Anion exchange polymers and membranes for electrolysis

Patent metadata

Field	Value
Publication number	US-11980879-B2
Application number	US-202117474198-A
Country	US
Kind code	B2
Filing date	Sep 14, 2021
Priority date	Sep 14, 2021
Publication date	May 14, 2024
Grant date	May 14, 2024

Abstract

Anion exchange polymers having high OH − conductivity, chemical stability, and mechanical stability have been developed for use in AEMs. The anion exchange polymers have stable hydrophobic polymer backbones, stable hydrophilic quaternary ammonium cationic groups, and hydrophilic phenolic hydroxyl groups on the polymer side chains. The polymers have polymer backbones free of ether bonds, hydrophilic polymer side chains, and piperidinium ion-conducting functionality, which enables efficient and stable operation in water or CO 2 electrolysis, redox flow battery, and fuel cell applications. The polymer comprises a plurality of repeating units of formula (I)

Anion exchange membranes and membrane electrode assemblies incorporating the anion exchange polymers are also described.

First claim

The invention claimed is:

1. A polymer comprising a plurality of repeating units of formula (I)

wherein Ar 1 is selected from the group consisting of:

and mixtures thereof;
Ar 2 is selected from the group consisting of:

and mixtures thereof;
X 1 is selected from the group consisting of:

optionally

and mixtures thereof;
wherein Y 1 − and Y 2 − are anions;
wherein R 1 -R 36 are each independently hydrogen, a halide, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl, or aryl groups are optionally substituted with a halide or a positively charged functional group;
wherein R 37 and R 38 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl groups are optionally substituted with a halide or a positively charged functional group;
wherein R 39 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and the alkyl, alkenyl, alkynyl or aryl group is optionally substituted with a halide or a positively charged functional group;
wherein A is O or S;
wherein m and n are independently integers from 5 to 500 and the molar ratio of n/m is in a range of 1:20 to 20:1;
wherein p is 1, 2, 3, or 4;
wherein q is 0, 1, 2, or 3;
wherein r, s, d, and o are independently 0, 1, 2, or 3; and
wherein t is 1, 2, 3, 4, 5, or 6.

2. The polymer of claim 1 wherein Ar 1 is selected from the group consisting of

and mixtures thereof;
wherein R 25 , R 26 , R 27 , and R 28 are each independently —H or —CH 3 ;
wherein p is 1 or 2; and
wherein q is 0 or 1.

3. The polymer of claim 1 wherein Are is selected from the group consisting of

and mixtures thereof;
wherein R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , and R 36 are each independently —CH 3 or —CF 3 ; and
wherein r, s, d, and o are each independently 0 or 1.

4. The polymer of claim 1 wherein X 1 is

and wherein R 37 and R 38 are each independently —H, —CH 3 , —CH 2 CH 3 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —CH 2 —C 6 H 5 , or —CH 2 —CH(CH 3 ) 2 ; and
wherein Y 1 − is OH − or I − .

5. The polymer of claim 1 wherein X 1 is

wherein t is 1, 2, 3, 4, 5, or 6; and
wherein Y 2 − is OH − or I − .

6. The polymer of claim 1 wherein X 1 is a mixture of

wherein R 37 and R 38 are each independently —H, —CH 3 , —CH 2 CH 3 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —CH 2 —C 6 H 5 , or —CH 2 —CH(CH 3 ) 2 ;
wherein t is 1, 2, 3, 4, 5, or 6; and
wherein Y 1 − and Y 2 − are the same and are selected from OH − or I − .

7. The polymer of claim 1 wherein X 1 is a mixture of

wherein R 37 and R 38 are each independently —H, —CH 3 , —CH 2 CH 3 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —CH 2 —C 6 H 5 , or —CH 2 —CH(CH 3 ) 2 ;
wherein t is 1, 2, 3, 4, 5, or 6;
wherein Y 1 − and Y 2 − are the same and are selected from OH − or I − ; and
wherein R 39 is —CH 3 , —CH 2 CH 3 , —C 6 H 5 , or —(CH 2 ) 5 —N + (CH 3 ) 3 .

8. The polymer of claim 1 wherein the polymer is synthesized from monomers Ar 1 ′, Ar 2 ′, and X 1 ′ wherein Ar 1 ′ is selected from the group consisting of:

and mixtures thereof;
Ar 2 ′ is selected from the group consisting of:

and mixtures thereof; and
X 1 ′ is selected from the group consisting of:

optionally

and mixtures thereof.

9. The polymer of claim 8 wherein Ar 1 ′ is selected from the group consisting of:

and mixtures thereof;
wherein R 25 , R 26 , R 27 , and R 28 are each independently —H or —CH 3 ;
wherein p is 1 or 2; and
wherein q is 0 or 1.

10. The polymer of claim 8 wherein Ar 2 ′ is selected from the group consisting of:

and mixtures thereof;
wherein R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , and R 36 are each independently —CH 3 or —CF 3 ; and
wherein r, s, d, and o are independent 0 or 1.

11. The polymer of claim 8 wherein X 1 ′ is

and wherein R 37 is —H, —CH 3 , —CH 2 CH 3 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —CH 2 —C 6 H 5 , or —CH 2 —CH(CH 3 ) 2 .

12. The polymer of claim 8 wherein X 1 ′ is

and wherein t is 1, 2, 3, 4, 5, or 6.

13. The polymer of claim 8 wherein X 1 ′ is a mixture of

wherein R 37 is —H, —CH 3 , —CH 2 CH 3 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —CH 2 —C 6 H 5 , or —CH 2 —CH(CH 3 ) 2 ;
and wherein t is 1, 2, 3, 4, 5, or 6.

14. The polymer of claim 8 wherein X 1 ′ is a mixture of

wherein R 37 is —H, —CH 3 , —CH 2 CH 3 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —CH 2 —C 6 H 5 , or —CH 2 —CH(CH 3 ) 2 ;
wherein R 39 is —CH 3 , —CH 2 CH 3 , —C 6 H 5 , or —(CH 2 ) 5 —N + (CH 3 ) 3 ; and
wherein t is 1, 2, 3, 4, 5, or 6.

15. An anion exchange membrane comprising the polymer of claim 1 .

16. The anion exchange membrane of claim 15 , wherein the anion exchange membrane is used in a fuel cell, an electrolyzer, a flow battery, an electrodialyzer, a waste metal recovery system, an electrocatalytic hydrogen production system, a desalinator, a water purifier

Assignees

• Uop Llc

Inventors

• Ba Chaoyi
• Liu Chunqing
• Dong Xueliang

Classifications

• C08G61/00

  Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule (C08G2/00 - C08G16/00 take precedence) · CPC title

• C08G2261/42

  Non-organometallic coupling reactions, e.g. Gilch-type or Wessling-Zimmermann type · CPC title

• C09D165/00

  Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers · CPC title

• C08L65/00

  Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers · CPC title

• Y02P20/133

  Renewable energy sources, e.g. sunlight · CPC title