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PIPERIDINIUM-CONTAINING ANION EXCHANGE POLYMERS

20240246070 ยท 2024-07-25

    Inventors

    Cpc classification

    International classification

    Abstract

    Poly(aryl alkylene) polymers with pendant piperidinium-functionalized groups are provided which have an alkaline-stable cation, such as imidazolium, introduced into a rigid aromatic polymer backbone free of ether bonds. Hydroxide exchange membranes or hydroxide exchange ionomers formed from these polymers exhibit superior chemical stability, hydroxide conductivity, decreased water uptake, good solubility in selected solvents, and improved mechanical properties in an ambient dry state as compared to conventional hydroxide exchange membranes or ionomers. Hydroxide exchange membrane fuel cells and hydroxide exchange membrane electrolyzers comprising the poly(aryl alkylene) polymers with pendant piperidinium-functionalized groups exhibit enhanced performance and durability at relatively high temperatures.

    Claims

    1. An anion exchange polymer comprising: structural units of formulae 1A, 2A, 3A, optionally 1A-2, and optionally 4A; or structural units of formulae 1A, 1A-2, 3A, and optionally 4A; and wherein: a sum of mole fractions of the structural units of formulae 1A, 1A-2, 2A and 4A is equal to a mole fraction of formula 3A in the polymer calculated from an amount of monomers used in a polymerization reaction to form the polymer, and a mole ratio of the structural unit of Formula 1A or 1A-2 or 2A or 4A to the structural unit of Formula 3A is from 0.01 to 1 calculated from the amount of monomers used in the polymerization reaction; and the structural units of Formulae 1A, 1A-2, 2A, 3A, and 4A have the structures: ##STR00089## wherein: A.sup.? is an anion; n is 0, 1, 2 or 3; q is 0, 1, 2, 3, 4, 5 or 6; R.sub.10 and R.sub.11 are each independently hydrogen, alkyl, alkenyl, alkynyl, aryl, a nitrogen-containing heterocyclic group, or a quaternary ammonium or phosphonium group having the formula (6A), the alkyl, alkenyl, alkynyl or aryl being optionally substituted with halide ##STR00090## and the nitrogen-containing heterocyclic group being 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.sub.20, R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.28, R.sub.29, R.sub.30, R.sub.40, R.sub.50, R.sub.60, R.sub.70, R.sub.80, R.sub.90, R.sub.104, R.sub.130, R.sub.140, R.sub.150, R.sub.160, and R.sub.170 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R.sub.30 and R.sub.60 are optionally linked to form a five membered ring optionally substituted with halide or alkyl; R.sub.71, R.sub.72, R.sub.73, R.sub.74 and R.sub.75 are each independently alkyl, alkenyl, alkynyl or aryl; R.sub.76 and R.sub.77 are each independently alkylene; each R.sub.100 is independently alkyl, alkenyl, alkynyl, or ##STR00091## each R.sub.101 is independently ##STR00092## each R.sub.200 is independently alkylene, arylene, alkenylene, or alkynylene; X is N, S or O; Y is C or N; and Z is N or P.

    2. An anion exchange polymer comprising a reaction product of a polymerization mixture comprising: a piperidone monomer or salt or hydrate thereof of formula 1, a ketone monomer of formula 2, an aromatic monomer of formula 3, optionally a trifluoromethyl ketone monomer of formula 4, and optionally a quaternized piperidone of formula 1-2; or the piperidone monomer of formula 1, the quaternized piperidone of formula 1-2, the aromatic monomer of formula 3, and optionally the trifluoromethyl ketone monomer of formula 4; and wherein: (i) a piperidone monomer or salt or hydrate thereof has the formula: ##STR00093## or (ii) a quaternized piperidone has the formula: ##STR00094## (iii) a ketone monomer has the formula: ##STR00095## (iv) an aromatic monomer has the formula: ##STR00096## and (v) a trifluoromethyl ketone monomer has the formula: ##STR00097## wherein: A.sup.? is an anion; n is 0, 1, 2 or 3; R.sub.1,l R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.12, R.sub.13, R.sub.15, R.sub.16, R.sub.17, R.sub.18, R.sub.19, R.sub.31, R.sub.32, R.sub.33, R.sub.34, R.sub.35, R.sub.36, R.sub.37, R.sub.38, R.sub.39, R.sub.52, R.sub.61 and R.sub.62 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R.sub.3 and R.sub.6 are optionally linked to form a five membered ring optionally substituted with halide or alkyl; each R.sub.14 is independently alkyl, alkenyl, alkynyl, or ##STR00098## and the alkyl, alkenyl, or alkynyl are optionally substituted with fluoride; each R.sub.51 is independently ##STR00099## X is N, S or O; and Y is C or N.

    3. An anion exchange polymer comprising: structural units of formulae 1A, 3A, 4A, 5A, optionally 1A-2, and optionally 2A; or structural units of formulae 1A, 2A, 3A, 5A, optionally 1A-2 and optionally 4A; and wherein: a sum of mole fractions of the structural units of formulae 1A, 1A-2, 2A, 4A and 5A is equal to a mole fraction of formulae 3A in the polymer calculated from amounts of monomers used in a polymerization reaction to form the polymer, and a mole ratio of the structural unit of formula 1A or 1A-2 or 4A or 5A to the structural unit of formula 3A is from 0.01 to 1 calculated from the amounts of the monomers used in the polymerization reaction; and the structural units of formulae 1A, 1A-2, 2A, 3A, 4A and 5A have the structures: ##STR00100## wherein: A.sup.? is an anion; n is 0, 1, 2 or 3; q is 0, 1, 2, 3, 4, 5 or 6; R.sub.10 and R.sub.11 are each independently hydrogen, alkyl, alkenyl, alkynyl, aryl, a nitrogen-containing heterocyclic group, or a quaternary ammonium or phosphonium group having the formula (6A), the alkyl, alkenyl, alkynyl or aryl being optionally substituted with halide ##STR00101## and the nitrogen-containing heterocyclic group being 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.sub.20, R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.28, R.sub.29, R.sub.30, R.sub.40, R.sub.50, R.sub.60, R.sub.70, R.sub.80, R.sub.90, R.sub.104, R.sub.130, R.sub.140, R.sub.150, R.sub.160, and R.sub.170 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R.sub.30 and R.sub.60 are optionally linked to form a five membered ring optionally substituted with halide or alkyl; R.sub.71, R.sub.72, R.sub.73, R.sub.74 and R.sub.75 are each independently alkyl, alkenyl, alkynyl or aryl; R.sub.76 and R.sub.77 are each independently alkylene; each R.sub.100 is independently alkyl, alkenyl, alkynyl, or ##STR00102## each R.sub.101 is independently ##STR00103## R.sub.102 and R.sub.103 are each independently alkyl, alkenyl, alkynyl, amine or aryl, and the alkyl, alkenyl, alkynyl, amine or aryl are optionally substituted with halide or alkyl, and wherein R.sub.102 and R.sub.103 are optionally linked to form a five or six membered ring or a polycycle; each R.sub.200 is independently alkylene, arylene, alkenylene, or alkynylene; X is N, S or O; Y is C or N; and Z is N or P.

    4. An anion exchange polymer comprising a reaction product of a polymerization mixture comprising: a piperidone monomer or salt or hydrate thereof of formula 1, an aromatic monomer of formula 3, a trifluoromethyl ketone monomer of formula 4, a diketone monomer of formula 5, optionally a quaternized piperidone of formula 1-2 and optionally a ketone monomer of formula 2; or the piperidone monomer of formula 1, the ketone monomer of formula 2, the aromatic monomer of formula 3, the diketone monomer of formula 5, optionally the quaternized piperidone of formula 1-2 and optionally the trifluoromethyl ketone monomer of formula 4; and wherein: (i) the piperidone monomer or salt or hydrate thereof has the formula: ##STR00104## (ii) the quaternized piperidone has the formula; ##STR00105## (iii) the ketone monomer has the formula: ##STR00106## (iv) the aromatic monomer has the formula: ##STR00107## (v) the trifluoromethyl ketone monomer has the formula: ##STR00108## and (vi) the diketone monomer has the formula: ##STR00109## wherein: A.sup.?is an anion; n is 0, 1, 2 or 3; R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.12, R.sub.13, R.sub.15, R.sub.16, R.sub.17, R.sub.18, R.sub.19, R.sub.31, R.sub.32, R.sub.33, R.sub.34, R.sub.35, R.sub.36, R.sub.37, R.sub.38, R.sub.39, R.sub.52, R.sub.61 and R.sub.62 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R.sub.3 and R.sub.6 are optionally linked to form a five membered ring optionally substituted with halide or alkyl; each R.sub.14 is independently alkyl, alkenyl, alkynyl, or ##STR00110## and the alkyl, alkenyl, or alkynyl are optionally substituted with fluoride; R.sub.41 and R.sub.42 are each independently alkyl, alkenyl, alkynyl, amine or aryl, and the alkyl, alkenyl, alkynyl, amine or aryl are optionally substituted with halide or alkyl, and wherein R.sub.41 and R.sub.42 are optionally linked to form a five or six membered ring or a polycycle; each R.sub.51 is independently ##STR00111## X is N, S or O; and Y is C or N.

