Anion exchange membranes based on polymerization of long chain alpha olefins

Patent metadata

Field	Value
Publication number	US-11834544-B2
Application number	US-201916980320-A
Country	US
Kind code	B2
Filing date	Mar 11, 2019
Priority date	Mar 12, 2018
Publication date	Dec 5, 2023
Grant date	Dec 5, 2023

Abstract

Described herein are cationic polymers having a plurality of quaternary amino groups, methods of making such polymers, and uses of such polymers as ion exchange membranes in electrochemical devices.

First claim

What is claimed is:

1. A method for preparing a cationic polymer having a plurality of quaternary amino groups, the method comprising:
obtaining or providing a precursor polymer comprising x repeat units of Formula (I) and y repeat units of Formula (II)

wherein
each R 1 is independently aralkyl or substituted aralkyl;
each R 2 is independently pendant *—R 3 -L groups,
R 3 is alkylene having at least four carbon atoms;
L is a leaving group;
the asterisk (*) represents the point of attachment of R 3 to the polymer backbone;
the variable x represents an overall mole fraction of the repeat units of Formula (I) in the precursor polymer, with random or block repeat unit distribution;
the variable y represents an overall mole fraction of the repeat units of Formula (II) in the precursor polymer, with random or block monomer repeat unit distribution, wherein y is in a range of about 0.15 to about 0.35; and

reacting the pendant *—R 3 -L groups of the precursor polymer with a cationic amine compound having at least one tertiary amino group and at least one quaternary amino group to form the cationic polymer having the plurality of pendant quaternary amino groups, wherein the cationic polymer having the plurality of pendant quaternary amino groups comprises x repeat units of Formula (I) and z repeat units of Formula (IV)

wherein
each R 4 is independently a cationic group of the Formula (V) or Formula (VI)
*—R 3 —[N(R 5 ) 2 ] + —R 6 —{[N(R 5 ) 2 ] + —R 6 } v —[N(R 5 ) 3 ] +   (V)

each R 5 is independently alkyl;
each R 6 is independently alkylene;
v is an integer in a range of 0 to 10;
each R 7 is an alkyl;
each R 8 is an alkylene;
each R 9 is an alkyl;
each q is independently an integer in a range of 1 to 2; and
p is an integer in a range of 0 to 10; and
the variable z represents the overall mole fraction of the repeat units of Formula (IV) in the cationic polymer, with random or block monomer repeat unit distribution, wherein z is in a range of 0.15 to about 0.35; and
the cationic group has corresponding anionic counter ions.

2. The method of claim 1 , wherein each R 3 is independently (C 6 -C 12 )alkylene.

3. The method of claim 1 , wherein each R 6 is independently (C 4 -C 9 )alkylene.

4. The method of claim 1 , wherein the cationic amine compound that is reacted with the precursor polymer is of Formula (VII)
N(R 5 ) 2 -R 6 —{[N(R 5 ) 2 ] + —R 6 } v —[N(R 5 ) 3 ] +   (VII)

wherein
each R 5 is independently alkyl;
each R 6 is independently alkylene;
v is an integer in a range of 0 to 10; and
the cationic groups have corresponding anionic counter ions.

5. A cationic polymer comprising x repeat units of Formula (I) and z repeat units of Formula (IV)

wherein
each R 1 is independently aralkyl or substituted aralkyl;
the variable x represents an overall mole fraction of the repeat units of Formula (I) in the cationic polymer, with random or block repeat unit distribution;
each R 4 is independently a cationic group of the Formula (V) or Formula (VI)
*—R 3 —[N(R 5 ) 2 ] + —R 6 —{[N(R 5 ) 2 ] + —R 6 } v —[N(R 5 ) 3 ] +   (V)

each R 5 is independently alkyl;
each R 6 is independently alkylene;
v is an integer in a range of 0 to 10;
each R 7 is an alkyl;
each R 8 is an alkylene;
each R 9 is an alkyl;
each q is independently an integer in a range of 1 to 2; and
p is an integer in a range of 0 to 10;
the variable z represents the overall mole fraction of the repeat units of Formula (IV) in the cationic polymer, with random or block monomer repeat unit distribution, wherein z is in a range of 0.15 to about 0.35; and
the cationic group has corresponding anionic counter ions.

6. The cationic polymer of claim 5 , wherein each R 3 is independently (C 6 -C 12 )alkylene.

7. The cationic polymer of claim 5 , wherein each R 6 is independently (C 4 -C 9 )alkylene.

8. The cationic polymer of claim 5 , wherein:
each R 4 is independently a cationic group of the formula:
*—R 3 —N + (CH 3 ) 2 —(CH 2 ) m —{[N(CH 3 ) 2 ] + —(CH 2 ) m } 0-8 —[N(CH 3 ) 3 ] + ,

*—R 3 —N + (CH 3 ) 2 —(CH 2 ) 6-8 —{[N(CH 3 ) 2 ] + —(CH 2 ) 6-8 } v —[N(CH 3 ) 3 ] + or

*—R 3 —N + (CH 3 ) 2 —(CH 2 ) 6-8 —{[N(CH 3 ) 2 ] + —(CH 2 ) 6-8 } 3-8 —[N(CH 3 ) 3 ] + ;

m is a variable in a range of 4 to 9;
v is a variable in a range of 0 to 10; and

the cationic group has corresponding anionic counter ions.

9. The cationic polymer of claim 8 , wherein the anionic counter ions are chloride, bromide, iodide, bicarbonate, carbonate, hydroxide, alkoxide, acetate or sulfate.

10. A membrane comprising the cationic polymer of claim 5 .

11. The membrane of claim 10 , wherein the membrane further comprises reinforcement material.

12. The membrane of claim 10 , wherein the membrane has a positive charge density equal to at least 1 milliequivalent per gram of cationic polymer.

13. The membrane of claim 10 , wherein the membrane has a charge density up to 5 milliequivalent per gram of cationic polymer.

14. An electrochemical device comprising:
an anode;
a cathode; and
a membrane positioned between the anode and cathode, wherein the membrane is according to claim 10 .

15. The electrochemical device of claim 14 , wherein the electrochemical device is a solid-state fuel cell.

Assignees

• 3M Innovative Properties Company
• Penn State Res Found

Inventors

• Yandrasits Michael A
• Laskowski Carl A
• Gillard Timothy M
• Hickner Michael
• Zhu Liang

Classifications

• C08F8/32 Primary

  by reaction with amines · CPC title

• C08F8/44

  Preparation of metal salts or ammonium salts · CPC title

• C08F210/08

  Butenes · CPC title

• C08F212/12

  Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical · CPC title

• C08F214/16

  Monomers containing bromine or iodine · CPC title