WO2019079513A1 - Polymères ayant des groupes pendants cationiques stables pour une utilisation en tant que membranes échangeuses d'anions et ionomères - Google Patents

Polymères ayant des groupes pendants cationiques stables pour une utilisation en tant que membranes échangeuses d'anions et ionomères Download PDF

Info

Publication number
WO2019079513A1
WO2019079513A1 PCT/US2018/056370 US2018056370W WO2019079513A1 WO 2019079513 A1 WO2019079513 A1 WO 2019079513A1 US 2018056370 W US2018056370 W US 2018056370W WO 2019079513 A1 WO2019079513 A1 WO 2019079513A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
independently
sebs
membrane
hydroxide
Prior art date
Application number
PCT/US2018/056370
Other languages
English (en)
Inventor
Yushan Yan
Lan Wang
Junhua Wang
Bingjun Xu
Yun Zhao
Original Assignee
Yushan Yan
Lan Wang
Junhua Wang
Bingjun Xu
Yun Zhao
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yushan Yan, Lan Wang, Junhua Wang, Bingjun Xu, Yun Zhao filed Critical Yushan Yan
Publication of WO2019079513A1 publication Critical patent/WO2019079513A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/923—Compounds thereof with non-metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • AEMs anion exchange membrane fuel cells
  • AEIs anion exchange membrane fuel cells
  • hydroxide exchange polymers are provided which are capable of forming hydroxide-exchange membranes (HEMs), hydroxide exchange membrane electrolyzers (HEMEL), and ionomers (HEIs) for use in hydroxide exchange membrane fuel cells (HEMFCs).
  • PEMFCs Proton exchange membrane fuel cells
  • the polymer backbone of most base polymers for HEM/HEI applications (e.g., polysulfone and poly(phenylene oxide)) unavoidably contains ether linkages along the backbone, which makes the HEMs/HEIs potentially labile under high pH conditions.
  • Lee et al. Acs Macro Lett 2015, 4, 453;
  • Lee et al. Acs Macro Lett 2015, 4, 814.
  • the strongly nucleophilic hydroxide ions attack these weak bonds and degrade the polymer backbone.
  • alternative cationic groups, organic tethers, and polymer backbones are needed to enhance chemical stability of HEMs/HEIs.
  • HEMs/HEIs Another concern regarding current HEMs/HEIs is their hydroxide conductivity. In comparison to Nafion, HEMs have intrinsically lower ionic conductivities under similar conditions, because the mobility of OH " is lower than that of H + . Hibbs et al., Chem Mater 2008, 20, 2566. Greater ion-exchange capacity (IEC) is needed for HEMs/HEIs to achieve greater hydroxide conductivity. However, high IEC usually leads to a membrane having high water uptake (i.e. , a high swelling ratio), decreasing the morphological stability and mechanical strength of the membrane, especially after repeated wet-dry cycles.
  • IEC ion-exchange capacity
  • HEMs An additional obstacle to using HEMs is achievement of mechanical flexibility and strength in an ambient dry state. Most HEMs exhibit low mechanical strength and are very brittle in a completely dry state especially after being completely swollen. It is difficult to obtain and handle thin membranes that are large in size as needed for commercial use of HEMs. Without good mechanical properties, the ionomers cannot form and keep an adequate triple phase structure in the fuel cell electrode at high temperature, such as at or above 80 °C. Li et al., J Am Chem Soc 2013, 135, 10124.
  • an HEI is that the polymer be soluble in a mixture of lower boiling alcohol and water but insoluble in pure alcohol or water so that the HEIs can be readily incorporated into an electrode catalyst layer yet not be dissolved away by water or alcohol.
  • PEMFCs have recently been deployed as zero-emission power sources in commercially sold automobiles, with demonstrated long driving range and short refuelling time, which are two features preferred for customer acceptance.
  • PEMFCs use platinum electrocatalysts and are not yet cost competitive with gasoline engines.
  • Major approaches to PEMFC cost reduction include development of low- platinum-loading, high power density membrane electrode assemblies (MEAs), and platinum-group-metal-free (PGM-free) cathode catalysts.
  • MEAs high power density membrane electrode assemblies
  • PGM-free cathode catalysts platinum-group-metal-free cathode catalysts.
  • a fundamentally different pathway to low cost fuel cells is to switch from PEMFCs to hydroxide exchange membrane fuel cells (HEMFCs) that, due to their basic operating environment, can work with PGM-free anode and cathode catalysts, and thus are potentially economically viable.
  • HEMFCs hydroxide exchange membrane fuel cells
  • HEMFCs have to provide a performance that matches PEMFCs, performance which in turn requires highly active anode and cathode catalysts as well as the highly chemically stable, ionically conductive, and mechanically robust hydroxide exchange membranes (HEMs)/hydroxide exchange ionomers (HEIs) to build an efficient triple phase boundary and thus drastically improve the utilization of the catalyst particles and reduce the internal resistance.
  • HEMs hydroxide exchange membranes
  • HIs hydrooxide exchange ionomers
  • HEMs/HEIs are typically composed of organic cations tethered on a polymer backbone, with OH- being the balancing anion.
  • a chemically stable HEM/HEI requires a stable organic cation and a stable polymer backbone.
  • These hydroxide conductive organic cations have been obtained by introducing quaternary ammonium, imidazolium, guanidinium, phosphonium, sulfonium, ruthenium and cobaltocenium using chloromethylation of aromatic rings or bromination on the benzylic methyl groups of the polymers.
  • an anion exchange polymer is provided.
  • the anion exchange polymer can comprise either a styrene-ethylene-butylene-styrene (SEBS)-type block copolymer or a norbornene-pyrrolidinium random or block copolymer.
  • SEBS styrene-ethylene-butylene-styrene
  • the SEBS block copolymer can comprise the structure A-B-A, wherein each A is independently a polystyrene-containing block comprising structural units of Formulae 1 and 2 or Formulae 1 and 3, and B is a polyalkylene block comprising polyethylene structural unit 4 and polybutylene structural unit 5.
  • A is independently a polystyrene-containing block comprising structural units of Formulae 1 and 2 or Formulae 1 and 3
  • B is a polyalkylene block comprising polyethylene structural unit 4 and polybutylene structural unit 5.
  • D is a nitrogen-containing heterocycle comprising 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,
  • the norbornene-pyrrolidinium random or block copolymer can comprise structural units of Formulae 6 and 7 or Formulae 6 and 8, wherein Formulae 6, 7 and 8 have the structure:
  • R12 and R13 are each independently halide, alkyl, alkenyl, alkynyl or aryl and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide; and X " is an anion.
  • the method comprises: reacting an acylating agent and an SEBS polymer in the presence of an organic solvent and a polymerization catalyst to form an acylated SEBS polymer; reacting the acylated SEBS polymer and a deacylating agent in the presence of an organic solvent to form a deacylated SEBS polymer; and reacting the deacylated SEBS polymer and either a quaternary ammonium or phosphonium compound or the nitrogen-containing heterocycle in the presence of an organic solvent to form the SEBS block copolymer.