    5.-22. (canceled)

    23. A polymer comprising a reaction product of a base and the polymer of claim 2.

    24. A polymer comprising a reaction product of an alkylating agent and the polymer of claim 23.

    25. A polymer comprising a reaction product of an ion exchange solution and the polymer of claim 1.

    26. A polymer comprising a reaction product of a base and the polymer of claim 23.

    27. A polymer comprising a second reaction product of a second polymerization mixture comprising: a base, an alkylating reagent, and an intermediate polymer; wherein: the intermediate polymer comprises a first reaction product of a first polymerization mixture comprising the monomers of claim 2.

    28.-42. (canceled)

    43. A method of making an anion exchange polymer of claim 2, the method comprising: reacting the quaternized piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form a piperidinium-functionalized polymer; and exchanging anions of the piperidinium-functionalized polymer with halide, hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the anion exchange polymer.

    44. A method of making an anion exchange polymer of claim 2, the method comprising: reacting the piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; reacting the acidified intermediate polymer with a base to form a piperidine-functionalized polymer; alkylating the piperidine-functionalized intermediate polymer in the presence of an organic solvent to form a piperidinium-functionalized intermediate polymer; and reacting the piperidinium-functionalized intermediate polymer with halide, hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the anion exchange polymer.

    45. A method of making an anion exchange polymer membrane comprising the polymer of claim 2, the method comprising: reacting the piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; reacting the acidified intermediate polymer with a base to form a neutral piperidine-functionalized polymer; reacting the neutral piperidine-functionalized polymer with an alkylating agent to form a piperidinium-functionalized polymer; exchanging anions of the piperidinium-functionalized polymer with hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the anion exchange polymer; dissolving the anion exchange polymer in a solvent to form a polymer suspension or solution; and casting the polymer suspension or solution to form the anion exchange polymer membrane.

    46. A method of making a crosslinked anion exchange polymer comprising the anion exchange polymer of claim 2, the method comprising: reacting the piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified polymer; reacting the acidified polymer with a base to form a neutral piperidine-functionalized polymer; partially quaternizing the neutral piperidine-functionalized polymer with an alkylating agent to form a partially quaternized piperidinium-functionalized polymer having piperidine groups available for crosslinking; reacting the partially quaternized piperidinium-functionalized polymer with a crosslinking reagent to form a crosslinked polymer; exchanging anions of the crosslinked polymer with halide, hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the crosslinked anion exchange polymer; and optionally reacting the crosslinked anion exchange polymer with trimethyl amine to quaternize partially reacted crosslinking reagent.

    47. A method of making a crosslinked anion exchange polymer comprising the anion exchange polymer of claim 2, the method comprising: reacting the piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified polymer; reacting the acidified polymer with a base to form a neutral piperidine- functionalized polymer; partially quaternizing the neutral piperidine-functionalized polymer with a crosslinking regent to form a crosslinked polymer; reacting the crosslinked polymer with an alkylating agent to form a fully quaternized crosslinked polymer; and exchanging anions of the polymer with halide, hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the crosslinked anion exchange polymer.

    48. A method of making a crosslinked polymer membrane or a crosslinked anion exchange polymer membrane comprising the anion exchange polymer of claim 2, the method comprising: reacting the piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified polymer; reacting the acidified polymer with a base to form a neutral piperidine-functionalized polymer; reacting the neutral piperidine-functionalized polymer with an alkylating agent to form a piperidinium-functionalized polymer while leaving part of the neutral piperidine intact for crosslinking; optionally exchanging anions of the piperidinium-functionalized polymer with hydroxide, bicarbonate, or carbonate ions or a combination thereof to form an anion exchange polymer membrane; dissolving the piperidinium-functionalized polymer or the anion exchange polymer membrane in a solvent to form a polymer suspension or solution; adding a crosslinking reagent to the polymer suspension or solution and casting to form the crosslinked polymer membrane or the crosslinked anion exchange polymer membrane; optionally reacting the crosslinked polymer membrane or the crosslinked anion exchange polymer membrane with trimethyl amine to quaternize partially reacted crosslinking reagent; and optionally exchanging anions of the crosslinked polymer membrane or the crosslinked anion exchange polymer membrane with hydroxide, bicarbonate, or carbonate ions or a combination thereof.

    49.-53. (canceled)

    54. An anion exchange membrane configured and sized to be suitable for use in a fuel cell, electrolyzer, electrodialyzer, solar hydrogen generator, flow battery, desalinator, sensor, demineralization of water, ultra-pure water production, wastewater treatment, ion exchanger, or CO2 separator, and comprising the polymer of of claim 1.

    55. An anion exchange membrane fuel cell, electrolyzer, electrodialyzer, solar hydrogen generator, flow battery, desalinator, sensor, demineralization of water, ultra-pure water production, wastewater treatment, ion exchanger, or CO2 separator comprising the polymer of claim 1.

    56. A reinforced ion exchange membrane or electrolyte membrane, optionally configured and sized to be suitable for use in a fuel cell, electrolyzer, electrodialyzer, solar hydrogen generator, flow battery, desalinator, sensor, demineralizer, water purifier, waste water treatment system, ion exchanger, or CO2 separator, the reinforced membrane comprising a porous substrate impregnated with the polymer of claim 1.

    57.-58. (canceled)

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0078] FIG. 1A illustrates an exemplary hydroxide exchange membrane fuel cell.

    [0079] FIG. 1B illustrates an exemplary hydroxide exchange membrane electrolyzer.

    [0080] FIG. 2 depicts an 1H NMR spectrum of P-Neutral-0.85 in CDCl.sub.3

    [0081] FIG. 3 depicts an 1H NMR spectrum of P-Me-0.85-0.15 in DMSO-d6.

    DESCRIPTION OF THE PREFERRED EMBODIMENTS

    [0082] Anion exchange polymers have now been discovered which, when crosslinked, exhibit reduced swelling and water uptake and increased conductivity, which are beneficial to a membrane and its performance in electrochemical devices. Such polymers can be fluorine-free polymers.

    [0083] HEMs/HEIs formed from poly(aryl alkylene) polymers with various pendant piperidinium-functionalized groups and having intrinsic hydroxide conduction channels have been discovered which can provide increased chemical stability, greater conductivity, decreased water uptake, good solubility in selected solvents, and/or mechanical properties, and other attributes relevant to HEM/HEI performance. For example, HEMs/HEIs formed from these polymers can exhibit superior chemical stability, anion conductivity, decreased water uptake, good solubility in selected solvents, and improved mechanical properties in an ambient dry state as compared to conventional HEM/HEIs. The inventive HEMFCs can exhibit enhanced performance and durability at relatively high temperatures.

    [0084] First and second aspects of the invention are directed to an anion exchange polymer which comprises structural units of formulae 1A, 2A, 3A, optionally 1A-2, and optionally 4A (first aspect); or structural units of formulae 1A, 1A-2, 3A, and optionally 4A (second aspect). A sum of mole fractions of the structural units of formulae 1A, 1A-2, 2A and 4A is equal to a mole fraction of formula 3A in the polymer calculated from an amount of monomers used in a polymerization reaction to form the polymer, and a mole ratio of the structural unit of Formula 1A or 1A-2 or 2A or 4A to the structural unit of Formula 3A is from 0.01 to 1 calculated from the amount of monomers used in the polymerization reaction. The structural units of Formulae 1A, 1A-2, 2A, 3A, and 4A have the structures:

    ##STR00024##

    wherein: [0085] A.sup.? is an anion; [0086] n is 0, 1, 2 or 3; [0087] q is 0, 1, 2, 3, 4, 5 or 6; [0088] R.sub.10 and R.sub.11 are each independently hydrogen, alkyl, alkenyl, alkynyl, aryl, a nitrogen-containing heterocyclic group, or a quaternary ammonium or phosphonium group having the formula (6A), the alkyl, alkenyl, alkynyl or aryl being optionally substituted with halide

    ##STR00025##

    and the nitrogen-containing heterocyclic group being 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; [0089] R.sub.20, R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.28, R.sub.29, R.sub.30, R.sub.40, R.sub.50, R.sub.60, R.sub.70, R.sub.80, R.sub.90, R.sub.104, R.sub.130, R.sub.140, R.sub.150, R.sub.160, and R.sub.170 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R.sub.30 and Reo are optionally linked to form a five membered ring optionally substituted with halide or alkyl; [0090] R.sub.71, R.sub.72, R.sub.73, R.sub.74 and R.sub.75 are each independently alkyl, alkenyl, alkynyl or aryl; [0091] R.sub.76 and R.sub.77 are each independently alkylene; [0092] each R.sub.100 is independently alkyl, alkenyl, alkynyl, or

    ##STR00026## [0093] each R.sub.101 is independently

    ##STR00027## [0094] each R.sub.200 is independently alkylene, arylene, alkenylene, or alkynylene; [0095] X is N, S or O; [0096] Y is C or N; and [0097] Z is N or P.

