Granted Patent B2

US 12,503,548 · App. 17/662,676 · Granted Dec 23, 2025

Inventors: Chunqing Liu (Arlington Heights, IL); Xueliang Dong (Schaumburg, IL)

Assignee: UOP LLC

C08G61/121B01J41/09B01J41/14C07D209/86C07D487/10C25B9/23C25B1/04

Abstract

Claims (91)

1 . An anion exchange 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,

wherein X 1 is a mixture of

or

wherein X 1 is a mixture of

wherein F 1 − -F 6 − , Y 1 − , and Y 2 − are each independently anions;

wherein R 1 -R 28 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 29 , R 34 , and R 35 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 36 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 R 37 -R 52 are each independently an alkyl group, an alkenyl group, or an aryl group;

wherein A is O, S, or NR 100 ;

wherein R 100 is 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 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; and

wherein t, k1, and k2 are independently 1, 2, 3, 4, 5, or 6.

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

and mixtures thereof,

wherein R 37 , R 41 , R 45 , R 46 , R 47 , and R 50 are each independently —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 5 —, —(CH 2 ) 6 —, or —C 6 H 4 —; and

wherein F 1 − -F 6 − are each independently OH − , I − , or Br − .

4 . The anion exchange polymer of claim 1 wherein X 1 is the mixture of

or wherein X 1 is the mixture of

and wherein R 34 and R 35 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 anion exchange polymer of claim 1 wherein X 1 is the mixture of

or wherein X 1 is the mixture of

wherein Y 2 − is OH − or I − .

6 . The anion exchange polymer of claim 1 wherein X 1 is the mixture of

wherein R 34 and R 35 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 anion exchange polymer of claim 1 wherein X 1 is the mixture of

wherein R 34 and R 35 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 R 36 is —CH 3 , —CH 2 CH 3 , —C 6 H 5 , or —(CH 2 ) 5 —N + (CH 3 ) 3 ;

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 − .

8 . The anion exchange polymer of claim 1 wherein the anion exchange 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

wherein X 1 ′ is a mixture of

or wherein X 1 ′ is a mixture of

wherein Y 2 − , F 3 − , and F 4 − are each independently an anion;

wherein R 1 -R 28 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 29 , R 34 , R 48 , and R 51 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 36 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 R 37 , R 41 , R 45 , R 46 , R 47 , and R 50 are each independently an alkyl group, an alkenyl group, an aryl group, or combinations thereof,

wherein B 1 and B 2 are each independently a halide functional group;

wherein A is O, S, or NR 100 ;

wherein R 100 is 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 p is 1, 2, 3, or 4;

wherein q is 0, 1, 2, or 3; and

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

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

and mixtures thereof,

wherein R 37 , R 41 , R 45 , R 46 , R 47 , and R 50 are each independently —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 5 —, —(CH 2 ) 6 —, or —C 6 H 4 —; and

wherein F 3 − and F 4 − are independently Br or I − .

11 . The anion exchange polymer of claim 8 wherein X 1 ′ is the mixture of

wherein X 1 ′ is the mixture of

wherein R 34 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 anion exchange polymer of claim 8 wherein X 1 ′ is the mixture of

wherein R 34 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 t is 1, 2, 3, 4, 5, or 6.

13 . The anion exchange polymer of claim 8 wherein X 1 ′ is the mixture of

wherein R 34 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 36 is —Ch 3 , —CH 2 CH 3 , —C 6 H 5 , or —(CH 2 ) 5 —N + (CH 3 ) 3 ; and

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

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

15 . The anion exchange membrane of claim 14 , 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, a waste water treatment system, an ion exchanger, or a CO 2 separator.

16 . The anion exchange membrane of claim 14 wherein the anion exchange membrane comprises a nonporous symmetric dense film membrane, an integrally-skinned asymmetric membrane, a reinforced composite membrane, or a thin film composite membrane.

17 . The anion exchange membrane of claim 16 wherein the integrally-skinned asymmetric membrane, the reinforced composite membrane, or the thin film composite membrane comprises a porous substrate membrane impregnated or coated with the anion exchange polymer.

18 . A membrane electrode assembly, comprising:

an anion exchange membrane comprising the anion exchange polymer of claim 1 ;

an anode comprising an anode catalyst on a first surface of the anion exchange membrane; and

a cathode comprising a cathode catalyst on a second surface of the anion exchange membrane.

19 . The membrane electrode assembly of claim 18 further comprising:

an anode porous transport layer adjacent to the anode; and

a cathode porous transport layer adjacent to the cathode.

Assignments (2)

Continuity (1)

References Cited (64)