  • the quaternary ammonium or phosphonium compound has the formula:
  • the SEBS polymer comprises the structural units of Formulae 1 , 4 and 5;
  • the acylated SEBS polymer comprises the structural units of Formulae 1 , 2A, 4 and 5;
  • the deacylated SEBS polymer comprises the structural units of Formulae 1 , 2B, 4 and 5; and the formulae 2A and
  • Ri 4 is alkylene
  • X is an anion
  • a method of making the norbornene-pyrrolidinium random or block copolymer comprises reacting norbornene, a haloalkylnorbornene, or a combination thereof in the presence of an organic solvent and a polymerization catalyst to form a norbornene polymer; and reacting the norbornene polymer with a secondary amine or a nitrogen- containing heterocycle in the presence of an organic solvent to form the norbornene- pyrrolidinium random or block copolymer.
  • the secondary amine has the formula H N R15R16 wherein R15 and R16 are each independently alkyl; the norbornene polymer comprises structural units of formulae 6 and 7A; and the structural unit having formula 7A has the structure:
  • an hydroxide exchange polymer comprising a poly(norbornene-pyrrolidinium) backbone free of ether linkages or a styrene-ethylene-butylene-styrene (SEBS) backbone free of ether linkages, and having water uptake not more than 150% based on the dry weight of the polymer when immersed in pure water at room temperature, or having hydroxide conductivity in pure water at room temperature of at least 20 mS/cm, wherein at least one of the following: the polymer is stable to degradation (as evidenced by no change in conductivity) when immersed in 1 M potassium hydroxide at 80 °C for 500 hours; or the polymer has a tensile strength of at least 40 MPa and/or elongation at break of at least 100%; or the polymer has a tensile strength of at least 60 MPa and/or elongation at break of at least 150%.
  • SEBS styrene-ethylene-butylene-styren
  • hydroxide exchange polymer comprising a poly(norbornene-pyrrolidinium) backbone free of ether linkages or a styrene-ethylene-butylene-styrene (SEBS) backbone free of ether linkages, and having: a peak power density of at least 160 mW/cm 2 when the polymer is used as an hydroxide exchange membrane of an hydroxide exchange membrane fuel cell and is loaded at 20% as an hydroxide exchange ionomer in cathodic and anodic catalyst layers of the fuel cell, the fuel cell having a 50% Pt/C catalyst and catalyst loading of 0.4 mg Pt/cm2, and test conditions being hydrogen and oxygen flow rates of 0.6 LJmin, no back pressure, cell temperature of 60 °C, and anode and cathode humidifiers at 65 °C and 65 °C, respectively; or a decrease in voltage over 5.5 hours of operation of not more than 20% and an increase in resistance over 5.5 hours
  • a method of making an anion exchange polymer membrane comprising the anion exchange polymer as described herein comprising: dissolving the SEBS block copolymer or the norbornene-pyrrolidinium random or block copolymer in a solvent to form a polymer solution; casting the polymer solution to form a polymer membrane; and exchanging anions of the polymer membrane with hydroxide, bicarbonate, or carbonate ions or a combination thereof to form the anion exchange polymer membrane.
  • An anion exchange membrane configured and sized to be suitable for use in a fuel cell is also provided, the membrane comprising the anion exchange polymer as described herein.
  • An anion exchange membrane fuel cell is provided, the fuel cell comprising the anion exchange polymer as described herein.
  • a reinforced electrolyte membrane configured and sized to be suitable for use in a fuel cell, the membrane comprising a porous substrate impregnated with the anion exchange polymer as described herein.
  • Figure 1 illustrates an exemplary hydroxide exchange membrane fuel cell
  • Figure 2 depicts an 1 H NMR spectrum of a SEBS-COCsBr polymer
  • Figure 3 depicts an 1 H NMR spectrum of a SEBS-C6Br polymer
  • Figure 4 depicts a graph of SEBS- CeQN HEMFC performance (SEBS- C6QN membrane, 5 ⁇ and AS-4 ionomer) when tested at 60 °C under these test conditions: ionomer (20 wt%), 0.4 mg Pt cm-2 on both anode and cathode, humidifier temperatures of 65 °C and 65 °C for H2 and 02, respectively, gas flow rate of 0.6 L min-1 and no back pressure.
  • HEMs/HEIs formed from functionalized polymers with various pendant cationic 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 functionalized polymers have an alkaline-stable cation, introduced into a rigid aromatic polymer backbone free of ether bonds.
  • the attachment of the pendant side chains to the rigid aromatic polymer backbone of the polymer allows fine tuning of the mechanical properties of the membrane and incorporation of alkaline stable cations, such as imidazoliums, phosphoniums and ammoniums, provides enhanced stability to the polymer.
  • HEMs/HEIs formed from these polymers 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 exhibit enhanced performance and durability at relatively high temperatures.
  • an anion exchange polymer is provided.
  • the anion exchange polymer can comprise either a styrene-ethylene-butylene-styrene (SEBS)-type block copolymer or a norbornene-pyrrolidinium random or block copolymer.
  • SEBS styrene-ethylene-butylene-styrene
  • the SEBS block copolymer can comprise the structure A-B-A, wherein each A is independently a polystyrene-containing block comprising structural units of Formulae 1 and 2 or Formulae 1 and 3, and B is a polyalkylene block comprising polyethylene structural unit 4 and polybutylene structural unit 5.
  • the structural units of Formulae 1 , 2, 3, 4 and 5 have the structures:
  • D is a nitrogen-containing heterocycle comprising 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;
  • Ri , R6 and R7 are each independently alkylene
  • R2, R3, R4, and R5 are each independently alkyl, alkenyl, aryl, or alkynyl;
  • q is O, 1 , 2, 3, 4, 5, or 6;
  • n, xi, and x 2 are each independently a mole fraction from about 0.01 to about 0.99;
  • X " is an anion
  • Z is N or P.
  • the ratio of the mole fraction of the structural units of Formulae 1 and 2 or Formulae 1 and 3 in the polymer to the mole fraction of the structural unit of Formulae 4 and 5 in the polymer is from about 0.01 to about 0.99, preferably from about 0.2 to about 0.8, and more preferably from about 0.4 to about 0.6.
  • preferred mole fractions can be from about 0.05 to about 0.95, from about 0.05 to about 0.9, from about 0.05 to about 0.8, from about 0.05 to about 0.7, or from about 0.05 to about 0.6, from about 0.05 to about 0.5, or from about 0.05 to about 0.4, from about 0.05 to about 0.3, or from about 0.05 to about 0.2. All combinations of these ranges of mole fractions can be combined for the structural units of any anion exchange polymer as described herein.
  • preferred substituents can include, for example, where (1 ) Ri and R6 are each independently C1-C22 alkylene, R2, R3, R4, and Rs are each independently C1-C6 alkyl, q is 0, 1 , 2, 3, 4, 5, or 6, X2 is from about 0.01 to about 0.99, and Z is N or P; or (2) Ri and R6 are each independently C1-C6 alkylene, R2, R3, R4, and R5 are each independently C1-C6 alkyl, q is 0, 1 , 2, or 3, X2 is from about 0.01 to about 0.99, and Z is N or P; or (3) Ri and R6 are each independently C8-C22 alkylene; R2, R3, R4, and R5 are each independently C1-C6 alkyl; q is 0, 1 , 2, or 3, X2 is from about 0.01 to about 0.99, and Z is N or P; or (4) Ri and R6 are each independently C2-C6 alkylene, R2, R3, R4, and Rs are each independently C1-C
