# US 2019/0169372 A1 · Crosslinking of Hydroxide Stable, Polybenzimidazoliums and Polyimidazoliums Membranes and Ionomers

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- Number: US 2019/0169372 A1
- Document ID: US20190169372A1
- Status: Published application
- Kind: A1
- Application number: 16/322,920
- Filed: 2017-08-01
- Published: 2019-06-06
- Earliest claimed: 2016-08-04
- Assignees: Simon Fraser University
- Applicants: Simon Fraser University
- Inventors: Steven Holdcroft; Thomas Weissbach; Timothy James Peckham; Andrew Wright; Benjamin Britton
- Web page: https://patentgrep.com/patent/US20190169372A1

## CPC

- C08G 73/18: Polybenzimidazoles
- C08J 3/24: Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K)
- C08J 5/2256: {based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation}
- C08J 5/2287: {After-treatment}
- C08L 79/04: Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C25B 1/04: by electrolysis of water
- C25B 9/23: comprising ion-exchange membranes in or on which electrode material is embedded
- C25B 9/73: of the filter-press type
- C25B 13/08: based on organic materials
- H01M 8/103: having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
- C08J 2379/04: Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- H01M 2008/1095: {Fuel cells with polymeric electrolytes}
- H01M 2300/0082: Organic polymers
- Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
- Y02E 60/50: Fuel cells
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Described herein are crosslinked alkylated poly(benzimidazole) and poly(imidazole) polymer materials and devices (e.g., fuel cells, water electrolyzers) including these polymer materials. The polymer materials can be prepared in a convenient manner, allowing for applications such as anion exchange membranes (AEMs). The membranes provide high anion conductivities over a wider range of operating conditions when compared to the analogous membranes that are not cross-linked. The crosslinked polymer materials have improved alkaline stability, when compared to the analogous non-crosslinked polymer materials.

## Claims

### Claim 1

A crosslinked polymer comprising repeating units of Formula (A):
wherein
R101, R102, R104, and R105 are each independently selected from absent, a bond, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a crosslinking moiety;
wherein the crosslinking moiety crosslinks a first repeating unit and a second repeating unit of Formula (A), wherein
in the first repeating unit of Formula (A), at least one of R101, R102, R104, and R105 is the crosslinking moiety; and
in the second repeating unit of Formula (A), at least one of R101, R102, R104, and R105 is a bond connected to the crosslinking moiety on the first crosslinked repeating unit of Formula (A);
provided that
at least one of R101, R102, R104, and R105 is selected from a crosslinking moiety and a bond, wherein the bond is configured to connect to a crosslinking moiety;
at least one of R101 and R102 is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
when one of R101 and R102 is absent, the benzimidazolyl group comprising the absent R101 or R102 is neutral;
at least one of R104 and R105 is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; and
when one of R104 and R105 is absent, the benzimidazolyl group comprising the absent R104 or R105 is neutral;
R103, R106, R115, R117, R118, and R119 are each independently selected from hydrogen (H), alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R116 is selected from a bond, alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene, wherein said alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo;
R107, R110, R111, and R114 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, alkoxy, perfluoroalkoxy, halo, aryl, and heteroaryl; and
R108, R109, R112, and R113 are each independently selected from hydrogen (H), alkyl, perfluoroalkyl, and heteroalkyl.