    [0098] In the first aspect, the polymer can comprise the structural units of formulae 1A, 2A, and 3A; 1A, 1A-2, 2A, and 3A; 1A, 2A, 3A and 4A; or 1A, 1A-2, 2A, 3A and 4A.

    [0099] In the second aspect, the polymer can comprise the structural units of formulae 1A, 1A-2, and 3A; or 1A, 1A-2, 3A and 4A.

    [0100] In the first and second aspects of the invention, the mole ratio of a sum of the mole fractions of the structural unit of Formula 1A or Formula 1A-2, Formula 2A and Formulae 4A to the mole fraction of Formulae 3A in the polymer can be from about 0.95:1 to about 1.4:1, and the ratio of the mole fraction of the structural unit of Formula 1A or Formula 1A-2 to the mole fraction of the structural unit of Formula 3A can be from about 0.01 to 1. Alternatively, the mole ratio of a sum of the mole fractions of the structural unit of Formula 1A or Formula 1A-2, Formula 2A and Formulae 4A to the mole fraction of Formulae 3A in the polymer can be from about 1:1 to about 1.2:1.

    [0101] The first and second aspects of the invention can be provided in terms of monomer reactants rather than as structural units of the polymer. When the first and second aspects of the invention are expressed in terms of monomer reactants, an anion exchange polymer is provided that comprises a reaction product of a polymerization mixture comprising: a piperidone monomer or salt or hydrate thereof of formula 1, a ketone monomer of formula 2, an aromatic monomer of formula 3, optionally a trifluoromethyl ketone monomer of formula, 4 and optionally a quaternized piperidone of formula 1-2 (first aspect); or the piperidone monomer of formula 1, the quaternized piperidone of formula 1-2, the aromatic monomer of formula 3, and optionally the trifluoromethyl ketone monomer of formula 4 (second aspect). The piperidone monomer or salt or hydrate thereof has the formula:

    ##STR00028## [0102] the quaternized piperidone has the formula:

    ##STR00029## [0103] the ketone monomer has the formula:

    ##STR00030## [0104] the aromatic monomer has the formula:

    ##STR00031##

    and [0105] the trifluoromethyl ketone monomer has the formula:

    ##STR00032##

    wherein: [0106] A.sup.? is an anion; [0107] n is 0, 1, 2 or 3;

    [0108] R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.12, R.sub.13, R.sub.15, R.sub.16, R.sub.17, R.sub.18, R.sub.19, R.sub.31, R.sub.32, R.sub.33, R.sub.34, R.sub.35, R.sub.36, R.sub.37, R.sub.38, R.sub.39, R.sub.52, R.sub.61 and R.sub.62 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R.sub.3 and R.sub.6 are optionally linked to form a five membered ring optionally substituted with halide or alkyl; [0109] each R.sub.14 is independently alkyl, alkenyl, alkynyl, or

    ##STR00033##

    and the alkyl, alkenyl, or alkynyl are optionally substituted with fluoride; [0110] each R.sub.51 is independently

    ##STR00034## [0111] X is N, S or O; and [0112] Y is C or N.

    [0113] In the first aspect, the polymer can comprise the monomers of formulae 1, 2, and 3; 1, 1-2, 2, and 3; 1, 2, 3 and 4; or 1, 1-2, 2, 3 and 4.

    [0114] In the second aspect, the polymer can comprise the monomers of formulae 1, 1-2, and 3; or 1, 1-2, 3 and 4.

    [0115] A third and fourth aspect of the invention is directed to an anion exchange polymer comprising structural units of formulae 1A, 3A, 4A, 5A, optionally 1A-2, and optionally 2A (third aspect); or structural units of formulae 1A, 2A, 3A, 5A, optionally 1A-2 and optionally 4A (fourth aspect). A sum of mole fractions of the structural units of formulae 1A, 1A-2, 2A, 4A and 5A is equal to a mole fraction of formulae 3A in the polymer calculated from amounts of monomers used in a polymerization reaction to form the polymer, and a mole ratio of the structural unit of formula 1A or 1A-2 or 4A or 5A to the structural unit of formula 3A is from 0.01 to 1 calculated from the amounts of the monomers used in the polymerization reaction. The structural units of formulae 1A, 1A-2, 2A, 3A, 4A and 5A have the structures:

    ##STR00035##

    wherein: [0116] A.sup.? is an anion; [0117] n is 0, 1, 2 or 3; [0118] q is 0, 1, 2, 3, 4, 5 or 6; [0119] R.sub.10 and R.sub.11 are each independently hydrogen, alkyl, alkenyl, alkynyl, aryl, a nitrogen-containing heterocyclic group, or a quaternary ammonium or phosphonium group having the formula (6A), the alkyl, alkenyl, alkynyl or aryl being optionally substituted with halide

    ##STR00036##

    and the nitrogen-containing heterocyclic group being 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; [0120] R.sub.20, R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.28, R.sub.29, R.sub.30, R.sub.40, R.sub.50, R.sub.60, R.sub.70, R.sub.80, R.sub.90, R.sub.104, R.sub.130, R.sub.140, R.sub.150, R.sub.160, and R.sub.170 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R.sub.30 and R.sub.60 are optionally linked to form a five membered ring optionally substituted with halide or alkyl; [0121] R.sub.71, R.sub.72, R.sub.73, R.sub.74 and R.sub.75 are each independently alkyl, alkenyl, alkynyl or aryl; [0122] R.sub.76 and R.sub.77 are each independently alkylene; [0123] each R.sub.100 is independently alkyl, alkenyl, alkynyl, or

    ##STR00037## [0124] each R.sub.101 is independently

    ##STR00038## [0125] R.sub.102 and R.sub.103 are each independently alkyl, alkenyl, alkynyl, amine or aryl, and the alkyl, alkenyl, alkynyl, amine or aryl are optionally substituted with halide or alkyl, and wherein R.sub.102 and R.sub.103 are optionally linked to form a five or six membered ring or a polycycle; [0126] each R.sub.200 is independently alkylene, arylene, alkenylene, or alkynylene; [0127] X is N, S or O; p1 Y is C or N; and [0128] Z is N or P.

    [0129] In the third aspect, the polymer can comprise the structural units of formulae 1A, 3A, 4A, and 5A; 1A, 1A-2, 3A, 4A, and 5A; or 1A, 2A, 3A, 4A, and 5A.

    [0130] In the fourth aspect, the polymer can comprise the structural units of formulae 1A, 2A, 3A, and 5A; 1A, 1A-2 2A, 3A, and 5A; 1A, 2A, 3A, 4A, and 5A; or 1A, 1A-2, 2A, 3A, 4A, and 5A.

    [0131] In the third and fourth aspects of the invention, the mole ratio of a sum of the mole fractions of the structural unit of Formula 1A or Formula 1A-2, Formula 2A, Formulae 4A and Formulae 5A to the mole fraction of Formulae 3A in the polymer can be from about 0.95:1 to about 1.4:1, and the ratio of the mole fraction of the structural unit of Formula 1A or Formula 1A-2 to the mole fraction of the structural unit of Formula 3A can be from about 0.01 to 1. Alternatively, the mole ratio of a sum of the mole fractions of the structural unit of Formula 1A or Formula 1A-2, Formula 2A, Formulae 4A and Formulae 5A to the mole fraction of Formulae 3A in the polymer can be from about 1:1 to about 1.2:1.

