO solvent over 4 hours, followed by annealing at 120°C for 16 hours. The glass plate with the membrane film was then placed in deionized water and peeled off. After drying at ambient temperature and removing defective edges, the final membrane was obtained.

[0187] (4) Ion exchange. The membrane (Br form) was immersed in 1M aqueous NaHCO3 (at least 30 equivalents relative to the repeating unit) at 80 °C for 1 h. After each exchange, the NaHCO3 solution was replaced with fresh solution. This process was repeated four times, and finally the bromide / bromine concentration on the membrane was checked by X-ray fluorescence spectrometer (XRF) (typically less than 0.1 wt% bromide / bromine remained). OH-exchange can be performed five times using the same method with 1M aqueous NaOH.

[0188] (5) Ionomer preparation. 1 g of PAP-MQN-TMPH was dissolved in a solvent mixture of 9.5 g of deionized water and 9.5 g of n-propanol. The yellow solution was filtered through a small piece of medical cotton to obtain the ionomer.

[0189] [Table 1]

[0190] (6) Oxidation stability of PAP-MQN-TMPH. HCO3 -Anion exchange membranes in the form of PAP-MQN-TMPH were placed in freshly prepared Fenton's reagent (20 ppm FeSO4 in 10% H2O2 solution) at room temperature for 72 h. After that, the PAP-MQN-TMPH membrane was still flexible and retained good mechanical properties, while the PAP-MQN membrane (without TEMPO-like units) was almost dissolved. 1H NMR data showed that the backbone of PAP-MQN was degraded (a new peak appeared at approximately 8 ppm), but there was no backbone degradation for PAP-MQN-TMPH after 72 h of testing (no peak appeared at 8 ppm). As a comparison, the oxidation stability of PAP-TP-85 (without oxidation-resistant groups) was tested. HCO3 - The TP85 anion exchange membranes in the form of PAP-TP-85 were placed in freshly prepared Fenton's reagent (4 ppm FeSO4 in H2O2 solutions of different concentrations) at room temperature. The PAP-TP-85 membranes were stable in 3% H2O2 Fenton's reagent. However, PAP-TP-85 was unstable in high-concentration H2O2 solutions. After 24 hours, all the membranes were broken into small pieces, as summarized in Table 2 below. 1H NMR data showed that the framework of PAP-TP-85 was decomposed (a new peak appeared around 8 ppm), as shown in Figure 7D.

[0191] [Table 2]

[0192] Example 2 The oxidation-resistant HEM may be a terphenyl, such as p-terphenyl, m-terphenyl, or a mixture of these two monomers, of formula (3) according to the first and second aspects of the present invention, ORGThe present invention is based on the Friedel-Crafts reaction of 2,2,6,6-tetramethyl-4-piperidone monomers (e.g., 2,2,6,6-tetramethyl-4-piperidone) of formula (1) and piperidone monomers (e.g., 4-methyl-1-piperidone) of formula (6). Terphenyl-based poly(aryl 2,2,6,6-tetramethylpiperidone-co-piperidinium) polymers (PATMP-PIP-TP) were synthesized by three major steps: (1) Friedel-Crafts reaction of terphenyl, 2,2,6,6-tetramethylpiperidone and 4-methyl-1-piperidone to prepare PATMP-TP, (2) quaternization of PATMP-TP with methyl halide (e.g., iodomethane), and (3) membrane casting and hydroxide ion exchange. The reaction scheme is shown below.

[0193] [ka]

[0194] (1) Synthesis of PATMP-TP-60. In a 100 mL three-neck flask equipped with an overhead mechanical stirrer, N-methyl-4-piperidone (0.6790 g, 6 mmol), 2,2,6,6-tetramethylpiperidone (0.6210 g, 4 mmol), and p-terphenyl (2.3031 g, 10 mmol) were dissolved in methylene chloride (10 mL). Then, trifluoroacetic acid (TFA) (0.5 mL) and trifluoromethanesulfonic acid (TFSA) (10 mL) were added dropwise at 0°C over 30 min. The reaction was then continued at this temperature for 36 h. The resulting viscous brown solution was slowly poured into an aqueous ethanol solution. The white fibrous solid was filtered, washed with water, and immersed in 1 M K2CO3 at room temperature for 12 h. Finally, the white fibrous product was filtered, washed with water, and dried completely under high vacuum at 60°C. The polymer yield was nearly 100%. 1H NMR (CDCI3, δ, ppm): 7.77-7.19 (m, 12H), 2.51 (2.4H), 2.22 (4H), and 1.25, 1.22 (4.8H).

[0195] (2) Quaternization of PATMP-TP-60. In a 50 mL one-neck flask equipped with a magnetic bar, PATMP polymer (1.0 g) was dissolved in DMSO (20 mL). Methyl iodide (1 mL) was added quickly. The solution was stirred at room temperature for 12 h. The resulting viscous yellow solution was added dropwise to ether. The yellow solid was filtered, washed with ether, and thoroughly dried under high vacuum at 60 °C. The yield of polymer PATMP-TP-60-MeI was nearly 100%. 1H NMR (DMSO-d6, δ, ppm): 7.98-7.17 (12H), 3.38 (2.4H), 3.17 (3.6H), 2.85 (4H), and 1.31, 1.28 (4.8H).

[0196] (3) Membrane Casting. 2 g of PATMP-TP-60-MeI was dissolved in 10 ml of DMSO at 80°C. The yellow DMSO solution was filtered through a small piece of medical cotton. The filtered polymer solution was deposited on a clean glass plate and cast into a thin film using a Mayer bar. The film on the glass plate was immediately transferred to a 40°C oven to remove most of the DMSO solvent over 4 hours, followed by annealing at 120°C for 16 hours. The glass plate with the membrane film was then placed in deionized water and peeled off. After drying at ambient temperature and removing defective edges, the final membrane was obtained.

[0197] (4) Ion exchange: The membrane was obtained in hydroxide form by ion exchange in 1 M KOH at 25° C. for 24 hours, followed by washing and immersion in deionized water under argon for 48 hours to remove residual KOH.

[0198] Example 3 Another oxidation-resistant HEM is a copolymer of an aromatic monomer of formula (3) (e.g., a terphenyl, such as p-terphenyl, m-terphenyl, or a mixture of these two monomers) and a copolymer of formula (1) according to the first and second aspects of the present invention. ORGPoly(aryl 2,2,6,6-tetramethylpiperidone) polymer (PATMP-TP-0) was synthesized by the Friedel-Crafts reaction of terphenyl with 2,2,6,6-tetramethylpiperidone to prepare PATMP-TP. The reaction scheme is shown below.

[0199] [ka]

[0200] (1) Synthesis of PATMP-TP-0. In a 100 mL three-neck flask equipped with an overhead mechanical stirrer, 2,2,6,6-tetramethylpiperidone (1.5524 g, 10 mmol) and p-terphenyl (2.3031 g, 10 mmol) were dissolved in methylene chloride (10 mL). Then, trifluoroacetic acid (TFA) (0.5 mL) and trifluoromethanesulfonic acid (TFSA) (10 mL) were added dropwise at 0°C over 30 min. The reaction was then continued at this temperature for 36 h. The resulting viscous brown solution was slowly poured into an aqueous ethanol solution. The white fibrous solid was filtered, washed with water, and immersed in 1 M K2CO3 at room temperature for 12 h. Finally, the white fibrous product was filtered, washed with water, and completely dried at 60°C under high vacuum. The polymer yield was nearly 100%. 1H NMR (CDCI3, δ, ppm): 7.77-7.19 (m, 12H), 2.22 (4H), and 1.25, 1.22 (12H).

[0201] Example 4 Another oxidation-resistant HEM is an aromatic monomer of formula (3) (e.g., biphenyl), of formula (1 ORGThe synthesis of biphenyl-based poly(aryl 2,2,6,6-tetramethylpiperidone-co-piperidinium) polymers (PATMP-PIP-BP) was carried out by three main steps: (1) Friedel-Crafts reaction of biphenyl, 2,2,6,6-tetramethylpiperidone and 4-methyl-1-piperidone to prepare PATMP-BP-x, (2) quaternization of PATMP-BP-x with methyl halide (e.g., iodomethane), and (3) membrane casting and hydroxide ion exchange. The reaction scheme is shown below.