### Claim 2 (depends on 1)

The crosslinked polymer of claim 1, wherein the polymer comprises repeating units of Formula (A-A):
wherein
R101, R102, R104, and R105 are each independently selected from absent, a bond, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a crosslinking moiety;
wherein the crosslinking moiety crosslinks a first repeating unit and a second repeating unit of Formula (A-A), wherein
in the first repeating unit of Formula (A-A), at least one of R101, R102, R104, and R105 is the crosslinking moiety; and
in the second repeating unit of Formula (A-A), at least one of R101, R102, R104, and R105 is a bond connected to the crosslinking moiety on the first crosslinked repeating unit of Formula (A-A);
provided that
at least one of R101, R102, R104, and R105 is selected from a crosslinking moiety and a bond, wherein the bond is configured to connect to a crosslinking moiety;
at least one of R101 and R102 is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
when one of R101 and R102 is absent, the benzimidazolyl group comprising the absent R101 or R102 is neutral;
at least one of R104 and R105 is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; and
when one of R104 and R105 is absent, the benzimidazolyl group comprising the absent R104 or R105 is connected is neutral;
R103, R106, R115, R117, R118, and R119 are each independently selected from hydrogen (H), alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R116 is selected from a bond, alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene, wherein said alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo;
R107, R110, R111, and R114 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, alkoxy, perfluoroalkoxy, halo, aryl, and heteroaryl; and
R108, R109, R112, and R113 are each independently selected from hydrogen (H), alkyl, perfluoroalkyl, and heteroalkyl.

### Claim at position 3

3-5. (canceled)

### Claim 6 (depends on 1)

The crosslinked polymer of claim 1, wherein at least one of R101, R102, R104, and R105 is a crosslinking moiety.

### Claim 7 (depends on 1)

The crosslinked polymer of claim 1, wherein at least one of R101, R102, R104, and R105 is a bond configured to connect to a crosslinking moiety.

### Claim at position 6

8-9. (canceled)

### Claim 10 (depends on 1)

The crosslinked polymer of claim 1, wherein R101, R102, R104, and R105 are each independently selected from absent, a bond, methyl, trifluoromethyl, and a crosslinking moiety; provided that
at least one of R101 and R102 is selected from methyl and trifluoromethyl; and
at least one of R104 and R105 is selected from methyl and trifluoromethyl.

### Claim 11 (depends on 1)

The crosslinked polymer of claim 1, wherein R103, R106, R115, R117, R118, and R119 are each independently selected from hydrogen and alkyl.

### Claim at position 9

12-13. (canceled)

### Claim 14 (depends on 1)

The crosslinked polymer of claim 1, wherein R116 is selected from arylene and heteroarylene each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo.

### Claim at position 11

15-16. (canceled)

### Claim 17 (depends on 1)

The crosslinked polymer of claim 1, wherein R107, R110, R111, and R114 are each independently alkyl.

### Claim 18

(canceled)

### Claim 19 (depends on 1)

The crosslinked polymer of claim 1, wherein R108, R109, R112, and R113 are each independently selected from hydrogen and alkyl.

### Claim at position 15

20-42. (canceled)

### Claim 43

A crosslinked polymer comprising repeating units of Formula (D-A), (D-B), (D-C), and (D-D)
wherein
R101a, R102a, R104a, and R105a are each independently selected from a bond, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a crosslinking moiety, provided that two of R101a, R102a, R104a, and R105a are selected from a crosslinking moiety and a bond, wherein the bond is configured to connect to a crosslinking moiety; and the remaining two of R101a, R102a, R104a, and R105a are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
R101b, R102b, R104b, and R105b are each independently selected from absent, a bond, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a crosslinking moiety, provided that one of R101b, R102b, R104b, and R105b is selected from a crosslinking moiety and a bond, wherein the bond is configured to connect to a crosslinking moiety; one of R101b, R102b, R104b, and R105b is absent and the benzimidazolyl group comprising the absent R101b, R102b, R104b, or R105b is neutral; and the remaining two of R101b, R102b, R104b, and R105b are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
R101c, R102c, R104c, and R105c are each independently selected from a bond, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a crosslinking moiety, provided that one of R101c, R102c, R104c, and R105c is selected from a crosslinking moiety and a bond, wherein the bond is configured to connect to a crosslinking moiety; and the remaining three of R101c, R102c, R104c, and R105c are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl,
R101d, R102d, R104d, and R105d are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
R103a, R106b, R115b, R117a, R118a, R119a, R103b, R106b, R115b, R117b, R118b, R119b, R103c, R106c, R115c, R117c, R118c, R119c, R103d, R106d, R115d, R117d, R118d, and R119d are each independently selected from hydrogen, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R107a, R110a, R111a, R114a, R107b, R110b, R111b, R114b, R107c, R110c, R111c, R114c, R107d, R110d, R111d, and R114d are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, alkoxy, perfluoroalkoxy, halo, aryl, and heteroaryl; and
R108a, R109a, R112a, R113a, R108b, R109b, R112b, R113b, R108c, R109c, R112c, R113c, R108d, R109d, R112d, and R113d are each independently selected from hydrogen, alkyl, perfluoroalkyl, and heteroalkyl,
wherein the polymer comprises comprising m mole percentage repeating units of Formula (D-A), n mole percentage repeating units of Formula (D-B), p mole percentage of repeating units (D-C), and q mole percentage of repeating units (D-D), and
m is from 1 mole percent to 95 mole percent,
n is from 1 mole percent to 50 mole percent,
p is from 1 mole percent to 95 mole percent,
q is from 5 mole percent to 95 mole percent, and
m+n+p+q=100%.