    [0132] The third and fourth aspects of the invention can be provided in terms of monomer reactants rather than as structural units of the polymer. Thus, the third and fourth aspects of the invention are also directed to an anion exchange polymer comprising a reaction product of a polymerization mixture comprising: a piperidone monomer or salt or hydrate thereof of formula 1, an aromatic monomer of formula 3, a trifluoromethyl ketone monomer of formula 4, a diketone monomer of formula 5, optionally a quaternized piperidone of formula 1-2 and optionally a ketone monomer of formula 2 (third aspect); or the piperidone monomer of formula 1, the ketone monomer of formula 2, the aromatic monomer of formula 3, the diketone monomer of formula 5, optionally the quaternized piperidone of formula 1-2 and optionally the trifluoromethyl ketone monomer of formula 4 (fourth aspect). The piperidone monomer or salt or hydrate thereof has the formula:

    ##STR00039## [0133] the quaternized piperidone has the formula;

    ##STR00040## [0134] the ketone monomer has the formula:

    ##STR00041## [0135] the aromatic monomer has the formula:

    ##STR00042## [0136] the trifluoromethyl ketone monomer has the formula:

    ##STR00043##

    and [0137] the diketone monomer has the formula.

    ##STR00044##

    wherein: [0138] A.sup.? is an anion; [0139] n is 0, 1, 2 or 3; [0140] R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.12, R.sub.13, R.sub.15, R.sub.16, R.sub.17, R.sub.18, R.sub.19, R.sub.31, R.sub.32, R.sub.33, R.sub.34, R.sub.35, R.sub.36, R.sub.37, R.sub.38, R.sub.39, R.sub.52, R.sub.61 and R.sub.62 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R.sub.3 and R.sub.6 are optionally linked to form a five membered ring optionally substituted with halide or alkyl; [0141] each R.sub.14 is independently alkyl, alkenyl, alkynyl, or

    ##STR00045##

    and the alkyl, alkenyl, or alkynyl are optionally substituted with fluoride;

    [0142] R.sub.41 and R.sub.42 are each independently alkyl, alkenyl, alkynyl, amine or aryl, and the alkyl, alkenyl, alkynyl, amine or aryl are optionally substituted with halide or alkyl, and wherein R.sub.41 and R.sub.42 are optionally linked to form a five or six membered ring or a polycycle; [0143] each R.sub.51 is independently

    ##STR00046## [0144] X is N, S or O; and [0145] Y is C or N.

    [0146] In the third aspect, the polymer can comprise the monomers of formulae 1, 3, 4, and 5; 1, 1-2, 3, 4, and 5; or 1, 2, 3, 4, and 5.

    [0147] In the fourth aspect, the polymer can comprise the monomers of formulae 1, 2, 3, and 5; 1, 1-2, 2, 3, and 5; 1, 2, 3, 4, and 5; or 1, 1-2, 2, 3, 4, and 5. [0148] R.sub.10 and R.sub.11 of the structural unit of formula (1A) or R.sub.10 of the structural unit of formula (1A-2) of any of the anion exchange polymers described herein can comprise alkyl, alkenyl, alkynyl or aryl, a quaternary ammonium or phosphonium compound of the formula (6A), or any combination of thereof.

    ##STR00047##

    [0149] Preferably, in the quaternary ammonium or phosphonium compound of formula (6A), R.sub.76 and R.sub.77 are each independently C.sub.1-C.sub.22 alkylene; R.sub.71, R.sub.72, R.sub.73, R.sub.74 and R.sub.75 are each independently C.sub.1-C.sub.6 alkyl; q is 0, 1, 2, 3, 4, 5, or 6; Z is N or P; and A.sup.? is an anion.

    [0150] Preferably, in the quaternary ammonium or phosphonium compound of formula (6A), R.sub.76 and R.sub.77 are independently C.sub.1-C.sub.6 alkylene; R.sub.71, R.sub.72, R.sub.73, R.sub.74 and R.sub.75 are each independently C.sub.1-C.sub.6 alkyl; q is 0, 1, 2 or 3; Z is N; and A.sup.? is an anion. For example the ammonium compound can have the formula:

    ##STR00048##

    or the structural unit:

    ##STR00049##

    [0151] The nitrogen-containing heterocycle in any of the anion exchange polymers described herein can comprise an imidazolium having the formula (7A):

    ##STR00050##

    wherein: R.sub.81, R.sub.82, R.sub.83, R.sub.84 and R.sub.86 are each independently optionally substituted alkyl, alkenyl, alkynyl, or aryl; and A.sup.? is an anion. Preferably, R.sub.84 is 2,4,6-alkylphenyl, and R.sub.81, R.sub.82, R.sub.83 and R.sub.86 are each independently C.sub.1-C.sub.6 alkyl. For example, the imidazolium can have the formula:

    ##STR00051##

    [0152] The piperidone monomer has the formula:

    ##STR00052##

    wherein R.sub.1 is each independently hydrogen, alkyl, alkenyl, or alkynyl, and the alkyl, alkenyl or alkynyl are optionally substituted with fluoride. Preferably, R.sub.1 is alkyl such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. Preferably, the piperidone monomer or salt or hydrate thereof comprises N-methyl-4-piperidone or 4-piperidone.

    [0153] The salt of the piperidone monomer can comprise hydrochloride, hydrofluoride, hydrobromide, hydroiodide, trifluoroacetate, acetate, triflate, methanesulfonate, sulfate, nitrate, tetrafluoroborate, hexafluorophosphate, formate, benzenesulfonate, toluate, perchlorate, or benzoate, or any hydrate of the salt, or any combination thereof.

    [0154] The salt of the piperidone monomer can comprise 4-piperidone hydrofluoride, 4-piperidone hydrochloride, 4-piperidone hydrobromide, 4-piperidone hydroiodide, 4-piperidone trifluoroacetate, 4-piperidone tetrafluoroborate, 4-piperidone hexafluorophosphate, 4-piperidone acetate, 4-piperidone triflate, 4-piperidone methanesulfonate, 4-piperidone formate, 4-piperidone benzenesulfonate, 4-piperidone toluate, 4-piperidone sulfate, 4-piperidone nitrate, 4-piperidone perchlorate, 4-piperidone benzoate, N-methyl-4-piperidone hydrofluoride, N-methyl-4-piperidone hydrochloride, N-methyl-4-piperidone hydrobromide, N-methyl-4-piperidone hydroiodide, N-methyl-4-piperidone trifluoroacetate, N-methyl-4-piperidone tetrafluoroborate, N-methyl-4-piperidone hexafluorophosphate, N-methyl-4-piperidone acetate, N-methyl-4-piperidone triflate, N-methyl-4-piperidone methanesulfonate, N-methyl-4-piperidone formate, N-methyl-4-piperidone benzenesulfonate, N-methyl-4-piperidone toluate, N-methyl-4-piperidone sulfate, N-methyl-4-piperidone nitrate, N-methyl-4-piperidone perchlorate, N-methyl-4-piperidone benzoate or any hydrate of the salt, or any combination thereof.

    [0155] The quaternized piperidone monomer has the formula:

    ##STR00053##

    wherein: R.sub.61 and R.sub.62 are each independently hydrogen, alkyl, alkenyl, or alkynyl, and the alkyl, alkenyl or alkynyl are optionally substituted with fluoride; and A is an anion such as halide, tetrafluoroborate, hexafluorophosphate, bicarbonate, carbonate or hydroxide. Preferably, both R.sub.61 and R.sub.62 are alkyl, and the anion is halide. Preferably, the quaternized piperidone monomer can comprise 1,1-dimethyl-4-oxopiperidin-1-ium iodide:

    ##STR00054##

    [0156] The structural unit of formula 2A can be:

    ##STR00055##

    wherein: [0157] each R.sub.101 is independently

    ##STR00056## [0158] R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.28, and R.sub.29 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide; [0159] R.sub.104 is hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide; [0160] X is N, S or O; and [0161] Y is C or N. Preferably, R.sub.104 is alkyl such as methyl, ethyl, propyl, butyl, pentyl, or hexyl; Y is N; X is N, S or O; and R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.28, R.sub.29 and R.sub.101 are each hydrogen.

    [0162] The ketone monomer has the formula:

    ##STR00057##

    wherein, R.sub.51 has a formula of:

    ##STR00058##

    R.sub.31, R.sub.32, R.sub.33, R.sub.34, R.sub.35, R.sub.36, R.sub.37, R.sub.38, R.sub.39 and R.sub.52 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide; Y is C or N; and X is N, S or O. Preferably, R.sub.52 is alkyl such as methyl, ethyl, propyl, butyl, pentyl, or hexyl; Y is N; X is N, S or O; and R.sub.31, R.sub.32, R.sub.33, R.sub.34, R.sub.35, R.sub.36, R.sub.37, R.sub.38, R.sub.39 and R.sub.52 are each hydrogen. Preferably, the ketone monomer of the formula (2) can be 4-acetylpyridine:

    ##STR00059##

    3-acetylpyridine, 2-acetylpyridine, 2-acetylpyrrole, 2-furyl methyl ketone or 3-acetylthiophene, or any combination thereof.