[0202] [ka]

[0203] (1) Synthesis of PATMP-BP-60. In a 100 mL three-neck flask equipped with an overhead mechanical stirrer, N-methyl-4-piperidone (0.6790 g, 6 mmol), 2,2,6,6-tetramethylpiperidone (0.6210 g, 4 mmol) and biphenyl (1.5421 g, 10 mmol) were dissolved in methylene chloride (10 mL). Then, trifluoroacetic acid (TFA) (0.5 mL) and trifluoromethanesulfonic acid (TFSA) (10 mL) were added dropwise at 0°C over 30 min. The reaction was then continued at this temperature for 36 h. The resulting viscous brown solution was slowly poured into an aqueous ethanol solution. The white fibrous solid was filtered, washed with water and immersed in 1 M K2CO3 at room temperature for 12 h. Finally, the white fibrous product was filtered, washed with water and completely dried at 60°C under high vacuum. The polymer yield was nearly 100%. 1H NMR (CDCI3, δ, ppm): 7.57-7.19 (m, 8H), 2.51 (2.4H), 2.22 (4H), and 1.25, 1.22 (4.8H).

[0204] (2) Quaternization of PATMP-BP-60. In a 50 mL one-neck flask equipped with a magnetic bar, PATMP polymer (1.0 g) was dissolved in DMSO (20 mL). Methyl iodide (1 mL) was added quickly. The solution was stirred at room temperature for 12 h. The resulting viscous yellow solution was added dropwise to ether. The yellow solid was filtered, washed with ether, and thoroughly dried under high vacuum at 60 °C. The yield of polymer PATMP-TP-60-MeI was nearly 100%. 1H NMR (DMSO-d6, δ, ppm): 7.77-7.17 (8H), 3.38 (2.4H), 3.17 (3.6H), 2.85 (4H), and 1.31, 1.28 (4.8H).

[0205] (3) Membrane Casting. 2 g of PATMP-TP-60-MeI was dissolved in 10 ml of DMSO at 80°C. The yellow DMSO solution was filtered through a small piece of medical cotton. The filtered polymer solution was deposited on a clean glass plate and cast into a thin film using a Mayer bar. The film on the glass plate was immediately transferred to a 40°C oven to remove most of the DMSO solvent over 4 hours, followed by annealing at 120°C for 16 hours. The glass plate with the membrane film was then placed in deionized water and peeled off. After drying at ambient temperature and removing defective edges, the final membrane was obtained.

[0206] (4) Ion exchange: The membrane was obtained in hydroxide form by ion exchange in 1 M KOH at 60° C. for 24 hours, followed by washing and immersion in deionized water under argon for 48 hours to remove residual KOH.

[0207] Example 5 Another oxidation-resistant HEM is a copolymer of an aromatic monomer of formula (3), such as biphenyl, and a monomer of formula (1), such as 2,2,6,6-tetramethylpiperidone, according to the first and second aspects of the present invention. ORGPoly(aryl 2,2,6,6-tetramethylpiperidone) polymer (PATMP-BP-0) was synthesized by the Friedel-Crafts reaction of biphenyl with 2,2,6,6-tetramethylpiperidone to prepare PATMP-BP-0. The reaction scheme is shown below.

[0208] [ka]

[0209] (1) Synthesis of PATMP-BP-0. In a 100 mL three-neck flask equipped with an overhead mechanical stirrer, 2,2,6,6-tetramethylpiperidone (1.5524 g, 10 mmol) and biphenyl (1.5421 g, 10 mmol) were dissolved in methylene chloride (10 mL). Then, trifluoroacetic acid (TFA) (0.5 mL) and trifluoromethanesulfonic acid (TFSA) (10 mL) were added dropwise at 0°C over 30 min. The reaction was then continued at this temperature for 36 h. The resulting viscous brown solution was slowly poured into an aqueous ethanol solution. The white fibrous solid was filtered, washed with water, and immersed in 1 M K2CO3 at room temperature for 12 h. Finally, the white fibrous product was filtered, washed with water, and completely dried at 60°C under high vacuum. The polymer yield was nearly 100%. 1H NMR (CDCI3, δ, ppm): 7.57-7.19 (m, 8H), 2.22 (4H), and 1.25, 1.22 (12H).

[0210] Example 6 Another oxidation-resistant HEM is an aromatic monomer of formula (3) according to the first and second aspects of the present invention (e.g., a terphenyl, such as p-terphenyl, m-terphenyl, or a mixture of these two monomers), a monomer of formula (2) such as 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one, ORGThe terphenyl-based poly(aryl trifluoromethyl ketone) polymers (PATF-TP-x) were synthesized by three major steps: (1) Friedel-Crafts reaction of terphenyl, 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one and 4-methyl-1-piperidone to prepare PATF-TP-x, (2) quaternization of PATF-TP-x with methyl halides (e.g., iodomethane), and (3) membrane casting and hydroxide ion exchange. The reaction scheme is shown below.

[0211] [ka]

[0212] (1) Synthesis of PATF-TP-60. In a 100 mL three-neck flask equipped with an overhead mechanical stirrer, N-methyl-4-piperidone (0.6790 g, 6 mmol), 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one (1.1174 g, 4 mmol) and p-terphenyl (2.3031 g, 10 mmol) were dissolved in methylene chloride (10 mL). Trifluoroacetic acid (TFA) (0.5 mL) and trifluoromethanesulfonic acid (TFSA) (10 mL) were then added dropwise at 0° C. over 30 min. The reaction was then continued at this temperature for 36 h. The resulting viscous brown solution was slowly poured into an aqueous ethanol solution. The white fibrous solid was filtered, washed with water and immersed in 1 M K2CO3 at room temperature for 12 h. Finally, the white fibrous product was filtered, washed with water and dried completely under high vacuum at 60°C. The polymer yield was nearly 100%. 1H NMR (CDCI3, δ, ppm): 7.77-7.19 (m, 12H), 2.51 (2.4H), 2.22 (4H), 1.48-1.28 (2.8H) and 1.25, 1.22 (4.8H).

[0213] (2) Quaternization of PATF-TP-60. In a 50 mL one-neck flask equipped with a magnetic bar, PAT polymer (1.0 g) was dissolved in DMSO (20 mL). Methyl iodide (1 mL) was added quickly. The solution was stirred at room temperature for 12 h. The resulting viscous yellow solution was added dropwise to ether. The yellow solid was filtered, washed with ether, and thoroughly dried under high vacuum at 60 °C. The yield of polymer PATF-TP-60-MeI was nearly 100%. 1H NMR (DMSO-d6, δ, ppm): 7.98-7.17 (12H), 3.38 (2.4H), 3.17 (3.6H), 2.85 (4H), 1.48-1.28 (2.8H), and 1.31, 1.28 (4.8H).

[0214] (3) Membrane Casting 2 g of PATF-TP-60-MeI was dissolved in 10 ml of DMSO at 80°C. The yellow DMSO solution was filtered through a small piece of medical cotton. The filtered polymer solution was deposited on a clean glass plate and cast into a thin film using a Mayer bar. The film on the glass plate was immediately transferred to a 40°C oven to remove most of the DMSO solvent over 4 hours, followed by annealing at 120°C for 16 hours. The glass plate with the membrane film was then placed in deionized water and peeled off. After drying at ambient temperature and removing defective edges, the final membrane was obtained.

[0215] (4) Ion exchange: The membrane was obtained in hydroxide form by ion exchange in 1 M KOH at 60° C. for 24 hours, followed by washing and immersion in deionized water under argon for 48 hours to remove residual KOH.

[0216] Example 7 Another oxidation-resistant HEM is a copolymer of an aromatic monomer of formula (3) (e.g., a terphenyl, such as p-terphenyl, m-terphenyl, or a mixture of these two monomers) according to the first and second aspects of the present invention and a terphenyl monomer of formula (2 ORGThe reaction is based on the Friedel-Crafts reaction of terphenyl with trifluoro-(2,2,6,6-tetramethylpiperidinyl) alkan-one monomers (e.g., 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one). Poly(aryl trifluoromethyl ketone) polymer (PATF-TP-0) was synthesized by the Friedel-Crafts reaction of terphenyl with 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one to prepare PATMP-TP. The reaction scheme is shown below.

