Polymers with stable cationic side groups for use as anion exchange membranes

Abstract

Provided are poly(aryl alkylene) polymers or poly(aryl-crown ether-alkylene) polymers with cationic side groups, the polymers having alkaline stable cations, such as imidazolium, introduced into rigid aromatic polymer backbones without ether bonds. Hydroxyl exchange membranes or hydroxide exchange ionomers formed by these polymers exhibit excellent chemical stability, hydroxide conductivity, reduced water absorption, good solubility in selected solvents, and improved mechanical properties under ambient dry conditions compared to conventional hydroxide exchange membranes or ionomers. Hydroxyl exchange membrane fuel cell units and hydroxide exchange membrane electrolyzers including poly(aryl alkylene) polymers or poly(aryl-crown ether-alkylene) polymers with cationic side groups exhibit enhanced performance and durability at relatively high temperatures.

Description

[0001] Government licensing rights

[0002] This invention was made in part with government support under Grant DE-AR0000814 awarded by the Advanced Research Projects Agency-Energy of the U.S. Department of Energy. The government has certain rights in this invention. Technical Field

[0003] Anion exchange polymers capable of forming anion exchange membranes (AEM) and ionomers (AEI) are provided for use in anion exchange membrane fuel cell units (AEMFC). More specifically, hydroxide exchange polymers capable of forming hydroxide exchange membranes (HEM) and ionomers (HEI) are provided for use in various applications, such as hydroxide exchange membrane fuel cell units (HEMFC) and hydroxide exchange membrane electrolyzers (HEMEL). Background Art

[0004] Proton exchange membrane fuel cells (PEMFC) are considered to be clean and efficient power sources. Steele et al., Nature 2001, 414, 345. However, the high cost and unsatisfactory durability of the catalyst are the main obstacles to the large-scale commercialization of PEMFC. Borup et al., Chem Rev 2007, 107, 3904. By converting the polymer electrolyte from "acidic" conditions to "alkaline" conditions, HEMFC is able to work with non-precious metal catalysts, and the catalysts are expected to be more durable. Other cheaper fuel cell components are also possible, such as metal bipolar plates. Varcoe et al., Fuel Cells 2005, 5, 187; Gu et al., Angew Chem Int Edit 2009, 48, 6499; Gu et al., Chem Commun 2013, 49, 131. However, currently available HEMs and HEIs exhibit low alkali / chemical stability, low hydroxide conductivity, high water absorption, and low mechanical integrity under dry conditions, especially after wetting-drying cycles.

[0005] The biggest challenge for HEM / HEI now is to achieve high chemical stability at the required operating temperature of 80°C or higher and ideally 95°C or higher (e.g., in the presence of nucleophilic hydroxide ions). Varcoe et al., Energ Environ Sci 2014, 7, 3135. The most common cationic functional groups (e.g., benzyltrimethylammonium and alkyl chain ammonium) can undergo many degradation processes in the presence of hydroxide ion nucleophiles through direct nucleophilic substitution and Hofmann elimination. In addition, the polymer backbone of most base polymers (e.g., polysulfone and poly(phenylene ether)) used for HEM / HEI applications inevitably contains ether bonds along the backbone, which makes HEM / HEI potentially unstable under high pH conditions. Lee et al., ACS Macro Lett 2015, 4, 453; Lee et al., ACS Macro Lett 2015, 4, 814. Strong nucleophilic hydroxide ions attack these weak bonds and degrade the polymer backbone. Therefore, alternative cationic groups, organic tethers, and polymer backbones are needed to enhance the chemical stability of HEM / HEI.

[0006] Another problem with current HEM / HEI is its hydroxide conductivity. Compared with perfluorosulfonic acid, HEM has an 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. HEM / HEI requires a larger ion exchange capacity (IEC) to achieve higher hydroxide conductivity. However, high IEC usually results in a membrane with high water absorption (i.e., high swelling rate), reducing the morphological stability and mechanical strength of the membrane, especially after repeated wetting-drying cycles. This highly swollen state when wet is the main reason for the reduced flexibility and brittleness of HEM when dry. Eliminating the balance between high hydroxide conductivity and low water absorption has always been a major obstacle to designing high-performance HEM / HEI. Pan et al., Energy and Environmental Science 2013, 6, 2912. Chemical cross-linking, physical reinforcement, side chain polymerization, and block copolymer construction have been attempted to reduce water absorption while maintaining acceptable hydroxide conductivity, but these techniques pose challenging issues such as reduced mechanical flexibility, reduced alkali stability, and / or increased cost. Gu et al., Chemical Communications 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. Additionally, due to limited available synthetic methods, almost all side chain or block copolymer HEMs are based on flexible aliphatic polymer chains. Therefore, the membranes still cannot provide morphological stability (low swelling ratio) at high IEC and high temperature. Wang et al., Chemistry and Sustainability, Energy and Materials (Chemsuschem) 2015, 8, 4229; Ran et al., SciRep-Uk 2014, 4; Marino et al., Chemistry and Sustainability, Energy and Materials 2015, 8, 513; Li et al., M.Macromolecules 2015, 48, 6523.

[0007] Another obstacle to using HEM is obtaining mechanical flexibility and strength in the ambient dry state. Most HEMs exhibit low mechanical strength and are very brittle in the fully dry state, especially after full swelling. It is difficult to obtain and handle the large-scale films required for commercial use of HEM. Without good mechanical properties, ionomers cannot form and maintain a proper three-phase structure in fuel cell cell electrodes at high temperatures (such as at or above 80°C). Li et al., Journal of the American Chemical Society 2013, 135, 10124.

[0008] Another highly desirable feature of HEIs is that the polymer is soluble in a mixture of lower boiling alcohols and water, but insoluble in pure alcohol or water, so that the HEI can be easily incorporated into electrode catalyst layers without being dissolved away by water or alcohol.

[0009] PEMFC has recently been deployed as a zero-emission power source in commercially sold automobiles to demonstrate long driving range and short refueling time, two preferred features accepted by customers. However, PEMFC uses platinum electrocatalysts and is not yet cost-competitive compared to gasoline engines. The main methods to reduce the cost of PEMFC include developing low platinum loading, high power density membrane electrode assemblies (MEAs) and platinum group metal-free (PGM-free) cathode catalysts. A fundamentally different approach to low-cost fuel cell units is to convert from PEMFC to hydroxide exchange membrane fuel cell units (HEMFCs), which can work on PGM-free anode and cathode catalysts due to their alkaline operating environment and may therefore be economically feasible. However, in order to replace PEMFC, HEMFC must provide performance that matches the performance of PEMFC, which in turn requires highly active anode and cathode catalysts and highly chemically stable, ionically conductive and mechanically robust hydroxide exchange membranes (HEM) / hydroxyl exchange ionomers (HEIs) to establish effective three-phase boundaries, and thus greatly improve the utilization of catalyst particles and reduce internal resistance.

[0010] HEM / HEIs are usually composed of organic cations tethered to a polymer backbone, with OH- as the counter anion. Chemically stable HEM / HEIs require stable organic cations and stable polymer backbones. These hydroxide-conductive organic cations have been obtained by introducing quaternary ammonium, imidazolium, guanidinium, phosphonium, sulfonium, ruthenium, and cobaltocene groups using chloromethylation of aromatic rings or bromination on the benzylmethyl groups of the polymer. Various polymer backbone structures—poly(olefins), poly(styrenes), poly(phenylene oxides), poly(phenylenes), poly(arylene ethers)—have been recently investigated. To date, most HEM / HEIs based on traditional cationic groups (e.g., benzyltrimethylammonium) and aromatic polymer backbones (e.g., polysulfones) have low alkali / chemical stability, low hydroxide conductivity, high water absorption, and poor mechanical properties in terms of drying time.

[0011] Polymer backbones with ether bonds are generally fragile in alkaline media, and therefore HEM / HEIs with ether-free polymer backbones are highly desirable. Acid-catalyzed hydroxylation reactions have been shown to be effective in producing ether-free polymer backbones, and HEM / HEIs with such backbones have been shown to have good alkaline stability and mechanical properties. Zolotukhin et al., Chemical Communications, 2004, 1030. Diaz et al., Macromol. Rapid Commun., 2007, 28, 183. Lee et al., ACS Macro Express, 2015, 4, 814. Bae et al., U.S. Patent Application 15 / 527,967.

[0012] In order to further enhance the alkaline stability of HEM / HEI at both high temperature and low relative humidity, cations other than conventional ammonium cations are highly desirable. Imidazolium cations, when appropriately substituted, show improved alkaline stability. Gu et al. Polymers, 2014, 47, 208. Wang et al. Chemistry & Sustainability, Energy & Materials, 2013, 6, 2079. Hugar et al. Journal of the American Chemical Society, 2015, 137, 8730. Summary of the invention

[0013] Provided is a polymer comprising a structural unit having the following formula: formula (1A); (3A) or (3'A); and optionally (4A), wherein the structural unit having formula (1A), (3A), (3'A) and (4A) has the following structure:

[0014]

[0015]

[0016] as well as

[0017]

[0018] in:

[0019] R 11 Each is independently a quaternary ammonium or phosphonium group or a nitrogen-containing heterocyclic group or a salt thereof, wherein the quaternary ammonium or phosphonium group has the formula (5A):

[0020]

[0021] and 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, wherein each substituent is independently alkyl, alkenyl, alkynyl, aryl, or aralkyl;

[0022] R 20 , R 30 , R 40 , R 50 , R 60 , R 70 , R 80 , R 90 , R 130 , R 140 , R 150 , R 160 and R 170 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with halide, and wherein R 30 and R 60 optionally linked to form a five-membered ring optionally substituted with halide or alkyl;

[0023] Each R 100 are independently alkyl, alkenyl, alkynyl or a substituent having the formula (4B):

[0024]

[0025] and the alkyl, alkenyl or alkynyl group is optionally substituted with fluoride;

[0026] R 180 and R 240 are each independently an alkylene group;

[0027] R 190 , R 200 , R 210 , R 220 and R 230 are each independently alkyl, alkenyl or alkynyl;

[0028] q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20;

[0029] m is 0, 1, 2, 3, 4, 5 or 6;

[0030] n is 0, 1, 2 or 3;

[0031] Each m' and each n' are independently 0, 1 or 2;

[0032] X - is an anion; and

[0033] When the structural unit having formula (3A) is present in the polymer but the structural unit having formula (3'A) is not present in the polymer, Z is P, and when the structural unit having formula (3'A) is present in the polymer, Z is N or P.

[0034] Also provided is a polymer comprising a reaction product of a polymerization mixture, the polymer comprising:

[0035] (i) a cationically functionalized trifluoroketone monomer having the formula:

[0036]

[0037] (ii) an aromatic monomer having the formula:

[0038]

[0039] A crown ether monomer having the formula:

[0040] as well as

[0041] (iii) optionally, a trifluoromethyl ketone monomer having the formula:

[0042]

[0043] in:

[0044] R1 is each independently a quaternary ammonium or phosphonium group or a nitrogen-containing heterocyclic group or a salt thereof, wherein the quaternary ammonium or phosphonium group has the formula (5A):

[0045]

[0046] and 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, wherein each substituent is independently alkyl, alkenyl, alkynyl, aryl, or aralkyl;

[0047] R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 and R 17 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with halide, and wherein R3 and R6 are optionally linked to form a five-membered ring optionally substituted with halide or alkyl;

[0048] Each R 12 are independently alkyl, alkenyl, alkynyl or a substituent having the formula (4C):

[0049]

[0050] and the alkyl, alkenyl or alkynyl group is optionally substituted with fluoride;

[0051] R 180 and R 240 are each independently an alkylene group;

[0052] R 190 , R 200 , R 210 , R 220 and R 230 are each independently alkyl, alkenyl or alkynyl;

[0053] m is 0, 1, 2, 3, 4, 5 or 6;

[0054] n is 0, 1, 2 or 3;

[0055] Each m' and each n' are independently 0, 1 or 2;

[0056] q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20;

[0057] X - is an anion; and

[0058] When the aromatic monomer of formula (3) is present in the polymerization mixture but the crown ether monomer of formula (3') is not present in the polymerization mixture, Z is P, and when the crown ether monomer of formula (3') is present in the polymerization mixture, Z is N or P.

[0059] Another polymer comprising the second reaction product of the second polymerization mixture is provided, the polymer comprising:

[0060] A quaternary ammonium or phosphonium compound or a nitrogen-containing heterocycle or a salt thereof; and

[0061] Intermediate polymers;

[0062] in:

[0063] The intermediate polymer comprises a first reaction product of a first polymerization mixture, the first reaction product comprising:

[0064] (i) a halogenated trifluoromethyl ketone monomer having the formula:

[0065]

[0066] (ii) an aromatic monomer having the formula (3) as shown above, or a crown ether monomer having the formula (3') as shown above; and

[0067] (iii) optionally, a trifluoromethyl ketone monomer having formula (4) as shown above, wherein:

[0068] The quaternary phosphonium compound has the formula (5):

[0069]

[0070] Nitrogen-containing heterocyclic ring, m', n', n, q, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 As described above;

[0071] R 18 and R 24 are each independently an alkylene group;

[0072] R 19 , R 20 , R 21 , R 22 and R 23 are each independently alkyl, alkenyl or alkynyl;

[0073] R 111 For halides;

[0074] m is 0, 1, 2, 3, 4, 5 or 6;

[0075] X - is an anion; and

[0076] When the aromatic monomer having formula (3) is present in the first polymerization mixture but the crown ether monomer having formula (3') is not present in the first polymerization mixture, Z is P, and when the crown ether monomer having formula (3') is present in the first polymerization mixture, Z is N or P.