  • preferred substituents can include, for example, where (1 ) R7 is C1-C22 alkylene, X2 is from about 0.01 about 0.99, and the nitrogen-containing heterocycle D comprises a fully substituted pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, or quinoline, wherein each substituent is independently alkyl or aryl; (2) R7 is C1 -C6 alkylene, X2 is from about 0.01 to about 0.99, and the nitrogen-containing heteroc cle D comprises an imidazole having the formula:
  • R7 is C7-C22 alkylene
  • X2 is from about 0.01 to about 0.99
  • the nitrogen-containing heterocycle D comprises the imidazole of formula 10 wherein Rs, R9, and Rio are each independently C1-C6 alkyl, and R11 is 2,4,6- alkylphenyl
  • R7 is n-hexylene
  • X2 is from about 0.01 to about 0.99
  • the nitrogen-containing heterocycle D comprises 1 -butyl-2-mesityl-4,5-dimethyl-1 /-/- imidazole which has the formula:
  • n can be from about 0.05 to about 0.95, from about 0.1 to about 0.9, from about 0.2 to about 0.8, from about 0.3 to about 0.7, or from about 0.4 to about 0.6.
  • preferred ranges of m can be from about 0.05 to about 0.95, from about 0.1 to about 0.9, from about 0.2 to about 0.8, from about 0.3 to about 0.7, or from about 0.4 to about 0.6.
  • the norbornene-pyrrolidinium random or block copolymer can comprise structural units of Formulae 6 and 7 or Formulae 6 and 8, wherein Formulae 6, 7 and 8 have the structure:
  • R12 and R13 are each independently halide, alkyl, alkenyl, alkynyl or aryl and the alkyl, alkenyl, alkynyl or aryl are optionally substituted with halide; and X- is an anion.
  • the ratio of the mole fraction of the structural unit of Formula 7 or 8 to the mole fraction of the structural unit of Formula 6 in the anion exchange polymer is from about 0.01 to 1 .
  • preferred substituents can include, for example, where R12 and R13 are each independently C1-C22 alkyl, C1-C6 alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl, or Cs-C22 alkyl.
  • preferred ranges of p can be 1 , 2 or 3.
  • preferred substituents for the anion X " can comprise a halide, BF 4 ⁇ , PF6 “ , CO3 2" or HCO3 " , and more preferably a halide,
  • the anion X or X- can comprise a halide, BF 4 ⁇ PF6 ⁇ , CO3 2" or HCO3-, and more preferably a halide, CO3 2"
  • An SEBS block copolymer as described herein can be prepared by a method which comprises reacting the SEBS polymer and an acylating agent in the presence of an organic solvent and a polymerization catalyst to form an acylated SEBS polymer; reacting the acylated SEBS polymer and a deacylating agent in the presence of an organic solvent to form a deacylated SEBS polymer; and reacting the deacylated SEBS polymer with the quaternary ammonium or phosphonium compound or the nitrogen-containing heterocycle in the presence of an organic solvent to form the SEBS block copolymer.
  • the SEBS block copolymer can be reacted with a base to exchange the anion of the SEBS block copolymer for the anion of the base.
  • the SEBS polymer can comprise the structural units of Formulae 1 , 4 and A representative SEBS polymer has the formula:
  • m, n, x, y, and z are each independently from about 0.01 to about 0.99; and X " is an anion.
  • the acylated SEBS polymer can comprise the structural units of Formulae 1 , 2A, 4 and 5.
  • a representative acylated SEBS polymer has the formula:
  • Ri 4 is alkylene
  • m, n, x1 , x2, y, z1 , and z2 are each independently from about 0.01 to about 0.99
  • X " is an anion
  • Ri 4 is alkylene
  • X is an anion
  • the deacylated SEBS polymer can comprise the structural units of Formulae 1 , 2B, 4 and 5.
  • a representative deacylated SEBS polymer has the formula:
  • Ri 4 is alkylene
  • m, n, x1 , x2, y, z1 and z2 ar eeach independently from about 0.01 to about 0.99
  • X- is an anion
  • Ri 4 is alkylene
  • X is an anion
  • the acylating agent can comprise an acyl halide.
  • the deacylating agent can comprise triethylsilane, hydrogen, hydrazine, diphenylsilane, aluminium nickel alloy, or dimethylmonochlorosilane.
  • the nitrogen-containing heterocycle comprises 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.
  • the nitrogen- containing heterocycle is unsaturated such as pyrrole, pyrroline, pyrazole, pyrazoline, imidazole, imidazoline, triazole, pyridine, triazine, pyrazine, pyridazine, pyrimidine, azepine, or quinoline, and each substitutable position of the heterocycle is substituted independently with alkyl (e.g., methyl, ethyl, propyl, n-butyl) or aryl groups (e.g., phenyl with alkyl substituents).
  • alkyl e.g., methyl, ethyl, propyl, n-butyl
  • aryl groups e.g., phenyl with alkyl substituents
  • the nitrogen-containing heterocycle can comprise an imidazole having the formula 10 wherein Rs, R9, Rio.and Rn are each independently optionally substituted alkyl, alkenyl, alkynyl, or aryl.
  • An example of such as imidazole is 1 -butyl-2-mesityl-4,5-dimethyl-1 /-/-imidazole-imidazole.
  • the quaternary ammonium or phosphonium compound has the formula: wherein: Ri and R6 are each independently alkylene; R2, R3, R 4 , and R5 are each independently alkyl, alkenyl, aryl, or alkynyl; q is 0, 1 , 2, 3, 4, 5, or 6; X- is an anion; and Z is N or P.
  • Ri and R6 are each independently C1-C22 alkylene, such as C1-C6 alkylene (e.g. , ethylene, n-propylene, n-pentylene or n-hexylene), or Cs-C22 alkylene;
  • R2, R3, R4, and R5 are each independently C1-C6 alkyl such as methyl, ethyl, n-propyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl;
  • q is 1 , 2, 3, 4, 5, or 6;
  • X " is a halide; and Z is N.
  • the base used in the methods described herein can comprise an 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.
  • an hydroxide-containing base such as sodium hydroxide or potassium hydroxide
  • a bicarbonate-containing base such as sodium bicarbonate or potassium bicarbonate
  • a carbonate-containing base such as sodium carbonate or potassium carbonate.
  • acylation of SEBS can be a Friedel-Crafts acylation reaction.
  • the SEBS polymer and an acylating agent such as a haloalkanoyi halide can be placed in a stirred container and dissolved or dispersed into an organic solvent such as methylene chloride.
  • a polymerization catalyst such as aluminium chloride in a solvent can then be added dropwise over up to 60 minutes at -78 to 60 °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 ethanol.
  • the product obtained is filtered, washed with water and ethanol and dried completely under vacuum to form an acylated SEBS polymer (such as an SEBS polymer having haloalkanoyi substituents on at least a portion of the styrene of the SEBS polymer).
  • an acylated SEBS polymer such as an SEBS polymer having haloalkanoyi substituents on at least a portion of the styrene of the SEBS polymer.
  • the acylated SEBS polymer is dissolved into an organic solvent in a stirred container.
  • a deacylating agent such as triethylsilane
  • an organic solvent such as trifluoroacetic acid
  • the resulting solution is poured slowly into an aqueous solution of ethanol.
  • the product obtained is filtered, washed with water and ethanol and dried completely under vacuum to form the deacylated SEBS polymer (such as an SEBS polymer having haloalkyl substituents on at least a portion of the styrene of the SEBS polymer).