[0217] [ka]

[0218] (1) Synthesis of PATF-TP-0. In a 100 mL three-neck flask equipped with an overhead mechanical stirrer, 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one (2.7935 g, 10 mmol) and p-terphenyl (2.3031 g, 10 mmol) were dissolved in methylene chloride (10 mL). Then, trifluoroacetic acid (TFA) (0.5 mL) and trifluoromethanesulfonic acid (TFSA) (10 mL) were added dropwise at 0°C over 30 min. The reaction was then continued at this temperature for 36 h. The resulting viscous brown solution was slowly poured into an aqueous ethanol solution. The white fibrous solid was filtered, washed with water, and immersed in 1 M K2CO3 at room temperature for 12 h. Finally, the white fibrous product was filtered, washed with water, and completely dried at 60°C under high vacuum. The polymer yield was nearly 100%. 1H NMR (CDCI3, δ, ppm): 7.77-7.19 (m, 12H), 2.22 (4H), 1.48-1.28 (7H) and 1.25, 1.22 (12H).

[0219] Example 8 Another oxidation-resistant HEM is an aromatic monomer of formula (3) (e.g., terphenyl), of formula (2) according to the first and second aspects of the present invention. ORGBased on the Friedel-Crafts reaction of trifluoro-(2,2,6,6-tetramethylpiperidinyl) alkan-one monomers (e.g., 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one) of formula (9) and halogenated trifluoromethyl ketone monomers (e.g., 7-bromo-1,1,1-trifluoroheptan-2-one) of formula (9), the terphenyl-based poly(aryl trifluoromethyl ketone-co-alkylene ammonium) polymers (PATF-AA-TP) were synthesized by the following three major steps: (1) Friedel-Crafts reaction of terphenyl, 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one and 7-bromo-1,1,1-trifluoroheptan-2-one to prepare PATF-AB-TP-x, (2) quaternization of PATF-TP-x with trimethylamine, and (3) membrane casting and hydroxide ion exchange. The reaction scheme is shown below.

[0220] [ka]

[0221] (1) Synthesis of PATF-TP-60. In a 100 mL three-neck flask equipped with an overhead mechanical stirrer, 7-bromo-1,1,1-trifluoroheptan-2-one (1.4823 g, 6 mmol), 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one (1.1174 g, 4 mmol) and terphenyl (2.3031 g, 10 mmol) were dissolved in methylene chloride (10 mL). Trifluoroacetic acid (TFA) (0.5 mL) and trifluoromethanesulfonic acid (TFSA) (10 mL) were then added dropwise at 0° C. over 30 min. The reaction was then continued at this temperature for 36 h. The resulting viscous brown solution was slowly poured into aqueous ethanol. The white fibrous solid was filtered, washed with water and immersed in 1 M K2CO3 at room temperature for 12 h. Finally, the white fibrous product was filtered, washed with water and dried completely under high vacuum at 60°C. The polymer yield was nearly 100%. 1H NMR (CDCI3, δ, ppm): 7.57-7.19 (m, 12H), 2.51 (2.4H), 2.22 (4H), 1.48-1.28 (2.8H) and 1.25, 1.22 (4.8H).

[0222] (2) Quaternization of PATF-TP-60. In a 50 mL one-neck flask equipped with a magnetic bar, PATF polymer (1.0 g) was dissolved in DMSO (20 mL). Trimethylamine (1 mL) was added quickly. The solution was stirred at room temperature for 12 h. The resulting viscous yellow solution was added dropwise to ether. The yellow solid was filtered, washed with ether, and thoroughly dried under high vacuum at 60 °C. The yield of polymer PATF-BP-60-MeI was nearly 100%. 1H NMR (DMSO-d6, δ, ppm): 7.77-7.17 (12H), 3.38 (2.4H), 3.17 (3.6H), 2.85 (4H), 1.48-1.28 (2.8H), and 1.31, 1.28 (4.8H).

[0223] (3) Membrane Casting 2 g of PATF-TP-60-MeI was dissolved in 10 ml of DMSO at 80°C. The yellow DMSO solution was filtered through a small piece of medical cotton. The filtered polymer solution was deposited on a clean glass plate and cast into a thin film using a Mayer bar. The film on the glass plate was immediately transferred to a 40°C oven to remove most of the DMSO solvent over 4 hours, followed by annealing at 120°C for 16 hours. The glass plate with the membrane film was then placed in deionized water and peeled off. After drying at ambient temperature and removing defective edges, the final membrane was obtained.

[0224] (4) Ion exchange: The membrane was obtained in hydroxide form by ion exchange in 1 M KOH at 60° C. for 24 hours, followed by washing and immersion in deionized water under argon for 48 hours to remove residual KOH.

[0225] Example 9 Another oxidation-resistant HEM is a copolymer of an aromatic monomer of formula (3) (e.g., biphenyl) and a monomer of formula (2) according to the first and second aspects of the present invention. ORG The poly(aryl trifluoromethyl ketone) polymer (PATF-BP-0) was synthesized by the Friedel-Crafts reaction of biphenyl with 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one to prepare PATF-BP-0. The reaction scheme is shown below.

[0226] [ka]

[0227] (1) Synthesis of PATMP-BP-0. In a 100 mL three-neck flask equipped with an overhead mechanical stirrer, 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one (2.7935 g, 10 mmol) and biphenyl (1.5421 g, 10 mmol) were dissolved in methylene chloride (10 mL). Then, trifluoroacetic acid (TFA) (0.5 mL) and trifluoromethanesulfonic acid (TFSA) (10 mL) were added dropwise at 0°C over 30 min. The reaction was then continued at this temperature for 36 h. The resulting viscous brown solution was slowly poured into an aqueous ethanol solution. The white fibrous solid was filtered, washed with water, and immersed in 1 M K2CO3 at room temperature for 12 h. Finally, the white fibrous product was filtered, washed with water, and completely dried at 60°C under high vacuum. The polymer yield was nearly 100%. 1H NMR (CDCI3, δ, ppm): 7.57-7.19 (m, 8H), 2.22 (4H), 1.48-1.28 (2.8H) and 1.25, 1.22 (12H).

[0228] Example 10 Another oxidation-resistant poly(aryl trifluoromethyl ketone) polymer is 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one (formula (2 ORG )), 7-bromo-1,1,1-trifluoroheptan-2-one (formula (9)), terphenyl (p-terphenyl, m-terphenyl, or a mixture of these two monomers of formula (3)), and quaternization with trimethylamine. The reaction scheme for the synthesis of the polymer is shown below.

[0229] [ka]

[0230] Example 11 Another oxidation-resistant poly(aryl trifluoromethyl ketone) polymer is 1,1,1-trifluoro-5-(2,2,6,6-tetramethylpiperidin-4-yl)pentan-2-one (formula (2 ORG )), 7-bromo-1,1,1-trifluoroheptan-2-one (formula (9)), biphenyl (formula (3)) and trimethylamine. The reaction scheme for the synthesis of the polymer is shown below.

[0231] [ka]

[0232] Example 12 Another oxidation-resistant poly(arylpiperidinium) polymer is a piperidone monomer of formula (6) (e.g., 4-methyl-1-piperidone), formula (4 ORG The polymer is based on a nitrogen heterocycle-aryl monomer of formula (e.g., 1,1,3,3-tetramethylisoinodline) and an aromatic monomer of formula (3) (e.g., terphenyl). The reaction scheme for the synthesis of the polymer is shown below.

[0233] [ka]

[0234] Example 13 Another oxidation-resistant poly(arylpiperidinium) polymer is based on 4-methyl-piperidone, 2,2,2-trifluoroacetophenone, terphenyl and MQN-TMPH-C2 according to the fifth aspect of the present invention. The reaction scheme for the synthesis of the polymer is shown below.

[0235] [ka]

[0236] Example 14 Another oxidation-resistant poly(arylpiperidinium) polymer is based on 4-methyl-piperidone, 2,2,2-trifluoroacetophenone, terphenyl, iodomethane and MQN-TMPH-C2 according to the fifth aspect of the present invention. The reaction scheme for the synthesis of the polymer is shown below.

[0237] [ka]

[0238] Example 15 Another oxidation-resistant poly(arylpiperidinium) polymer is based on 4-methyl-piperidone, 2,2,2-trifluoroacetophenone, terphenyl, iodomethane and bromohexenyl TMPH ether, according to the fifth aspect of the invention.

[0239] Example 16 Another oxidation-resistant polybenzimidazole polymer is based on polybenzimidazole, MQN-TMPH, sodium hydride and potassium hydroxide according to the ninth aspect of the present invention. The reaction schemes for the synthesis of the polymers of Examples 15 and 16 are shown below.