    [0163] The structural unit of formula 3A can be:

    ##STR00060##

    wherein R.sub.20, R.sub.30, R.sub.40, R.sub.50, R.sub.60, R.sub.70, R.sub.80, and R.sub.90 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R.sub.30 and R.sub.60 are optionally linked to form a five membered ring optionally substituted with halide or alkyl; and n is 0, 1, 2 or 3. Preferably, R.sub.20, R.sub.30, R.sub.40, R.sub.50, R.sub.60, R.sub.70, R.sub.80, and R.sub.90 are each independently hydrogen, or alkyl optionally substituted with fluoride, such as methyl, ethyl, propyl, butyl, pentyl or hexyl or methyl, ethyl, propyl, butyl, pentyl, or hexyl substituted with fluoride.

    [0164] The aromatic monomer has the formula:

    ##STR00061##

    wherein R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.12 and R.sub.13 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide, and wherein R.sub.3 and R.sub.6 are optionally linked to form a five membered ring optionally substituted with halide or alkyl; and n is 0, 1, 2 or 3. Preferably, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.12 and R.sub.13 are each independently hydrogen, or alkyl optionally substituted with fluoride, such as methyl, ethyl, propyl, butyl, pentyl or hexyl or methyl, ethyl, propyl, butyl, pentyl, or hexyl substituted with fluoride. Preferably, the aromatic monomer comprises biphenyl, para-terphenyl, m-terphenyl, para-quaterphenyl, 1,3,5-Triphenylbenzene, 9,9-dimethylfluorene, benzene or any combination thereof.

    [0165] The structural unit of formula 4A can be: 1

    ##STR00062##

    wherein each R.sub.100 is independently alkyl, alkenyl, alkynyl, or

    ##STR00063##

    and

    [0166] R.sub.130, R.sub.140, R.sub.150, R.sub.160, and R.sub.170 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide. Preferably, R.sub.130, R.sub.140, R.sub.150, R.sub.160 and R.sub.170 are each independently hydrogen or alkyl optionally substituted with fluoride, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl substituted with fluoride.

    [0167] The trifluoromethyl ketone monomer has the formula:

    ##STR00064##

    wherein each R.sub.4 is independently alkyl, alkenyl, alkynyl, or

    ##STR00065##

    and the alkyl, alkenyl, or alkynyl are optionally substituted with halide; R.sub.15, R.sub.16, R.sub.17, R.sub.18 and R.sub.19 are each independently hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide. Preferably, R.sub.15, R.sub.16, R.sub.17, R.sub.18 and R.sub.19 are each independently hydrogen or alkyl optionally substituted with fluoride, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl substituted with fluoride. Preferably, the trifluoromethyl ketone monomer comprises 2,2,2-trifluoroacetophenone or 1,1,1-trifluoroacetone.

    [0168] The structural unit of formula 5A can be:

    ##STR00066##

    wherein R.sub.102 and R.sub.103 are each independently alkyl, alkenyl, alkynyl, amine or aryl, and the alkyl, alkenyl, alkynyl, amine or aryl are optionally substituted with halide or alkyl, and wherein R.sub.102 and R.sub.103 are optionally linked to form a five or six membered ring or a polycycle. The polycycle can have two or more hydrocarbon rings which can be substituted with heteroatoms such as nitrogen or oxygen. The polycycle can be aromatic or non-aromatic. Preferably, the structural unit of formula 5A is derived from isatin, 5-bromoisatin, 5-methylisatin, 5-nitroisatin, acenaphthenequinone, benzil or 9,10-phenanthrenequinone. For example. the structural units of formula 5A can be:

    ##STR00067##

    [0169] The diketone monomer has the formula:

    ##STR00068##

    wherein R.sub.41 and R.sub.42 are each independently alkyl, alkenyl, alkynyl, amine or aryl, and the alkyl, alkenyl, alkynyl, amine or aryl are optionally substituted with halide or alkyl. R.sub.41 and R.sub.42 are optionally linked to form a five or six membered ring. When R.sub.41 and R.sub.42 are both aryl groups they are optionally fused to form a polycycle such as a naphthalene-type structure. Preferably, R.sub.41 is aryl, and the aryl is optionally substituted with fluoride, such as phenyl substituted with fluoride; and R.sub.42 is independently amine or aryl, and the aryl is optionally substituted with fluoride, such as phenyl substituted with fluoride. Preferably, the diketone monomer comprises isatin, 5-bromoisatin, 5-methylisatin, 5-nitroisatin, acenaphthenequinone, benzil or 9,10-phenanthrenequinone.

    [0170] Representative polycycles of formula 5 include, but are not limited to:

    ##STR00069##

    [0171] The anion A.sup.? of the structural units (1A), (1A-2) or (6A) or the monomer of formula (1-2) can comprise a halide, carbonate, bicarbonate, hydroxide, trifluoroacetate, acetate, triflate, methanesulfonate, sulfate, nitrate, tetrafluoroborate, hexafluorophosphate, formate, benzenesulfonate, toluate, perchlorate, or benzoate or any combination thereof.

    [0172] A polymer is provided which comprises a reaction product of a mixture comprising the piperidone monomer, the other ketone monomer(s), the aromatic monomer and optionally the diketone monomer in the presence of an organic solvent and a polymerization catalyst. This polymer is referred to herein as an acidified polymer.

    [0173] A polymer is provided which comprises a reaction product of a mixture comprising a base and a polymer comprising the reaction product of a polymerization mixture comprising the piperidone monomer. This polymer is referred to herein as a piperidine-functionalized polymer.

    [0174] A polymer is provided which comprises a reaction product of a mixture comprising an alkylating reagent and a piperidine-functionalized polymer. This polymer is referred to herein as a piperidinium-functionalized polymer.

    [0175] A polymer is provided which comprises a reaction product of a polymerization mixture comprising a quaternized piperidone monomer. This polymer is also referred to herein as a piperidinium-functionalized polymer.

    [0176] A polymer is provided which comprises a reaction product of an ion exchange solution and a piperidinium-functionalized polymer.

    [0177] A polymer is provided which comprises a reaction product of a hydroxide solution and a piperidinium-functionalized polymer. This polymer is referred to herein as a hydroxide exchange polymer.

    [0178] A crosslinked anion exchange polymer or membrane can comprise the structural unit of formula (1A-2) wherein the anion A comprises a halide, tetrafluoroborate, hexafluorophosphate, bicarbonate, carbonate or hydroxide or a combination thereof.

    [0179] A method of making an anion exchange polymer as described herein is provided. The method comprises: reacting the quaternized piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form a piperidinium-functionalized polymer; and exchanging anions of the piperidinium-functionalized polymer with halide, hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the anion exchange polymer.

    [0180] Another method of making an anion exchange polymer as described herein is provided. The method comprises: [0181] reacting the piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; [0182] reacting the acidified intermediate polymer with a base to form a piperidine-functionalized polymer; [0183] alkylating the piperidine-functionalized intermediate polymer in the presence of an organic solvent to form a piperidinium-functionalized intermediate polymer; and [0184] reacting the piperidinium-functionalized intermediate polymer with halide, hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the anion exchange polymer.

    [0185] For example, the monomers can be placed in a stirred container and dissolved or dispersed into an organic solvent. A polymerization catalyst in a solvent can then be added dropwise over up to 60 minutes at ?78 to 60? C., such as from ?78 to 0? C. Thereafter, the reaction is continued at this temperature for about 1 to about 120 hours. The resulting solution is poured slowly into an aqueous solution of an alcohol such as ethanol. The solid obtained is filtered, washed with water and immersed in 1 M a base such as K2CO3 at room temperature for about 1 to 48 hours. Finally, the product is filtered, washed with water and dried completely under vacuum to form the polymer. The polymer can then be subjected to anion exchange, for example in 1 M KOH for hydroxide exchange, at about 20 to 100? C. for about 12 to 48 hours, followed by washing and immersion in DI water for about 12 to 48 hours under an oxygen-free atmosphere to remove residual KOH.

    [0186] Yet another method of making an anion exchange polymer as described herein is provided. The method comprises:

    [0187] reacting the piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified intermediate polymer; [0188] reacting the acidified intermediate polymer with a base to form a neutral piperidine-functionalized polymer; [0189] reacting the neutral piperidine-functionalized polymer with an alkylating agent to form a piperidinium-functionalized polymer; [0190] exchanging anions of the piperidinium-functionalized polymer with hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the anion exchange polymer; [0191] dissolving the anion exchange polymer in a solvent to form a polymer suspension or solution; and [0192] casting the polymer suspension or solution to form the anion exchange polymer membrane.