  • the deacylated SEBS polymer is dissolved into an organic solvent in a stirred container.
  • the quaternary ammonium or phosphonium compound or the nitrogen-containing heterocycle is added quickly.
  • the solution is stirred over about 1 to 48 hours at 0 to 100°C.
  • the resulting viscous solution is added dropwise into ethanol to form a solid.
  • the solid is washed with ether and dried completely under vacuum to form the SEBS block copolymer.
  • the SEBS block copolymer can 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 Dl water for about 12 to 48 hours under an oxygen-free atmosphere to remove residual KOH to form the anion- exchanged SEBS block copolymer.
  • 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 Dl water for about 12 to 48 hours under an oxygen-free atmosphere to remove residual KOH to form the anion- exchanged SEBS block copolymer.
  • the norbornene-pyrrolidinium random or block copolymers can be prepared by a method which comprises reacting the norbornene, the
  • haloalkylnorbornene or a combination thereof in the presence of an organic solvent and a polymerization catalyst to form a norbornene polymer; and reacting the norbornene polymer with the secondary amine or the nitrogen-containing heterocycle in the presence of an organic solvent to form the norbornene-pyrrolidinium random or block copolymer. Then, the norbornene-pyrrolidinium random or block copolymer can be reacted with a base to form the anion-exchanged norbornene-pyrrolidinium random or block copolymer.
  • the haloalkylnorbornene can be prepared by a method which comprises reacting maleic anhydride with cyclopentadiene in the presence of an organic solvent to form nadic anhydride; reacting nadic anhydride with a reducing agent (such as lithium aluminium hydride) in the presence of an organic solvent to form 4,5- di(hydroxylmethyl)norbornene; and reacting the 4,5-di(hydroxylmethyl) norbornene with a halide salt (such as phosphorus tribromide) to form the haloalkylnorbornene.
  • a reducing agent such as lithium aluminium hydride
  • a halide salt such as phosphorus tribromide
  • the secondary amine has the formula H N R15R16 wherein R15 and R16 are each independently alkyl, such as lower alkyl.
  • the norbornene polymer comprises structural units of formulae 6 and 7A.
  • the norbornene or haloalkylnorbornene monomer such as 4,5-di(dibromomethyl)norbornene can be placed in a stirred container and dissolved or dispersed into an organic solvent such as anhydrous tetrahydrofuran under nitrogen.
  • a polymerization catalyst such as Grubbs' catalyst (second generation) is added quickly at -78 to 60 °C. Thereafter, the reaction is continued at this temperature for about 1 to about 120 hours with stirring.
  • the resulting solution is added dropwise to ethanol.
  • the product obtained is filtered, washed with ethanol and dried completely under vacuum to form the norbornene polymer.
  • the norbornene polymer is dissolved into an organic solvent such as chloroform in a stirred container.
  • the quaternary ammonium compound or the nitrogen-containing heterocycle (such as piperidine) is added dropwise.
  • the solution is stirred over about 1 to 48 hours at 0 to 100°C.
  • a reductant such as p-Tos-HNNhb
  • the polymer solution is added dropwise into ethanol.
  • the solid is filtered, washed and dried completely under vacuum to form the norbornene-pyrrolidinium random or block copolymer.
  • the norbornene-pyrrolidinium random or block copolymer can 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 Dl water for about 12 to 48 hours under an oxygen-free atmosphere to remove residual KOH and form the anion-exchanged norbornene-pyrrolidinium random or block copolymer.
  • 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 Dl water for about 12 to 48 hours under an oxygen-free atmosphere to remove residual KOH and form the anion-exchanged norbornene-pyrrolidinium random or block copolymer.
  • Another aspect of the invention provides a hydroxide exchange polymer comprising a poly(norbornene-pyrrolidinium) backbone free of ether linkages or a styrene-ethylene-butylene-styrene (SEBS) backbone free of ether linkages, and having water uptake not more than 150% based on the dry weight of the polymer when immersed in pure water at room temperature, or having hydroxide conductivity in pure water at room temperature of at least 20 mS/cm, wherein at least one of the following: the polymer is stable to degradation (as evidenced by no change in conductivity) when immersed in 1 M potassium hydroxide at 80 °C for 500 hours; or
  • the polymer has a tensile strength of at least 40 MPa and/or elongation at break of at least 100%;
  • the polymer has a tensile strength of at least 60 MPa and/or elongation at break of at least 150%.
  • hydroxide exchange polymer comprising a poly(norbornene-pyrrolidinium) backbone free of ether linkages or a styrene-ethylene-butylene-styrene (SEBS) backbone free of ether linkages, and having: a peak power density of at least 160 mW/cm 2 when the polymer is used as an hydroxide exchange membrane of an hydroxide exchange membrane fuel cell and is loaded at 20% as an hydroxide exchange ionomer in cathodic and anodic catalyst layers of the fuel cell, the fuel cell having a 50% Pt/C catalyst and catalyst loading of 0.4 mg Pt/cm 2 , and test conditions being hydrogen and oxygen flow rates of 0.6 LJmin, no back pressure, cell temperature of 60 °C, and anode and cathode humidifiers at 65 °C and 65 °C, respectively; or
  • the polymer is used as an hydroxide exchange membrane of an hydroxide exchange membrane fuel cell and is loaded at 20% as an hydroxide exchange ionomer in cathodic and anodic catalyst layers of the fuel cell, the fuel cell having a 50% Pt/C catalyst and catalyst loading of 0.4 mg Pt/cm 2 , and test conditions being constant current density of 400 mA/cm 2 , hydrogen and oxygen flow rates of 0.6 L/min, no back pressure, cell temperature of 60 °C, and anode and cathode humidifiers at 65 °C and 65 °C, respectively.
  • the peak power density can be at least 200 or 400 mW/cm 2 for the hydroxide exchange polymer described herein.
  • a decrease in voltage over 60 hours of operation can be not more than 20% and an increase in resistance over 60 hours of operation can be not more than 20% when the polymer is used as an hydroxide exchange membrane of an hydroxide exchange membrane fuel cell and is loaded at 20% as an hydroxide exchange ionomer in cathodic and anodic catalyst layers of the fuel cell, the fuel cell having a 50% Pt/C catalyst and catalyst loading of 0.4 mg Pt/cm 2 , and test conditions being constant current density of 200 mA/cm 2 , hydrogen and oxygen flow rates of 0.6 L/min, no back pressure, cell temperature of 60 °C, and anode and cathode humidifiers at 65 °C and 65 °C, respectively.
  • the pyrrolidinium linkages can comprise hydroxide, bicarbonate, or carbonate anions, or a combination thereof
  • the pyrrolidinium linkages can be derived from a norbornene polymer and a secondary amine or a nitrogen-containing heterocycle as described herein.
  • any of the random or block copolymers as described herein can be made into anion exchange membranes such as hydroxide exchange membranes.