[0240] [ka]

[0241] [ka]

[0242] Example 17 Another oxidation-resistant polymer is based on polyfluorene derivatives according to the eighth aspect of the invention. The reaction schemes for small molecule and polymer synthesis are shown below.

[0243] [ka]

[0244] S3 synthesis:

[0245] [ka] KO t A solution of Bu (16 mmol) in THF (10 mL) was added to a solution of (methoxymethyl)triphenylphosphonium chloride (15 mmol) in THF (10 mL) at 0° C. under nitrogen. The solution was stirred for an additional hour, after which a solution of S1 (10 mmol) in THF (5 mL) was added dropwise. The mixture was warmed to room temperature and stirred until S1 was completely consumed. Aqueous HCl (35%, 3 mL) was added to the mixture and the mixture was stirred until S2 was completely consumed. After the solvent was removed under high vacuum, the mixture was extracted with dichloromethane (20 mL×3). The combined aqueous extracts were basified with NaHCO3 and extracted with dichloromethane (20 mL×3), and the extracted organics were combined, washed with water, dried over MgSO4, and concentrated to give a brown solid S3, which was used directly in the next step.

[0246] Synthesis of S5:

[0247] [ka] KO t A solution of Bu (16 mmol) in THF (10 mL) was added to a solution of (methoxymethyl)triphenylphosphonium chloride (15 mmol) in THF (10 mL) at 0° C. under nitrogen. The solution was stirred for an additional hour, after which a solution of S3 (10 mmol) in THF (5 mL) was added dropwise. The mixture was warmed to room temperature and stirred until S3 was completely consumed. Aqueous HCl (35%, 3 mL) was added to the mixture and the mixture was stirred until S4 was completely consumed. After the solvent was removed under high vacuum, the mixture was extracted with dichloromethane (20 mL×3). The combined aqueous extracts were basified with NaHCO3 and extracted with dichloromethane (20 mL×3), and the extracted organics were combined, washed with water, dried over MgSO4, and concentrated to give a brown liquid S5, which was used directly in the next step.

[0248] Synthesis of S6:

[0249] [ka] Dimethylamine hydrochloride (21.7 mmol) and KOH (0.47 g) were added to a flask under nitrogen. Methanol (5 mL) was added at 0° C. and the mixture was stirred at room temperature until the base was dissolved. S5 (5.54 mmol) in methanol (2.5 mL) was added and the suspension was heated at 50° C. for 45 min. A solution of sodium cyanoborohydride (21.7 mmol) in methanol (5 mL) was added at 50° C. over 45 min. The mixture was stirred for an additional hour and then cooled to 0° C. KOH (77 mmol) was added. The mixture was stirred until the pellets were dissolved. The mixture was quenched with water. The solvent was removed under high vacuum. The mixture was then extracted with dichloromethane (20 mL×3). The combined organic extracts were washed with water (20 mL), saturated aqueous NaCl (5 mL) and dried over Na2SO4. The solvent was removed under high vacuum. The residue was purified by distillation to give a colorless oil S6.

[0250] Synthesis of S8:

[0251] [ka] Fluorene (S7, 24 mmol) and tetrabutylammonium bromide (3 mmol) were added to the flask. The flask was degassed three times. 50% aqueous NaOH (20 mL) was added to the flask under nitrogen. 1,5-dibromopentane was added dropwise at 70° C. The mixture was stirred for another 4 h, then cooled to room temperature and extracted with dichloromethane (20 mL×3). The combined organic extracts were washed with water and dried over MgSO4. The solvent was removed under high vacuum. The crude mixture was purified by column chromatography using hexane as eluent. The desired white solid product S8 was obtained.

[0252] Synthesis of S9:

[0253] [ka] S8 (10 mmol), biphenyl (10 mmol) and 1,1,1-trifluoroacetone (13 mmol) were dissolved in dichloromethane (mL) in a flask. Trifluoromethanesulfonic acid (mL) was added dropwise at 0°C. The mixture was stirred for 4 hours and poured into ethanol. The white polymer was filtered and dried overnight at room temperature under high vacuum.

[0254] Synthesis of S8:

[0255] [ka] S9 (5 mmol) was dissolved in methylpyrrolidone (20 mL) at room temperature. S6 (50 mmol) was added. The reaction mixture was stirred for 12 hours. The mixture was poured into tetrahydrofuran. The white polymer PFu-BP-C2-50 was filtered and dried under high vacuum at room temperature overnight.

[0256] Oxidative stability of Pfu-TMA and PFu-BP-C2-TEMPO: HCO3 - The anion exchange membranes of the form were examined by placing them in freshly prepared Fenton's reagent (10 ppm FeSO4 in 10% H2O2 solution) at room temperature for 24 and 48 hours. After the test, the PFu-BP-C2-TEMPO membrane still retained good mechanical properties, while the PFu-TMA membrane became very brittle and broke into small pieces, as shown in Figure 10A and Table 3. The water uptake of the PFu-C2-TEMPO membrane was almost unchanged. However, the conductivity decreased slightly, as shown in Figure 10B and Figure 10C.

[0257] [ka]

[0258] [Table 3]

[0259] Example 18 Another example of an oxidation-resistant HEM is the PPO-based polymer PPO-C2-TEMPO according to the eighth aspect of the present invention, the synthesis of which is detailed below.

[0260] [ka]

[0261] Synthesis of PPO-C2-TEMPO. BrPPO (1 g) was dissolved in methylpyrrolidone (20 mL) at room temperature. C2-TEMPO (0.62 g) was added. The reaction mixture was stirred at room temperature for 24 h. The mixture was poured into tetrahydrofuran. The yellow polymer PPO-C2-TEMPO was filtered, washed three times with THF, and then dried under high vacuum at 60° C. for 24 h.

[0262] Example 19 Another oxidation-resistant HEM is based on the Friedel-Crafts reaction of tert-phenyl, TEMPO derivatives and 7-bromo-1,1,1-trifluoroheptan-2-one. Poly(aryl trifluoromethyl ketone) polymer (PATF-TP-Br) was synthesized by three major steps: (1) Friedel-Crafts reaction of tert-phenyl and 7-bromo-1,1,1-trifluoroheptan-2-one to prepare PATF-TP-Br, (2) quaternization of PATF-TP-Br first with C2-TEMPO and then with trimethylamine, and (3) hydroxide ion exchange. The reaction scheme is shown below.

[0263] [ka]

[0264] (1) Synthesis of PATF-TP-Br. In a 100 mL three-neck flask equipped with an overhead mechanical stirrer, tert-phenyl (25.0 g, 108.6 mmol) and 7-bromo-1,1,1-trifluoroheptan-2-one (26.84 g, 108.6 mmol) were dissolved in methylene chloride (127 mL). Then, trifluoromethanesulfonic acid (TFSA) (1270 mL) was added dropwise at 0°C over 30 min. The reaction was then continued at this temperature for 12 h. The resulting viscous brown solution was slowly poured into an aqueous ethanol solution. The white fibrous solid was filtered, washed with water, and immersed in 1 M K2CO3 at room temperature for 12 h. Finally, the white fibrous product was filtered, washed with water, and completely dried at 60°C under high vacuum. The polymer yield was nearly 100%. 1H NMR (CDCl3-d3, δ, ppm): 7.71 (4H), 7.62 (4H), 7.40 (4H), 3.35 (2H), 2.48 (2H), 1.82 (2H), 1.48 (2H), 1.30 (2H).

[0265] (2) Quaternization of PATF-TP-Br. In a 50 mL one-neck flask equipped with a magnetic bar, PATF polymer (1.0 g, 2.18 mmol), C2-TEMPO (481 mg, 2.18 mmol) were dissolved in DMSO (20 mL). After stirring at room temperature for 24 h, trimethylamine (257.24 mg, 5.3 mmol) was quickly added. The solution was stirred at room temperature for 12 h. The resulting solution was dropped into ether. The yellow solid was filtered, washed with ether, and completely dried under high vacuum at 60 °C. The yield of polymer PATF-TP-C2-TEMPO-0.9 was 82%. 1H NMR(DMSO-d6,δ,ppm):7.85-7.43(12H),3.28(2H),3.18(2H),3.02(0.98H),2.97(5. 4H), 1.71-1.63(3.0H), 1.51-1.48(3.7H), 1.30(4H), 1.07-0.97(11.9H), 0.76(1.8H).