[0077] Also provided is an anion exchange polymer comprising the reaction product of a base and any of the polymers described above.

[0078] A method for preparing an anion exchange polymer membrane comprising an anion exchange polymer is also provided. The method comprises:

[0079] reacting the cationically functionalized trifluoroketone monomer, optionally the trifluoromethylketone monomer, and the aromatic monomer or the crown ether monomer in the presence of an organic solvent and a polymerization catalyst to form a cationically functionalized polymer;

[0080] dissolving the cationically functionalized polymer in a solvent to form a polymer solution;

[0081] casting the polymer solution to form a polymer film; and

[0082] The anions of the polymer membrane are exchanged with hydroxide, bicarbonate or carbonate ions or a combination thereof to form the anion exchange polymer membrane.

[0083] Another method for preparing an anion exchange polymer membrane comprising an anion exchange polymer is provided. The method comprises:

[0084] reacting the halogenated trifluoroketone monomer, optionally the trifluoromethyl ketone monomer, and the aromatic monomer in the presence of an organic solvent and a polymerization catalyst to form a halogen-functionalized polymer;

[0085] reacting the halogen-functionalized polymer with the quaternary phosphonium compound or the nitrogen-containing heterocycle or a salt thereof in the presence of an organic solvent to form a cationically functionalized polymer;

[0086] dissolving the cationically functionalized polymer in a solvent to form a polymer solution;

[0087] casting the polymer solution to form a polymer film; and

[0088] The anions of the polymer membrane are exchanged with hydroxide, bicarbonate or carbonate ions or a combination thereof to form the anion exchange polymer membrane.

[0089] Another method for preparing an anion exchange polymer membrane comprising an anion exchange polymer is provided. The method comprises:

[0090] reacting the halogenated trifluoroketone monomer, optionally the trifluoromethyl ketone monomer, and the crown ether monomer in the presence of an organic solvent and a polymerization catalyst to form a halogen-functionalized polymer;

[0091] reacting the halogen-functionalized polymer with the quaternary ammonium compound or quaternary phosphonium compound or the nitrogen-containing heterocycle or a salt thereof in the presence of an organic solvent to form a cationic-functionalized polymer;

[0092] dissolving the cationically functionalized polymer in a solvent to form a polymer solution;

[0093] casting the polymer solution to form a polymer film; and

[0094] The anions of the polymer membrane are exchanged with hydroxide, bicarbonate or carbonate ions or a combination thereof to form the anion exchange polymer membrane.

[0095] Also provided is an anion exchange membrane, which is optionally configured and sized to be suitable for use in a fuel cell unit, an electrolyzer, an electrodialyzer, a solar hydrogen generator, a flow battery, a desalter, a sensor, a desalter, a water purifier, a wastewater treatment system, an ion exchanger or a CO2 separator, and the anion exchange membrane comprises the anion exchange polymer.

[0096] Also provided is an anion exchange membrane fuel cell unit, an electrolyzer, an electrodialyzer, a solar hydrogen generator, a liquid flow battery, a desalter, a sensor, a desalter, a water purifier, a wastewater treatment system, an ion exchanger or a CO2 separator, wherein the fuel cell unit, the electrolyzer, the electrodialyzer, the solar hydrogen generator, the liquid flow battery, the desalter, the sensor, the desalter, the water purifier, the wastewater treatment system, the ion exchanger or the CO2 separator comprises the anion exchange polymer.

[0097] Also provided is a reinforced electrolyte membrane, which is optionally configured and sized to be suitable for use in a fuel cell unit, an electrolyzer, an electrodialyzer, a solar hydrogen generator, a flow battery, a desalter, a sensor, a desalter, a water purifier, a wastewater treatment system, an ion exchanger, or a CO2 separator. The membrane comprises a porous substrate impregnated with the anion exchange polymer.

[0098] Other objects and features will be in part apparent and in part pointed out hereinafter. BRIEF DESCRIPTION OF THE DRAWINGS

[0099] Figure 1A An exemplary hydroxide exchange membrane fuel cell unit is shown.

[0100] Figure 1B An exemplary hydroxide exchange membrane electrolyzer is shown.

[0101] Figure 2 The 1H NMR spectrum of BP-CF3-Br-1 in CDCl3 is depicted.

[0102] Figure 3 The 1H NMR spectrum of BP-CF3-IM-1 in DMSO-d6 is depicted.

[0103] Figure 4A Shown are 1H NMR spectra of BP-CF3-IM-1 before and after alkaline stability testing in 1 M KOH (10% TFA in DMSO-d6) at 130°C for 1200 hours.

[0104] Figure 4B Shown are 1H NMR spectra of TP-CF3-IM-1 before and after alkaline stability testing in 10 M KOH (in DMSO-d6) at 80°C for 300 hours. Figure 4C Shown are 1H NMR spectra of TP-CF3-IM-1 before and after alkaline stability testing at 95°C and RH of 50.9% and 23.3% (10% TFA in DMSO-d6) for 300 hours.

[0105] Figure 5 The 1H NMR spectrum of TP-CF3-Br-1 in CDCl3 is depicted.

[0106] Figure 6 The 1H NMR spectrum of TP-CF3-IM-1 in DMSO-d6 is shown.

[0107] Figure 7 is a graph depicting tensile stress as a function of elongation for TP-CF3-IM-1 polymer in the bicarbonate form.

[0108] Figure 8 Polarization (voltage as a function of current density) and power density (power density as a function of current density) curves of HEMFC at 95°C are shown. Materials: TP-CF3-IM-1 membrane, 20% ionomer loading, catalyst: 0.4 mgPt cm-2PtRu / C on anode, 0.4 mgPt cm-2PtRu / C on cathode. Test conditions: 95°C, anode humidifier temperature: 90°C, cathode anode humidifier temperature: 97°C, H2 flow rate: 1.0 L / min, O2 flow rate: 2.0 L / min.

[0109] Fig. 9 The polarization (voltage as a function of current density) curve of HEMEL at 80°C is shown. Materials: TP-CF3-IM-1 membrane, 30% ionomer loading, catalyst: 4.0 mg on anodePt cm-2Pt / C, 2.9mg cm-2IrO2 on cathode. Test conditions: 80℃ water and electrolyzer, water flow rate: 3.0ml / min.

[0110] Fig.10 The 1H NMR spectrum of PCE-C5-Br-1 in CDCl3 is depicted.

[0111] Fig.11 The 1H NMR spectrum of PCE-C5-IM-Br-1 in DMSO-d6 is depicted. DETAILED DESCRIPTION

[0112] HEM / HEI formed from polymers having various pendant cationic groups and having inherent hydroxide conducting channels have been found to simultaneously provide improved chemical stability, conductivity, water absorption, good solubility in selected solvents, mechanical properties, and other attributes related to HEM / HEI performance. Pendant side chains attached to the rigid aromatic polymer backbone of the polymer without ether bonds allow fine tuning of the mechanical properties of the membrane and incorporation of base-stable cations such as imidazolium, phosphonium, and ammonium, and provide enhanced stability to the polymer. Compared to conventional HEM / HEI, the HEM / HEI formed from these polymers exhibits excellent chemical stability, anionic conductivity, reduced water absorption, good solubility in selected solvents, and improved mechanical properties in ambient dry conditions. The HEMFC of the present invention exhibits improved performance and durability at relatively high temperatures.

[0113] As a first aspect of the present invention, a polymer is provided, which comprises structural units having formula (1A); (3A) and / or (3′A); and optionally (4A).

[0114] The structural unit having formula (1A) has the following structure:

[0115]

[0116] wherein q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; and R 11 Each is independently a quaternary ammonium or phosphonium group or a nitrogen-containing heterocyclic group or a salt thereof;

[0117] The quaternary ammonium or phosphonium group has formula (5A):

[0118]

[0119] Where R 180 and R 240 Each is independently an alkylene group; R 190 , R200 , R 210 , R 220 and R 230 Each is independently alkyl, alkenyl or alkynyl; m is 0, 1, 2, 3, 4, 5 or 6; X - is an anion; and when the structural unit having formula (3A) is present in the polymer but the structural unit having formula (3'A) is not present in the polymer, Z is P, and when the structural unit having formula (3'A) is present in the polymer, Z is N or P. Preferably, X - Including halide ions, BF4 - PF6 - 、CO3 2- or HCO3 - .

[0120] For example, the quaternary ammonium or quaternary phosphonium group R of formula (5A) 180 and R 240 Can be independently C1-C 22 Alkylene; R 190 , R 200 , R 210 , R 220 and R 230 may each independently be a C1-C6 alkyl group; m may be 0, 1, 2, 3, 4, 5 or 6; and Z may be N or P.

[0121] As an example, the quaternary ammonium or quaternary phosphonium group R of formula (5A) is 180 and R 240 may be independently C1-C6 alkylene; R 190 , R 200 , R 210 , R 220 and R 230 may each independently be a C1-C6 alkyl group; m may be 0, 1, 2 or 3; and Z is N or P.

[0122] As yet another example, the quaternary ammonium or quaternary phosphonium group having formula (5A) is 180 and R 240 Can be independently C8-C 22 Alkylene; R 190 , R 200 , R 210 , R 220 and R 230 are each independently a C1-C6 alkyl group; m is 0, 1, 2 or 3; and Z is N or P.

[0123] In other cases, the quaternary ammonium or quaternary phosphonium group of formula (5A) is 180 and R240 may each be a C2-C6 alkylene group; R 190 , R 200 , R 210 , R 220 and R 230 are each independently methyl; m is 1; and Z is N or P.

[0124] In yet other cases, the quaternary ammonium or quaternary phosphonium group having formula (5A) is 180 and R 240 Each of them may be n-hexylene; R 190 , R 200 , R 210 , R 220 and R 230 each is methyl; m is 1; and Z is N or P.

[0125] The nitrogen-containing heterocyclic group can be 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, wherein each substituent is independently alkyl, alkenyl, alkynyl, aryl or aralkyl.

[0126] Preferably, the nitrogen-containing heterocyclic group is unsaturated, such as pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine or quinoline, and each substitutable position of the heterocyclic ring is independently substituted by an alkyl group (e.g., methyl, ethyl, propyl, n-butyl) or an aryl group (e.g., phenyl having an alkyl substituent).

[0127] The nitrogen-containing heterocyclic group may include an imidazolium having the formula (6A):

[0128]

[0129] Where: R 25 , R 26 , R 27 and R 28 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with halide. 28 is 2,4,6-alkylphenyl, and R 25 , R 26 and R 27Each is independently a C1-C6 alkyl group. An example of an imidazole as a nitrogen-containing heterocyclic ring is 1-butyl-2-mesityl-4,5-dimethyl-1H-imidazole-imidazole, which has the following formula:

[0130]

[0131] The structural unit of formula (3A) has the following structure:

[0132]

[0133] Where n is 0, 1, 2 or 3; R 20 , R 30 , R 40 , R 50 and R 60 , R 70 , R 80 and R 90 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with halide; and wherein R 30 and R 60 Optionally linked to form a five-membered ring optionally substituted with halide or alkyl.

[0134] For example, in the structural unit having formula (3A), R 20 , R 30 , R 40 , R 50 , R 60 , R 70 , R 80 and R 90 At least one of may be a halide or an aryl group, and the aryl group may be optionally substituted with a halide.

[0135] As another example, in the structural unit having formula (3A), R 30 and R 60 Can be linked to form a five-membered ring optionally substituted with halide or alkyl.

[0136] The structural unit having formula (3A) may be derived from an aromatic monomer, including biphenyl, p-terphenyl, m-terphenyl, p-quaterphenyl, 9,9-dimethyl-9H-fluorene or benzene.

[0137] The structural unit having formula (3'A) has the following structure:

[0138]

[0139] Where R 20 , R 40 , R 50 , R70 , R 80 and R 90 Each is independently hydrogen, a halide, an alkyl, an alkenyl, an alkynyl or an aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with a halide. The benzo ring and R shown by the dotted line in formula (3'A) 90 The group may be present or absent. If the benzo ring shown by the dotted line in formula (3'A) does not exist, then R 90 If the benzo ring shown by the dotted line in formula (3'A) is present, then R 90 The group exists because it has R 90 The benzo ring of the radical will be monovalent.

[0140] For example, the structural unit can be derived from a dibenzo-18-crown-6 polyether as in formula (3'A-1), wherein m' and n' are 0, a dibenzo-21-crown-7 polyether as in formula (3'A-1), wherein m' is 0 and n' is 1, a dibenzo-24-crown-8 polyether as in formula (3'A-1), wherein m' and n' are 1, or a dibenzo-30-crown-10 polyether as in formula (3'A-1), wherein m' and n' are 2, and R 20 , R 40 , R 50 , R 70 , R 80 and R 90 As defined for formula (3'A):

[0141]

[0142] or a benzo-18-crown-6 polyether as in formula (3'A-2), wherein m' and n' are 2, and R 70 and R 80 As defined for formula (3'A):

[0143]

[0144] For example, in the structural unit having any of the formulae (3'A) to (3'A-2), R 20 , R 40 , R 50 , R 70 , R 80 and R 90 , if present, may be hydrogen or a halide.