  • Such hydroxide exchange polymer membranes can be prepared by any of the preparation methods described herein by dissolving the random or block copolymer in a solvent and casting the polymer solution to form a polymer membrane before exchanging anions of the polymer membrane with hydroxide ions to form the hydroxide exchange polymer membrane.
  • any of the random or block copolymers as described herein can be made into reinforced hydroxide exchange membranes as described below.
  • Such reinforced hydroxide exchange membranes can be prepared by a method which comprises wetting a porous substrate in a liquid to form a wetted substrate; dissolving the functionalized polymer in a solvent to form a homogeneous solution; applying the solution onto the wetted substrate to form the reinforced membrane; drying the reinforced membrane; and exchanging anions of the reinforced membrane with hydroxide ions to form the reinforced hydroxide exchange polymer membrane.
  • the solution can be applied to the wetted substrate by any known membrane formation technique such as casting, spraying, or doctor knifing.
  • the resulting reinforced membrane can be impregnated with the random or block polymer multiple times if desired by wetting the reinforced membrane again and repeating the dissolving, casting and drying steps.
  • the polymerization catalyst used in the methods as described herein can comprise trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1- propanesulfonic acid, trifluoroacetic acid, perfluoropropionic acid, heptafluorobutyric acid, or a combination thereof.
  • Each of the organic solvents used in the above methods can be independently selected from polar aprotic solvents (e.g., dimethyl sulfoxide, 1 -methyl-2- pyrrolidinone, 1 -methyl-2-pyrrolidone, 1 -methyl-2-pyrrolidone, or dimethylformamide) or other suitable solvents including, but are not limited to, methylene chloride,
  • trifluoroacetic acid trifluoromethanesulfonic acid, chloroform, 1 , 1 ,2,2-tetrachloroethane, dimethylacetamide or a combination thereof.
  • the solvent in the dissolving step can comprise methanol, ethanol, n- propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, a pentanol, a hexanol, dimethyl sulfoxide, 1 -methyl-2pyrrolidone, dimethylformamide, chloroform, ethyl lactate, tetrahydrofuran, 2-methyltetrahydrofuran, water, phenol, acetone, or a combination thereof.
  • the liquid used to wet the porous substrate can be a low boiling point solvent such as a lower alcohol (e.g., methanol, ethanol, propanol, isopropanol) and/or water.
  • a lower alcohol e.g., methanol, ethanol, propanol, isopropanol
  • the liquid is anhydrous ethanol.
  • An anion exchange membrane such as a hydroxide exchange membrane is also provided.
  • the membrane is configured and sized to be suitable for use in a fuel cell and comprises any of the random or block copolymers as described herein.
  • a reinforced electrolyte membrane such as a reinforced hydroxide exchange membrane is also provided to increase the mechanical robustness of the anion exchange membrane for stability through numerous wet and dry cycles (relative humidity cycling) in a fuel cell.
  • the membrane is configured and sized to be suitable for use in a fuel cell, and comprises a porous substrate impregnated with any of the random or block copolymers 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.
  • the porous substrate can comprise a membrane comprised of polytetrafluoroethylene, polypropylene, polyethylene, poly(ether ketone),
  • polyaryletherketone poly(aryl piperidinium), poly(aryl piperidine), polysulfone, perfluoroalkoxyalkane, or a fluorinated ethylene propylene polymer, or other porous polymers known in the art such as the dimensionally stable membrane from Giner for use in preparing reinforced membranes for fuel cells.
  • porous substrates are commercially available, for example, from W.L. Gore & Associates.
  • the porous substrate can have a porous microstructure of polymeric fibrils.
  • Such substrates comprised of polytetrafluoroethylene are commercially available.
  • the porous substrate can comprise a microstructure of nodes interconnected by fibrils.
  • the interior volume of the porous substrate can be rendered substantially occlusive by impregnation with the random or block copolymer.
  • 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.
  • the porous substrate has a thickness from about 5 microns to about 30 microns, or from about 7 microns to about 20 microns.
  • An anion exchange membrane fuel cell which comprises any of the random or block copolymers as described herein.
  • the functionalized polymers can be used in HEMFCs such as a typical fuel cell 10 as shown in Figure 1.
  • Figure 1 illustrates a typical fuel cell 10 with an anode portion 12 (illustrated on the left) and a cathode portion 14 (illustrated on the right) which are separated by an electrolyte membrane 16.
  • the electrolyte membrane 16 can be any membrane comprising any of the random or block copolymers as described herein, and can be a reinforced membrane. Supporting members are not illustrated.
  • the anode portion carries out an anode half-reaction which oxidizes fuel releasing electrons to an external circuit and producing oxidized products.
  • the cathode portion carries out a cathode half-reaction which reduces an oxidizer consuming electrons from the external circuit.
  • the gas diffusion layers (GDLs) 18 and 20 serve to deliver the fuel 22 and oxidizer 24 uniformly across the respective catalyst layers 26 and 28.
  • Charge neutrality is maintained by a flow of ions from the anode to the cathode for positive ions and from cathode to anode for negative ions.
  • the dimensions illustrated are not representative, as the electrolyte membrane is usually selected to be as thin as possible while maintaining the membrane's structural integrity.
  • the anode half-reaction consumes fuel and OH " ions and produces waste water (as well as carbon dioxide in the case of carbon containing fuels).
  • the cathode half reaction consumes oxygen and produces OH " ions, which flow from the cathode to the anode through the electrolyte membrane.
  • Fuels are limited only by the oxidizing ability of the anode catalyst and typically include hydrogen gas, methanol, ethanol, ethylene glycol, and glycerol.
  • the fuel is H 2 or methanol.
  • Catalysts are usually platinum (Pt), silver (Ag), or one or more transition metals, e.g., Ni.
  • the anode half-reaction consumes fuel and produces H + ions and electrons.
  • the cathode half reaction consumes oxygen, H + ions, and electrons and produces waste water, and H + ions (protons) flow from the anode to the cathode through the electrolyte membrane.
  • an electrolyte membrane made from a random or block copolymer as described herein significantly improves fuel cell performance.
  • greater fuel cell efficiency requires low internal resistance, and therefore, electrolyte membranes with greater ionic conductivity (decreased ionic resistance) are preferred.
  • greater power requires greater fuel cell currents, and therefore, electrolyte membranes with greater ion-current carrying capacity are preferred.
  • practical electrolyte membranes resist chemical degradation and are mechanically stable in a fuel cell environment, and also should be readily
