ANION EXCHANGE POLYMERS CAPABLE OF CONTROLLED CROSSLINKING

Abstract

Polymers based on poly(aryl alkylene) that are capable of crosslinking in a controlled manner are provided. Crosslinked anion exchange membranes or anion exchange ionomers formed from these polymers not only have superior chemical stability and hydroxide conductivity but also have decreased water uptake and improved mechanical stability.

Claims

1. A crosslinkable anion exchange polymer comprising: structural units of formulae 1A, 1A-2, 3A, optionally 2A and optionally 6A wherein a sum of mole fractions of the structural units of formulae 1A, 1A-2, 2A and 6A is equal to a sum of a mole fraction of formulae 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 6A to the structural unit of Formula 3A is from 0.01 to 1 calculated from the amount of monomers used in the polymerization reaction; or structural units of formulae 1A, 1A-2, 3A, 4A, optionally 2A and optionally 6A wherein a sum of mole fractions of the structural units of formulae 1A, 1A-2, 2A, 4A and 6A is equal to a sum of 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 or 6A 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, 4A and 6A have the structures: ##STR00030## wherein: A.sup. and A.sub.2.sup. are each independently an anion; L is Cl, Br or I; n are each independently 0, 1, 2 or 3; q is 0, 1, 2, 3, 4, 5 or 6; R.sub.10 and R.sub.12 are each independently, alkyl, alkenyl, alkynyl or aryl; R.sub.11 is each independently halide substituted alkyl, alkenyl, alkynyl, aryl, or 5A having structure: ##STR00031## 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; 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.72, R.sub.73, R.sub.74 and R.sub.75 are each independently alkyl, alkenyl, alkynyl or aryl; R.sub.100 is each independently alkyl, alkenyl, alkynyl, or ##STR00032## and the alkyl, alkenyl, or alkynyl are optionally substituted with fluoride; each R.sub.101 is independently 2B or 3B having structure: ##STR00033## 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; X is N, S or O; Y is C or N; and Z is N or P.

2. A polymer comprising a reaction product of a mixture comprising: an acid, a reagent having formula 5 and a polymer comprising structural units of formulae 1, 3A, optionally 1A-3, optionally 2A, and optionally 6A wherein a sum of mole fractions of the structural units of formulae 1, 2A, 1A-3 and 6A is equal to a sum of 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 1 or 1A-3 or 2A or 6A 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 a mole ratio of the acid or reagent of formula 5 to the structural unit of formula 1 in the polymer is from 0.01 to 0.99; or an acid, a reagent having formula 5 and a polymer comprising structural units of formulae 1, 3A, 4A, optionally 1A-3, optionally 2A, and optionally 6A wherein a sum of mole fractions of the structural units of formulae 1, 1A-3, 2A, 4A and 6A is equal to a sum of 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 1 or 1A-3 or 2A or 4A or 6A 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 a mole ratio of the acid or reagent of formula 5 to the structural unit of formula 1 in the polymer is from 0.01 to 0.99; and the structural units of Formulae 1, 1A-3, 2A, 3A, 4A, 5 and 6A have the structures: ##STR00034## wherein: A.sup. is an anion; n are each independently 0, 1, 2 or 3; q is 0, 1, 2, 3, 4, 5 or 6; L.sub.1 and L.sub.2 are each independently Cl, Br, I, a tosylate, a mesylate, or a triflate; R.sub.10 is independently alkyl, alkenyl, alkynyl or aryl; R.sub.13 is independently hydrogen, alkyl, alkenyl, alkynyl or aryl; 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, Rao, 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; 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.72, R.sub.73, R.sub.74 and R.sub.75 are each independently alkyl, alkenyl, alkynyl or aryl; each R.sub.100 is independently alkyl, alkenyl, alkynyl, or 1B having structure: ##STR00035## and the alkyl, alkenyl, or alkynyl are optionally substituted with fluoride; each R.sub.101 is independently 2B or 3B having structure: ##STR00036## 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; X is N, S or O; Y is C or N; and Z is N or P.

3. The polymer of claim 1, wherein; the mole ratio of a sum of the mole fractions of the structural unit of Formulae 1A, 1A-2, 2A and 6A to the mole fraction of Formula 3A in the polymer is from about 0.85:1 to about 1.4:1, and the ratio of the mole fraction of the structural unit of Formula 1A to the mole fraction of the structural unit of Formula 3A is from about 0.01 to 0.99; or the mole ratio of a sum of the mole fractions of the structural unit of Formula 1A, 1A-2, 2A and 6A to the mole fraction of Formula 3A in the polymer is from about 1:1 to about 1.2:1; or the mole ratio of a sum of the mole fractions of the structural unit of Formula 1A, 1A-2, 2A, 4A and 6A to the mole fraction of Formula 3A in the polymer is from about 0.85:1 to about 1.4:1, and the ratio of the mole fraction of the structural unit of Formula 1A to the mole fraction of the structural unit of Formula 3A is from about 0.01 to 0.99; or the mole ratio of a sum of the mole fractions of the structural unit of Formulae 1A, 1A-2, 2A, 4A and 6A to the mole fraction of Formula 3A in the polymer is from about 1:1 to about 1.2:1.