[0145] The structural unit of formula (3'A-1) can be derived from the corresponding dibenzo-crown ether, wherein R 20 , R 40 , R 50 , R70 , R 80 and R 90 Each is hydrogen. Dibenzo-18-crown-6 polyether can be made from catechol and bis(chloroethyl)ether, such as Charles J. Pedersen, "Org. Synth.", 1972, 52, 66 and is commercially available. Dibenzo-21-crown-7 polyether, dibenzo-24-crown-8 polyether and dibenzo-30-crown-10 polyether are also commercially available.

[0146] The structural unit having the formula (3'A-2) may be derived from benzo-18-crown-6 polyether, wherein R 70 and R 80 Each is hydrogen. Benzo-18-crown-6 polyether is commercially available.

[0147] The optional structural unit having formula (4A) has the following structure:

[0148]

[0149] Each R 100 are independently alkyl, alkenyl, alkynyl or a substituent having the formula (4B):

[0150]

[0151] and the alkyl, alkenyl or alkynyl is optionally substituted with fluoride; R 130 , R 140 , R 150 , R 160 and R 170 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with halide.

[0152] For example, in the structural unit having formula (4A), R 100 It may be an alkyl, alkenyl or alkynyl group, and the alkyl, alkenyl or alkynyl group may be optionally substituted with fluoride.

[0153] As another example, in the structural unit having formula (4A), R 100 can be the substituent having the formula (4B) and R 130 , R 140 , R 150 , R 160 and R 170 At least one of may be a halide or an aryl group, and the aryl group may be optionally substituted with a fluoride.

[0154] As yet another example, R 20 , R40 , R 50 , R 70 , R 80 , R 90 , R 130 , R 140 , R 150 , R 160 and R 170 may each independently be hydrogen or alkyl optionally substituted with fluoride, and R 100 It may be an alkyl group optionally substituted with a fluoride or the substituent having the formula (4B).

[0155] In other cases, R 20 , R 40 , R 50 , R 70 , R 80 , R 90 , R 130 , R 140 , R 150 , R 160 and R 170 may each independently be hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl, or methyl, ethyl, propyl, butyl, pentyl or hexyl, optionally substituted with fluoride, and R 100 It may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group which is optionally substituted with a fluoride or the substituent group having the formula (4B).

[0156] The sum of the mole fractions of the structural units having formula (1A) and formula (4A) in the polymer may be approximately equal to the sum of the mole fractions of the structural units having formula (3A) and formula (3'A) in the polymer, and the ratio of the mole fraction of the structural units having formula (1A) in the polymer to the sum of the mole fractions of the structural units having formula (3A) and (3'A) in the polymer may be approximately 0.01 to 1.

[0157] The molar ratio of the sum of the mole fractions of the structural units having formula (1A) and formula (4A) to the sum of the mole fractions of the structural units having formula (3A) and (3'A) in the polymer may be about 0.95:1 to about 1.4:1, and the ratio of the mole fraction of the structural units having formula (1A) to the sum of the mole fractions of the structural units having formula (3A) and (3'A) may be about 0.01 to 1.

[0158] The molar ratio of the sum of the mole fractions of the structural units having formula (1A) and formula (4A) to the sum of the mole fractions of the structural units having formula (3A) and (3'A) in the polymer may be about 1:1 to about 1.2:1.

[0159] As a second aspect of the present invention, there is provided a polymer comprising the reaction product of a polymerization mixture comprising a cationically functionalized trifluoroketone monomer; an aromatic monomer and / or a crown ether monomer; and optionally a trifluoromethyl ketone monomer.

[0160] The cationically functionalized trifluoroketone monomer has the formula:

[0161]

[0162] wherein q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; and R1 is each independently a quaternary ammonium or phosphonium group or a nitrogen-containing heterocyclic group or a salt thereof; the quaternary ammonium or phosphonium group and the nitrogen-containing heterocyclic group are as defined above for the first aspect of the invention.

[0163] The aromatic monomer has the formula:

[0164]

[0165] wherein n is 0, 1, 2 or 3; R2, R3, R4, R5, R6, R7, R8, R9 and R 10 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with halide, and wherein R3 and R6 are optionally connected to form a five-membered ring optionally substituted with halide or alkyl.

[0166] For example, in the aromatic monomer having formula (3), R2, R3, R4, R5, R6, R7, R8, R9 and R 10 At least one of is a halide or an aryl group, and the aryl group is optionally substituted with a halide.

[0167] As an example, in the aromatic monomer having formula (3), R3 and R6 are linked to form a five-membered ring optionally substituted with a halide or an alkyl group.

[0168] The aromatic monomer having formula (3) may include biphenyl, p-terphenyl, m-terphenyl, p-quaterphenyl, 9,9-dimethyl-9H-fluorene or benzene.

[0169] Crown ether monomers have the formula:

[0170]

[0171] Among them, R2, R4, R5, R7, R8, R9 and R 10, if present, are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with halide, and each n' is independently 0, 1 or 2. The benzo ring shown by the dotted line in formula (3') may be present or absent.

[0172] For example, the crown ether monomer can be a dibenzo-18-crown-6 polyether as in formula (3'-1), wherein m' and n' are 0, a dibenzo-21-crown-7 polyether as in formula (3'-1), wherein m' is 0 and n' is 1, a dibenzo-24-crown-8 polyether as in formula (3'-1), wherein m' and n' are 1, or a dibenzo-30-crown-10 polyether as in formula (3'-1), wherein m' and n' are 2, and R2, R4, R5, R7, R8, R9 and R 10 As defined for formula (3'):

[0173]

[0174] or a benzo-18-crown-6 polyether as in formula (3'-2), wherein m' and n' are 2, and R7, R 8、 R9 and R 10 As defined for formula (3'):

[0175]

[0176] The optional trifluoromethyl ketone monomer has the formula:

[0177]

[0178] Each R 12 are independently alkyl, alkenyl, alkynyl or a substituent having the formula (4C):

[0179]

[0180] and the alkyl, alkenyl or alkynyl is optionally substituted with fluoride; and R 13 , R 14 , R 15 , R 16 and R 17 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl.

[0181] For example, in the trifluoromethyl ketone monomer having formula (4), R 12 is an alkyl, alkenyl or alkynyl group, and the alkyl, alkenyl or alkynyl group is optionally substituted with fluoride.

[0182] As another example, in the trifluoromethyl ketone monomer having formula (4), R 12is a substituent having the formula (4C) and R 13 , R 14 , R 15 , R 16 and R 17 At least one of is a halide or an aryl group, and the aryl group is optionally substituted with a fluoride.

[0183] As yet another example, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently hydrogen or alkyl optionally substituted with fluorine, and R 12 is an alkyl group optionally substituted with fluoride or a substituent having the formula (4C).

[0184] In other cases, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl, or methyl, ethyl, propyl, butyl, pentyl or hexyl, optionally substituted with fluoride, and R 12 is methyl, ethyl, propyl, butyl, pentyl, or hexyl, optionally substituted with fluoride or a substituent having the formula (4C).

[0185] The third aspect of the present invention is a polymer comprising a second reaction product of a second polymerization mixture. The second polymerization mixture comprises a quaternary ammonium or phosphonium compound or a nitrogen-containing heterocycle or a salt thereof; and an intermediate polymer.

[0186] The intermediate polymer comprises a first reaction product of a first polymerization mixture. The first polymerization mixture comprises a halogenated trifluoromethyl ketone monomer; an aromatic monomer and / or a crown ether monomer; and optionally a trifluoromethyl ketone monomer.

[0187] The halogenated trifluoromethyl ketone monomer has the formula:

[0188]

[0189] wherein q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; and R 111 Preferably, the halide is fluoride, chloride, bromide or iodide.

[0190] The aromatic monomer has formula (3) and is as described for the polymer in the second aspect of the invention.

[0191] The crown ether has formula (3') and is as described for the polymer in the second aspect of the invention.

[0192] The trifluoromethyl ketone monomer has formula (4) and is as described for the polymer in the second aspect of the invention.

[0193] The quaternary ammonium or phosphonium compound has the formula (5):

[0194]

[0195] Wherein m is 0, 1, 2, 3, 4, 5 or 6; R 18 and R 24 Each is independently an alkylene group; R 19 , R 20 , R 21 , R 22 and R 23 Each is independently alkyl, alkenyl or alkynyl; X - is an anion; and when the aromatic monomer having formula (3) is present in the first polymerization mixture but the crown ether monomer having formula (3') is not present in the first polymerization mixture, Z is P, and when the crown ether monomer having formula (3') is present in the first polymerization mixture, Z is N or P. Preferably, X - Including halide ions, BF4 - PF6 - 、CO3 2- or HCO3 - .

[0196] For example, R of the quaternary ammonium or phosphonium compound having formula (5) 18 and R 24 Each independently is C1-C 22 Alkylene; R 19 , R 20 , R 21 , R 22 and R 23 may each independently be a C1-C6 alkyl group; m may be 0, 1, 2, 3, 4, 5 or 6; and Z may be N or P.

[0197] As another example, R of the quaternary ammonium or phosphonium compound having formula (5) 18 and R 24 may be independently C1-C6 alkylene; R 19 , R 20 , R 21 , R22 and R 23 may each independently be a C1-C6 alkyl group; m may be 0, 1, 2 or 3; and Z is N or P.

[0198] As yet another example, R of the quaternary ammonium or phosphonium compound having formula (5) 18 and R 24 Can be independently C8-C 22 Alkylene; R 19 , R 20 , R 21 , R 22 and R 23 may each independently be a C1-C6 alkyl group; m may be 0, 1, 2 or 3; and Z is N or P.

[0199] In other cases, R of the quaternary ammonium or phosphonium compound of formula (5) 18 and R 24 Each is a C2-C6 alkylene group; R 19 , R 20 , R 21 , R 22 and R 23 may each independently be methyl; m may be 1; and Z is N or P.

[0200] In yet other cases, R of the quaternary ammonium or phosphonium compound having formula (5) 18 and R 24 Each of them may be n-hexylene; R 19 , R 20 , R 21 , R 22 and R 23 each may be methyl; m may be 1; and Z may be N or P.

[0201] The nitrogen-containing heterocycle can be 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, wherein each substituent is independently alkyl, alkenyl, alkynyl, aryl or aralkyl.

[0202] Preferably, the nitrogen-containing heterocycle is unsaturated, such as pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine or quinoline, and each substitutable position of the heterocycle is independently substituted with an alkyl group (e.g., methyl, ethyl, propyl, n-butyl) or an aryl group (e.g., a phenyl group having an alkyl substituent).

[0203] The nitrogen-containing heterocycle may include an imidazole having the formula (6):

[0204]

[0205] Where: R 25 , R 26 , R 27 , R 28 and R 29 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with halide. 29 is hydrogen, R 28 is 2,4,6-alkylphenyl, and R 25 , R 26 and R 27 Each is independently a C1-C6 alkyl group. An example of an imidazole as a nitrogen-containing heterocyclic ring is 1-butyl-2-mesityl-4,5-dimethyl-1H-imidazole-imidazole, which has the following formula:

[0206]

[0207] The nitrogen-containing heterocycle can be 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, wherein each substituent is independently alkyl, alkenyl, alkynyl, aryl or aralkyl.

[0208] The fourth aspect of the present invention is an anion exchange polymer comprising a reaction product of a base and any one of the polymers described above in the first, second or third aspects of the present invention.

[0209] 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.

[0210] Representative anion exchange polymers include the following, where x is 0.01-1:

[0211]

[0212]

[0213] Poly(aryl-crown-ether-alkylene)-CF3-QA

[0214] Poly(aryl-crown-ether-alkylene)-CF3-d-QA

[0215] Poly(aryl-crown ether-alkylene)-CF3-IM.

[0216] The imidazolium tethered poly(aryl alkylene) polymer or imidazolium tethered poly(aryl-crown ether-alkylene) polymer may be a hydroxide exchange polymer comprising a poly(aryl alkylene) or poly(aryl-crown ether-alkylene) backbone without ether linkages and having: when immersed in pure water at 80°C, the hydroxide exchange polymer has a water absorption of no more than 47% based on the dry weight of the polymer; or when immersed in pure water at 20°C, the hydroxide exchange polymer has a hydroxide conductivity of at least 31 mS / cm. In addition, the polymer may be: stable to degradation (e.g., stable to degradation) when immersed in 1 M potassium hydroxide at 130°C for 1,200 hours. 1 H NMR spectrum); stable to degradation when immersed in 10 M potassium hydroxide at 80 °C for 300 h (as evidenced by no change in the 1 H NMR spectrum); stable to degradation when kept at 95°C at 23.3% and 50.9% relative humidity for 300 hours (as evidenced by no change in the H NMR spectrum); 1 H NMR spectrum); insoluble in pure water and isopropanol at 100° C., but soluble in a 50 / 50 by weight mixture of water and ethanol at 100° C. In addition, the polymer may have a tensile strength of at least 30 MPa and / or an elongation at break of at least 250%.

[0217] When the polymer is cross-linked with a cross-linking agent or chemically bonded to a membrane, the absorption rate of the imidazolium-tethered poly(aryl-crown-ether-alkylene) polymer can be no more than 47%. For example, the water absorption rate of the polycrown-ether-CF3-TMA (also known as PCE-C5-QA-1) of Example 10 is 364%, and the water absorption rate of the poly(aryl-crown-ether-alkylene)-CF3-IM of Example 7 is about 200% when measured, but can be reduced by cross-linking or chemically bonding the polymer to a membrane.