### Claim at position 17

44-62. (canceled)

### Claim 63

A crosslinked polymer comprising repeating units of Formula (I):
wherein in Formula (I):
R1, R2, R4, and R5 are each independently selected from absent, a bond, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a crosslinking moiety,
wherein the crosslinking moiety crosslinks a first repeating unit and a second repeating unit of Formula (I);
wherein in the first repeating unit of Formula (I), at least one of R1, R2, R4, and R5 is the crosslinking moiety; and
in the second repeating unit of Formula (I), at least one of R1, R2, R4, and R5 is a bond connected to the crosslinking moiety on the first crosslinked repeating unit of Formula (I);
provided that
at least one of R1, R2, R4, and R5 is selected from a crosslinking moiety and a bond, wherein the bond is configured to connect to a crosslinking moiety;
at least one of R1 and R2 is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
when one of R1 and R2 is absent, the imidazolyl group comprising the absent R1 or R2 is neutral;
at least one of R4 and R5 is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; and
when one of R4 and R5 is absent, the imidazolyl group comprising the absent R4 or R5 is neutral;
R3 and R6 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R15 is selected from alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo;
R16 is selected from a bond, arylene, and heteroarylene, wherein said arylene and heteroarylene is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo;
R7, R10, R11, and R14 are each independently selected from alkyl, perfluoroalkyl, and heteroalkyl; and
R8, R9, R12, and R13 are each independently selected from hydrogen, alkyl, perfluoroalkyl, and heteroalkyl.

### Claim 64 (depends on 63)

The crosslinked polymer of claim 63, wherein the polymer comprises repeating units of Formula (I-A):
wherein:
R1, R2, R4, and R5 are each independently selected from absent, a bond, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a crosslinking moiety;
wherein the crosslinking moiety crosslinks a first repeating unit and a second repeating unit of Formula (I-A),
wherein in the first repeating unit of Formula (I-A), at least one of R1, R2, R4, and R5 is the crosslinking moiety; and
in the second repeating unit of Formula (I-A), at least one of R1, R2, R4, and R5 is a bond connected to the crosslinking moiety on the first crosslinked repeating unit of Formula (I-A),
provided that
at least one of R1, R2, R4, and R5 is selected from a crosslinking moiety and a bond, wherein the bond is configured to connect to a crosslinking moiety;
at least one of R1 and R2 is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl,
when one of R1 and R2 is absent, the imidazolyl group comprising the absent R1 or R2 is neutral;
at least one of R4 and R5 is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl; and
when one of R4 and R5 is absent, the imidazolyl group comprising the absent R4 or R5 is neutral;
R3 and R6 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R15 is selected from alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo;
R16 is selected from a bond, arylene, and heteroarylene, wherein said arylene and heteroarylene is each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo;
R7, R10, R11, and R14 are each independently selected from alkyl, perfluoroalkyl, and heteroalkyl; and
R8, R9, R12, and R13 are each independently selected from hydrogen, alkyl, perfluoroalkyl, and heteroalkyl.