4.-6. (canceled)

7. The polymer of claim 2, wherein: the mixture comprising structural units of formulae 1, 3A, optionally 1A-3, optionally 2A, and optionally 6A, wherein; the mole ratio of a sum of the mole fractions of the structural unit of Formulae 1, 2A, 1A-3 and 6A to a mole fraction of formula 3A in the polymer is from about 0.85:1 to about 1.4:1, and the ratio of the mole fraction of the structural unit of Formula 1 to the mole fraction of the structural unit of Formula 3A is from about 0.01 to 0.99; or the mole ratio of the sum of the mole fractions of the structural units of formulae 1, 2A, 1A-3 and 6A to the mole fraction of formula 3A in the polymer is from about 1:1 to about 1.2:1; or the mixture comprising structural units of formulae 1, 3A, 4A, optionally 1A-3, optionally 2A, and optionally 6A, wherein: the mole ratio of a sum of the mole fractions of the structural unit of Formulae 1, 2A, 1A-3, 4A and 6A to a sum of the mole fraction of formula 3A in the polymer is from about 0.85:1 to about 1.4:1, and the ratio of the mole fraction of the structural unit of Formula 1 to the mole fraction of the structural unit of Formula 3A is from about 0.01 to 0.99; or the mole ratio of the sum of the mole fractions of the structural units of formulae 1, 2A, 1A-3, 4A and 6A to the sum of the mole fraction of formula 3A in the polymer is from about 1:1 to about 1.2:1.

8.-10. (canceled)

11. The polymer of claim 2, wherein the acid comprises hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, nitric acid, trifluoracetic acid, acetic acid, butyric acid, formic acid, trifluoromethanesulfonic acid or a combination thereof.

12. The polymer of claim 2, wherein: in the reagent of formula 5, A.sup. is an anion; L.sub.1 and L.sub.2 are each independently Cl, Br, I, a tosylate, a mesylate, or a triflate; q is 0, 1, 2, 3, 4, 5, or 6; R.sub.72, R.sub.74 and R.sub.75 are each independently C.sub.1-C.sub.6 alkyl; R.sub.73 is independently C.sub.1-C.sub.22 alkylene; and Z is N or P; or the reagent of formula 5 comprises 1-Bromo-6-chlorohexane, 1-chloro-6-iodoohexane, 1-bromo-6-iodoohexane, 1-Bromo-4-chlorobutane, 1-Chloro-4-iodobutane, 1-Bromo-4-chlorobutane, 1-Bromo-3-chloropropane, 1-Chloro-3-iodopropane, 1-Bromo-3-iodopropane, and preferably Reagent 5 is 1-Bromo-6-chlorohexane, 1-chloro-6-iodoohexane, 1-bromo-6-iodoohexane, 1-Bromo-4-chlorobutane, 1-Chloro-4-iodobutane, 1-Bromo-4-chlorobutane, 6-chlorohexyl methanesulfonate, 6-bromohexyl methanesulfonate, or a combination thereof.

13. (canceled)

14. The polymer of claim 1, wherein R.sub.10 and R.sub.12 of the structural units of formulae 1, 1A, 1A-2 and 1A-3 are each independently alkyl, alkenyl, alkynyl or aryl; or R.sub.10 and R.sub.12 of the structural units of formulae 1, 1A, 1A-2 and 1A-3 are each independently C.sub.1-C.sub.22 alkyl; or R.sub.10 and R.sub.12 of the structural units of formulae 1, 1A, 1A-2 and 1A-3 are each independently methyl, ethyl, n-propyl, n-butyl, isobutyl, tert-butyl, pentyl or hexyl.

15. The polymer of claim 1, wherein: R.sub.11 of formula 1A is each independently halide substituted alkyl, alkenyl, alkynyl, aryl, or formula 5A having structure: ##STR00037## wherein A.sup. is an anion; L is Cl, Br or I; q is 0, 1, 2, 3, 4, 5, or 6; R.sub.72, R.sub.74 and R.sub.75 are each independently C.sub.1-C.sub.6 alkyl; R.sub.73 is independently C.sub.1-C.sub.22 alkylene; and Z is N or P; or R.sub.11 of formula 1A is each independently halide substituted alkyl, alkenyl, alkynyl, aryl, or formula 5A having structure: ##STR00038## wherein A.sup. is an anion; L is Cl; g is 0, 1, 2, 3; R.sub.72, R.sub.74 and R.sub.75 are each independently C.sub.1-C.sub.6 alkyl; R.sub.73 is independently C.sub.1-C.sub.6 alkylene; and Z is N; or R.sub.11 of formula 1A is: ##STR00039##

16.-17. (canceled)

18. The polymer of claim 2, wherein R.sub.13 of formula 1A-3 comprises hydrogen, C.sub.1-C.sub.22 alkyl, C.sub.1-C.sub.22 alkenyl, C.sub.1-C.sub.22 alkynyl or aryl.