[0218] Cross-linking agents useful for cross-linking any of the polymers described herein include, for example, dibromoalkanes (dibromohexane, dibromobutane), diiodoalkanes (diiodohexane, diiodobutane), and dibromoalkanes and diiodoalkanes containing ammonium cations.

[0219] The imidazolium tethered poly(aryl alkylene) polymer or the imidazolium tethered poly(aryl-crown ether-alkylene) polymer may be a hydroxide exchange polymer comprising an imidazolium tethered poly(aryl alkylene) or poly(aryl-crown ether-alkylene) backbone without ether linkages and having the following: the polymer is used as a hydroxide exchange membrane of a hydroxide exchange membrane fuel cell unit and as a hydroxide exchange ionomer in the cathode and anode catalyst layers of the fuel cell unit at a peak power density of at least 130 mW / cm at 20% loading 2 The anode of the fuel cell unit has 0.4 mg Pt cm -2 PtRu / C, with 0.4 mg on the cathode Pt cm -2 PtRu / C, and the test conditions were a hydrogen flow rate of 1.0 L / min, an oxygen flow rate of 2.0 L / min, a cell temperature of 95°C, and anode and cathode humidifier temperatures of 90°C and 97°C, respectively.

[0220] Preferably, the aryl bonds of the imidazolium-tethered poly(aryl alkylene) polymer backbone containing no ether bonds include p-phenyl groups, and the alkylene bonds include hydroxide, bicarbonate or carbonate anions or combinations thereof. The imidazolium-tethered poly(aryl-crown ether-alkylene) polymer backbone containing no ether bonds also preferably includes dibenzo-18-crown-6, diphenyl-21-crown-7 polyether, diphenyl-24-crown-8 polyether or dibenzo-30-crown-10 polyether.

[0221] The aryl bonds of the imidazolium-tethered poly(arylalkylene) polymer backbone can be derived from, for example, biphenyl, p-terphenyl, m-terphenyl, p-quaterphenyl, 9,9-dimethyl-9H-fluorene or benzene monomers. The imidazolium-tethered poly(aryl-crown-ether-alkylene) polymer backbone without ether bonds can be derived from, for example, dibenzo-18-crown-6, diphenyl-21-crown-7 polyether, diphenyl-24-crown-8 polyether or dibenzo-30-crown-10 polyether.

[0222] The alkylene linkages of the imidazolium tethered poly(arylalkylene) backbone are derived from 7-bromo-1,1,1-trifluoroheptan-2-one monomers.

[0223] The imidazolium tethered poly(aryl alkylene) polymer backbone or the imidazolium tethered poly(aryl-crown ether-alkylene) polymer backbone may further include a 2,2,2-trifluoroethylbenzene linkage derived from a 2,2,2-trifluoroacetophenone monomer, or a trifluoromethylmethylene linkage derived from a trifluoromethylketone monomer, such as a 1,1,1-trifluoropropane linkage derived from 1,1,1-trifluoroacetone.

[0224] The fifth aspect of the present invention is a method for preparing an anion exchange polymer membrane comprising the anion exchange polymer in the fourth aspect of the present invention. The method comprises: reacting the cation functionalized trifluoroketone monomer, the optional trifluoromethyl ketone monomer and the aromatic monomer and / or crown ether monomer in the presence of an organic solvent and a polymerization catalyst to form a cation functionalized polymer; dissolving the cation functionalized polymer in a solvent to form a polymer solution; casting the polymer solution to form a polymer membrane; and exchanging the anions of the polymer membrane with hydroxide, bicarbonate or carbonate ions or a combination thereof to form the anion exchange polymer membrane.

[0225] For example, a cationically functionalized trifluoroketone monomer, such as imidazolium functionalized 7-bromo-1,1,1-trifluoroheptane-2-one, an optional trifluoromethylketone monomer, such as 2,2,2-trifluoroacetophenone or 1,1,1-trifluoroacetone, and an aromatic monomer, such as benzene, biphenyl, p-terphenyl, m-terphenyl or p-quaterphenyl, or a crown ether monomer, such as dibenzo-18-crown-6, dibenzo-21-crown-7 polyether, dibenzo-24-crown-8 polyether or dibenzo-30-crown-10 polyether, can be placed in a stirred container and dissolved or dispersed in an organic solvent. A polymerization catalyst in a solvent can then be added dropwise at -78°C to 60°C for up to 60 minutes. Thereafter, the reaction is continued at this temperature for about 1 to about 120 hours. The resulting solution is slowly poured into an ethanol aqueous solution. The solid obtained is filtered, washed with water and immersed in 1M K2CO3 at room temperature for about 1 to 48 hours. Finally, the product is filtered, washed with water and completely dried under vacuum to form a cationically functionalized polymer. The cationically functionalized polymer is then subjected to anion exchange, such as hydroxide exchange in 1M KOH, at about 20° C. to 100° C. for about 12 to 48 hours, followed by washing and immersion in DI water in an oxygen-free atmosphere for about 12 to 48 hours to remove residual KOH.

[0226] A representative reaction scheme of the fifth aspect of the present invention is shown below, wherein R5, R6, R7, R8 and R 100 R is independently hydrogen, alkyl, alkenyl, phenyl or alkynyl, and the alkyl, alkenyl, phenyl or alkynyl is optionally substituted with halide; 11 is phosphonium or a nitrogen-containing heterocycle; n is the number of repeating units in the polymer; q is 0-20; and x' is 0.01-1:

[0227]

[0228]

[0229] The sixth aspect of the present invention is a method for preparing an anion exchange polymer membrane comprising the anion exchange polymer in the fourth aspect of the present invention. The method comprises: reacting the halogenated trifluoroketone monomer, the optional trifluoromethyl ketone monomer and the aromatic monomer and / or crown ether monomer in the presence of an organic solvent and a polymerization catalyst to form a halogen-functionalized polymer; reacting the halogen-functionalized polymer with the quaternary phosphonium compound or the nitrogen-containing heterocycle or its salt in the presence of an organic solvent to form a cation-functionalized polymer; dissolving the cation-functionalized polymer in a solvent to form a polymer solution; casting the polymer solution to form a polymer membrane; and exchanging the anions of the polymer membrane with hydroxide, bicarbonate or carbonate ions or a combination thereof to form the anion exchange polymer membrane.

[0230] For example, a halogenated trifluoroketone monomer, such as 7-bromo-1,1,1-trifluoroheptane-2-one, an optional trifluoromethylketone monomer, such as 2,2,2-trifluoroacetophenone or 1,1,1-trifluoroacetone, and an aromatic monomer, such as benzene, biphenyl, p-terphenyl, m-terphenyl or p-quaterphenyl, or a crown ether monomer, such as dibenzo-18-crown-6, dibenzo-21-crown-7 polyether, dibenzo-24-crown-8 polyether or dibenzo-30-crown-10 polyether, can be placed in a stirred container and dissolved or dispersed in an organic solvent. A polymerization catalyst in a solvent can then be added dropwise at -78°C to 60°C for up to 60 minutes. Thereafter, the reaction is continued at this temperature for about 1 to about 120 hours. The resulting solution is slowly poured into an ethanol aqueous solution. The solid obtained is filtered, washed with water and immersed in 1M K2CO3 at room temperature for about 1 to 48 hours. Finally, the product was filtered, washed with water and completely dried under vacuum to form the halogen-functionalized polymer.

[0231] The halogen functionalized polymer is then placed in a stirred vessel with a quaternary phosphonium compound or a nitrogen-containing heterocycle or salt thereof, such as a functionalized imidazole, and dissolved or dispersed in an organic solvent. The reaction is continued at a temperature of about 50°C to 100°C for about 1 to about 120 hours. The resulting solution is then cast to form a polymer membrane. The polymer membrane is then subjected to anion exchange, such as hydroxide exchange in 1M KOH, at about 20°C to 100°C for about 12 to 48 hours, followed by washing and immersion in DI water in an oxygen-free atmosphere for about 12 to 48 hours to remove residual KOH.

[0232] A representative reaction scheme of the sixth aspect of the present invention is shown below, wherein R5, R6, R7, R8 and R 100 R is independently hydrogen, alkyl, alkenyl, phenyl or alkynyl, and the alkyl, alkenyl, phenyl or alkynyl is optionally substituted with halide; 11is a quaternary ammonium or phosphonium group and a nitrogen-containing heterocyclic group as defined in the first aspect of the present invention; n is the number of repeating units in the polymer; q is 0-20; and x' is 0.01-1:

[0233]

[0234]

[0235] The seventh aspect of the present invention is an anion exchange membrane, which is optionally configured and sized to be suitable for a fuel cell unit, an electrolyzer, an electrodialyzer, a solar hydrogen generator, a flow battery, a desalter, a sensor, a desalter, a water purifier, a wastewater treatment system, an ion exchanger or a CO2 separator, and includes the anion exchange polymer of the fourth aspect of the present invention.

[0236] The anion exchange polymer can be made into an enhanced hydroxide exchange membrane as described below. Such an enhanced hydroxide exchange membrane can be prepared by a method comprising: wetting a porous substrate in a liquid to form a wetted substrate; dissolving a poly(aryl alkylene) polymer in a solvent to form a uniform solution; applying the solution to the wetted substrate to form the enhanced membrane; drying the enhanced membrane; and exchanging the anions of the enhanced membrane with hydroxide ions to form an enhanced hydroxide exchange polymer membrane. The solution can be applied to the wetted substrate by any known membrane forming technique, such as casting, spraying or doctor blade.

[0237] If desired, the resulting reinforced membrane can be impregnated multiple times with the poly(aryl alkylene) polymer by rewetting the reinforced membrane and repeating the dissolving, casting, and drying steps.

[0238] The polymerization catalyst used to form the polymer may include trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, heptafluorobutyric acid, or a combination thereof.

[0239] Each of the organic solvents used in any of the above methods can be independently selected from polar aprotic solvents (e.g., dimethyl sulfoxide, 1-methyl-2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-methyl-2-pyrrolidone or dimethylformamide) or other suitable solvents, including but not limited to dichloromethane, trifluoroacetic acid, trifluoromethanesulfonic acid, chloroform, 1,1,2,2-tetrachloroethane, dimethylacetamide or a combination thereof.

[0240] The solvent in the dissolving step may include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, pentanol, hexanol, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, chloroform, ethyl lactate, tetrahydrofuran, 2-methyltetrahydrofuran, water, phenol, acetone or a combination thereof.

[0241] The liquid used to wet the porous substrate may be a low boiling point solvent, such as a lower alcohol (eg, methanol, ethanol, propanol, isopropanol) and / or water. Preferably, the liquid is anhydrous ethanol.

[0242] Additional aspects of the present invention are further described below.

[0243] Anion exchange membranes, such as hydroxide exchange membranes, are also provided. The membranes are configured and sized to be suitable for use in fuel cell units, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalters, sensors, demineralizers, water purifiers, wastewater treatment systems, ion exchangers, or CO2 separators, and include any of the poly(aryl alkylene) polymers described herein.

[0244] Enhanced electrolyte membranes, such as enhanced hydroxide exchange membranes, are also provided to improve the mechanical robustness of anion exchange membranes through many wetting and drying cycles (relative humidity cycles) in fuel cell units to improve stability. The membrane is configured and sized to be suitable for fuel cell units, electrolyzers, electrodialyzers, solar hydrogen generators, flow batteries, desalters, sensors, desalters, water purifiers, wastewater treatment systems, ion exchangers, or CO2 separators, and includes a porous substrate impregnated with any polymer in a poly(aryl alkylene) polymer as described herein. Methods for preparing enhanced membranes are well known to those of ordinary skill in the art, such as those disclosed in U.S. Patents RE37,656 and RE37,701, which are incorporated herein by reference for their enhanced membrane synthesis and material descriptions.

[0245] The porous substrate may include a membrane comprising polytetrafluoroethylene, polypropylene, polyethylene, poly(etherketone), polyaryletherketone, imidazolium-tethered poly(arylalkylene), imidazole-tethered poly(arylalkylene), polysulfone, perfluoroalkoxyalkane, or fluorinated ethylene propylene polymer or other porous polymers known in the art, such as dimensionally stable membranes from Giner, for preparing reinforced membranes for fuel cell cells. Such porous substrates are commercially available, for example, from WL Gore & Associates.

[0246] The porous substrate may have a porous microstructure of polymeric fibrils. Such substrates comprising polytetrafluoroethylene are commercially available. The porous substrate may include a microstructure of nodes interconnected by fibrils.

[0247] The interior volume of the porous substrate may be rendered substantially closed by impregnation with a poly(arylalkylene) polymer as described herein.

[0248] The thickness of the porous substrate can be 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 thickness of the porous substrate is from about 5 microns to about 30 microns, or from about 7 microns to about 20 microns.

[0249] Also provided is an anion exchange membrane fuel cell unit, an electrolyzer, an electrodialyzer, a solar hydrogen generator, a liquid flow battery, a desalter, a sensor, a desalter, a water purifier, a wastewater treatment system, an ion exchanger or a CO2 separator, wherein the fuel cell unit, the electrolyzer, the electrodialyzer, the solar hydrogen generator, the liquid flow battery, the desalter, the sensor, the desalter, the water purifier, the wastewater treatment system, the ion exchanger or the CO2 separator comprises the anion exchange polymer.