    [0193] A method of making a crosslinked anion exchange polymer comprising the anion exchange polymer as described herein is provided. The method comprises: [0194] reacting the piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified polymer; [0195] reacting the acidified polymer with a base to form a neutral piperidine-functionalized polymer; [0196] partially quaternizing the neutral piperidine-functionalized polymer with an alkylating agent to form a partially quaternized piperidinium-functionalized polymer having piperidine groups available for crosslinking; [0197] reacting the partially quaternized piperidinium-functionalized polymer with a crosslinking reagent to form a crosslinked polymer; [0198] exchanging anions of the crosslinked polymer with halide, hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the crosslinked anion exchange polymer; and [0199] optionally reacting the crosslinked anion exchange polymer with trimethyl amine to quaternize partially reacted crosslinking reagent.

    [0200] Another method of making a crosslinked anion exchange polymer comprising the anion exchange polymer as described herein is provided. The method comprises: [0201] reacting the piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified polymer; [0202] reacting the acidified polymer with a base to form a neutral piperidine- functionalized polymer; [0203] partially quaternizing the neutral piperidine-functionalized polymer with a crosslinking regent to form a crosslinked polymer; [0204] reacting the crosslinked polymer with an alkylating agent to form a fully quaternized crosslinked polymer; and [0205] exchanging anions of the polymer with halide, hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the crosslinked anion exchange polymer.

    [0206] Yet another method of making a crosslinked polymer membrane or a crosslinked anion exchange polymer membrane comprising the anion exchange polymer as described herein is provided. The method comprises: [0207] reacting the piperidone monomer with the aromatic monomer, the optional ketone monomer, the optional trifluoromethyl ketone and the optional diketone monomer in the presence of an organic solvent and a polymerization catalyst to form an acidified polymer; [0208] reacting the acidified polymer with a base to form a neutral piperidine-functionalized polymer; [0209] reacting the neutral piperidine-functionalized polymer with an alkylating agent to form a piperidinium-functionalized polymer while leaving part of the neutral piperidine intact for crosslinking; [0210] optionally exchanging anions of the piperidinium-functionalized polymer with hydroxide, bicarbonate, or carbonate ions or a combination thereof to form an anion exchange polymer membrane; [0211] dissolving the piperidinium-functionalized polymer or the anion exchange polymer in a solvent to form a polymer suspension or solution; [0212] adding a crosslinking reagent to the polymer suspension or solution and casting to form the crosslinked polymer membrane or the crosslinked anion exchange polymer membrane; [0213] optionally reacting the crosslinked polymer membrane or the crosslinked anion exchange polymer membrane with trimethyl amine to quaternize partially reacted crosslinking reagent; and [0214] optionally exchanging anions of the crosslinked polymer membrane or the crosslinked anion exchange polymer membrane with hydroxide, bicarbonate, or carbonate ions or a combination thereof.

    [0215] The polymerization catalyst used in any of the methods described herein can comprise trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, heptafluorobutyric acid, or a combination thereof.

    [0216] Each of the organic solvents used in the any of the above methods can be independently selected from polar aprotic solvents (e.g., dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylacetamide, or dimethylformamide) or other suitable solvents including, but not limited to, methylene chloride, trifluoroacetic acid, trifluoromethanesulfonic acid, chloroform, 1,1,2,2-tetrachloroethane, dimethylacetamide or a combination thereof.

    [0217] The solvent in the dissolving step of any of the above methods can comprise methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, a pentanol, a hexanol, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, chloroform, ethyl lactate, tetrahydrofuran, 2-methyltetrahydrofuran, water, phenol, acetone, or a combination thereof.

    [0218] The crosslinking reagent used for casting the crosslinked membrane in the methods described herein can comprise 1,6-dibromohexane, 1,4-dibromobutane, 1,8-dibromooctane, 1,4-dibromohepane, 1,7-dibromohepane, 1,10-dibromodecane, 1,12-dibromododecane, 1,6-diiodohexane, 1,4-diiodobutane, 1,10-diiododecane, 1,5-diiodopentane, 1,8-diiodooctane, ?,?-dichloro-p-xylene, 4,4-bis(chloromethyl)-1,1-biphenyl, or any combination thereof.

    [0219] The base used in any of the above methods can comprise 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.

    [0220] The alkylating agent used in the any of the methods described herein can comprise methyl iodide, iodoethane, 1-iodopropane, 1-iodobutane, 1-iodopentane, 1-iodohexane, methyl bromide, bromoethane, 1-bromopropane, methyl chloride, chloroethane, 1-chloropropane, methyl fluorosulfonate, methyl trifluoromethanesulfonate, or a combination of thereof.

    [0221] The alkylating agent used in the any of the methods described herein can comprise a quaternary ammonium or phosphonium group having the formula (6) or a combination of thereof.

    ##STR00070##

    wherein: R.sub.76 and R.sub.77 are each independently alkylene; R.sub.71, R.sub.72, R.sub.73, R.sub.74 and R.sub.75 are each independently alkyl, alkenyl, alkynyl or aryl; q is 0, 1, 2, 3, 4, 5 or 6; A.sup.? is an anion; L is Cl, Br or I; and Z is N or P.

    [0222] Preferably, R.sub.76 and R.sub.77 are each independently C.sub.1-C.sub.22 alkylene, such as C.sub.1-C.sub.6 alkylene (e.g. methylene, ethylene, n-propylene, n-pentylene or n-hexylene) or C.sub.7-C.sub.22 alkylene; R.sub.71, R.sub.72, R.sub.73, R.sub.74 and R.sub.75 are each independently C.sub.1-C.sub.6 alkyl such as methyl, ethyl, n-propyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl; q is 0, 1, 2, 3, 4, 5, or 6; A is an anion such as a halide and Z is N. For example, the quaternary ammonium or phosphonium compound can have formula:

    ##STR00071##

    [0223] The alkylating agent used in the any of the methods described herein can comprise a nitrogen-containing heterocyclic group such as 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, caprolactam, or any combination thereof, wherein each substituent is independently alkyl, alkenyl, alkynyl, aryl, or aralkyl.

    [0224] The nitrogen-containing heterocycle can comprise an imidazolium having the formula (7):

    ##STR00072##

    wherein: R.sub.81, R.sub.82, R.sub.83, R.sub.84 and R.sub.86 are each independently optionally substituted alkyl, alkenyl, alkynyl, or aryl; L is Cl, Br or I; and A.sup.?is an anion. Preferably, R.sub.84 is 2,4,6-alkylphenyl, and R.sub.81, R.sub.82, R.sub.83 and R.sub.86 are each independently C.sub.1-C.sub.6 alkyl, L is Br or I, A.sup.? is a halide.

    [0225] Preferably, the imidazolium compound has formula (7C):

    ##STR00073##

    [0226] An anion exchange membrane, optionally configured and sized to be suitable for use in a fuel cell, electrolyzer, electrodialyzer, solar hydrogen generator, flow battery, desalinator, sensor, demineralizer, water purifier, waste water treatment system, ion exchanger, or CO.sub.2 separator, and comprising any of the anion exchange polymers as described herein is provided.

    [0227] A reinforced electrolyte membrane such as a reinforced anion exchange membrane is also provided to increase the mechanical robustness of the anion exchange membrane for stability through numerous wet and dry cycles. The reinforced membrane comprises a porous substrate impregnated with any of the anion exchange polymers as described herein. Methods for preparing reinforced membranes are well known to those of ordinary skill in the art such as those disclosed in U.S. Patent Nos. RE37,656 and RE37,701 , which are incorporated herein by reference for their description of reinforced membrane synthesis and materials.

    [0228] A reinforced ion exchange membrane including any polymer membrane of the invention can be optionally configured and sized to be suitable for use in a fuel cell, electrolyzer, electrodialyzer, solar hydrogen generator, flow battery, desalinator, sensor, demineralizer, water purifier, waste water treatment system, ion exchanger, or CO.sub.2 separator.

    [0229] The porous substrate of the reinforced electrolyte membrane can comprise a membrane comprised of polytetrafluoroethylene, polypropylene, polyethylene, poly(ether) ketone, polyaryletherketone, imidazole-tethered poly(aryl alkylene), imidazolium-tethered poly(aryl alkylene), polysulfone, perfluoroalkoxyalkane, or a fluorinated ethylene propylene polymer, and the membrane is optionally a dimensionally stable membrane.