19. The polymer of claim 1, wherein the structural unit of formula 3A comprises ##STR00040## or a combination thereof.

20. The polymer of claim 1, wherein the structural unit of formula 6A comprises ##STR00041## or a combination thereof.

21. The polymer of claim 1, wherein A.sup. and/or A.sub.2.sup. is an anion comprising a halide, carbonate, bicarbonate, hydroxide, trifluoroacetate, acetate, triflate, methanesulfonate, sulfate, nitrate, tetrafluoroborate, hexafluorophosphate, formate, benzenesulfonate, toluate, perchlorate, benzoate or a combination thereof.

22. A method of making a crosslinked anion exchange polymer comprising: (i) reacting a reagent of formula 5, optionally an acid, and a polymer comprising structural units of formulae 1, 3A, optionally 1A-3, optionally 2A and optionally 6A or structural units of formulae 1, 3A, 4A, optionally 1A-3, optionally 2A and optionally 6A to form the crosslinkable polymer of any one of claims 1, 3-6, 14-17 and 19-21; precipitating the crosslinkable polymer; rinsing and drying the crosslinkable polymer; mixing the crosslinkable polymer and a base capable of initiating crosslinking while controlling reaction temperature and reaction time to obtain a crosslinked polymer having about 1 to 100% crosslinking; and optionally exchanging anions of the crosslinked polymer with hydroxide, bicarbonate, or carbonate ions or a combination thereof to form a crosslinked anion exchange polymer; or (ii) reacting a reagent of formula 5, optionally an acid, and a polymer comprising structural units of formulae 1, 3A, optionally 1A-3, optionally 2A and optionally 6A or structural units of formulae 1, 3A, 4A, optionally 1A-3, optionally 2A and optionally 6A to form the crosslinkable polymer of any one of claims 1, 3-6, 14-17 and 19-21; precipitating the crosslinkable polymer; rinsing and drying the crosslinkable polymer; dissolving the crosslinkable polymer in a solvent to form a polymer solution; casting a crosslinkable membrane from the polymer solution; mixing the crosslinkable membrane and a base capable of initiating crosslinking while controlling reaction temperature and reaction time to obtain a crosslinked membrane having about 1 to 100% crosslinking; and optionally exchanging anions of the crosslinked membrane with hydroxide, bicarbonate, or carbonate ions or a combination thereof to form a crosslinked anion exchange membrane.

23. (canceled)

24. A method of making a membrane electrode assembly (MEA) with crosslinked ionomer comprising: reacting a reagent of formula 5, optionally an acid, and a polymer comprising structural units of formulae 1, 3A, optionally 1A-3, optionally 2A and optionally 6A or structural units of formulae 1, 3A, 4A, optionally 1A-3, optionally 2A and optionally 6A to form the crosslinkable polymer of any one of claims 1, 3-6, 14-17 and 19-21; precipitating the crosslinkable polymer; rinsing and drying the crosslinkable polymer; dissolving the crosslinkable polymer in a solvent to form a polymer suspension; mixing the polymer suspension with a catalyst to form a catalyst ink; applying the catalyst ink to a membrane to form a MEA; drying the MEA; mixing the MEA and a base capable of initiating crosslinking while controlling reaction temperature and reaction time to obtain a crosslinked MEA having about 1 to 100% crosslinking; and optionally exchanging anions of the crosslinked MEA with hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the MEA with crosslinked ionomer.

25. The method of claim 22, wherein; the solvent comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, a pentanol, a hexanol, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, chloroform, ethyl lactate, tetrahydrofuran, N-Methyl-2-pyrrolidone, 2-methyltetrahydrofuran, water, phenol, acetone, or a combination thereof; or the base comprises a solution or suspension of KOH, NaOH, NaHCO.sub.3, KHCO.sub.3, Na.sub.2CO3, K.sub.2CO.sub.3 or a combination thereof; or the crosslinked polymer, the crosslinked membrane or the crosslinked MEA has about 2% to about 75%, about 3% to about 50%, about 4% to about 40%, about 5% to about 35%, about 5% to about 30%, about 5% to about 25%, about 5% to about 20% or about 5% to about 15% crosslinking.

26.-27. (canceled)

28. 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 CO.sub.2 separator, and comprising the polymer of claim 1.

29. 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 CO.sub.2 separator comprising the polymer of claim 1.

30. 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.

31. The membrane of claim 30, wherein the porous substrate comprises 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.