  • the anion/hydroxide exchange ionomers and membranes can be used for many other purposes such as use in fuel cells (e.g., hydrogen/alcohol/ammonia fuel cells); electrolyzers (e.g., water/carbon dioxide/ammonia electrolyzers), electrodialyzers; ion-exchangers; solar hydrogen generators; desalinators (e.g., desalination of sea/brackish water); demineralization of water; ultra-pure water production; waste water treatment; concentration of electrolyte solutions in the food, drug, chemical, and biotechnology fields; electrolysis (e.g., chlor-alkali production and H2/02 production); energy storage (e.g., super capacitors, metal air batteries and redox flow batteries); sensors (e.g.
  • SEBS-C6QN styrene ethylene butylene styrene
  • SEBS-C6QN a commercial triblock polymer known as styrene ethylene butylene styrene (SEBS) and a long side chain quaternary ammonium cation.
  • SEBS-C6QN was prepared by four major steps: (1 ) Friedel-Crafts acylation of SEBS (SEBS-COCsBr), (2) reduction of acylated SEBS (SEBS-CeBr), (3) membrane casting and amination of SEBS-C6Br with trimethylamine (SEBS-C6QN), and (4) hydroxide ion exchange.
  • the reaction scheme is depicted below:
  • the membrane was peeled off from the glass plate and soaked in 45% trimethylamine aqueous solution at room temperature for 24 h.
  • the membrane in hydroxide form were obtained by ion exchange in 1 M KOH at room temperature for 24 h, followed by washing and immersion in Dl water for 48 h under Ar to remove residual KOH.
  • SEBS-CeQN membrane was stable in 1 M KOH at 80 °C for 500 h.
  • SEBS-C6QN membrane at room temperature showed 98% water uptake, 13% swelling ratio and 30 mS/cm hydroxide conductivity in water.
  • SEBS-C6QN membrane was insoluble in methylene chloride, chloroform, toluene, tetrahydrofuran, acetone, ethyl ether, ethanol, methanol, 2-propanol, hexanes, dimethyl sulfoxide, N-Methyl-2- pyrrolidone, dimethylformamide, or water.
  • HEMFC Hydroxide exchange membrane fuel cell
  • SEBS-C6IM was prepared by four major steps: (1 ) Friedel-Crafts acylation of SEBS (SEBS-COCsBr), (2) reduction of acylated SEBS (SEBS-CeBr), (3) amination of SEBS-CeBr with 1 -butyl-2-mesityl-4,5- dimethyl-1 H-imidazole (SEBS-C6IM), and (4) membrane casting and hydroxide ion exchange.
  • the reaction scheme for preparing the polymer is as follows:
  • SEBS-COCsBr polymer was prepared by Friedel-Crafts acylation of SEBS as in Example 1 .
  • SEBS-CeBr polymer was prepared by reduction of acylated SEBS as in Example 1 .
  • SEBS-C6-I M membrane was prepared by dissolving the SEBS-C6Br polymer (1.0 g) in toluene (20 mL) by casting on a clear glass plate at 80 °C for 8 h. The membrane was peeled off from the glass plate and refluxed with 1 g of 1-butyl-2-mesityl-4,5-dimethyl-1 H-imidazole in THF for 24 h. The membrane in hydroxide form was obtained by ion exchange in 1 M KOH at room temperature for 24 h, followed by washing and immersion in Dl water for 48 h under Ar to remove residual KOH.
  • Membrane was prepared by dissolving the SEBS-C6IM polymer (1.0 g) in NMP (20 mL) by casting on a clear glass plate at 80 °C for 8 h. The membrane (in bromide form) was peeled off from the glass plate in contact with deionized (Dl) water. The membrane in hydroxide form were obtained by ion exchange in 1 M KOH at room temperature for 24 h, followed by washing and immersion in Dl water for 48 h under Ar to remove residual KOH.
  • thermoplastic HEM/HEI is based on ring opening metathesis polymerization (ROMP) of norbornene derivatives and quaternization of amine into ammonium cation.
  • ROMP ring opening metathesis polymerization
  • PPNB Poly-pyrrolidinium-norbornene
  • (1 ) ROMP of norbornene (4,5-di(bromomethyl)norbornene, or mixture with norbornene), (2) quaternization of poly-di(bromomethyl)norbornene, (3) C C double bond reduction and (4) membrane casting and hydroxide ion exchange.
  • the reaction scheme is shown below, wherein step (a) is the preparation of 4,5- di(bromomethyl)norbornene via Diels-Alder reaction, reduction and bromination: a)
  • Bromination was carried out by slowly dropping PBr3 (2.2 ml_) into a THF solution (100 ml_) of 4,5-di(hydroxylmethyl)norbornene (5.4 g) at 0 °C. The reaction was allowed to stir at 0 °C for 4 h after addition. After quenching and washing with water (3 washes of 10 ml_), the organic phase was combined and dried over vacuum to give the 4,5-di(bromomethyl)norbornene monomer in 90% yield.
  • the other PPNBs can be synthesized in the same fashion by adding corresponding dialkylamine (HNMe 2 , HNEt 2 , HNPr 2 ... ).
  • Membrane was prepared by dissolving the PPNB-Pip polymer (1 .0 g) in NMP (20 mL) by casting on a clear glass plate at 80 °C for 8 h. The membrane (in iodide form) was peeled off from the glass plate in contact with deionized (Dl) water. The membrane in hydroxide form were obtained by ion exchange in 1 M KOH at room temperature for 24 h, followed by washing and immersion in Dl water for 48 h under Ar to remove residual KOH.
  • suitable substituent is intended to mean a chemically acceptable functional group, preferably a moiety that does not negate the activity of the inventive compounds.
  • alkylaminocarbonyl groups dialkylamino carbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, and arylsulfonyl groups.
  • substituents can be substituted by additional substituents.
  • alkyl 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, 1 1 , 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.
  • alkenyl refers to a straight, branched or cyclic hydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 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.
  • alkynyl refers to a straight, branched or cyclic hydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 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
  • 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.
  • aryl also includes heteroaryl.
  • 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.
  • cycloalkyl 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.
  • alkylene 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.
  • alkylene denotes a bivalent alkyl group such as ethylene (- CH2CH2-) or isopropylene (-CH2(CH3)CH2-).
  • -CH2CH2- isopropylene
  • alkylene denotes an optionally
  • ether as used herein represents a bivalent (i.e.,
  • difunctional group including at least one ether linkage (i.e., -0-).
  • heteroaryl refers to a monocyclic, bicyclic, or tricyclic aromatic heterocyclic group containing one or more heteroatoms (e.g. , 1 to 3 heteroatoms) selected from O, S and N in the ring(s).
  • Heteroaryl groups include, but are not limited to, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl, furyl, imidazolyl, pyrrolyl, oxazolyl (e.g., 1 ,3-oxazolyl, 1 ,2-oxazolyl), thiazolyl (e.g.
  • Heteroaryl groups can be unsubstituted or substituted by one or more suitable substituents, preferably 1 to 5 suitable substituents, as defined above.
  • suitable substituents preferably 1 to 5 suitable substituents, as defined above.
  • hydrocarbon as used herein describes a compound or radical consisting exclusively of the elements carbon and hydrogen.
  • 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 (-N02), 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.
  • substituent groups such as hydroxy (-OH), alkylthio, phosphino, amido (-CON(RA)(RB),
  • 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.”