[0266] definition The substituents associated with the compounds of formulae (1)-(12), (1A)-(9A), (8A-1) and (9A-1) are defined as follows:

[0267] [ka] represents a polymer backbone comprising at least one polyaryletherketone (PAEK) derivative, polysulfone (PSU) derivative, polystyrene (PS) derivative, poly(p-phenylene oxide) derivative, styrene-ethylene-butylene-styrene (SEBS) derivative, polyethylene derivative, poly(norbornene) derivative, or poly(arylalkylene) derivative structural unit; A is aryl; m is 0, 1, 2, 4, 5, 6, 7, 8, 9, or 10; m1, m2, and m6 are each independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; m3, m4, m5, and m7 are each independently 0, 1, 2, 3, or 4; m8 and m10 are each independently 0, 1, 2, 3, or 4; m9 is independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; n is 1, 2, 3, 4, 5, 6, 7 or 8; n1 is 1, 2, 3, or 4; n2 is 0, 1, 2, 3 or 4; n3 and n5 are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; n4 is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; Q is N or P; R1, R 13 , and R 18 are each independently alkylene, alkenylene, alkynylene, or arylene, the alkylene, alkenylene, alkynylene, or arylene being optionally substituted with a halide, or R13 does not exist, R2 and R 19 are each independently -NH2, -NHR3, -NR3R4, -NO, -NS, or a nitrogen-containing heterocycle, wherein the nitrogen of the heterocycle has an oxygen, sulfur, or hydrogen substituent; R3 and R4 are each independently an alkyl, alkenyl, alkynyl, or aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R5, R6, R7, R8, R9, R 10 , R 11 , and R 12 are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; and R6 and R9 are optionally linked to form a 5-membered ring, optionally substituted with a halide or an alkyl; R 14 and R 15 are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R 16 and R 17 is independently alkylene optionally substituted with halide or alkyl; Each R 20 is independently hydrogen, hydroxyl, halide, alkyl, alkenyl, alkynyl, or aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with halide; Each R 21 is independently an alkyl, alkenyl, or alkynyl, or a substituent of formula (8A-1);

[0268] [ka] The alkyl, alkenyl, or alkynyl is optionally substituted with a halide; R 22 is a halide, or a quaternary ammonium or phosphonium group, or a nitrogen-containing heterocyclic group, or a salt thereof, the quaternary ammonium or phosphonium group having the formula (9A-1):

[0269] [ka] the nitrogen-containing heterocyclic group is an optionally substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, quinoline, piperidine, pyrrolidine, pyrazolidine, imidazolidine, azepane, isoxazole, isoxazoline, oxazole, oxazoline, oxadiazole, oxatriazole, dioxazole, oxazine, oxadiazine, isoxazolidine, morpholine, thiazole, isothiazole, oxathiazole, oxathiazine, or caprolactam, each substituent being independently alkyl, alkenyl, alkynyl, aryl, or aralkyl; R 23 , R 24 , R 25 , R 26 , and R 27 are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R 28 and R 29 are each independently alkylene; R 30 , R 31 , R 32 , R 33 , and R 34 are each independently alkyl, alkenyl, or alkynyl; R 35 , R 36 , R 37 , R 40 , R 41 , R 42 , and R 43are each independently alkylene, arylene, alkenylene, alkynylene, ether, thioether, keto, amino, ammonium, or piperidinyl, wherein the alkylene, arylene, alkenylene, or alkynylene is optionally substituted with a halide; R 38 is a halide, mesylate, tosylate, azide, alkenyl, or alkynyl; R 39 is an amine, a phosphine, a thiol, a hydroxyl, an alkenyl, or an alkynyl, or R 38 is an amine, a phosphine, a thiol, a hydroxyl, an alkenyl, or an alkynyl; R 39 is a halide, mesylate, tosylate, azide, alkenyl, or alkynyl; R 44 But -NH2, -NHR 45 , -NR 45 R 46 , -NO, -NS, or a nitrogen-containing heterocycle, the nitrogen of the heterocycle having an oxygen, sulfur, or hydrogen substituent; R 45 and R 46 is each independently an alkyl, alkenyl, alkynyl, or aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R 47 is a halide, mesylate, tosylate, azide, alkenyl, or alkynyl; R 48 , R 49 , R 50 , and R 51 are each independently alkylene, arylene, alkenylene, alkynylene, ether, thioether, keto, amino, ammonium, or piperidinyl, wherein the alkylene, arylene, alkenylene, or alkynylene is optionally substituted with a halide; R 52 But -NH2, -NHR 53 , -NR 53 R 54, -NO, -NS, or a nitrogen-containing heterocycle, the nitrogen of the heterocycle having an oxygen, sulfur, or hydrogen substituent; R 53 and R 54 is each independently an alkyl, alkenyl, alkynyl, or aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide. R 55 , R 56 , R 57 and R 58 are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R 59 But -(CH2) n3 -[Q(R 60 )(R 61 )-(CH2) n4 ] n5 -R 62 or -[(CH2) n3 -O] n5 -R 62 and R 60 and R 61 are each independently alkyl, alkenyl, or alkynyl; R 62 is a nitrogen-containing heterocycle, the nitrogen of the heterocycle having an oxygen, sulfur, or hydrogen substituent; X - is an anion, Z is independently hydrogen, hydroxyl, oxygen, or sulfur.

[0270] The term anion exchange membrane / ionomer / polymer is used interchangeably with hydroxide exchange membrane / ionomer / polymer.

[0271] The term "suitable substituent" as used herein is intended to mean a chemically acceptable functional group, preferably a moiety that does not negate the activity of the compound of the present invention.Such suitable substituents include, but are not limited to, halo group, perfluoroalkyl group, perfluoroalkoxy group, alkyl group, alkenyl group, alkynyl group, hydroxy group, oxo group, mercapto group, alkylthio group, alkoxy group, aryl or heteroaryl group, aryloxy or heteroaryloxy group, aralkyl or heteroaralkyl group, aralkoxy or heteroaralkoxy group, HO-(C=O)- group, heterocyclic group, cycloalkyl group, amino group, alkylamino group and dialkylamino group, carbamoyl group, alkylcarbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, arylcarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, and arylsulfonyl group.Those skilled in the art will understand that many substituents can be substituted by further substituents.

[0272] The term "alkyl," as used herein, 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 carbons), more preferably having 1 to 18 carbon atoms. Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, and tert-butyl. An alkyl group can be unsubstituted or substituted by one or more suitable substituents.

[0273] The term "alkenyl" as used herein refers to a straight-chain, branched-chain, 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 carbons, 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, ethenyl, 1-propenyl, 2-propenyl (allyl), iso-propenyl, 2-methyl-1-propenyl, 1-butenyl, and 2-butenyl. Alkenyl groups may be unsubstituted or substituted by one or more suitable substituents, as defined above.

[0274] The term "alkynyl" as used herein refers to a straight-chain, branched-chain, or cyclic hydrocarbon group having preferably 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 carbons, more preferably 1 to 18 carbon atoms, and having one or more carbon-carbon triple bonds. Alkynyl groups include, but are not limited to, ethynyl, propynyl, and butynyl. Alkynyl groups may be unsubstituted or substituted by one or more suitable substituents, as defined above.

[0275] The term "aryl" or "ar" as used herein alone or as part of another group (e.g., aralkyl) refers to a monocyclic, bicyclic, or tricyclic aromatic group such as phenyl, naphthyl, tetrahydronaphthyl, indanyl, and the like, optionally substituted with one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above. The term "aryl" also includes heteroaryl.

[0276] "Arylalkyl" or "aralkyl" means an aryl group attached to a parent molecule via an alkylene group. The number of carbon atoms in the aryl and alkylene groups is selected so that there are a total of about 6 to about 18 carbon atoms in the arylalkyl group. A preferred arylalkyl group is benzyl.

[0277] The term "cycloalkyl," as used herein, refers to a monocyclic, bicyclic, or tricyclic carbocyclic group (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclopentenyl, cyclohexenyl, bicyclo[2.2.1]heptanyl, bicyclo[3.2.1]octanyl, and bicyclo[5.2.0]nonanyl, etc.), optionally containing one or more double bonds. Cycloalkyl groups can be unsubstituted or substituted with one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.

[0278] The term "-ene" used as a suffix as part of another group denotes a divalent group in which a hydrogen atom has been removed from each of the two terminal carbons of the group, or, if the group is cyclic, from each of two different carbon atoms in the ring. For example, alkylene denotes a divalent alkyl group such as ethylene (-CHCH-) or isopropylene (-CH(CHCH-). For clarity, the addition of the -ene suffix is ​​not intended to alter the definition of the head word other than to indicate a divalent group. Thus, continuing with the above example, alkylene denotes a straight chain saturated divalent hydrocarbon group that is optionally substituted.