### Claim at position 20

65-67. (canceled)

### Claim 68 (depends on 63)

The crosslinked polymer of claim 63, wherein at least one of R1, R2, R4, and R5 is a crosslinking moiety.

### Claim 69 (depends on 63)

The crosslinked polymer of claim 63, wherein at least one of R1, R2, R4, and R5 is a bond configured to connect to a crosslinking moiety.

### Claim at position 23

70-71. (canceled)

### Claim 72 (depends on 63)

The crosslinked polymer of claim 63, wherein R1, R2, R4, and R5 are each independently selected from absent, a bond, methyl, trifluoromethyl, and a crosslinking moiety; provided that
at least one of R1 and R2 is selected from methyl and trifluoromethyl; and
at least one of R4 and R5 is selected from methyl and trifluoromethyl.

### Claim 73 (depends on 63)

The crosslinked polymer of claim 63, wherein R3 and R6 are each independently aryl.

### Claim at position 26

74-75. (canceled)

### Claim 76 (depends on 63)

The crosslinked polymer of claim 63, wherein R15 and R16 are each independently selected from arylene and heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl and halo.

### Claim at position 28

77-79. (canceled)

### Claim 80 (depends on 63)

The crosslinked polymer of claim 63, wherein R7, R10, R11, and R14 are each independently alkyl.

### Claim at position 30

81-96. (canceled)

### Claim 97

A crosslinked polymer comprising repeating units of Formula (IV-A), (IV-B), (IV-C), and (IV-D)
wherein
R1a, R2a, R4a, and R5a are each independently selected from a bond, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a crosslinking moiety, provided that two of R1a, R2a, R4a, and R5a is each independently selected from a crosslinking moiety and a bond, wherein the bond is configured to connect to a crosslinking moiety; and the remaining two of R1a, R2a, R4a, and R5a are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
R1b, R2b, R4b, and R5b are each independently selected from absent, a bond, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a crosslinking moiety, provided that one of R1b, R2b, R4b, and R5b is selected from a crosslinking moiety and a bond, wherein the bond is configured to connect to a crosslinking moiety; one of R1b, R2b, R4b, and R5b is absent and the imidazolyl group comprising the absent R1b, R2b, R4b, or R5b is neutral; and the remaining two of R1b, R2b, R4b, and R5b are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
R1c, R2c, R4c, and R5c are each independently selected from a bond, alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a crosslinking moiety, provided that one of R1c, R2c, R4c, and R5c is selected from a crosslinking moiety and a bond, wherein the bond is configured to connect to a crosslinking moiety; the remaining three of R1c, R2c, R4c, and R5c are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl,
R1d, R2d, R4d, and R5d are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
R3a, R6a, R3b, R6b, R3c, R6c, R3d, and R6d are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R7a, R10a, R11a, R14a, R7b, R10b, R11b, R14b, R7c, R10c, R11c, R14c, R7d, R10d, R11d, and R14d are each independently selected from alkyl, perfluoroalkyl, and heteroalkyl; and
R8a, R12a, R8b, R12b, R8c, R12c, R8d, and R12d are each independently selected from hydrogen, alkyl, perfluoroalkyl, and heteroalkyl,
wherein the polymer comprises comprising r mole percentage repeating units of Formula (IV-A), s mole percentage repeating units of Formula (IV-B), t mole percentage of repeating units (IV-C), and u mole percentage of repeating units (IV-D), and
r is from 1 mole percent to 95 mole percent,
s is from 1 mole percent to 50 mole percent,
t is from 1 mole percent to 95 mole percent,
u is from 5 mole percent to 95 mole percent, and
r+s+t+u=100%.

### Claim at position 32

98-119. (canceled)

### Claim 120 (depends on 1)

The crosslinked polymer of claim 1, wherein the crosslinking moiety is
wherein R120, R121, R122, and R123 are each independently selected from hydrogen, alkyl, and perfluoroalkyl.

### Claim at position 34

121-125. (canceled)

### Claim 126 (depends on 1)

An ionic membrane comprising a crosslinked polymer of claim 1.

### Claim at position 36

127-128. (canceled)