    [0230] The porous substrate of the reinforced electrolyte membrane can have at least one of the following: [0231] the porous substrate has a porous microstructure of polymeric fibrils; [0232] an interior volume of the porous substrate is rendered substantially occlusive by impregnation with the polymer; [0233] the porous substrate comprises a microstructure of nodes interconnected by fibrils; [0234] the porous substrate has a thickness from about 1 micron to about 100 microns; [0235] the membrane is prepared by multiple impregnations of the substrate with the polymer; or [0236] the membrane is 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 or suspension; [0237] applying the solution or suspension onto the wetted substrate to form the reinforced membrane; and drying the membrane.

    [0238] The porous substrate can have a thickness from about 1 micron to about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100 microns. Preferably, the porous substrate has a thickness from about 5 microns to about 30 microns, or from about 7 microns to about 20 microns.

    EXAMPLES

    [0239] The following non-limiting examples are provided to further illustrate the present invention.

    Example 1

    [0240] A non-crosslinked poly(aryl piperidinium) was prepared from N-methyl-4-piperidone, p-terphenyl, 4-acetylpyridine and optional 2,2,2-Trifluoroacetophenone. (referred to as P1-Me-x-a, wherein x is the mole ratio of N-methyl-4-piperidone to p-terphenyl and is from 0.01 to 0.99, a is the mole ratio of the quaternized 4-acetylpyridine to p-terphenyl and is from 0 to 0.99). P1-Me-x-a was prepared by three major steps: (1) synthesis of a piperidine-functionalized polymer, (2) synthesis of a piperidinium-functionalized polymer, and (3) membrane casting and hydroxide ion exchange. The reaction scheme is depicted below:

    [0241] (1) Synthesis of a Piperidine-Functionalized Polymer, P1-Neutral-0.85 (i.e. x=0.85). To a 100 mL three-necked flask equipped with overhead a mechanical stirrer, N-methyl-4-piperidone (0.962 g, 8.5 mmol), 4-acetylpyridine (0.218 g, 1.8 mmol) and p-terphenyl (2.303 g, 10 mmol) were suspended into methylene chloride (9 mL). Trifluoromethanesulfonic acid (TFSA) (9 mL) were then added dropwise over 30 minutes at lower than ?10? C. Thereafter, the reaction was continued at 0? C. temperature for 12 hours and then continued the reaction for another 24 h at 25? C. The resulting viscous solution was poured slowly into ethanol. The light yellow fibrous solid was filtered, washed with water and immersed in 1 M KOH at room temperature for 12 hours. Finally, the white fibrous product was filtered, washed with water and dried completely at 60? C. under vacuum. The yield of the polymer was nearly 100%. 1HNMR (0.7 ml CDCl3; ?, ppm): 8.55 (H9), 7.70-7.37 (H1, H2, H3, H1, H2 and H3) 7.23-7.13 (H8), 2.77-2.71 (H4 and H5), and 2.41(H6), 2.25 (H7) (see FIG. 2).

    [0242] (2) Synthesis of Piperidinium-Functionalized Polymer, P1-Me-0.85-0.15 (i.e. x=0.85, a=0.15). To a 50 mL one-necked flask equipped with magnetic bar, piperidine-functionalized polymer (1.0 g) was dissolved into 1-methyl-2-pyrrolidinone (10 mL). Methyl iodide (0.5 mL) was added to the mixture quickly. The solution was stirred over 12 hours at room temperature. The resulting viscous, yellow solution was added dropwise into ether. The yellow solid was filtered, washed with ether and dried completely at 60? C. under vacuum. The yield of the polymer P1-Me-0.85-0.15 was almost 100%. 1HNMR (DMSO-d6; ?, ppm): 8.94 (H9), 7.88 (H8), 7.76-7.60 (H1, H2, H3, H1and H3), 7.27 (H2), 4.35 (H10), 3.41 (H5), 3.20 (H6), 2.87 (H4), 2.30 (H7) (see FIG. 3).

    [0243] (3) Membrane Casting and Hydroxide Exchange. A membrane was prepared by dissolving the P1-Me-0.85-0.15 polymer (1.0 g) in NMP (10 mL) and by casting on a clear glass plate at 80? C. for 8 hours. The membrane (in iodide form) was peeled off from the glass plate in contact with deionized (DI) water. The membrane in hydroxide form were obtained by ion exchange in 1 M KOH at 60? C. for 24 hours, followed by washing and immersing the membrane in DI water for 48 hours under argon to remove residual KOH.

    [0244] Other P1-A-x-a membranes were prepared by using different mole ratios of N-methyl-4-piperidone and 4-acetylpyridine to p-terphenyl.

    ##STR00074##

    Example 2

    [0245] Crosslinked polymer based on the P1-Neutral-x piperidine-functionalized polymer.

    [0246] A crosslinked poly(aryl piperidinium) was prepared from N-methyl-4-piperidone, p-terphenyl, 4-acetylpyridine and optional 2,2,2-Trifluoroacetophenone. (referred to as P1-Me-x(b)-XL-c, wherein x is the mole ratio of N-methyl-4-piperidone to p-terphenyl and is from 0.01 to 0.99, b is the mole ratio of the methyl iodide-quaternized piperidine to p-terphenyl and is from 0.01 to 0.99, c is the mole ratio of crosslinking reagent-quaternized piperidine to p-terphenyl and is from 0.01 to 0.99). P1-Me-x(b)-XL-c was prepared by three major steps: (1) synthesis of a piperidine-functionalized polymer, (2) synthesis of a partially quaternized piperidinium-functionalized polymer, and (3) membrane casting with a crosslinking reagent and hydroxide ion exchange. The reaction scheme is depicted below:

    [0247] (1) Synthesis of a Piperidine-Functionalized Polymer, P1-Neutral-0.85 (i.e. x=0.85) To a 100 mL three-necked flask equipped with overhead a mechanical stirrer, N-methyl-4-piperidone (0.962 g, 8.5 mmol), 4-acetylpyridine (0.218 g, 1.8 mmol) and p-terphenyl (2.303 g, 10 mmol) were suspended into methylene chloride (9 mL). Trifluoromethanesulfonic acid (TFSA) (9 mL) were then added dropwise over 30 minutes at lower than ?10? C. Thereafter, the reaction was continued at 0? C. temperature for 12 hours and then continued the reaction for another 24 h at 25? C. The resulting viscous solution was poured slowly into ethanol. The light yellow fibrous solid was filtered, washed with water and immersed in 1 M KOH at room temperature for 12 hours. Finally, the white fibrous product was filtered, washed with water and dried completely at 60? C. under vacuum. The yield of the polymer was nearly 100%. 1HNMR (0.7 ml CDCl3; ?, ppm): 8.55 (H9), 7.70-7.37 (H1, H2, H3, H1, H2 and H3) 7.23-7.13 (H8), 2.77-2.71 (H4 and H5), and 2.41(H6), 2.25 (H7) (see FIG. 1).

    [0248] (2) Synthesis of the partially quaternized Piperidinium-Functionalized Polymer, P1-Me-0.85(0.75) (i.e. x=0.85, b=0.75,) To a 50 mL one-necked flask equipped with magnetic bar, piperidine-functionalized polymer (1.0 g) was dissolved into 1-methyl-2-pyrrolidinone (10 mL). Methyl iodide (0.17 mL) was added to the mixture quickly to partially quaternized the piperidine. The solution was stirred over 12 hours at room temperature. The resulting viscous, yellow solution was added dropwise into ether. The yellow solid was filtered, washed with ether and dried completely at 60? C. under vacuum. The yield of the polymer P1-Me-0.85(0.75) was almost 100%.

    [0249] (3) Membrane Casting and Hydroxide Exchange, P1-Me-0.85(0.75)-XL-0.10 (i.e. x=0.85, b=0.75, c=0.10) The crosslinked membrane was prepared by dissolving the P1-Me-0.85(0.75) polymer (1.0 g) and 1,6-dibromohexane (26.4 mg) in NMP (10 mL) and by casting on a clear glass plate at 80? C. for 8 hours. The membrane was peeled off from the glass plate in contact with deionized (DI) water. The membrane in hydroxide form were obtained by ion exchange in 1 M KOH at 60? C. for 24 hours, followed by washing and immersing the membrane in DI water for 48 hours under argon to remove residual KOH.

    [0250] Other P1-Me-x(b)-XL-c membranes were prepared by using different mole ratios of N-methyl-4-piperidone, 4-acetylpyridine to p-terphenyl and different amount of methyl iodide and 1,6-dibromohexane.

    ##STR00075##

    Example 3

    [0251] Polymers prepared from a mixture of piperidone, p-terphenvyl, 2,2,2-Trifluoroscatophenone. Isatin and optional 4-acetylpyridine monomers. The synthesis of the polymer is similar to the procedure described in example 1.