[0250] If the polymer is adhered to the catalyst layer so that it is not washed off during the operation of the electrolyzer or fuel cell unit, the polymer of the present invention with high water absorption can be used as an ionomer in the electrolyzer or fuel cell unit. Adhesion can be achieved by chemically combining the polymer with the membrane or catalyst layer in the electrolyzer or fuel cell unit, or by combining the polymer with a cross-linking agent such as those described above. For example, the functional group on the polymer of the present invention, such as bromoalkyl, can react with the functional group on the membrane, such as amine group to combine the polymer ionomer with the membrane.

[0251] When the polymer of the present invention is used as a film, it is preferred that the water absorption of the polymer be in the range of about 20% to about 50% in order to maintain the mechanical strength of the film.

[0252] Poly(aryl alkylene) polymers or poly(aryl-crown ether-alkylene) polymers can be used in HEMFCs, such as Figure 1A A typical fuel cell unit 10 is shown. Figure 1AA typical fuel cell unit 10 is shown, which has 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 including any of the poly(aryl alkylene) polymers or poly(aryl-crown ether-alkylene) polymers described herein, and can be a reinforced membrane. Support members are not shown. The anode portion performs an anode half reaction, which oxidizes the fuel, releases electrons to the external circuit and produces oxidation products. The cathode portion performs a cathode half reaction, which reduces the oxidant, consuming electrons from the external circuit. Gas diffusion layers (GDLs) 18 and 20 are used to uniformly transport fuel 22 and oxidant 24 across corresponding catalyst layers 26 and 28. Electrical neutrality is maintained by the flow of positive ions from the anode to the cathode and the flow of negative ions from the cathode to the anode. The dimensions shown are not representative because the electrolyte membrane is usually selected to be as thin as possible while maintaining the structural integrity of the membrane.

[0253] In the case of the hydroxyl exchange membrane fuel cell unit (HEMFC) shown, the anode half reaction consumes fuel and OH- ions and produces wastewater (and carbon dioxide in the case of carbonaceous fuels). The cathode half reaction consumes oxygen and produces OH- ions, which flow from the cathode to the anode through the electrolyte membrane. The fuel is limited only by the oxidizing capacity of the anode catalyst and typically contains hydrogen, 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 PEMFC, the anode half reaction consumes fuel and produces H+ ions and electrons. The cathode half reaction consumes oxygen, H+ ions and electrons and produces wastewater, and H+ ions (protons) flow from the anode to the cathode through the electrolyte membrane.

[0254] Thus, it can be understood how electrolyte membranes made from poly(aryl alkylene) polymers or poly(aryl-crown ether-alkylene) polymers can significantly improve fuel cell performance. First, higher fuel cell efficiency requires low 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. In addition, practical electrolyte membranes resist chemical degradation and are mechanically stable in the fuel cell environment, and should also be easily manufactured.

[0255] Poly(aryl alkylene) polymers or poly(aryl-crown ether-alkylene) polymers can be used in HEMELs, such as Figure 1B The electrolytic cell 30 is shown. Figure 1BAn electrolyzer 30 is shown 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 including any of a poly(aryl alkylene) polymer or a poly(aryl-crown ether-alkylene) polymer as described herein, and can be a reinforced membrane. Support members are not shown. The anode portion performs an anode half reaction, which oxidizes ions, releases electrons to an external circuit and produces oxidation products. The cathode portion performs a cathode half reaction, which reduces the oxidant, consuming electrons from the external circuit. Gas diffusion layers (GDLs) 38 and 40 are used to uniformly release the oxidant 42 and the fuel 44 across the respective catalyst layers 46 and 48. Electrical neutrality is maintained by the flow of positive ions from the anode to the cathode and the flow of negative ions from the cathode to the anode. The dimensions shown are not representative, as the electrolyte membrane is generally selected to be as thin as possible while maintaining the structural integrity of the membrane.

[0256] In the case of the illustrated hydroxyl exchange membrane fuel cell unit (HEMFC), the anode half reaction consumes OH- ions and produces oxygen. The cathode half reaction consumes water and produces hydrogen and OH- ions, which flow from the cathode to the anode through the electrolyte membrane. The fuel is limited only by the oxidizing capacity of the cathode catalyst and typically comprises hydrogen, 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.

[0257] Thus, it can be appreciated how electrolyte membranes made from poly(aryl alkylene) polymers or poly(aryl-crown ether-alkylene) polymers can significantly improve electrolyzer performance. First, higher electrolyzer efficiency requires low internal resistance, and therefore, electrolyte membranes with higher ionic conductivity (reduced ionic resistance) are preferred. Second, higher fuel production requires greater electrolyzer current, and therefore electrolyte membranes with higher ionic current carrying capacity are preferred. Furthermore, practical electrolyte membranes resist chemical degradation and are mechanically stable in the electrolyzer environment, and should also be easily manufactured.

[0258] Although the main application of poly(aryl alkylene) polymers or poly(aryl-crown ether-alkylene) polymers is for energy conversion, for example for anion exchange membranes, hydroxide exchange membranes, anion exchange membrane fuel cell cells and hydroxide exchange membrane fuel cell cells, anion / hydroxyl exchange ionomers and membranes can be used for many other purposes, such as for fuel cell cells (e.g., hydrogen / alcohol / ammonia fuel cell cells); electrolyzers (e.g., water / carbon dioxide / ammonia electrolyzers), electrodialyzers; ion exchangers; solar hydrogen generators; desalters (e.g., seawater / brackish water desalination); desalters (e.g., water desalination); water purifiers (e.g., ultrapure water production); wastewater treatment systems; electrolyte concentration in the food, pharmaceutical, 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 in which anion conducting ionomers have advantages.

[0259] Also provided is a reinforced electrolyte membrane, which is optionally configured and sized to be suitable for use in a fuel cell unit, an electrolyzer, an electrodialyzer, a solar hydrogen generator, a flow battery, a desalter, a sensor, a desalter, a water purifier, a wastewater treatment system, an ion exchanger, or a CO2 separator. The membrane comprises a porous substrate impregnated with the anion exchange polymer.

[0260] 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.

[0261] Examples

[0262] The following non-limiting examples are provided to further illustrate the present invention.

[0263] Example 1

[0264] Imidazolium tethered poly(arylalkylene) polymers were prepared from 7-bromo-1,1,1-trifluoroheptane-2-one, 1,1,1-trifluoroacetone and biphenyl (referred to as BP-CF3-IM-x, where x is the molar ratio of 7-bromo-1,1,1-trifluoroheptane-2-one to biphenyl and is 1 to 100). BP-CF3-IM-x was prepared by the following three main steps: (1) synthesis of bromide functionalized polymer, (2) synthesis of imidazolium functionalized polymer, and (3) film casting and hydroxide exchange. The reaction scheme is depicted below, where n is the number of repeating units in the polymer:

[0265]

[0266] (1) Synthesis of bromide functionalized polymer (BP-CF3-Br-1).In a 100mL three-necked flask equipped with an overhead mechanical stirrer, 7-bromo-1,1,1-trifluoroheptane-2-one (3.000g, 12.1mmol) and biphenyl (1.560g, 10.1mmol) were dissolved in dichloromethane (6.7mL). Trifluoromethanesulfonic acid (TFSA) (6.7mL) was then added dropwise at 0°C over 30 minutes. The reaction was continued at this temperature for 24 hours. The resulting viscous brown solution was slowly poured into ethanol. The precipitated solid was filtered, washed with water and immersed in 1M K2CO3 at room temperature for 12 hours. Finally, the product was filtered, washed with water and completely dried under vacuum at 60°C. The yield of the polymer was close to 100%. 1 H NMR (CDCl3, δ, ppm): 7.58 (H2, 4H), 7.36 (H1, 4H), 3.33 (H3, 2H), 2.45 (H4, 2H), 1.80 (H5, 2H), 1.45 (H7, 2H) and 1.27 (H6, 2H) (see Figure 2 ).

[0267] (2) Synthesis of imidazolium functionalized polymer (BP-CF3-IM-1). In a 50mL one-necked flask equipped with a magnetic bar, bromide functionalized polymer (2.0g, 5.2mmol) and imidazole (1.7g, 6.3mmol) were added to NMP (37mL). The solution was stirred at 75°C for 12 hours. The resulting yellow solution was used for casting the film. The film was then washed three times with hydrochloride solution (pH 1) and DI water and completely dried under 60°C vacuum. The yield of polymer BP-CF3-IM-1 was almost 100%. 1H NMR (DMSO-d6, δ, ppm): 7.70 (H2, 4H), 7.29 (H1, 4H), 7.02 (H3, 2H), 3.67 (H4, 4H), 2.27-2.19 (H5, H6, H12, 11H), 1.89 (H7, 6H), 1.38-1.07 (H8, H9, H10, 10H), 0.68 (H11, 3H) (see Figure 3 ).

[0268] (3) BP-CF3-IM-1 membrane casting and hydroxide exchange. The membrane was prepared by dissolving BP-CF3-IM-1 polymer (1.0 g) in NMP (10 mL) and casting it on a clear glass plate at 80°C for 8 hours. The membrane (in bromide form) was peeled off the glass plate in contact with deionized (DI) water. The membrane in hydroxide form was obtained by ion exchange in 1 M KOH at 60°C for 24 hours, followed by washing under argon and immersion in DI water for 48 hours to remove residual KOH.

[0269] Other BP-CF3-IM-x membranes were prepared by using different molar ratios of 7-bromo-1,1,1-trifluoroheptan-2-one to biphenyl.

[0270] (4) Alkaline stability. The alkaline stability of the imidazolium-containing polymer was evaluated under various conditions to explore its high chemical stability. The BP-CF3-IM-1 membrane was immersed in a 1M KOH aqueous solution at 130°C for 1200 hours, and the 1H NMR spectrum showed no change before and after the alkaline test ( Figure 4A ). The TP-CF3-IM-1 membrane was immersed in 10 M KOH solution at 80 °C for 300 h, and based on Figure 4B No degradation was observed from the 1H NMR spectrum shown in FIG. 1. In addition, the TP-CF3-IM-1 film was kept at 95° C. for 300 hours at low relative humidity (RH) of 23.3% and 50.9%, respectively, and showed no signs of degradation, as shown in FIG. Figure 4C These results strongly suggest that tethering highly basic, stable imidazolium cations to rigid poly(arylalkylene) polymer backbone structures can indeed yield remarkably chemically stable HEMs.

[0271] (5) Water absorption and hydroxide conductivity. The ideal material for HEM / HEI should have good ionic conductivity and low water absorption. All membranes are expected to show very high conductivity in pure water. For example, at 20°C, the hydroxide conductivity of BP-CF3-IM-x polymer is expected to be much greater than PSFQN (benchmark HEM) with an IEC value of 36 mS / cm. PSFQN is derived from benzyltrimethylammonium polysulfone and has the following formula:

[0272]

[0273] Increasing the temperature also enhances the hydroxide conductivity of the membrane samples.

[0274] (6) Solubility and mechanical properties. The BP-CF3-IM-x polymer is expected to show excellent solubility in dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and isopropanol / water (1 / 1 weight ratio), but is expected to be insoluble in pure water and isopropanol.

[0275] (7) Hydroxyl exchange membrane fuel cell (HEMFC) performance. Although the BP-CF3-IM-x polymer membranes are expected to have excellent chemical stability, hydroxide conductivity, low water absorption, good solubility, and mechanical properties, the most practical evaluation of these materials is their performance as HEI in the catalyst layer and as HEM in a HEMFC single cell. The membrane electrode assembly (MEA) can be prepared by coating 5 cm 2Electrodes were deposited on both sides of the BP-CF3-IM-x polymer membrane. Electrode ink was prepared by adding 250 mg of catalyst (Tanaka Kikinzoku Kogyo, or TKK, 50% Pt on high surface area C) and the desired amount of ionomer (BP-CF3-IM-x polymer, prepared by dissolving BP-CF3-IM-x polymer in a mixture of water and isopropanol) to 10 g of water and 10 g of isopropanol, followed by ultrasonic treatment for 1 hour. The catalyst loading was 0.4 mg Pt / cm 2 The sandwich was completed by adding a rubber gasket, GDL (SGL25CC) and graphite flow field (ElectroChem) to each side of the MEA. Performance was characterized using a fuel cell test system equipped with a back pressure module (Scribner 850e). Typically, the cell was operated at 100 mA / cm 2 30 min at 200 mA / cm 2 After activation, the performance was recorded by scanning the current.

[0276] Example 2

[0277] Imidazolium tethered poly(arylalkylene) polymers were prepared from 7-bromo-1,1,1-trifluoroheptane-2-one, 1,1,1-trifluoroacetone and p-terphenyl (referred to as TP-CF3-IM-x, where x is the molar ratio of 7-bromo-1,1,1-trifluoroheptane-2-one to p-terphenyl and is 1 to 100). TP-CF3-IM-x was prepared by the following three main steps: (1) synthesis of bromide functionalized polymer, (2) synthesis of imidazolium functionalized polymer, and (3) film casting and hydroxide exchange. The reaction scheme is depicted below, where n is the number of repeating units in the polymer:

[0278]

[0279] (1) Synthesis of bromide functionalized polymer (TP-CF3-Br-1). In a 100mL three-necked flask equipped with an overhead mechanical stirrer, 7-bromo-1,1,1-trifluoroheptane-2-one (3.600g, 14.6mmol) and p-terphenyl (2.797g, 12.1mmol) were dissolved in dichloromethane (30mL). Trifluoromethanesulfonic acid (TFSA) (30mL) was then added dropwise at 0°C over 30 minutes. The reaction was continued at this temperature for 24 hours. The resulting viscous brown solution was slowly poured into ethanol. The precipitated solid was filtered, washed with water and immersed in 1M K2CO3 at room temperature for 12 hours. Finally, the product was filtered, washed with water and completely dried under vacuum at 60°C. The yield of the polymer was close to 100%. 1H NMR (CDCl3, δ, ppm): 7.70 (H 13 ,4H),7.62(H1,4H),7.40(H2,4H),3.34(H4,2H),2.47(H 12 ,2H),1.82(H8,2H),1.47(H 10 ,2H),1.30(H9,2H)( Figure 5 ).

