Anion exchange polymers and membranes for electrolysis

Patent metadata

Field	Value
Publication number	US-12503548-B2
Application number	US-202217662676-A
Country	US
Kind code	B2
Filing date	May 10, 2022
Priority date	May 10, 2022
Publication date	Dec 23, 2025
Grant date	Dec 23, 2025

Abstract

Anion exchange polymers comprise a plurality of repeating units of formula (I). The polymer may be synthesized from a super acid catalyzed polyhydroxyalkylation reaction of monomers Ar 1 ′, Ar 2 ′, and X 1 ′ to form a neutral precursor polymer followed by a Menshutkin reaction to convert the neutral precursor polymer to the anion exchange polymer.

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

First claim

What is claimed is:

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 s

Assignees

• Uop Llc

Inventors

• Liu Chunqing
• Dong Xueliang

Classifications

• C07D487/10

  Spiro-condensed systems · CPC title

• C07D209/86

  with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system · CPC title

• C25B1/04

  by electrolysis of water · CPC title

• B01J41/09

  Organic material · CPC title

• C25B9/23

  comprising ion-exchange membranes in or on which electrode material is embedded · CPC title