    ##STR00076##

    Example 4

    [0252] Crosslinked polymer based on the P2-Neutral piperidine-functionalized polymer. The synthesis of the polymer is similar to the procedure described in example 2.

    ##STR00077##

    Example 5

    [0253] Polymers prepared from a mixture of piperidone, p-terphenyl, 4-acetylpyridine, Isatin and optional 2,2,2-Trifluoroacetophenone monomers. The synthesis of the polymer is similar to the procedure described in example 1.

    ##STR00078##

    Example 6

    [0254] A crosslinked polymer based on the P3-Neutral piperidine-functionalized polymer. The synthesis of the polymer is similar to the procedure described in example 2.

    ##STR00079##

    Example 7

    [0255] A non-crosslinked polymer prepared from a mixture of piperidone, p-terphenyl, optional 2,2,2-Trifluoroacetophenone and optional 4-acetylpyridine monomers. The synthesis of the polymer is similar to the procedure described in example 1

    ##STR00080##

    Example 8

    [0256] A crosslinked polymer prepared from a mixture of piperidone, p-terphenyl, optional 2,2,2-Trifluoroacetophenone and optional 4-acetylpyridine monomer. The synthesis of the polymer is similar to the procedure described in example 2.

    ##STR00081## ##STR00082##

    [0257] Crosslinked polymers, P4-1(0.85)-XL-(0.05), P4-1(0.85)-XL-(0.10), P4-1(0.85)-XL-(0.15), were prepared from P4-Neutral. The properties of the crosslinked polymers are summarized in the table below showing the decreased swelling ratio, decreased water uptake and increased conductivity with increased crosslinking.

    TABLE-US-00001 Conductivity (OH) Water Swelling mS/cm IEC.sup.Cl, uptake ratio, @ 80 C., polymer membrane mmol/g.sup.1 at 80 C..sup.2 80 C..sup.2 100% RH P4-1(0.85)-XL-(0) 2.45 83% 14% 212 P4-1(0.85)-XL-(0.11) 2.67 65% 11% 235 P4-1(0.85)-XL-(0.15) 2.81 42% 7% 264 .sup.1IEC was obtained with titration of the chloride form membrane .sup.2Membrane was in bicarbonate form

    Example 9

    [0258] A non-crosslinked polymer prepared from a mixture of piperidone, p-terphenyl, 4-acetylpyridine and optional 2,2,2-Trifluoroacetophenone. The synthesis of the polymer is similar to the procedure described in example 1.

    ##STR00083## ##STR00084##

    Example 10

    [0259] A crosslinked polymer prepared from P5-Neutral-x. The synthesis of the polymer is similar to the procedure described in example 2.

    ##STR00085## ##STR00086##

    Example 11

    [0260] A crosslinked polymer prepared from a mixture of piperidone, p-biphenyl, and optional 2,2,2-Trifluoroacetophenone. The synthesis of the polymer is similar to the procedure described in example 1.

    ##STR00087## ##STR00088##

    [0261] Crosslinked polymers, P11-1(0.76)-XL-(0), P11-1(0.76)-XL-(0.1), P11-1(0.76)-XL-(0.25), having 0, 10% and 25% degree of crosslinking, respectively, were prepared from P11-Neutral-x. The properties of the crosslinked polymers are summarized in the table below showing the decreased swelling ratio, decreased water uptake and increased conductivity with increased crosslinking.

    TABLE-US-00002 Conductivity (OH) Water Swelling mS/cm IEC.sup.Cl, uptake ratio, @ 80 C., polymer membrane mmol/g.sup.1 at 80 C..sup.2 80 C..sup.2 100% RH P11-1(0.76)-XL-(0) 2.2 459% 48% 200 P11-1(0.76)-XL-(0.1) 2.4 226% 26% 220 P11-1(0.76)-XL-(0.25) 2.6 190% 23% 270 .sup.1IEC was obtained with titration of the chloride form membrane .sup.2Membrane was in bicarbonate form

    DEFINITIONS

    [0262] The term suitable substituent, as used herein, is intended to mean a chemically acceptable functional group, preferably a moiety that does not negate the activity of the inventive compounds. Such suitable substituents include, but are not limited to halo groups, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroaralkyl groups, aralkoxy or heteroaralkoxy groups, HO(C?O) groups, heterocylic groups, cycloalkyl groups, amino groups, alkyland dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylamino carbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, and arylsulfonyl groups. Those skilled in the art will appreciate that many substituents can be substituted by additional substituents.

    [0263] The term alkyl, as used herein, refers to a linear, branched or cyclic hydrocarbon radical, 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 groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, secondary-butyl, and tertiary-butyl. Alkyl groups can be unsubstituted or substituted by one or more suitable substituents.

    [0264] The term alkenyl, as used herein, refers to a straight, branched or cyclic hydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbons, more preferably having 1 to 18 carbon atoms, and having one or more carbon-carbon double bonds. Alkenyl groups include, but are not limited to, ethenyl, 1-propenyl, 2-propenyl (allyl), iso-propenyl, 2-methyl-1-propenyl, 1-butenyl, and 2-butenyl. Alkenyl groups can be unsubstituted or substituted by one or more suitable substituents, as defined above.

    [0265] The term alkynyl, as used herein, refers to a straight, branched or cyclic hydrocarbon radical, 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 groups include, but are not limited to, ethynyl, propynyl, and butynyl. Alkynyl groups can be unsubstituted or substituted by one or more suitable substituents, as defined above.

    [0266] The term aryl or ar, as used herein alone or as part of another group (e.g., aralkyl), means monocyclic, bicyclic, or tricyclic aromatic radicals such as phenyl, naphthyl, tetrahydronaphthyl, indanyl and the like; optionally substituted by one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above. The term aryl also includes heteroaryl.

    [0267] Arylalkyl or aralkyl means an aryl group attached to the parent molecule through an alkylene group. The number of carbon atoms in the aryl group and the alkylene group is selected such that there is a total of about 6 to about 18 carbon atoms in the arylalkyl group. A preferred arylalkyl group is benzyl.

    [0268] The term cycloalkyl, as used herein, refers to a mono, bicyclic or tricyclic carbocyclic radical (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclopentenyl, cyclohexenyl, bicyclo[2.2.1]heptanyl, bicyclo[3.2.1 ]octanyl and bicyclo[5.2.0]nonanyl, etc.); optionally containing 1 or 2 double bonds. Cycloalkyl groups can be unsubstituted or substituted by one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.

    [0269] The term -ene as used as a suffix as part of another group denotes a bivalent radical in which a hydrogen atom is removed from each of two terminal carbons of the group, or if the group is cyclic, from each of two different carbon atoms in the ring. For example, alkylene denotes a bivalent alkyl group such as ethylene (CH.sub.2CH.sub.2) or isopropylene (CH(CH.sub.3)CH.sub.2). For clarity, addition of the -ene suffix is not intended to alter the definition of the principal word other than denoting a bivalent radical. Thus, continuing the example above, alkylene denotes an optionally substituted linear saturated bivalent hydrocarbon radical.

    [0270] The term hydrocarbon as used herein describes a compound or radical consisting exclusively of the elements carbon and hydrogen.

    [0271] The term polycycle as used herein describes a compound or radical having two or more hydrocarbon rings which can be substituted with heteroatom(s) such as nitrogen or oxygen. The polycycle can be aromatic or non-aromatic.

    [0272] The term substituted means that in the group in question, at least one hydrogen atom bound to a carbon atom is replaced with one or more substituent groups 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), an ether (-ORA wherein RA is alkyl or aryl), an ester (OC(O)RA wherein RA is alkyl or aryl), keto ((O)RA wherein RA is alkyl or aryl), heterocyclo, and the like. When the term substituted introduces or follows a list of possible substituted groups, it is intended that the term apply to every member of that group. That is, the phrase optionally substituted alkyl or aryl is to be interpreted as optionally substituted alkyl or optionally substituted aryl. Likewise, the phrase alkyl or aryl optionally substituted with fluoride is to be interpreted as alkyl optionally substituted with fluoride or aryl optionally substituted with fluoride.

    [0273] The term tethered means that the group in question is bound to the specified polymer backbone. For example, an imidazolium-tethered poly (aryl alkylene) polymer is a polymer having imidazolium groups bound to a poly (aryl alkylene) polymer backbone.

    [0274] When introducing elements of the present invention or the preferred embodiments(s) 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.

    [0275] In view of the above, it will be seen that the several objects of the invention are achieved, and other advantageous results attained.

    [0276] 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.