[0280] (2) Synthesis of imidazolium functionalized polymer (TP-CF3-IM-1). In a 50mL one-necked flask equipped with a magnetic bar, bromide functionalized polymer (2.0g, 4.4mmol) and functionalized imidazole (1.5g, 5.5mmol) were added to NMP (25mL). The solution was stirred at 75°C for 12 hours. The resulting yellow solution was used for casting the film. The film was then washed three times with hydrochloride solution (PH=1) and DI water and completely dried under 60°C vacuum. The yield of polymer TP-CF3-IM-x was almost 100%. 1H NMR(DMSO-d6,δ,ppm):7.80(H13,4H),7.72(H1,4H),7.30(H2,4H),7.05(H3,4H),3.69-3.67(H4 ,4H),2.29-2.23(H5,H6,H12,11H),1.91(H7,6H),1.38-1.01(H8,H9,H10,10H),0.68(H11,3H)( Figure 6 ).

[0281] (3) TP-CF3-IM-x membrane casting and hydroxide exchange. The membrane was prepared by dissolving TP-CF3-IM-x polymer (1.0 g) in NMP (10 mL) and casting it on a transparent glass plate at 80°C for 8 hours. The membrane (in bromide form) was peeled off from the glass plate in contact with deionized (DI) water. The membrane in hydroxide form was obtained by ion exchange in 1 M KOH at 60°C for 24 hours, followed by washing under argon and immersion in DI water for 48 hours to remove residual KOH.

[0282] (4) Water absorption and hydroxide conductivity. When x = 1, the conductivity of TP-CF3-IM-1 at 20° C. is 31.4 mS / cm. It has low water absorption and dimensional swelling rate in the form of bicarbonate in pure water at 20° C. to 80° C. (as shown in Table 1).

[0283] Table 1. Water absorption and dimensional swelling of TP-CF3-IM-1 membrane

[0284] Temperature(℃) Water absorption (%) Swelling rate (%) 20 43 21 80 47 28

[0285] (5) Hydroxyl exchange membrane fuel cell (HEMFC) performance.Although the TP-CF3-IM-x polymer membranes are expected to have excellent chemical stability, hydroxide conductivity, low water absorption, good solubility, and mechanical properties, the most practical evaluation of these materials is their performance as HEI in the catalyst layer and as HEM in a HEMFC single cell. The membrane electrode assembly (MEA) can be prepared by coating 5 cm 2 Electrodes were deposited on both sides of the TP-CF3-IM-x polymer membrane to make. Electrode ink was prepared by adding 250 mg of catalyst (Tanaka Kikinzoku Kogyo, or TKK, 50% Pt on high surface area C) and the desired amount of ionomer (TP-CF3-IM-x polymer, prepared by dissolving BP-CF3-IM-x polymer in a mixture of water and isopropanol) to 10 g of water and 10 g of isopropanol, followed by ultrasonic treatment for 1 hour. The catalyst loading was 0.4 mg on the anode. Pt cm -2 PtRu / C, 0.4 mg on cathode Pt cm -2 PtRu / C. The sandwich was completed by adding a rubber gasket, GDL (SGL25CC) and graphite flow field (ElectroChem) to each side of the MEA. The performance was characterized using a fuel cell test system equipped with a back pressure module (Scribner 850e) (materials: TP100-CF3-IM-1 membrane, ionomer loading 20%, catalyst: 0.4 mg on anode Pt cm -2 PtRu / C, 0.4 mg on cathode Pt cm -2 PtRu / C. Test conditions: 95°C, anode humidifier temperature: 90°C, cathode anode humidifier temperature: 97°C, H2 flow rate: 1.0 L / min, O2 flow rate: 2.0 L / min). Usually, the battery cell is at 100 mA / cm 2 30 min at 200 mA / cm 2 After activation, the performance was recorded by scanning the current. The results are shown in Figure 8 middle.

[0286] (6) Hydroxide exchange membrane electrolyzer (HEMEL) performance.Although the TP-CF3-IM-x polymer membranes are expected to have excellent chemical stability, hydroxide conductivity, low water absorption, good solubility, and mechanical properties, the most practical evaluation of these materials is their performance as HEI in the catalyst layer and as HEM in HEMEL cells. The membrane electrode assembly (MEA) was prepared by coating 5 cm 2 Electrodes were deposited on both sides of the TP-CF3-IM-x polymer membrane. Electrode ink was prepared by adding 250 mg of catalyst (Tanaka Kikinzoku Kogyo, or TKK, 50% Pt on high surface area C) and the desired amount of ionomer (TP-CF3-IM-x polymer, prepared by dissolving TP-CF3-IM-x polymer in a water and ethanol mixture) to 10 g of water and 10 g of ethanol, followed by ultrasonic treatment for 1 hour. The catalyst loading was 4 mg Pt / cm 2 . Pt-coated titanium plates and TGP-H-060 Toray carbon paper (5% moisture proof) were the gas diffusion layers on the anode and cathode sides, respectively. The temperature of the battery cell and deionized water were kept at a constant temperature. The performance was characterized by an Arbin test system (material: TP100-CF3-IM-1 membrane, 30% ionomer loading, catalyst: 4.0 mg on the anode Pt cm -2 Pt / C, 2.9 mg cm on cathode -2 IrO2. Test conditions: 80℃ water and electrolytic cell, water flow rate: 3.0 ml / min). Usually, the battery cell is at 100mA / cm 2 30 min at 200 mA / cm 2 After activation, the performance was recorded by scanning the current. The results are shown in Fig. 9 middle.

[0287] Example 3

[0288] Another imidazolium-tethered poly(arylalkylene) polymer was prepared from 7-bromo-1,1,1-trifluoroheptane-2-one, 1,1,1-trifluoroacetone and m-terphenyl (referred to as mTP-CF3-IM-x, where x is the molar ratio of 7-bromo-1,1,1-trifluoroheptane-2-one to biphenyl and ranges from 1 to 100). mTP-CF3-IM-x was prepared by three major steps, similar to TP-CF3-IM-x: (1) synthesis of bromide-functionalized polymer, (2) synthesis of imidazolium-functionalized polymer, and (3) film casting and hydroxide exchange. The reaction scheme is depicted below, where n is the number of repeating units in the polymer:

[0289]

[0290] Example 4

[0291] Another method for preparing the BP-CF3-IM-x polymer of Example 1 is to react imidazolium functionalized 7-bromo-1,1,1-trifluoroheptane-2-one, 1,1,1-trifluoroacetone and biphenyl (referred to as BP-CF3-IM-x, where x is the molar ratio of imidazolium functionalized 7-bromo-1,1,1-trifluoroheptane-2-one to biphenyl and is 1 to 100). BP-CF3-IM-x is prepared by two main steps: (1) synthesis of the imidazolium functionalized polymer and (2) film casting and hydroxide exchange. The reaction scheme is depicted below, where n is the number of repeating units in the polymer:

[0292]

[0293] Example 5

[0294] Another method for preparing the TP-CF3-IM-x polymer of Example 2 is by reacting imidazolium functionalized 7-bromo-1,1,1-trifluoroheptane-2-one, 1,1,1-trifluoroacetone and p-terphenyl (referred to as TP-CF3-IM-x, where x is the molar ratio of imidazolium functionalized 7-bromo-1,1,1-trifluoroheptane-2-one to p-terphenyl and is 1 to 100). TP-CF3-IM-x is prepared by two main steps: (1) synthesis of the imidazolium functionalized polymer and (2) film casting and hydroxide exchange. The reaction scheme is depicted below, where n is the number of repeating units in the polymer:

[0295]

[0296] Example 6

[0297] Another method for preparing the TP-CF3-IM-x polymer of Example 3 is by reacting imidazolium functionalized 7-bromo-1,1,1-trifluoroheptane-2-one, 1,1,1-trifluoroacetone and m-terphenyl (referred to as mTP-CF3-IM-x, where x is the molar ratio of imidazolium functionalized 7-bromo-1,1,1-trifluoroheptane-2-one to p-terphenyl and is 1 to 100). mTP-CF3-IM-x is prepared by two main steps: (1) synthesis of the imidazolium functionalized polymer and (2) film casting and hydroxide exchange. The reaction scheme is depicted below, where n is the number of repeating units in the polymer:

[0298]

[0299] Example 7

[0300] Imidazolium tethered poly(crown ether) polymers were prepared from 7-bromo-1,1,1-trifluoroheptane-2-one, 1,1,1-trifluoroacetone, and dibenzo-18-crown-6 (referred to as PCE-C5-IM-x, where x is the molar ratio of 7-bromo-1,1,1-trifluoroheptane-2-one to dibenzo-18-crown-6 and ranges from 1 to 100). PCE-C5-IM-x was prepared by the following three main steps: (1) synthesis of bromide functionalized polymer, (2) synthesis of imidazolium functionalized polymer, and (3) film casting and hydroxide exchange. The reaction scheme is depicted below, where n is the number of repeating units in the polymer:

[0301]

[0302] Synthesis of bromide-functionalized polymer (PCE-C5-Br-1). In a 250mL three-necked flask equipped with an overhead mechanical stirrer, dibenzo-18-crown-6 (7.2082g, 20.00mmol) and 7-bromo-1,1,1-trifluoroheptane-2-one (5.9294g, 24.00mmol) were suspended in chloroform (35mL). TFSA (30mL) was then slowly added dropwise at -15°C. Thereafter, the reaction was continued at 0°C for 8 hours. The resulting viscous solution was slowly poured into ethanol. The white fibrous solid was filtered, washed with water and immersed in 1M K2CO3 at 50°C for 12 hours. Finally, the white fibrous product was filtered, washed with water and completely dried at 60°C under vacuum. The yield of the polymer was 95%. 1 H NMR (CDCl3, δ, ppm): 6.82-6.68 (6H), 4.15-3.96 (16H), 3.33 (2H), 2.27 (2H), 1.76 (2H), 1.38 (2H), 1.15 (2H) (see Fig.10 ).

[0303] Synthesis of Imidazolium Functionalized Polymer (PCE-C5-IM-Br-1) . In a 50 mL one-necked flask equipped with a magnetic bar, the bromide functionalized polymer (1.0 g, 1.7 mmol) and imidazole (0.5 g, 1.9 mmol) were added to DMSO (20 mL). The solution was stirred at 60 °C for 24 hours. The resulting yellow solution was used to cast a membrane. The membrane was then washed three times with hydrochloride solution (pH 1) and DI water and completely dried under vacuum at 60 °C. The yield of polymer PCE-C5-IM-Br-1 was 90%. 1H NMR (DMSO-d6, δ, ppm): 7.14 (2H), 6.91-6.61 (6H), 4.06-3.66 (20H), 2.34 (2H), 2.34-2.30 (9H), 1.94 (6H), 1.40-1.38 (6H), 1.16-1.14 (4H), 0.72 (3H) (see Fig.11)

[0304] PCE-C5-IMOH-1 membrane casting and hydroxide exchange. The membrane was prepared by dissolving PCE-C5-IM-Br-1 polymer (1.0 g) in NMP (10 mL) and casting it on a clear glass plate at 80° C. for 8 hours. The membrane (in bromide form) was peeled off the glass plate in contact with deionized (DI) water. The membrane in hydroxide form was obtained by ion exchange in 1 M KOH at 60° C. for 24 hours, followed by washing under argon and immersion in DI water for 48 hours to remove residual KOH.

[0305] Example 8

[0306] Another imidazolium-tethered poly(crown ether) polymer was prepared from 7-bromo-1,1,1-trifluoroheptane-2-one, 1,1,1-trifluoroacetone, and dibenzo-18-crown-6 (referred to as PCE-C5-IM-x, where x is the molar ratio of 7-bromo-1,1,1-trifluoroheptane-2-one to dibenzo-18-crown-6 and is 1 to 100). PCE-C5-IM-x was prepared similarly to PCE-C5-IM-1 by the following three main steps: (1) synthesis of bromide-functionalized polymer, (2) synthesis of imidazolium-functionalized polymer, and (3) film casting and hydroxide exchange. The reaction scheme is depicted below, where n is the number of repeating units in the polymer.