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des copolymères blocs SEBS ou des copolymères séquencés ou aléatoires de norbornène-pyrrolidinium avec des groupes cationiques pendants qui ont un cation stable alcalin introduit dans un squelette polymère aromatique rigide exempt de liaisons éther. Des membranes d'échange d'hydroxyde ou des ionomères d'échange d'hydroxyde formés à partir de ces polymères présentent une stabilité chimique supérieure, une conductivité d'hydroxyde supérieure, une absorption d'eau réduite, une bonne solubilité dans des solvants sélectionnés, et des propriétés mécaniques améliorées dans un état sec ambiant par rapport aux membranes ou ionomères d'échange d'hydroxyde classiques. Des piles à combustible à membrane échangeuse d'hydroxyde comprenant les copolymères à blocs SEBS ou les copolymères aléatoires ou séquencés de norbornène-pyrrolidinium avec des groupes cationiques pendants présentent des performances et une durabilité améliorées à des températures relativement élevées.
PCT/US2018/056370 2017-10-17 2018-10-17 Polymères ayant des groupes pendants cationiques stables pour une utilisation en tant que membranes échangeuses d'anions et ionomères WO2019079513A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201762573545P 2017-10-17 2017-10-17
US201762573550P 2017-10-17 2017-10-17
US62/573,545 2017-10-17
US62/573,550 2017-10-17