32. The membrane of claim 30, wherein either: the porous substrate has a porous microstructure of polymeric fibrils; an interior volume of the porous substrate is rendered substantially occlusive by impregnation with the polymer; the porous substrate comprises a microstructure of nodes interconnected by fibrils; the porous substrate has a thickness from about 1 micron to about 100 microns; the membrane is prepared by multiple impregnations of the substrate with the polymer; or 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; applying the solution or suspension onto the wetted substrate to form the reinforced membrane; and drying the membrane.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0049] FIG. 1A illustrates an exemplary anion exchange membrane or hydroxide exchange membrane fuel cell;

[0050] FIG. 1B illustrates an exemplary anion exchange membrane or hydroxide exchange membrane electrolyzer;

[0051] FIG. 2 depicts a 1HNMR spectrum of TP-1-CI-0.8 in DMSO-d6;

[0052] FIG. 3 depicts how the crosslinked membrane swells in DMSO; and

[0053] FIG. 4 is a graph of water uptake percentage in DI water as a function of temperature from 20 C. to 80 C. for crosslinked and non-crosslinked membranes.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0054] Herein, a series of anion exchange polymers were prepared, and the membranes and MEA were crosslinked under a controlled manner in that the crosslinking was triggered simply by introduction of an alkaline solution to the polymer without addition of a crosslinking reagent. Crosslinked AEMs/AEIs showed reduced swelling, water uptake and increased conductivity.

[0055] AEMs/AEIs formed from poly(aryl alkylene) polymers with various pendant piperidinium-functionalized groups and having intrinsic hydroxide conduction channels have been discovered which simultaneously provide improved chemical stability, conductivity, water uptake, good solubility in selected solvents, mechanical properties, and other attributes relevant to HEM/HEI performance. The inventive polymers and membranes are capable of crosslinking in an alkaline solution or suspension to form crosslinked polymers and membranes that further enhance their conductivity, water uptake, mechanical stability at relatively high temperatures.

[0056] The first through fourth aspects of the invention are described in the summary above.

[0057] In the first aspect, the polymer can comprise the structural units of formulae 1A, 1A-2 and 3A; or 1A, 1A-2, 3A and 2A; or 1A, 1A-2, 3A and 6A; or 1A, 1A-2, 3A, 2A and 6A.

[0058] In the second aspect, the polymer can comprise the structural units of formulae 1A, 1A-2, 3A and 4A; or 1A, 1A-2, 3A, 4A and 2A; or 1A, 1A-2, 3A, 4A and 6A; or 1A, 1A-2, 3A, 4A, 2A and 6A.

[0059] In the first aspect of the invention, the mole ratio of a sum of the mole fractions of the structural unit of Formulae 1A, 1A-2, 2A and 6A to a sum of the mole fraction of Formula 3A in the polymer can be from about 0.85:1 to about 1.4:1, and the ratio of the mole fraction of the structural unit of Formula 1A to the mole fraction of the structural unit of Formula 3A can be from about 0.01 to 0.99. Alternatively, the mole ratio of a sum of the mole fractions of the structural unit of Formulae 1A, 1A-2, 2A and 6A to the mole fraction of Formulae 3A in the polymer can be from about 1:1 to about 1.2:1.

[0060] In the second aspect of the invention, the mole ratio of a sum of the mole fractions of the structural unit of Formulae 1A, 1A-2, 2A, 4A and 6A to the mole fraction of Formula 3A in the polymer can be from about 0.85:1 to about 1.4:1, and the ratio of the mole fraction of the structural unit of Formula 1A to the mole fraction of the structural unit of Formula 3A can be from about 0.01 to 0.99. Alternatively, the mole ratio of a sum of the mole fractions of the structural unit of Formulae 1A, 1A-2, 2A, 4A and 6A to the mole fraction of Formulae 3A in the polymer can be from about 1:1 to about 1.2:1.

[0061] Regarding the polymer in the reaction mixture in the third aspect of the invention, the mole ratio of a sum of the mole fractions of the structural unit of Formulae 1, 1A-3, 2A and 6A to a sum of the mole fraction of Formula 3A in the polymer can be from about 0.85:1 to about 1.4:1, and the ratio of the mole fraction of the structural unit of Formula 1A to the mole fraction of the structural unit of Formula 3A can be from about 0.01 to 0.99. Alternatively, the mole ratio of a sum of the mole fractions of the structural unit of Formulae 1, 1A-3, 2A and 6A to the mole fraction of Formula 3A in the polymer can be from about 1:1 to about 1.2:1.

[0062] Regarding the polymer in the fourth aspect of the invention, the mole ratio of a sum of the mole fractions of the structural unit of Formulae 1, 1A-3, 2A, 4A and 6A to the mole fraction of Formulae 3A in the polymer can be from about 0.85:1 to about 1.4:1, and the ratio of the mole fraction of the structural unit of Formula 1A to the mole fraction of the structural unit of Formula 3A can be from about 0.01 to 0.99. Alternatively, the mole ratio of a sum of the mole fractions of the structural unit of Formula 1, 1A-3, 2A, 4A and 6A to the mole fraction of Formulae 3A in the polymer can be from about 1:1 to about 1.2:1.