[0307]

[0308] Example 9

[0309] Another method for preparing PCE-C5-IM-x of Example 8 is by reacting imidazolium functionalized 7-bromo-1,1,1-trifluoroheptane-2-one, 1,1,1-trifluoroacetone and dibenzo-18-crown-6 (referred to as PCE-C5-IM-x, where x is the molar ratio of imidazolium functionalized 7-bromo-1,1,1-trifluoroheptane-2-one to PCE-C5-IM-x and is 1 to 100). PCE-C5-IM-x is prepared by two main steps: (1) synthesis of imidazolium functionalized polymer and (2) film casting and hydroxide exchange. The reaction scheme is depicted below, where n is the number of repeating units in the polymer:

[0310]

[0311] Example 10

[0312] Quaternary ammonium tethered poly(crown ether) polymers were prepared from 7-bromo-1,1,1-trifluoroheptane-2-one and dibenzo-18-crown-6 (referred to as PCE-C5-QA-x, where x is the molar ratio of 7-bromo-1,1,1-trifluoroheptane-2-one to dibenzo-18-crown-6 and is 1 to 100). PCE-C5-QA-x was prepared by the following three main steps: (1) synthesis of bromide functionalized polymer, (2) synthesis of quaternary ammonium functionalized polymer, and (3) film casting and hydroxide exchange. The reaction scheme is depicted below, where n is the number of repeating units in the polymer:

[0313]

[0314] Example 11

[0315] Quaternary ammonium tethered poly(crown ether) polymers were prepared from 7-bromo-1,1,1-trifluoroheptane-2-one, 1,1,1-trifluoroacetone, and dibenzo-18-crown-6 (referred to as PCE-C5-IM-x, where x is the molar ratio of 7-bromo-1,1,1-trifluoroheptane-2-one to dibenzo-18-crown-6 and is 1 to 100). PCE-C5-QA-x was prepared by the following three main steps: (1) synthesis of bromide functionalized polymer, (2) synthesis of quaternary ammonium functionalized polymer, and (3) film casting and hydroxide exchange. The reaction scheme is depicted below, where n is the number of repeating units in the polymer:

[0316]

[0317] definition

[0318] As used herein, the term "suitable substituent" is intended to mean a chemically acceptable functional group, preferably a part that does not invalidate the activity of the compounds of the invention. Such suitable substituents include, but are not limited to, halo, perfluoroalkyl, perfluoroalkoxy, alkyl, alkenyl, alkynyl, hydroxyl, oxo, sulfhydryl, alkylthio, alkoxy, aryl or heteroaryl, aryloxy or heteroaryloxy, aralkyl or heteroaralkyl, aralkyloxy or heteroaralkyloxy, HO-(C═O)-yl, heterocyclic, cycloalkyl, amino, alkyl and dialkylamino, carbamoyl, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylcarbonyl, aryloxycarbonyl, alkylsulfonyl and arylsulfonyl. Those skilled in the art will appreciate that many substituents can be substituted by other substituents.

[0319] As used herein, the term "alkyl" refers to a straight chain, branched chain 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), and more preferably having 1 to 18 carbon atoms. Alkyl includes but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Alkyl can be unsubstituted or substituted with one or more suitable substituents.

[0320] As used herein, the term "alkenyl" refers to a straight chain, branched or cyclic hydrocarbon group, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31 or 32 carbons, more preferably, having 1 to 18 carbon atoms, and having one or more carbon-carbon double bonds. Alkenyl includes but is not limited to vinyl, 1-propenyl, 2-propenyl (allyl), iso-propenyl, 2-methyl-1-propenyl, 1-butenyl and 2-butenyl. Alkenyl can be unsubstituted or substituted by one or more suitable substituents, as defined above.

[0321] As used herein, the term "alkynyl" refers to a straight chain, branched or cyclic hydrocarbon group, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31 or 32 carbons, more preferably, having 1 to 18 carbon atoms, and having one or more carbon-carbon triple bonds. Alkynyl includes but is not limited to ethynyl, propynyl and butynyl. Alkynyl can be unsubstituted or substituted with one or more suitable substituents, as defined above.

[0322] As used herein, the term "aryl" or "ar" (e.g., aralkyl), alone or as part of another group, means a monocyclic, bicyclic or tricyclic aromatic group, such as phenyl, naphthyl, tetrahydronaphthyl, dihydroindanyl, etc., optionally substituted with one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above. The term "aryl" also includes heteroaryl.

[0323] "Arylalkyl" or "aralkyl" means an aryl group attached to the parent molecule through 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 aralkyl group. The preferred aralkyl group is benzyl.

[0324] As used herein, the term "cycloalkyl" refers to a mono-, bi- or tricyclic carbocyclic group (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclopentenyl, cyclohexenyl, bicyclo[2.2.1]heptyl, bicyclo[3.2.1]octyl and bicyclo[5.2.0]nonyl, etc.); optionally containing 1 or 2 double bonds. The cycloalkyl group may be unsubstituted or substituted with one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.

[0325] The term "-ene", as used as a suffix as part of another group, represents a divalent group in which a hydrogen atom is removed from each of the two terminal carbon atoms of the group, or if the group is cyclic, from each of two different carbon atoms in the ring. For example, alkylene represents a divalent alkyl group, such as ethylene (-CH2CH2-) or isopropylene (-CH2(CH3)CH2-). For the sake of clarity, the addition of the -ene suffix is ​​intended not to change the definition of the main word, except to represent a divalent group. Thus, continuing with the above example, alkylene represents an optionally substituted straight-chain saturated divalent hydrocarbon radical.

[0326] As used herein, the term "ether" refers to a divalent (ie, difunctional) group containing at least one ether linkage (ie, -O-).

[0327] As used herein, the term "heteroaryl" refers to a monocyclic, bicyclic or tricyclic aromatic heterocyclic group containing one or more heteroatoms (e.g., 1 to 3 heteroatoms) selected from O, S and N in the ring. Heteroaryl includes, but is not limited to, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl, furanyl, 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, benzofuranyl and indolyl. Heteroaryl may be unsubstituted or substituted by one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.

[0328] As used herein, the term "hydrocarbon" describes a compound or group consisting solely of the elements carbon and hydrogen.

[0329] The term "substituted" means that in the group in question, at least one hydrogen atom bonded to a carbon atom is replaced by one or more substituents, such as hydroxy (-OH), alkylthio, phosphino, amido (-CON(RA)(RB), wherein RA and RB are independently hydrogen alkyl or aryl), amino (-N(RA)(RB), wherein RA and RB are independently hydrogen alkyl or aryl), halo (fluoro, chloro, bromo or iodo), silyl, nitro (-NO2), ether (-ORA, wherein RA is alkyl or aryl), ester (-OC(O)RA, wherein RA is alkyl or aryl), ketone (-C(O)RA, wherein RA is alkyl or aryl), heterocyclyl, etc. When the term "substituted" is introduced or follows a list of possible substituted groups, it is intended that the term applies to every member of the group. That is, the phrase "optionally substituted alkyl or aryl" can be understood as "optionally substituted alkyl or optionally substituted aryl". Likewise, the phrase "alkyl or aryl optionally substituted by fluorine" may be understood as "alkyl optionally substituted by fluorine or aryl optionally substituted by fluorine".

[0330] The term "tethered" means that the group in question is bound to a designated polymer backbone. For example, an imidazolium tethered poly(arylalkylene) polymer is a polymer having an imidazolium group bound to a poly(arylalkylene) polymer backbone.

[0331] When introducing elements of the present invention or the preferred embodiments thereof, the articles "a," "an," "the," and "said" are intended to mean that there are one or more of the 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.

[0332] In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.

[0333] As various changes could be made in the above products and methods 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. An anion exchange polymer comprising structural units of the following formulae: (1A), (3'A), optionally (3A) and optionally (4A), wherein the structural units of the formulae (1A), (3A), (3'A) and (4A) have the following structures: R 11 wherein each: is independently a quaternary ammonium or phosphonium group or a nitrogen-containing heterocyclic group or a salt thereof, wherein the quaternary ammonium or phosphonium group has the formula (5A): and 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, wherein each substituent is independently alkyl, alkenyl, alkynyl, aryl, or aralkyl; R 20 , R 30 , R 40 , R 50 , R 60 , R 70 , R 80 , R 90 , R 130 , R 140 , R 150 , R 160 and R 170 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with halide, and wherein R 30 and R 60 optionally linked to form a five-membered ring optionally substituted with halide or alkyl; Each R 100 are independently alkyl, alkenyl, alkynyl or a substituent having the formula (4B): and the alkyl, alkenyl or alkynyl group is optionally substituted with fluoride; R 180 and R 240 are each independently an alkylene group; R 190 , R 200 , R 210 , R 220 and R 230 are each independently alkyl, alkenyl or alkynyl; q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; m is 0, 1, 2, 3, 4, 5 or 6; n is 0, 1, 2 or 3; Each m' and each n' are independently 0, 1 or 2; The benzo ring shown by the dotted line in formula (3'A) is present or absent; X - is an anion; and Z is N or P.

2. A polymer comprising the reaction product of a polymerization mixture, the polymer comprising: (i) a cationically functionalized trifluoromethyl ketone monomer having the formula: (ii) A crown ether monomer having the formula: (iii) optionally, an aromatic monomer having the formula: as well as (iv) optionally, a trifluoromethyl ketone monomer having the formula: in: R1 is each independently a quaternary ammonium or phosphonium group or a nitrogen-containing heterocyclic group or a salt thereof, wherein the quaternary ammonium or phosphonium group has the formula (5A): and 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, wherein each substituent is independently alkyl, alkenyl, alkynyl, aryl, or aralkyl; R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 and R 17 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with halide, and wherein R3 and R6 are optionally linked to form a five-membered ring optionally substituted with halide or alkyl; Each R 12 are independently alkyl, alkenyl, alkynyl or a substituent having the formula (4C): and the alkyl, alkenyl or alkynyl group is optionally substituted with fluoride; R 180 and R 240 are each independently an alkylene group; R 190 , R 200 , R 210 , R 220 and R 230 are each independently alkyl, alkenyl or alkynyl; m is 0, 1, 2, 3, 4, 5 or 6; n is 0, 1, 2 or 3; Each m' and each n' are independently 0, 1 or 2; q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; The benzo ring shown by the dotted line in formula (3') is present or absent; X - is an anion; and Z is N or P.

3. A polymer comprising the second reaction product of the second polymerization mixture, the polymer comprising: Quaternary ammonium or phosphonium compounds or nitrogen-containing heterocycles or their salts; as well as Intermediate polymers; The intermediate polymer comprises a first reaction product of a first polymerization mixture, the first reaction product comprising: (i) a halogenated trifluoromethyl ketone monomer having the formula: (ii) A crown ether monomer having the formula: (iii) optionally, an aromatic monomer having the formula: as well as (iv) optionally, a trifluoromethyl ketone monomer having the formula: in: The quaternary ammonium or phosphonium compound has the formula (5): The nitrogen-containing heterocycle is 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, wherein each substituent is independently alkyl, alkenyl, alkynyl, aryl, or aralkyl; R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 and R 17 Each is independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl is optionally substituted with halide, and wherein R3 and R6 are optionally linked to form a five-membered ring optionally substituted with halide or alkyl; Each R 12 are independently alkyl, alkenyl, alkynyl or a substituent having the formula (4C): and the alkyl, alkenyl or alkynyl group is optionally substituted with fluoride; R 18 and R 24 are each independently an alkylene group; R 19 , R 20 , R 21 , R 22 and R 23 are each independently alkyl, alkenyl or alkynyl; R 111 For halides; m is 0, 1, 2, 3, 4, 5 or 6; n is 0, 1, 2 or 3; Each m' and each n' are independently 0, 1 or 2; q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; The benzo ring shown by the dotted line in formula (3') is present or absent; X - It is an anion; X is said anion which has no negative charge; and Z is N or P.

4. An anion exchange polymer comprising a reaction product of a base and the polymer according to claim 1.

5. An anion exchange polymer comprising a reaction product of a base and the polymer according to claim 2.

6. An anion exchange polymer comprising a reaction product of a base and the polymer according to claim 3.

7. The polymer of any one of claims 4 to 6, wherein the base comprises a hydroxide, bicarbonate or carbonate containing base.

8. The polymer of claim 7, wherein the hydroxide-containing base comprises sodium hydroxide or potassium hydroxide; the bicarbonate-containing base comprises sodium bicarbonate or potassium bicarbonate; or the carbonate-containing base comprises sodium carbonate or potassium carbonate.

9. The polymer according to any one of claims 1, 2, 4 and 5, wherein R1 or R 11 is an optionally substituted nitrogen-containing heterocyclic group or a salt thereof.

10. The polymer of claim 9, wherein the optionally substituted nitrogen-containing heterocyclic group comprises a fully substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, or quinoline, wherein each substituent is independently alkyl or aryl.

11. The polymer of claim 9, wherein the optionally substituted nitrogen-containing heterocyclic group comprises an imidazolium having formula (6A): Where R 25 , R 26 , R 27 and R 28 Each is independently hydrogen or optionally substituted alkyl, alkenyl, alkynyl or aryl.

12. The polymer according to claim 11, wherein R 28 is 2,4,6-alkylphenyl, and R 25 , R 26 and R 27 Each is independently a C1-C6 alkyl group.

13. The polymer of claim 9, wherein the optionally substituted nitrogen-containing heterocyclic group has the formula 14. The polymer according to any one of claims 1 to 6, wherein the R having a quaternary ammonium or phosphonium group of formula (5A) 180 and R 240 Each independently is C1-C 22 Alkylene; R 190 , R 200 , R 210 , R 220 and R 230 are each independently a C1-C6 alkyl group; m is 0, 1, 2, 3, 4, 5 or 6; and Z is N or P; or R of the quaternary ammonium or phosphonium compound of formula (5) 18 and R 24 Each independently is C1-C 22 Alkylene; R 19 , R 20 , R 21 , R 22 and R 23 are each independently C1-C6 alkyl; m is 0, 1, 2, 3, 4, 5 or 6; and Z is N or P.