Publications (1)

Publication Number Publication Date
WO2019079513A1 true WO2019079513A1 (fr) 2019-04-25

Family

ID=66173877

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2018/056370 WO2019079513A1 (fr) 2017-10-17 2018-10-17 Polymères ayant des groupes pendants cationiques stables pour une utilisation en tant que membranes échangeuses d'anions et ionomères

Country Status (1)

Country Link
WO (1) WO2019079513A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110284144A (zh) * 2019-06-29 2019-09-27 华南理工大学 一种电催化合成氨的有机电解液及其制备方法与应用
CN110921781A (zh) * 2019-12-11 2020-03-27 西安交通大学 基于太阳能的海水脱盐系统及脱盐方法
CN111607117A (zh) * 2020-06-18 2020-09-01 长春工业大学 燃料电池用多种侧链型阴离子交换膜及其制备方法
CN114824391A (zh) * 2022-04-07 2022-07-29 上海交通大学 一种含三唑基长侧链的聚苯醚阴离子膜及其制备方法和应用
CN115109235A (zh) * 2022-07-18 2022-09-27 烟台九目化学股份有限公司 一种咪唑型基团功能化的聚合物及其制备方法和应用
CN115873286A (zh) * 2022-12-14 2023-03-31 武汉轻工大学 一种半互穿网络阴离子交换膜及其制备方法
CZ309781B6 (cs) * 2022-06-03 2023-10-04 Ústav makromolekulární chemie AV ČR, v. v. i. Anion-výměnný materiál na bázi blokového polymeru styrenu a olefinů
CN117116520A (zh) * 2023-08-16 2023-11-24 西南科技大学 一种强碱性高氟铀废水深度净化及铀资源回收的方法
CN117802532A (zh) * 2023-12-25 2024-04-02 碳谐科技(上海)有限公司 复合隔膜及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6413298B1 (en) * 2000-07-28 2002-07-02 Dais-Analytic Corporation Water- and ion-conducting membranes and uses thereof
US20170203289A1 (en) * 2014-07-22 2017-07-20 Rensselaer Polytechnic Institute Anion exchange membranes and polymers for use in same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6413298B1 (en) * 2000-07-28 2002-07-02 Dais-Analytic Corporation Water- and ion-conducting membranes and uses thereof
US20170203289A1 (en) * 2014-07-22 2017-07-20 Rensselaer Polytechnic Institute Anion exchange membranes and polymers for use in same

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GAO, X ET AL.: "High performance anion exchange ionomer for anion exchange membrane fuel cells", THE ROYAL SOCIETY OF CHEMISTRY ADVANCES, vol. 7, no. 31, 30 March 2017 (2017-03-30), pages 19153 - 19161, XP055593165 *
SERPICO, JM ET AL.: "Transport and Structural Studies of Sulfonated Styrene-Ethylene Copolymer Membranes", MACROMOLECULES, vol. 35, 2002, pages 5916 - 5921, XP055006564, DOI: doi:10.1021/ma020251n *
WANG, Z ET AL.: "Anion Exchange Membranes Based on Polystyrene-Block- Poly (ethyleine-ran-butylene)-Block-Polystyrene Triblock Copolymers: Cation Stability and Fuel Cell Performance", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 164, no. 12, 6 September 2017 (2017-09-06), pages F1216 - F1225 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110284144A (zh) * 2019-06-29 2019-09-27 华南理工大学 一种电催化合成氨的有机电解液及其制备方法与应用
CN110284144B (zh) * 2019-06-29 2021-05-14 华南理工大学 一种电催化合成氨的有机电解液及其制备方法与应用
CN110921781A (zh) * 2019-12-11 2020-03-27 西安交通大学 基于太阳能的海水脱盐系统及脱盐方法
CN110921781B (zh) * 2019-12-11 2020-12-25 西安交通大学 基于太阳能的海水脱盐系统及脱盐方法
CN111607117A (zh) * 2020-06-18 2020-09-01 长春工业大学 燃料电池用多种侧链型阴离子交换膜及其制备方法
CN114824391A (zh) * 2022-04-07 2022-07-29 上海交通大学 一种含三唑基长侧链的聚苯醚阴离子膜及其制备方法和应用
CN114824391B (zh) * 2022-04-07 2023-11-24 上海交通大学 一种含三唑基长侧链的聚苯醚阴离子膜及其制备方法和应用
CZ309781B6 (cs) * 2022-06-03 2023-10-04 Ústav makromolekulární chemie AV ČR, v. v. i. Anion-výměnný materiál na bázi blokového polymeru styrenu a olefinů
CN115109235B (zh) * 2022-07-18 2023-07-04 烟台九目化学股份有限公司 一种咪唑型基团功能化的聚合物及其制备方法和应用
CN115109235A (zh) * 2022-07-18 2022-09-27 烟台九目化学股份有限公司 一种咪唑型基团功能化的聚合物及其制备方法和应用
CN115873286A (zh) * 2022-12-14 2023-03-31 武汉轻工大学 一种半互穿网络阴离子交换膜及其制备方法
CN117116520A (zh) * 2023-08-16 2023-11-24 西南科技大学 一种强碱性高氟铀废水深度净化及铀资源回收的方法
CN117116520B (zh) * 2023-08-16 2024-02-06 西南科技大学 一种强碱性高氟铀废水深度净化及铀资源回收的方法
CN117802532A (zh) * 2023-12-25 2024-04-02 碳谐科技(上海)有限公司 复合隔膜及其制备方法和应用

Similar Documents

Publication Publication Date Title
US11512156B2 (en) Poly(aryl piperidinium) polymers including those with stable cationic pendant groups for use as anion exchange membranes and ionomers
US10290890B2 (en) Poly(aryl piperidinium) polymers for use as hydroxide exchange membranes and ionomers
WO2019079513A1 (fr) Polymères ayant des groupes pendants cationiques stables pour une utilisation en tant que membranes échangeuses d'anions et ionomères
US11827743B2 (en) Polymers having stable cationic pendant groups for use as anion exchange membranes
Si et al. Alkaline stable imidazolium-based ionomers containing poly (arylene ether sulfone) side chains for alkaline anion exchange membranes
WO2022170022A1 (fr) Polymères résistant à l'oxydation destinés à être utilisés en tant que membranes échangeuses d'anions et ionomères
JPWO2014157389A1 (ja) 電解質膜用組成物、固体高分子電解質膜、該電解質膜の製造方法、膜−電極接合体、固体高分子型燃料電池、水電解セルおよび水電解装置
US20240246070A1 (en) Piperidinium-containing anion exchange polymers
Wang Anion Exchange and Bipolar Membranes for Electrochemical Energy Conversion and Storage
CN118271489A (zh) 离子交换聚合物及其制备方法、离子交换膜及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18869023

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18869023

Country of ref document: EP

Kind code of ref document: A1