Proton exchange membranes for electrochemical reactions

Patent metadata

Field	Value
Publication number	US-12567598-B2
Application number	US-202217822846-A
Country	US
Kind code	B2
Filing date	Aug 29, 2022
Priority date	Oct 22, 2021
Publication date	Mar 3, 2026
Grant date	Mar 3, 2026

Abstract

A proton-conducting polymer comprises a plurality of repeating units of formula (I) for electrochemical reactions. The polymer may be synthesized from a super acid catalyzed polyhydroxyalkylation reaction of monomers Ar 1 ′, Ar 2 ′, and X 1 ′ followed by a nucleophilic substitution reaction or a grafting reaction, and optionally an acidification reaction.

Proton-exchange membranes and membrane electrode assemblies made from the polymer are also described.

First claim

What is claimed is:

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

wherein one or more of Ar 1 , Ar 2 , and X 1 comprises an acid functional group, wherein the acid functional group comprises —SO 3 − Z + , —COO − Z + , or —PO 3 H − Z + , and wherein Z + is H + , a metal cation, a quaternary ammonium cation, or mixtures thereof;
wherein Ar 1 is selected from the group consisting of:

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

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

or a mixture of

one or more of:

wherein R 1 -R 36 are each independently hydrogen, a halogen, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and wherein the alkyl group, the alkenyl group, the alkynyl group, or the aryl group is optionally substituted with a halogen, an acid functional group, or the halogen and the acid functional group, and wherein the acid functional group is —SO 3 − Z 1 + , —COO − Z 1 + , or —PO 3 H − Z 1 + , and wherein Z 1 + is H + , a metal cation, a quaternary ammonium cation, or mixtures thereof;
wherein R 37 -R 39 are each independently hydrogen, a halogen, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or an alkoxy group, and wherein the alkyl group, the alkenyl group, the alkynyl group, or the aryl group is optionally substituted with a halogen, an acid functional group, or the halogen and the acid functional group, and wherein the acid functional group is —SO 3 − Z 2 + , —COO − Z 2 + , or —PO 3 H − Z 2 + , and wherein Z 2 + is H + , a metal cation, a quaternary ammonium cation, or mixtures thereof;
wherein R 40 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and wherein the alkyl group, the alkenyl group, the alkynyl group, or the aryl group is optionally substituted with a halogen, an acid functional group, or the halogen and the acid functional group, and wherein the acid functional group is —SO 3 − Z 3 + , —COO − Z 3 + , or —PO 3 H − Z 3 + , and wherein Z 3 + is H + , a metal cation, a quaternary ammonium cation, or mixtures thereof;
wherein R 50 , R 50 ′, R 50 ″, and R 50 ′″ are each independently hydrogen, a substituted alkyl group, a substituted alkenyl group, a substituted alkynyl group, or a substituted aryl group, and wherein the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, or the substituted aryl group are substituted with an acid functional group or are substituted with a halogen and the acid functional group; wherein the acid functional group is —SO 3 − Z 4 + , —COO − Z 4 + , or —PO 3 H − Z 4 + , and wherein Z 4 + is H + , a metal cation, a quaternary ammonium cation, or mixtures thereof; with the proviso that one or more of R 50 and R 50 ′ is not hydrogen, or one or more of R 50 , R 50 ′, R 50 ″, and R 50 ′″ is not hydrogen;
wherein R 100 is independently a substituted alkyl group, a substituted alkenyl group, a substituted alkynyl group, or a substituted aryl group, and wherein the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, or the substituted aryl group is substituted with an acid functional group or is substituted with a halogen and the acid functional group; wherein the acid functional group is —SO 3 − Z 4 + , —COO − Z 4 + , or —PO 3 H − Z 4 + , and wherein Z 4 + is H + , a metal cation, a quaternary ammonium cation, or mixtures thereof;
wherein the halogen is F, Cl, Br, or I;
wherein A 1 , A 2 , and A 3 are each independently O, S, or N—R 200 and wherein R 200 is hydrogen, a substituted alkyl group, a substituted alkenyl group, a substituted alkynyl group, or a substituted aryl group, and wherein the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, or the substituted aryl group is substituted with an acid functional group or is substituted with a halogen and the acid functional group;
wherein the acid functional group is —SO 3 − Z 4 + , —COO − Z 4 + , or —PO 3 H − Z 4 + , and wherein Z 4 + is H + , a metal cation, a quaternary ammonium cation, or mixtures thereof;
wherein p is 1, 2, 3, or 4;
wherein q is 0, 1, 2, or 3;
wherein r, s, t, and o are independently 0, 1, 2, 3, 4, 5, or 6; and
wherein n is an integer from 0 to 5000;
wherein m is an integer from 5 to 5000; and
wherein a molar ratio of n/m is in a range of 0:1 to 20:1.

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 Ar 2 is selected from the group consisting of

and mixtures thereof;
wherein R 29 -R 36 are each independently —CH 3 or —CF 3 ;
wherein R 50 , R 50 ′, R 50 ″, and R 50 ′″ are each independently hydrogen or —(CH 2 ) 3 SO 3 − Z 4 + and wherein Z 4 + is H + , a metal cation, a quaternary ammonium cation, or mixtures thereof, with the proviso that one or more of R 50 and R 50 ′ is not hydrogen, or one or more of R 50 , R 50 ′, R 50 ″, and R 50 ′″ is not hydrogen; and
wherein r, s, t, and o are each independently 0 or 1.

4 . The polymer of claim 1 wherein X 1 is

wherein R 37 , R 38 , and R 39 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 R 100 is —(CH 2 ) 3 SO 3 − Z 4 + and wherein Z 4 + is H + , a metal cation, a quaternary ammonium cation, or mixtures thereof.

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

wherein R 37 , R 38 , and R 39 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 40 is —CH 3 , —CH 2 CH 3 , or —C 6 H 5 ; and
wherein R 100 is —(CH 2 ) 3 SO 3 − Z 4 + and wherein Z 4 + is H + , a metal cation, a quaternary ammonium cation, or mixtures thereof.

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

wherein R 37 , R 38 , and R 39 are each independently —H, —CH 3 , —CH 2 CH 3 , —CH(

Assignees

• Uop Llc

Inventors

• Liu Chunqing
• Ba Chaoyi
• Karns Nicole
• Dong Xueliang

Classifications

• C08G65/4006

  (I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X) · CPC title

• C08G65/48

  Polymers modified by chemical after-treatment · CPC title

• C08J2371/10

  from phenols · CPC title

• C08J5/2256 Primary

  based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation · CPC title

• Y02E60/50

  Fuel cells · CPC title