[0279] The term "ether," as used herein, refers to a divalent (ie, difunctional) group that contains at least one ether linkage (ie, --O--).

[0280] The term "heteroaryl," as used herein, refers to a monocyclic, bicyclic, or tricyclic aromatic heterocyclic group containing in one or more rings one or more heteroatoms (e.g., 1 to 3 heteroatoms) selected from O, S, and N. Heteroaryl groups include, but are not limited to, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl, furyl, imidazolyl, pyrrolyl, oxazolyl (e.g., 1,3-oxazolyl, 1,2-oxazolyl), thiazolyl (e.g., 1,2-thiazolyl, 1,3-thiazolyl), pyrazolyl, tetrazolyl, triazolyl (e.g., 1,2,3-triazolyl, 1,2,4-triazolyl), oxadiazolyl (e.g., 1,2,3-oxadiazolyl), thiadiazolyl (e.g., 1,3,4-thiadiazolyl), quinolyl, isoquinolyl, benzothienyl, benzofuryl, and indolyl. A heteroaryl group can be unsubstituted or optionally substituted with one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.

[0281] The term "hydrocarbon" as used herein describes compounds or radicals consisting solely of the elements carbon and hydrogen.

[0282] The term "substituted" means that in the group in question, at least one hydrogen atom bonded to a carbon atom is replaced with one or more substituents, such as hydroxy (-OH), alkylthio, phosphino, amido (-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), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (-NO), ether (-ORA, where RA is alkyl or aryl), ester (-OC(O)RA, where RA is alkyl or aryl), keto (-C(O)RA, where RA is alkyl or aryl), heterocyclo, and the like. When the term "substituted" introduces or follows a list of possible substituted groups, it is intended that the term apply to all members of that group. That is, the phrase "optionally substituted alkyl or aryl" should be interpreted as "optionally substituted alkyl or optionally substituted aryl." Similarly, the phrase "optionally substituted alkyl or aryl" should be interpreted as "optionally substituted with fluorine or optionally substituted with fluorine."

[0283] The term "tethered" means that the group in question is attached to a particular polymer backbone. For example, an imidazolium-tethered poly(arylalkylene) polymer is a polymer having imidazolium groups attached to the poly(arylalkylene) polymer backbone.

[0284] When introducing elements of the present invention or preferred embodiments thereof, the articles "a," "an," "the," and "said" are intended to mean that there are one or more elements. The terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0285] In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.

[0286] Because various changes can be made in the products and methods described above without departing from the scope of the invention, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.

Claims

1. A polymer for providing improved oxidation resistance, the polymer having the formula (1A ＯＲＧ ) and / or (2A ＯＲＧ and structural units of formula (3A), (4A ＯＲＧ ) and (5A ＯＲＧ and at least one structural unit of the formula (1A ＯＲＧ ), (2A ＯＲＧ ), (3A), (4A ＯＲＧ ) and (5A ＯＲＧ The structural unit of the formula (I) has the following structure: 【Chemistry 1】 having During the ceremony, A is aryl; n １ is 1, 2, 3, or 4; n ２ is 0, 1, 2, 3 or 4, R １ , R １３ , and R １８ are each independently an alkylene, alkenylene, alkynylene, or arylene, the alkylene, alkenylene, alkynylene, or arylene being optionally substituted with a halide, or R １３ does not exist, R ２ and R １９ each independently represents -NH ２ , -NHR ３ , -NR ３ R ４ , -N-O, -N-S, or a nitrogen-containing heterocycle, the nitrogen of which has an oxygen, sulfur, or hydrogen substituent; R ３ and R ４ is each independently an alkyl, alkenyl, alkynyl, or aryl, said alkyl, alkenyl, alkynyl, or aryl being optionally substituted with a halide; R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , and R １２ are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R ６ and R ９ are optionally linked to form a 5-membered ring, optionally substituted with halide or alkyl; R １６ and R １７ is independently alkylene optionally substituted with halide or alkyl; A polymer wherein Z is independently hydrogen, hydroxyl, oxygen, or sulfur.

2. Formula (1A ＯＲＧ ) and (2A ＯＲＧ The sum of the molar fractions of the structural units of the formulas (3A), (4A) in the polymer ＯＲＧ ), and (5A ＯＲＧ The molar ratio of the structural units of formula (1A) to the sum of the molar fractions of the structural units of formula (1A) may be from about 0.95:1 to about 1.4:1; ＯＲＧ ) and (2A ＯＲＧ The sum of the mole fractions of the structural units of the formulas (3A), (4A) ＯＲＧ ), and (5A ＯＲＧ 2. The polymer of claim 1, wherein the ratio of the molar fractions of the structural units of (a) to (b) may be about 0.01 to 1.

3. The structural unit (2A ＯＲＧ ) is expressed as follows: 【Chemistry 2】 or The structural unit (4A ORG ) is represented by the following formula: 【Chemistry 3】 Or, 【Chemistry 4】 The polymer of claim 1 or 2, comprising a structural unit having the formula:

4. The polymer comprises the following structural unit: 【Chemistry 5】 and further comprising at least one of: During the ceremony, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; n is 1, 2, 3, 4, 5, 6, 7 or 8; q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; Q is N or P; Each R ２０ is independently hydrogen, hydroxyl, halide, alkyl, alkenyl, alkynyl, or aryl, said alkyl, alkenyl, alkynyl, or aryl being optionally substituted with halide; Each R ２１ is independently an alkyl, alkenyl, or alkynyl, or a substituent of formula (8A-1), 【Chemistry 6】 the alkyl, alkenyl, or alkynyl is optionally substituted with a halide; R ２２ is a halide, or a quaternary ammonium or phosphonium group, or a nitrogen-containing heterocyclic group, or a salt thereof, and the quaternary ammonium or phosphonium group has the formula (9A-1): 【Chemistry 7】 the nitrogen-containing heterocyclic group is an optionally substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, quinoline, piperidine, pyrrolidine, pyrazolidine, imidazolidine, azepane, isoxazole, isoxazoline, oxazole, oxazoline, oxadiazole, oxatriazole, dioxazole, oxazine, oxadiazine, isoxazolidine, morpholine, thiazole, isothiazole, oxathiazole, oxathiazine, or caprolactam, each substituent being independently alkyl, alkenyl, alkynyl, aryl, or aralkyl; R ２３ , R ２４ , R ２５ , R ２６ , and R ２７ are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein said alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R ２８ and R ２９ are each independently alkylene; R ３０ , R ３１ , R ３２ , R ３３ , and R ３４ are each independently alkyl, alkenyl, or alkynyl; X － The polymer of claim 2 or 3, wherein is an anion.

5. 1. A polymer for providing improved oxidation resistance, said polymer comprising: (i) a compound of the formula 【Chemistry 8】 and / or The following formula: 【Chemistry 9】 and (ii) at least one aromatic monomer, The following formula: 【Chemistry 10】 or The following formula: 【Chemistry 11】 or having a nitrogen-containing substituent and the formula: 【Chemistry 12】 The present invention comprises the reaction product of a polymerization mixture comprising at least one aromatic monomer, the aryl monomer having During the ceremony, A is aryl; n １ is 1, 2, 3, or 4; n ２ is 0, 1, 2, 3 or 4, R １ , R １３ , and R １８ are each independently alkylene, alkenylene, alkynylene, or arylene, said alkylene, alkenylene, alkynylene, or arylene being optionally substituted with halide or R is absent; R ２ and R １９ each independently represents -NH ２ , -NHR ３ , -NR ３ R ４ , -N-O, -N-S, or a nitrogen-containing heterocycle, the nitrogen of which has an oxygen, sulfur, or hydrogen substituent; R ３ and R ４ is each independently an alkyl, alkenyl, alkynyl, or aryl, said alkyl, alkenyl, alkynyl, or aryl being optionally substituted with a halide; R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １４ , and R １５ are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R ６ and R ９ are optionally linked to form a 5-membered ring, optionally substituted with halide or alkyl; R １６ and R １７ is independently alkylene optionally substituted with halide or alkyl; A polymer wherein Z is independently hydrogen, hydroxyl, oxygen, or sulfur.