[0063] R.sub.11 of the structural unit of formula 1A of any anion exchange polymers described herein can comprise halide substituted alkyl, alkenyl, alkynyl, aryl, or 5A having structure:

##STR00010##

[0064] Preferably, in the compound of formula 5A, R.sub.73 is independently C.sub.1-C.sub.22 alkylene; R.sub.72, 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; L is Cl, Br or I; and A.sup. is an anion.

[0065] Alternatively, in the compound of formula 5A, R.sub.73 is independently C.sub.1-C.sub.6 alkylene; R.sub.72, 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; L is Cl, Br or I; and A.sup. is an anion.

[0066] For example, formula 5A can have the structure:

##STR00011##

or a combination thereof.

[0067] R.sub.10 and R.sub.12 of the structural unit of formulae 1A, 1, 1A-3 and 1A-2 of any of the anion exchange polymers described herein can comprise alkyl, alkenyl, alkynyl or aryl.

[0068] R.sub.10 and R.sub.12 can be each independently C.sub.1-C.sub.22 alkylene and preferably, R.sub.10 and R.sub.12 is each independently C.sub.1-C.sub.6 alkylene.

[0069] The structural unit of formula 2A can be:

##STR00012##

wherein: each R.sub.101 is independently

##STR00013##

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; R.sub.104 is hydrogen, halide, alkyl, alkenyl, alkynyl or aryl, and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide; X is N, S or O; and 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.

[0070] The structural unit of formula 3A can be:

##STR00014##

wherein R.sub.20, R.sub.30, R.sub.40, R.sub.50, R.sub.60, R.sub.70, R.sub.80, and Roo 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.

[0071] The structural unit of formula 3A can comprise, for example, any of the following structures:

##STR00015##

or any combination thereof.

[0072] The structural unit of formula 4A can be:

##STR00016##

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

##STR00017##

and
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.

[0073] The structural unit of formula 6A can be:

##STR00018##

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.

[0074] The polycycle can have two or more hydrocarbon rings which can be substituted with heteroatoms such as nitrogen or oxygen.

[0075] The polycycle can be aromatic or non-aromatic.

[0076] Preferably, the structural unit of formula 6A is derived from isatin, 5-bromoisatin, 5-methylisatin, 5-nitroisatin, acenaphthenequinone, benzil or 9,10-phenanthrenequinone. For example, the structural units of formula 6A can be:

##STR00019##

or any combination thereof.

[0077] The anion A.sup. and A.sub.2.sup. of the structural units 1A, 1A-2, 1A-3 or 5A can comprise a halide, carbonate, bicarbonate, hydroxide, trifluoroacetate, acetate, triflate, methanesulfonate, sulfate, nitrate, tetrafluoroborate, hexafluorophosphate, formate, benzenesulfonate, toluate, perchlorate, benzoate or any combination thereof.

[0078] The acid used in the third and fourth aspects of the invention can comprise hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, nitric acid, trifluoracetic acid, acetic acid, butyric acid, formic acid, trifluoromethanesulfonic acid or any combination thereof.

[0079] Preferably, the acid used in the third and fourth aspects of the invention is hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, nitric acid, trifluoracetic acid or any combination thereof.

[0080] Reagent 5 used in the third and fourth aspects of the invention has structure:

##STR00020##

wherein R.sub.73 is independently C.sub.1-C.sub.22 alkylene; R.sub.72, 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; L.sub.1 and L.sub.2 are each independently Cl, Br, I, a tosylate, a mesylate, or a triflate; and A is an anion.

[0081] Preferably, in the reagent of formula 5, R.sub.73 is independently C.sub.1-C.sub.6 alkylene; R.sub.72, 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; L.sub.1 and L.sub.2 are each independently Cl, Br or I; and A.sup. is an anion.

[0082] Reagent of formula 5 used in the third and fourth aspects of the invention can comprise 1-Bromo-6-chlorohexane, 1-chloro-6-iodoohexane, 1-bromo-6-iodoohexane, 1-Bromo-4-chlorobutane, 1-Chloro-4-iodobutane, 1-Bromo-4-chlorobutane, 1-Bromo-3-chloropropane, 1-Chloro-3-iodopropane, 1-Bromo-3-iodopropane, or any combination thereof. Preferably, reagent of formula 5 is 1-Bromo-6-chlorohexane, 1-chloro-6-iodoohexane, 1-bromo-6-iodoohexane, 1-Bromo-4-chlorobutane, 1-Chloro-4-iodobutane, or 1-Bromo-4-chlorobutane.

[0083] The methods of making the polymers, membranes, and MEAs are described in the summary above.

[0084] The temperature for the crosslinking reaction in the methods described above can range from 0 C. to 100 C.

[0085] The crosslinking reaction time in the methods described above can range from 0.1 h to 100 h.

