# US 11,299,464 B2 · Stable poly(imidazolium) hydroxides

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- Number: US 11,299,464 B2
- Document ID: US11299464B2
- Status: Granted
- Kind: B2
- Application number: 16/321,414
- Filed: 2017-07-29
- Published: 2019-12-19
- Granted: 2022-04-12
- Earliest claimed: 2016-07-29
- Assignees: Simon Fraser University
- Applicants: Simon Fraser University
- Inventors: Steven Holdcroft; Jiantao Fan; Andrew Wright; Benjamin Britton; Thomas Weissbach; Timothy James Peckham; Jonathan William Ward
- Web page: https://patentgrep.com/patent/US11299464B2

## CPC

- C07D 233/64: with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
- A61P 31/00: Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- C08G 12/06: Amines
- C08G 73/0616: {with only two nitrogen atoms in the ring}
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- A61P: SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

Provided herein are imidazolium polymers having steric hindrance at the 4-position of the imidazole moieties in the polymeric chain. The sterically-protected, N-methylated imidazolium polymers exhibit hydroxide stability in concentrated caustic solutions at elevated temperatures, such as at 100° C. and higher.

## Claims

### Claim 1

A polymer comprising a repeating unit of Formula (I):
wherein:
R1, R2, R4, and R5 are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
provided that
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 to which the absent R1 or R2 is connected is neutral; and
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 to which the absent R4 or R5 is connected is neutral;
R3 and R6 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R15 is arylene optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo;
R16 is arylene 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 2 (depends on 1)

The polymer of claim 1, wherein the polymer comprises a repeating unit of Formula (I-A):
wherein:
R1, R2, R4, and R5 are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
provided that
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 to which the absent R1 or R2 is connected 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 to which the absent R4 or R5 is connected is neutral;
R3 and R6 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R15 is arylene optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo;
R16 is arylene 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 3 (depends on 1)

The polymer of claim 1, wherein the polymer comprises a repeating unit of Formula (I-B):
wherein:
R1, R2, R4, and R5 are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
provided that
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 to which the absent R1 or R2 is connected is neutral; and
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 to which the absent R4 or R5 is connected is neutral;
R3 and R6 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R15 is arylene optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo;
R16 is arylene 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 4 (depends on 1)

The polymer of claim 1, wherein the polymer comprises a repeating unit of Formula (I-C):
wherein:
R1, R2, R4, and R5 are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
provided that
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 to which the absent R1 and R2 is connected is neutral; and
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 to which the absent R4 or R5 is connected is neutral;
R3 and R6 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R15 is arylene optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo;
R16 is arylene 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 5 (depends on 1)

The polymer of claim 1, wherein the polymer comprises a repeating unit of Formula (I-D):
wherein:
R1, R2, R4, and R5 are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
provided that
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 to which the absent R1 or R2 is connected is neutral; and
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 to which the absent R4 or R5 is connected is neutral;
R3 and R6 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R15 is arylene optionally substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, perfluoroalkyl, heteroalkyl, and halo;
R16 is arylene 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 6 (depends on 1)

The polymer of claim 1, wherein R1, R2, R4, and R5 are each independently selected from absent, methyl, and trifluoromethyl; 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 7 (depends on 1)

The polymer of claim 1, wherein R3 and R6 are each independently aryl.

### Claim 8 (depends on 1)

The polymer of claim 1, wherein R3 and R6 are each independently methyl.

### Claim 9 (depends on 1)

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

### Claim 10 (depends on 1)

The polymer of claim 1, wherein R7, R10, R11, and R14 are each independently alkyl.

### Claim 11 (depends on 1)

The polymer of claim 1, further comprising one or more anions X− selected from iodide, bromide, chloride, fluoride, triiodide, hydroxide, carbonate, bicarbonate, cyanide, acetate, nitrate, sulfate, phosphate, triflate, tosylate, tetrakis (3,5-bis(trifluoromethyl)phenyl)borate, bis(trifluoromethane)sulfonamide, and any combination thereof, wherein the one or more anions X− counterbalance one or more positive charges in the polymer.

### Claim 12

A polymer comprising a repeating unit of Formula (II):
wherein:
R1, R2, R4, and R5 are each independently selected from absent, alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
provided that
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 to which the absent R1 or R2 is connected is neutral; and
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 to which the absent R4 or R5 is connected is neutral;
R3 and R6 are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R7, R10, R11, and R14 are each independently selected from alkyl, perfluoroalkyl, and heteroalkyl; and
R8 and R12 are each independently selected from hydrogen, alkyl, perfluoroalkyl, and heteroalkyl.

### Claim 13 (depends on 12)

The polymer of claim 12, wherein R1, R2, R4, and R5 are each independently selected from absent, methyl, and trifluoromethyl;
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 14 (depends on 12)

The polymer of claim 12, wherein R3 and R6 are each independently phenyl.

### Claim 15 (depends on 12)

The polymer of claim 12, wherein R3 and R6 are each independently methyl.

### Claim 16 (depends on 12)

The polymer of claim 12, wherein R7, R8, R10, R11, R12, and R14 are each independently methyl.

### Claim 17 (depends on 12)

The polymer of claim 12, further comprising one or more anions X− selected from iodide, bromide, chloride, fluoride, triiodide, hydroxide, carbonate, bicarbonate, cyanide, acetate, nitrate, sulfate, phosphate, triflate, tosylate, tetrakis (3,5-bis(trifluoromethyl)phenyl)borate, bis(trifluoromethane)sulfonamide, and any combination thereof, wherein the one or more anions X− counterbalance one or more positive charges in the polymer.

### Claim 18

A random polymer, comprising repeating units of Formula (IV-A), (IV-B), and (IV-C):
wherein
one of R1a and R2a is absent and the remaining R1a or R2a is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
one of R4a and R5a is absent and the remaining R4a or R5a is selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
one of R1b, R2b, R4b, and R5b is absent and the imidazolyl group to which the absent R1b, R2b, R4b, or R5b is connected is neutral, and the remaining three 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 alkyl, perfluoroalkyl, heteroalkyl, aryl, and aralkyl;
R3a, R6a, R3b, R6b, R3c, and R6c are each independently selected from alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and heteroaryl;
R7a, R10a, R11a, R14a, R7b, R10b, R11b, R14b, R7c, R10c, R11c, and R14c are each independently selected from alkyl, perfluoroalkyl, and heteroalkyl; and
R8a, R12a, R8b, R12b, R8c, and R12c are each independently selected from hydrogen, alkyl, perfluoroalkyl, and heteroalkyl;
wherein the polymer comprises m mole percentage repeating units of Formula (IV-A), n mole percentage repeating units of Formula (IV-B), and p mole percentage repeating units of Formula (IV-C), and
m is from 0 mole percent to 60 mole percent,
n+p is 40 mole percent to 100 mole percent, and
m+n+p=100%.

### Claim 19 (depends on 1)

An ionic membrane comprising a polymer of claim 1.

### Claim 20 (depends on 1)

An ionomer comprising a polymer of claim 1, wherein the ionomer is optionally incorporated into a catalyst layer of a fuel cell, of an electrolyzer, or of other electrochemical device.