15. The polymer according to any one of claims 1 to 6, wherein the R having a quaternary ammonium or phosphonium group of formula (5A) 180 and R 240 Each is independently C1-C6 alkylene; R 190 , R 200 , R 210 , R 220 and R 230 are each independently a C1-C6 alkyl group; m is 0, 1, 2 or 3; and Z is N or P; or R of the quaternary ammonium or phosphonium compound having formula (5) 18 and R 24 Each is independently C1-C6 alkylene; R 19 , R 20 , R 21 , R 22 and R 23 are each independently a C1-C6 alkyl group; m is 0, 1, 2 or 3; and Z is N or P.

16. The polymer according to any one of claims 1 to 6, wherein the R having a quaternary ammonium or phosphonium group of formula (5A) 180 and R 240 Each independently is C8-C 22 Alkylene; R 190 , R 200 , R 210 , R 220 and R 230 are each independently a C1-C6 alkyl group; m is 0, 1, 2 or 3; and Z is N or P; or R of the quaternary ammonium or phosphonium compound having formula (5) 18 and R 24 Each independently is C8-C 22 Alkylene; R 19 , R 20 , R 21 , R 22 and R 23 are each independently a C1-C6 alkyl group; m is 0, 1, 2 or 3; and Z is N or P.

17. The polymer according to any one of claims 1 to 6, wherein the R having a quaternary ammonium or phosphonium group of formula (5A) 180 and R 240 Each is a C2-C6 alkylene group; R 190 , R 200 , R 210 , R 220 and R 230 are each independently methyl; m is 1; and Z is N or P; or R of the quaternary ammonium or phosphonium compound having formula (5) 18 and R 24 Each is a C2-C6 alkylene group; R 19 , R 20 , R 21 , R 22 and R 23 are each independently methyl; m is 1; and Z is N or P.

18. The polymer according to any one of claims 1 to 6, wherein the R having a quaternary ammonium or phosphonium group of formula (5A) 180 and R 240 Each is n-hexylene; R 190 , R 200 , R 210 , R 220 and R 230 are each independently methyl; m is 1; and Z is N or P; or R of the quaternary ammonium or phosphonium compound having formula (5) 18 and R 24 Each is n-hexylene; R 19 , R 20 , R 21 , R 22 and R 23 are each independently methyl; m is 1; and Z is N or P.

19. A polymer according to any one of claims 1 to 6, wherein R1 or R 11 is a quaternary phosphonium group, or the second polymerization mixture includes a quaternary phosphonium compound.

20. The polymer according to any one of claims 1 to 6, wherein R1 or R 11 is a quaternary ammonium group, or the second polymerization mixture includes a quaternary ammonium compound.

21. The polymer of any one of claims 2, 3, 5 and 6, wherein the aromatic monomer having formula (3) comprises biphenyl, p-terphenyl, m-terphenyl, p-quaterphenyl, 9,9-dimethyl-9H-fluorene or benzene.

22. The polymer according to any one of claims 1 to 6, wherein in the structural unit having formula (3A), R 20 , R 30 , R 40 , R 50 , R 60 , R 70 , R 80 and R 90 At least one of them is a halide or an aryl group, and the aryl group is optionally substituted with a halide; or in the aromatic monomer having formula (3), R2, R3, R4, R5, R6, R7, R8, R9 and R 10 At least one of is a halide or an aryl group, and the aryl group is optionally substituted with a halide; or In the structural unit having the formula (3A), R 30 and R 60 are connected to form a five-membered ring optionally substituted with a halide or an alkyl group; or in the aromatic monomer having formula (3), R3 and R6 are connected to form a five-membered ring optionally substituted with a halide or an alkyl group; or In the structural unit having the formula (3'A), R 20 , R 40 , R 50 , R 70 , R 80 and R 90 Each is hydrogen; or in the crown ether monomer having formula (3'), R2, R4, R5, R7, R8, R9 and R 10 Each is hydrogen.

23. The polymer according to any one of claims 1 to 6, wherein the polymer comprises the structural unit having formula (4A), or the reaction product of the polymerization mixture further comprises the trifluoromethyl ketone monomer having formula (4).

24. The polymer of claim 23, wherein the trifluoromethyl ketone monomer comprises 2,2,2-trifluoroacetophenone or 1,1,1-trifluoroacetone.

25. The polymer according to any one of claims 1 to 6, wherein in the structural unit having formula (4A), R 100 is an alkyl, alkenyl or alkynyl group, and the alkyl, alkenyl or alkynyl group is optionally substituted with fluoride; or in the trifluoromethyl ketone monomer having formula (4), R 12 is alkyl, alkenyl or alkynyl, and the alkyl, alkenyl or alkynyl is optionally substituted with fluoride; or In the structural unit having the formula (4A), R 100 is the substituent having the formula (4B), and R 130 , R 140 , R 150 , R 160 and R 170 At least one of is a halide or an aryl group, and the aryl group is optionally substituted with a fluoride; or in the trifluoromethyl ketone monomer having the formula (4), R 12 is the substituent having the formula (4C), and R 13 , R 14 , R 15 , R 16 and R 17 At least one of is a halide or an aryl group, and the aryl group is optionally substituted with a fluoride.

26. A polymer according to any one of claims 1 to 6, wherein R 20 , R 30 , R 40 , R 50 , R 60 , R 70 , R 80 , R 90 , R 130 , R 140 , R 150 , R 160 and R 170 are each independently hydrogen or alkyl optionally substituted with fluoride, and R 100 is an alkyl group optionally substituted with a fluoride or a substituent of formula (4B); or R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently hydrogen or alkyl optionally substituted with fluoride, and R 12 is an alkyl group optionally substituted with fluoride or the substituent having the formula (4C).

27. A polymer according to any one of claims 1 to 6, wherein R 20 , R 30 , R 40 , R 50 , R 60 , R 70 , R 80 , R 90 , R 130 , R 140 , R 150 , R 160 and R 170 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl, or methyl, ethyl, propyl, butyl, pentyl or hexyl optionally substituted with fluoride, and R 100 is methyl, ethyl, propyl, butyl, pentyl or hexyl optionally substituted with fluoride or a substituent of formula (4B); or R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl, or methyl, ethyl, propyl, butyl, pentyl or hexyl optionally substituted with fluoride, and R 12 is methyl, ethyl, propyl, butyl, pentyl or hexyl, optionally substituted with fluoride or the substituent having the formula (4C).

28. A polymer according to any one of claims 1 to 6, wherein X - Including hydroxide, halide, BF4 - PF6 - 、CO3 2- or HCO3 - .

29. A polymer according to claim 1 or 4, wherein the sum of the mole fractions of the structural units having formula (1A) and formula (4A) in the polymer is equal to the sum of the mole fractions of the structural units having formula (3A) and formula (3'A) in the polymer, and the ratio of the mole fraction of the structural units having formula (1A) in the polymer to the sum of the mole fractions of the structural units having formula (3A) and (3'A) in the polymer is 0.01 to 1.

30. The polymer according to claim 1 or 4, wherein the molar ratio of the sum of the mole fractions of the structural units having formula (1A) and formula (4A) to the sum of the mole fractions of the structural units having formula (3A) and (3'A) in the polymer is 0.95:1 to 1.4:1, and the ratio of the mole fraction of the structural units having formula (1A) to the sum of the mole fractions of the structural units having formula (3A) and (3'A) is 0.01 to 1.

31. The polymer according to claim 1 or 4, wherein the molar ratio of the sum of the mole fractions of the structural units having the formula (1A) and the formula (4A) to the sum of the mole fractions of the structural units having the formula (3A) and (3'A) in the polymer is 1:1 to 1.2:

1.

32. A polymer according to any one of claims 1 to 6, wherein X - The polymer is a hydroxyl group, and when immersed in pure water at 80° C., the water absorption of the polymer is no more than 47% based on the dry weight of the polymer, or when immersed in pure water at 20° C., the polymer has a hydroxide conductivity of at least 31 mS / cm, wherein the polymer satisfies at least one of the following: The polymer is stable to degradation when immersed in 1 M potassium hydroxide at 130°C for 1,200 hours; or The polymer is stable to degradation when immersed in 10 M potassium hydroxide at 80°C for 300 hours; or Those The polymer is stable to degradation when maintained at 95°C and at relative humidity of 23.3% and 50.9% for 300 hours; or The polymer has a tensile strength of at least 30 MPa and / or an elongation at break of at least 250%.

33. The polymer of claim 9, wherein the nitrogen-containing heterocycle comprises imidazole, and X - is hydroxide, and: When the polymer is used as a hydroxide exchange membrane of a hydroxide exchange membrane fuel cell and as a hydroxide exchange ionomer at 20% loading in the cathode and anode catalyst layers of the fuel cell, the peak power density of the polymer is at least 130 mW / cm 2 The anode of the fuel cell unit has 0.4 mg Pt cm -2 PtRu / C, and The test conditions are H2 flow rate of 1.0 L / min, O2 flow rate of 2.0 L / min, cell temperature of 95°C, anode and cathode humidifier temperatures of 90°C and 97°C respectively; or When the polymer is used as a hydroxide exchange membrane in a hydroxide exchange membrane water electrolyzer and as a hydroxide exchange ionomer in the cathode and anode catalyst layers of the electrolyzer at 30% loading, the polymer has a current density of at least 20 mA / cm at a voltage of 1.8 volts. 2 The Pt / C catalyst on the cathode of the electrolyzer was 4.0 mg cm -2 , the IrO2 catalyst on the anode is 2.9 mg cm -2 , and the test conditions were a water flow rate of 3.0 ml / min, an electrolytic cell temperature and a water temperature of 80°C.

34. A method for preparing an anion exchange polymer membrane comprising the polymer according to claim 5, the method comprising: reacting the cationically functionalized trifluoromethyl ketone monomer, the optional trifluoromethyl ketone monomer, the optional aromatic monomer, and the crown ether monomer in the presence of an organic solvent and a polymerization catalyst to form a cationically functionalized intermediate polymer; dissolving the cationically functionalized intermediate polymer in a solvent to form a polymer solution; casting the polymer solution to form a polymer film; as well as The anions of the polymer membrane are exchanged with hydroxide, bicarbonate or carbonate ions or a combination thereof to form the anion exchange polymer membrane.

35. A method for preparing an anion exchange polymer membrane comprising the polymer according to claim 6, the method comprising: reacting the halogenated trifluoromethyl ketone monomer, optionally the trifluoromethyl ketone monomer, optionally the aromatic monomer, and the crown ether monomer in the presence of an organic solvent and a polymerization catalyst to form a halogen-functionalized polymer; reacting the halogen-functionalized polymer with the quaternary phosphonium compound or the nitrogen-containing heterocycle or a salt thereof in the presence of an organic solvent 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 film; as well as The anions of the polymer membrane are exchanged with hydroxide, bicarbonate or carbonate ions or a combination thereof to form the anion exchange polymer membrane.

36. The method of claim 34 or 35, wherein the polymerization catalyst comprises trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, heptafluorobutyric acid or a combination thereof; and / or wherein each of the organic solvents independently comprises dimethyl sulfoxide, 1-methyl-2-pyrrolidone, 1-methyl-2-pyrrolidone, dimethylformamide, dichloromethane, trifluoroacetic acid, trifluoromethanesulfonic acid, chloroform, 1,1,2,2-tetrachloroethane, dimethylacetamide or a combination thereof, and the solvent in the dissolving step comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, pentanol, hexanol, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, chloroform, ethyl lactate, tetrahydrofuran, 2-methyltetrahydrofuran, water, phenol, acetone or a combination thereof.

37. An anion exchange membrane, optionally configured and sized to be suitable for use in a fuel cell unit, an electrolyser, an electrodialyser, a solar hydrogen generator, a flow battery, a desalter, a sensor, water demineralization, ultrapure water production, wastewater treatment, an ion exchanger or a CO2 separator, and comprising a polymer according to any one of claims 4 to 6.

38. An anion exchange membrane fuel cell unit, electrolyser, electrodialyser, solar hydrogen generator, flow battery, desalter, sensor, desalter, water purifier, wastewater treatment system, ion exchanger or CO2 separator comprising a polymer according to any one of claims 4 to 6.

39. An enhanced electrolyte membrane, optionally configured and sized to be suitable for use in a fuel cell unit, an electrolyzer, an electrodialyzer, a solar hydrogen generator, a flow battery, a desalter, a sensor, a desalter, a water purifier, a wastewater treatment system, an ion exchanger or a CO2 separator, the membrane comprising a porous substrate impregnated with a polymer according to any one of claims 4 to 6.

40. The membrane of claim 39, wherein the porous substrate comprises a membrane comprising polytetrafluoroethylene, polypropylene, polyethylene, polyetherketone, polyaryletherketone, imidazole-tethered poly(arylalkylene), imidazolium-tethered poly(arylalkylene), polysulfone, perfluoroalkoxyalkane, or fluorinated ethylene propylene polymer, and the membrane is optionally a dimensionally stable membrane; and / or wherein at least one of the following: The porous substrate has a porous microstructure of polymeric fibrils; or The internal volume of the porous substrate is closed by impregnation with the polymer; or The porous substrate comprises a microstructure of nodes interconnected by fibrils; or The thickness of the porous substrate is 1 micrometer to 100 micrometers; or The membrane is prepared by multiple impregnation of the substrate with the polymer; or The membrane was prepared by: wetting the porous substrate in a liquid to form a wetted substrate; dissolving the polymer in a solvent to form a homogeneous solution; applying the solution to the wetted substrate to form the reinforced film; as well as The film was allowed to dry.

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