[0086] One of ordinary skill in the art would know how to vary the temperature and reaction time to obtain a desired degree of crosslinking using the methods as described herein.

[0087] Using any of the methods described herein, the crosslinked polymer, the crosslinked membrane or the crosslinked MEA can have about 1% to about 100%, about 1% to about 90%, about 1% to about 80%, about 2% to about 75%, about 2% to about 60%, about 3% to about 50%, about 4% to about 40%, about 5% to about 35%, about 5% to about 30%, about 5% to about 25%, about 5% to about 20% or about 5% to about 15% crosslinking.

[0088] The base used to crosslink the polymer, ionomer in the MEA or membrane described in the methods above can be KOH, NaOH, NaHCO.sub.3, KHCO3, Na2CO3, K2CO3 or any combination of thereof.

[0089] A crosslinked anion exchange membrane is also provided, 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 the anion exchange membrane comprising any of the anion exchange polymers as described above.

[0090] A crosslinked anion exchange membrane 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 is also provided, the 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 is provided, comprising any of the anion exchange polymers as described above.

[0091] Also provided is a reinforced and crosslinked 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 CO.sub.2 separator. The membrane comprises a porous substrate impregnated with any of the crosslinked anion exchange polymers as described above.

[0092] 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 CO2 separator, and comprising any of the anion exchange polymers as described herein is provided.

[0093] 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. Pat. Nos. RE37,656 and RE37,701, which are incorporated herein by reference for their description of reinforced membrane synthesis and materials.

[0094] 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 CO2 separator.

[0095] The porous substrate of the reinforced electrolyte membrane can comprise a 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.

[0096] The porous substrate of the reinforced electrolyte membrane can have at least one of the following: [0097] the porous substrate has a porous microstructure of polymeric fibrils; [0098] an interior volume of the porous substrate is rendered substantially occlusive by impregnation with the polymer; [0099] the porous substrate comprises a microstructure of nodes interconnected by fibrils; [0100] the porous substrate has a thickness from about 1 micron to about 100 microns; [0101] the membrane is prepared by multiple impregnations of the substrate with the polymer; or 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; [0102] applying the solution or suspension onto the wetted substrate to form the reinforced membrane; and drying the membrane.

[0103] 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

[0104] The following non-limiting examples are provided to further illustrate the present invention. In the reaction schemes in the examples, the symbol in any of the crosslinked polymer structures indicates that the depicted structural unit is crosslinked to another such structural unit not shown in the reaction scheme. For example, in scheme 1, TP-n-XL-y includes such a crosslinked structural unit shown as follows:

##STR00021##

Example 1

[0105] A crosslinkable polymer TP-n-CI-m and its crosslinked form was prepared from TP-n-Neu polymer (N is from 10 to 10000; n is from 0.1 to 1; m is from 0.1 to 1; x is from 0.1 to 1; y is from 0.1 to 1, z is from 0.01 to 0.1) was depicted in scheme 1. As an example, detailed synthesis of TP-1-CI-0.8 (n=1, m=0.8) and its crosslinking procedure was described below.

##STR00022##

[0106] (1) Synthesis of a crosslinkable polymer TP-1-CI-0.8. To a 300 ml three-neck flask equipped with an overhead stirrer, TP-1-Neu (10 g), 1-bromo-6-chlorohexane (22.926 ml, 153.63 mmol) and dimethyl sulfoxide (150 ml) were added at room temperature and then the mixture was mixed at 800 rpm. The mixture turned transparent after 4 hours, and trifluoracetic acid (6.1 mmol) was added. Thereafter, the reaction continued at room temperature for 16 hours. The resulting transparent and yellow solution was added dropwise into a solution of sodium chloride to precipitate white to pale yellow pellets of TP-1-CI-0.8 resin. The resin was washed thoroughly with ethanol and DI water to remove solvent and chemical residues. Finally, the yellow resin product was filtered and dried completely at 80 C. in an oven. The yield of polymer is 96%. .sup.1H NMR (DMSO-d6, , ppm): 3.54 (H.sub.9), 3.49 (H.sub.2), 3.42-3.35 (H.sub.2 and H.sub.4), 3.15 (H.sub.2), 3.08 (H.sub.3), 2.90 (H.sub.1), 2.78 (H.sub.1), 2.74 (H.sub.3), 2.37 (H.sub.1), 1.67, 1.66 (H.sub.5 and H.sub.8), 1.39 (H.sub.6), and 1.25 (H.sub.7). (FIG. 2). TP-1-CI-0.4 and TP-0.85-CI-0.6 can be synthesized following a similar procedure.