6. The trifluoromethyl ketone monomer (2 ＯＲＧ ) is expressed as follows: 【Chemistry 13】 or The nitrogen heterocycle-aryl monomer (4 ORG ) is represented by the following formula: 【Chemistry 14】 and an isoindoline monomer having the formula: wherein a dibenzo ring is optionally present. Or, the nitrogen heterocycle-aryl monomer (4 ORG ) is represented by the following formula: 【Chemistry 15】 Benzo[de]isoquinoline monomers having the formula: The polymer of claim 5.

7. The polymerization mixture comprises the following monomers: The following formula: 【Chemistry 16】 or a salt or hydrate thereof; or The following formula: 【Chemistry 17】 or an azoniaspiro salt monomer having the formula The following formula: 【Chemistry 18】 or The following formula: 【Chemistry 19】 and further comprising at least one halogenated trifluoromethyl ketone monomer having the formula: During the ceremony, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; n is 1, 2, 3, 4, 5, 6, 7 or 8; q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; Q is N or P; Each R ２０ is independently hydrogen, hydroxyl, halide, alkyl, alkenyl, alkynyl, or aryl, said alkyl, alkenyl, alkynyl, or aryl being optionally substituted with halide; Each R ２１ is independently an alkyl, alkenyl, or alkynyl, or a substituent of formula (8A-1), 【Chemistry 20】 the alkyl, alkenyl, or alkynyl is optionally substituted with a halide; R ２２ is a halide, or a quaternary ammonium or phosphonium group, or a nitrogen-containing heterocyclic group, or a salt thereof, and the quaternary ammonium or phosphonium group has the formula (9A-1): 【Chemistry 21】 the nitrogen-containing heterocyclic group is an optionally substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, quinoline, piperidine, pyrrolidine, pyrazolidine, imidazolidine, azepane, isoxazole, isoxazoline, oxazole, oxazoline, oxadiazole, oxatriazole, dioxazole, oxazine, oxadiazine, isoxazolidine, morpholine, thiazole, isothiazole, oxathiazole, oxathiazine, or caprolactam, each substituent being independently alkyl, alkenyl, alkynyl, aryl, or aralkyl; R ２３ , R ２４ , R ２５ , R ２６ , and R ２７ are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein said alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R ２８ and R ２９ are each independently alkylene; R ３０ , R ３１ , R ３２ , R ３３ , and R ３４ are each independently alkyl, alkenyl, or alkynyl; X － The polymer according to claim 5 or 6, wherein is an anion.

8. A polymer for providing improved oxidation resistance, the polymer having the formula (4A ＯＲＧ ) and / or (5A ＯＲＧ and a structural unit of formula (1A ＯＲＧ ), (2A ＯＲＧ and at least one of the formula (1A): ＯＲＧ ), (2A ＯＲＧ ), (4A ＯＲＧ , (5A ＯＲＧ , (6A), (7A), (8A) and (9A) are structural units having the following structure: 【Chemical formula 22】 having During the ceremony, A is aryl; m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; n is 1, 2, 3, 4, 5, 6, 7 or 8; q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; Q is N or P; R １ and R １８ are each independently an alkylene, alkenylene, alkynylene, or arylene, the alkylene, alkenylene, alkynylene, or arylene being optionally substituted with a halide, or R １３ does not exist, R ２ and R １９ each independently represents -NH ２ , -NHR ３ , -NR ３ R ４ , -N-O, -N-S, or a nitrogen-containing heterocycle, the nitrogen of which has an oxygen, sulfur, or hydrogen substituent; R ３ and R ４ is each independently an alkyl, alkenyl, alkynyl, or aryl, said alkyl, alkenyl, alkynyl, or aryl being optionally substituted with a halide; R １６ and R １７ is independently alkylene optionally substituted with halide or alkyl; Each R ２０ is independently hydrogen, hydroxyl, halide, alkyl, alkenyl, alkynyl, or aryl, said alkyl, alkenyl, alkynyl, or aryl being optionally substituted with halide; Each R ２１ is independently an alkyl, alkenyl, or alkynyl, or a substituent of formula (8A-1), 【Chemistry 23】 the alkyl, alkenyl, or alkynyl is optionally substituted with a halide; R ２２ is a halide, or a quaternary ammonium or phosphonium group, or a nitrogen-containing heterocyclic group, or a salt thereof, and the quaternary ammonium or phosphonium group has the formula (9A-1): 【Chemistry 24】 the nitrogen-containing heterocyclic group is an optionally substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, quinoline, piperidine, pyrrolidine, pyrazolidine, imidazolidine, azepane, isoxazole, isoxazoline, oxazole, oxazoline, oxadiazole, oxatriazole, dioxazole, oxazine, oxadiazine, isoxazolidine, morpholine, thiazole, isothiazole, oxathiazole, oxathiazine, or caprolactam, each substituent being independently alkyl, alkenyl, alkynyl, aryl, or aralkyl; R ２３ , R ２４ , R ２５ , R ２６ , and R ２７ are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein said alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R ２８ and R ２９ are each independently alkylene; R ３０ , R ３１ , R ３２ , R ３３ , and R ３４ are each independently alkyl, alkenyl, or alkynyl; X － is an anion, A polymer wherein Z is independently hydrogen, hydroxyl, oxygen, or sulfur.

9. 1. A polymer for providing improved oxidation resistance, said polymer comprising: (i) a compound of the formula 【Chemistry 25】 and / or having a nitrogen-containing substituent and the formula: 【Chemistry 26】 and (ii) the following monomers: The following formula: 【Chemical 27】 A piperidone monomer having the formula The following formula: 【Chemistry 28】 a trifluoromethyl ketone monomer having the formula The following formula: 【Chemical formula 29】 or a salt or hydrate thereof; The following formula: 【Chemistry 30】 an azoniaspiro salt monomer having the formula The following formula: 【Chemistry 31】 or The following formula: 【Chemistry 32】 and wherein the reaction product of the polymerization mixture includes at least one halogenated trifluoromethyl ketone monomer having the formula: During the ceremony, A is aryl; m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; n is 1, 2, 3, 4, 5, 6, 7 or 8; q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; Q is N or P; R １ and R １８ are each independently an alkylene, alkenylene, alkynylene, or arylene, the alkylene, alkenylene, alkynylene, or arylene being optionally substituted with a halide, or R １３ does not exist, R ２ and R １９ each independently represents -NH ２ , -NHR ３ , -NR ３ R ４ , -N-O, -N-S, or a nitrogen-containing heterocycle, the nitrogen of which has an oxygen, sulfur, or hydrogen substituent; R ３ and R ４ is each independently an alkyl, alkenyl, alkynyl, or aryl, said alkyl, alkenyl, alkynyl, or aryl being optionally substituted with a halide; R １６ and R １７ is independently alkylene optionally substituted with halide or alkyl; Each R ２０ is independently hydrogen, hydroxyl, halide, alkyl, alkenyl, alkynyl, or aryl, said alkyl, alkenyl, alkynyl, or aryl being optionally substituted with halide; Each R ２１ is independently an alkyl, alkenyl, or alkynyl, or a substituent of formula (8A-1), 【Chemical 33】 the alkyl, alkenyl, or alkynyl is optionally substituted with a halide; R ２２ is a halide, or a quaternary ammonium or phosphonium group, or a nitrogen-containing heterocyclic group, or a salt thereof, and the quaternary ammonium or phosphonium group has the formula (9A-1): 【Chemical 34】 the nitrogen-containing heterocyclic group is an optionally substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, quinoline, piperidine, pyrrolidine, pyrazolidine, imidazolidine, azepane, isoxazole, isoxazoline, oxazole, oxazoline, oxadiazole, oxatriazole, dioxazole, oxazine, oxadiazine, isoxazolidine, morpholine, thiazole, isothiazole, oxathiazole, oxathiazine, or caprolactam, each substituent being independently alkyl, alkenyl, alkynyl, aryl, or aralkyl; R ２３ , R ２４ , R ２５ , R ２６ , and R ２７ are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein said alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R ２８ and R ２９ are each independently alkylene; R ３０ , R ３１ , R ３２ , R ３３ , and R ３４ are each independently alkyl, alkenyl, or alkynyl; X － is an anion, A polymer wherein Z is independently hydrogen, hydroxyl, oxygen, or sulfur.