[0107] (2) Crosslinking of TP-1-CI-0.8 in an alkaline solution. 1 g of TP-1-CI-0.8 was first dissolved in 10 mL of DSMO and then a 44 inch membrane was cast with the solution at 80 C. This membrane was not crosslinked at this point. Then the membrane was immersed in 1M NaOH at 60 C. for 6-24 hours to finish the crosslinking (XL) of the membrane. Crosslinking degree was determined by a titration process, and it can be manipulated between 5% to 15% with the duration of soaking in the NaOH solution. FIG. 4 shows the 15% crosslinked (XL) membrane TP-1-XL-0.15 swells but not dissolves in DMSO as a sign of successful crosslinking. FIG. 5 shows that the TP-1-XL-0.15 membrane (bicarbonate form) had a much lower water uptake ratio than the non-XL membrane ((bicarbonate form)) in DI water from 20 C. to 80 C. Trimethylamine can be optionally added to quaternize all the unreacted Chloro groups in the crosslinked membrane to form TP-1-XL-0.15-TMA.

Example 2

[0108] A crosslinkable polymer BP-n-CI-m and its crosslinked form was prepared from BP-n-Neu polymer (N is from 10 to 10000; n is from 0.1 to 1; m is from 0.1 to 1; x is from 0.1 to 1; y is from 0.1 to 1, z is from 0.01 to 0.1) was depicted in scheme 2. As an example, detailed preparation of BP-1-CI-0.33 (n=1, m=0.33) and its crosslinked membrane BP-1-CI-XL-0.24 (n=1, y=0.24) was described below.

##STR00023##

[0109] (1) Synthesis of a crosslinkable polymer BP-1-CI-0.33. To a 300 ml three-neck flask equipped with an overhead stirrer, BP-1-Neu (7 g), 1-bromo-6-chlorohexane (22.926 ml, 153.63 mmol) and dimethyl sulfoxide (150 ml) were added at room temperature and then the mixture was mixed at 800 rpm. The mixture turned transparent after 4 hours, and trifluoracetic acid (18 mmol) was added. Thereafter, the reaction continued at room temperature for 16 hours. The resulting transparent and yellow solution was added dropwise into a solution of sodium chloride to precipitate white to pale yellow pellets of BP-CI-0.33 resin. The resin was washed thoroughly with ethanol and DI water to remove solvent and chemical residues. Finally, the yellow resin product was filtered and dried completely at 80 C. in an oven. The yield of polymer is 91%. BP-1-CI-0.4, BP-0.3-CI-0.2 and BP-0.3-CI-0.4 can be synthesized following a similar procedure.

[0110] (2) Crosslinking of BP-1-CI-0.2 in an alkaline solution. 1 g of BP-1-CI-0.2 was first dissolved in 15 mL of DSMO and then a 44 inch membrane was cast with the solution at 80 C. This membrane was not crosslinked at this point. Then the membrane was immersed in 1M NaOH at 60 C. for 6-24 hours to finish the crosslinking (XL) of the membrane. Crosslinking degree was determined by a titration process, and it can be manipulated between 5% to 15% with the duration of soaking in the NaOH solution.

Example 3

[0111] A crosslinkable polymer TP2-CI and its crosslinked form was prepared from TP2-Neu polymer (N is from 10 to 10000; a is from 0.1 to 0.95; b is from 0.01 to 0.9; c is from 0 to 0.9; d is from 0 to 0.9. The sum of a, b, c and d equals 1. e is from 0.01 to 0.95, x is from 0.01 to 0.95, y is from 0.01 to 0.90, z is from 0.01 to 0.50 and the sum of x, y and z is from 0.1 to 0.95) was depicted in scheme 3. Preparation of TP2-CI (a=0.7, b=0.1, c=0.1, d=0.1, e=0.33) and its crosslinked membrane was described briefly below.

##STR00024## ##STR00025##

[0112] (1) Synthesis of a crosslinkable polymer TP2-CI (a=0.7. b=0.1. c=0.1, d=0.1, e=0.33). To a 300 ml three-neck flask equipped with an overhead stirrer, TP2-Neu (14 g), 1-bromo-6-chlorohexane (22.926 ml, 153.63 mmol) and dimethyl sulfoxide (150 ml) were added at room temperature and then the mixture was mixed at 800 rpm. The mixture turned transparent after 4 hours, and trifluoracetic acid (17.6 mmol) was added. Thereafter, the reaction continued at room temperature for 16 hours. The resulting transparent and yellow solution was added dropwise into a solution of sodium chloride to precipitate white to pale yellow pellets of TP2-CI resin. The resin was washed thoroughly with ethanol and DI water to remove solvent and chemical residues. Finally, the yellow resin product was filtered and dried completely at 80 C. in an oven. The yield of polymer is 94%.

[0113] (2) Crosslinking of TP2-CI in an alkaline solution. 1 g of TP2-CI was first dissolved in 12 mL of DSMO and then a 44 inch membrane was cast with the solution at 80 C. This membrane was not crosslinked at this point. Then the membrane was immersed in 1M NaOH at 60 C. for 6-24 hours to finish the crosslinking (XL) of the membrane. Crosslinking degree was determined by a titration process, and it can be manipulated between 5% to 25% with the duration of soaking in the NaOH solution.