10. 1. A polymer for providing improved oxidation resistance, said polymer comprising: (i) a compound of the formula 【Chemistry 35】 and (ii) a compound of the formula 【Chemical 36】 and a reaction product of a mixture comprising an oxidation resistant group (ORG) containing compound having the formula: During the ceremony, 【Chemical 37】 represents a polymer backbone comprising at least one polyaryletherketone (PAEK) derivative, polysulfone (PSU) derivative, polystyrene (PS) derivative, poly(p-phenylene oxide) derivative, styrene-ethylene-butylene-styrene (SEBS) derivative, polyethylene derivative, poly(norbornene) derivative, polycyclic aromatic derivative, or poly(arylalkylene) derivative structural unit; m1, m2, and m6 are each independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; m3, m4, m5, and m7 are each independently 0, 1, 2, 3, or 4; R ３５ , R ３６ , R ３７ , R ４０ , R ４１ , R ４２ , and R ４３ are each independently alkylene, arylene, alkenylene, alkynylene, ether, thioether, keto, amino, ammonium, or piperidinyl, wherein said alkylene, arylene, alkenylene, or alkynylene is optionally substituted with a halide; R ３８ is a halide, mesylate, tosylate, azide, alkenyl, or alkynyl; R ３９ is an amine, a phosphine, a thiol, a hydroxyl, an alkenyl, or an alkynyl, or R ３８ is an amine, a phosphine, a thiol, a hydroxyl, an alkenyl, or an alkynyl; R ３９ is a halide, mesylate, tosylate, azide, alkenyl, or alkynyl; R ４４ But -NH ２ , -NHR ４５ , -NR ４５ R ４６ , -N-O, -N-S, or a nitrogen-containing heterocycle, the nitrogen of which has an oxygen, sulfur, or hydrogen substituent; R ４５ and R ４６ is each independently an alkyl, alkenyl, alkynyl, or aryl, wherein said alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide.

11. 1. A polymer for providing improved oxidation resistance, said polymer comprising: (i) a polymer having a backbone that includes a nitrogen-containing heterocyclic ring or a nitrogen-containing heterocyclic ring attached to an aryl or heterocyclic ring; or The following formula: 【Chemical Formula 38】 A polymer comprising at least two of the structural units of formulae (3A), (6A), (7A), (8A) and (9A) having the formula and (ii) Formula (12) 【Chemical 39】 and a product of the mixture comprising an ORG-containing compound having During the ceremony, m is 0, 1, 2, 4, 5, 6, 7, 8, 9, or 10; m8 and m10 each independently represent 0, 1, 2, 3, or 4; m9 is independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; n is 1, 2, 3, 4, 5, 6, 7 or 8; n １ is 1, 2, 3, or 4; n ２ is 0, 1, 2, 3 or 4, n3 and n5 are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; n4 is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; Q is N or P; R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , and R １２ are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R ６ and R ９ are optionally linked to form a 5-membered ring, optionally substituted with halide or alkyl; R １３ is absent or is alkylene, alkenylene, alkynylene, or arylene, said alkylene, alkenylene, alkynylene, or arylene optionally substituted with halide; Each R ２０ is independently hydrogen, hydroxyl, halide, alkyl, alkenyl, alkynyl, or aryl, said alkyl, alkenyl, alkynyl, or aryl being optionally substituted with halide; Each R ２１ is independently an alkyl, alkenyl, or alkynyl, or a substituent of formula (8A-1), 【Chemistry 40】 the alkyl, alkenyl, or alkynyl is optionally substituted with a halide; R ２２ is a halide, or a quaternary ammonium or phosphonium group, or a nitrogen-containing heterocyclic group, or a salt thereof, and the quaternary ammonium or phosphonium group has the formula (9A-1): 【Chemistry 41】 the nitrogen-containing heterocyclic group is an optionally substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, quinoline, piperidine, pyrrolidine, pyrazolidine, imidazolidine, azepane, isoxazole, isoxazoline, oxazole, oxazoline, oxadiazole, oxatriazole, dioxazole, oxazine, oxadiazine, isoxazolidine, morpholine, thiazole, isothiazole, oxathiazole, oxathiazine, or caprolactam, each substituent being independently alkyl, alkenyl, alkynyl, aryl, or aralkyl; R ２３ , R ２４ , R ２５ , R ２６ , and R ２７ are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein said alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R ２８ and R ２９ are each independently alkylene; R ３０ , R ３１ , R ３２ , R ３３ , and R ３４ are each independently alkyl, alkenyl, or alkynyl; R ４７ is a halide, mesylate, tosylate, azide, alkenyl, or alkynyl; R ４８ , R ４９ , R ５０ , and R ５１ are each independently alkylene, arylene, alkenylene, alkynylene, ether, thioether, keto, amino, ammonium, or piperidinyl, wherein said alkylene, arylene, alkenylene, or alkynylene is optionally substituted with a halide; R ５２ But -NH ２ , -NHR ５３ , -NR ５３ R ５４ , -N-O, -N-S, or a nitrogen-containing heterocycle, the nitrogen of which has an oxygen, sulfur, or hydrogen substituent; R ５３ and R ５４ is each independently an alkyl, alkenyl, alkynyl, or aryl, said alkyl, alkenyl, alkynyl, or aryl being optionally substituted with a halide; X － is an anion.

12. An anion exchange polymer comprising the reaction product of an alkylating agent and a polymer according to any one of claims 1 to 11.

13. An anion exchange polymer comprising the reaction product of an amine with a polymer according to any one of claims 1 to 12.

14. An anion exchange polymer comprising the reaction product of a base and a polymer according to any one of claims 1 to 13.

15. A method of making a polymeric film for providing oxidation resistance, the method comprising: reacting the monomers in the presence of an organic solvent and a polymerization catalyst to form a polymer according to any one of claims 1 to 11, optionally reacting the polymer with an alkylating agent or an amine or a phosphine or a cation-containing group, after one or more reaction steps dissolving the polymer in a solvent to form a polymer solution, casting the polymer solution to form the polymer membrane, and optionally exchanging anions of the polymer with hydroxide ions, bicarbonate ions, or carbonate ions, or a combination thereof, before or after the casting step to form an anion exchange polymer membrane; Or, dissolving the polymer of any one of claims 1 to 11 and an anion exchange polymer in a solvent; casting the polymer solution to form the polymer membrane; exchanging the anions of the polymer with hydroxide ions, bicarbonate ions, or carbonate ions, or a combination thereof, to form an anion exchange polymer membrane; A method comprising:

16. Fuel cells, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalination devices, sensors, water desalination, ultrapure water production, wastewater treatment, ion exchangers, or CO ２ configured and sized to be suitable for use in a separator; An anion exchange membrane comprising a porous substrate comprising the polymer according to any one of claims 1 to 11 or impregnated with the polymer according to any one of claims 1 to 11.

17. An anion exchange membrane fuel cell, an electrolyzer, an electrodialyzer, a solar hydrogen generator, a flow battery, a desalination device, a sensor, a demineralizer, a water purifier, a wastewater treatment system, an ion exchanger, or a CO ２ separator.

18. A polymer for providing improved oxidation resistance, the polymer having the formula (6A ＯＲＧ ) and (3A) 【Chemistry 42】 The structural unit During the ceremony, n １ is 1, 2, 3, or 4; n ２ is 0, 1, 2, 3 or 4, n3 and n5 are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; n4 is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; Q is N or P; R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , and R １２ are each independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl, or an aryl, wherein the alkyl, alkenyl, alkynyl, or aryl is optionally substituted with a halide; R ６ and R ９ are optionally linked to form a 5-membered ring, optionally substituted with halide or alkyl; R １３ are each independently an alkylene, alkenylene, alkynylene, or arylene, the alkylene, alkenylene, alkynylene, or arylene being optionally substituted with a halide, or R １３ does not exist, Each R ２０ is independently hydrogen, hydroxyl, halide, alkyl, alkenyl, alkynyl, or aryl, said alkyl, alkenyl, alkynyl, or aryl being optionally substituted with halide; R ５９ But -(CH ２ ) ｎ３ - [Q(R ６０ ) (R ６１ )-(CH ２ ) ｎ４ ] ｎ５ -R ６２ or -[(CH ２ ) ｎ３ -O] ｎ５ -R ６２ and R ６０ and R ６１ are each independently alkyl, alkenyl, or alkynyl; R ６２ is a nitrogen-containing heterocycle, the nitrogen of said heterocycle having an oxygen, sulfur, or hydrogen substituent; X － is an anion.

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