Example 4

[0114] A crosslinkable polymer BP2-CI and its crosslinked form was prepared from BP2-Neu polymer (N is from 10 to 10000; a is from 0.1 to 0.95; b is from 0.01 to 0.9; c is from 0 to 0.9; d is from 0 to 0.9. The sum of a, b, c and d equals 1. e is from 0.01 to 0.95, x is from 0.01 to 0.95, y is from 0.01 to 0.90, z is from 0.01 to 0.50 and the sum of x, y and z is from 0.1 to 0.95) was depicted in scheme 4. Preparation of BP2-CI (a=0.65, b=0.15, c=0.1, d=0.1, e=0.37) and its crosslinked membrane was described briefly below.

##STR00026## ##STR00027##

[0115] (1) Synthesis of a crosslinkable polymer BP2-CI (a=0.65, b=0.15, c=0.1, d=0.1, e=0.37). To a 300 ml three-neck flask equipped with an overhead stirrer, BP2-Neu (8 g), 1-bromo-6-chlorohexane (22.926 ml, 153.63 mmol) and dimethyl sulfoxide (150 ml) were added at room temperature and then the mixture was mixed at 800 rpm. The mixture turned transparent after 4 hours, and trifluoracetic acid (13 mmol) was added. Thereafter, the reaction continued at room temperature for 16 hours. The resulting transparent and yellow solution was added dropwise into a solution of sodium chloride to precipitate white to pale yellow pellets of BP2-CI resin. The resin was washed thoroughly with ethanol and DI water to remove solvent and chemical residues. Finally, the yellow resin product was filtered and dried completely at 80 C. in an oven. The yield of polymer is 83%.

[0116] (2) Crosslinking of BP2-CI in an alkaline solution. 1 g of BP2-CI was first dissolved in 8 mL of DSMO and then a 44 inch membrane was cast with the solution at 80 C. This membrane was not crosslinked at this point. Then the membrane was immersed in 1M NaOH at 60 C. for 6-24 hours to finish the crosslinking (XL) of the membrane. Crosslinking degree was determined by a titration process, and it can be manipulated between 5% to 32% with the duration of soaking in the NaOH solution.

Example 5

[0117] A crosslinkable polymer BPTP-CI and its crosslinked form was prepared from BPTP-Neu polymer (N is from 10 to 10000; m, n, p and k are respectively, from 0.01 to 0.99, and the sum of m, n, p and k equals 1. a, b, c, d are respectively from 0.01 to 0.99, and the sum of a, b equals to m. the sum of a, b equals to n. x, y, z, t, r and s are respectively from 0.01 to 0.99, and the sum of x, y equals to a. the sum of y, z equals to b; the sum of t, r equals to b; the sum of r, s equals to d). Preparation of BPTP-CI (m=0.4, n=0.4, p=0.1, k=0.1, a+c=0.27) and and its crosslinked membrane was described briefly below.

##STR00028## ##STR00029##

[0118] (1) Synthesis of a crosslinkable polymer TPBP-CI (m=0.4, n=0.4, p=0.1, k=0.1. a+c=0.27). To a 300 ml three-neck flask equipped with an overhead stirrer, TPBP-Neu (9 g), 1-bromo-6-chlorohexane (22.926 ml, 153.63 mmol) and dimethyl sulfoxide (150 ml) were added at room temperature and then the mixture was mixed at 800 rpm. The mixture turned transparent after 4 hours, and trifluoracetic acid (17 mmol) was added. Thereafter, the reaction continued at room temperature for 16 hours. The resulting transparent and yellow solution was added dropwise into a solution of sodium chloride to precipitate white to pale yellow pellets of TPBP-CI resin. The resin was washed thoroughly with ethanol and DI water to remove solvent and chemical residues. Finally, the yellow resin product was filtered and dried completely at 80 C. in an oven. The yield of polymer is 87%.

[0119] (2) Crosslinking of TPBP-CI in an alkaline solution. 1 g of TPBP-CI was first dissolved in 10 mL of DSMO and then a 44 inch membrane was cast with the solution at 80 C. This membrane was not crosslinked at this point. Then the membrane was immersed in 1M NaOH at 60 C. for 6-24 hours to finish the crosslinking (XL) of the membrane. Crosslinking degree was determined by a titration process, and it can be manipulated between 5% to 21% with the duration of soaking in the NaOH solution.

Definitions

[0120] 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(CO) groups, heterocylic groups, cycloalkyl groups, amino groups, alkyl- and 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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 (CH2CH2-) or isopropylene (CH(CH3)CH2-). 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.

[0128] The term hydrocarbon as used herein describes a compound or radical consisting exclusively of the elements carbon and hydrogen.

[0129] 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.

[0130] 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 (C(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.

[0131] 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.

[0132] 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.

[0133] In view of the above, it will be seen that the several objects of the invention are achieved, and other advantageous results attained.

[0134] 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.