Hydroxide-stable ionenes

Patent metadata

Field	Value
Publication number	US-10005886-B2
Application number	US-201515304464-A
Country	US
Kind code	B2
Filing date	Apr 15, 2015
Priority date	Apr 15, 2014
Publication date	Jun 26, 2018
Grant date	Jun 26, 2018

Abstract

Described herein are stable hydroxide ion-exchange polymers. The polymers include ionenes, which are polymers that contain ionic amines in the backbone. The polymers are alcohol-soluble and water-insoluble. The polymers have a water uptake and an ionic conductivity that are correlated to a degree of N-substitution. Methods of forming the polymers and membranes including the polymers are also provided. The polymers are suitable, for example, for use as ionomers in catalyst layers for fuel cells and electrolyzers.

First claim

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A polymer comprising one or more repeating units, wherein at least one of the repeating units comprises one or more benzimidazolium-containing moieties of Formulas (I)-(V):

wherein:
R 1 is independently selected from the group consisting of alkyl, perfluoroalkyl, heteroalkyl, alkoxy, perfluoroalkoxy, halo, aryl, heteroaryl group and a polymer;
R 2 is independently selected from the group consisting of hydrogen, alkyl, and a polymer;
R 3 is independently selected from the group consisting of alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a polymer;
R 5 is independently selected from the group consisting of hydrogen, alkyl, and a polymer;
wherein at least one of R 1 , R 2 , R 3 , and R 5 , is a polymer; and
X is independently selected from the group consisting of alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and no group.

2. The polymer of claim 1 , wherein the polymer is a salt formed with an anion selected from the group consisting of iodide, triiodide, hydroxide, chloride, bromide, fluoride, cyanide, acetate, carbonate, nitrate, sulfate, phosphate, triflate, and tosylate.

3. The polymer of claim 1 , wherein the benzimidazolium-containing moiety is included in a main chain of the polymer, in a pendant chain of the polymer, or is part of a crosslink of the polymer.

4. The polymer of claim 1 , further comprising a second repeating unit defined by Formula (VI):

wherein:
R 1 is independently selected from the group consisting of alkyl, perfluoroalkyl, heteroalkyl, alkoxy, perfluoroalkoxy, halo, aryl, heteroaryl group and a polymer;
R 2 is independently selected from the group consisting of hydrogen, alkyl, and a polymer;
R 3 is independently selected from the group consisting of alkyl, perfluoroalkyl, heteroalkyl, aryl, aralkyl, and a polymer;
R 5 is independently selected from the group consisting of hydrogen, alkyl, and a polymer;
wherein at least one of R 1 , R 2 , R 3 , and R 5 , is a polymer; and
X is independently selected from the group consisting of alkylene, perfluoroalkylene, heteroalkylene, arylene, aralkylene, and no group.

5. The polymer of claim 4 , wherein the polymer is a random copolymer of Formulas (I), (V), and (VI).

6. The polymer of claim 1 , wherein R 1 is methyl.

7. The polymer of claim 1 , wherein R 2 is independently selected from the group consisting of hydrogen and methyl.

8. The polymer of claim 1 , wherein R 3 is methyl.

9. The polymer of claim 1 , wherein R 5 is independently selected from the group consisting of hydrogen and a polymer.

10. The polymer of claim 1 , wherein X is 1,4-phenylene.

11. A polymer of Formula (VIII):

wherein:
R 11a , R 11b , R 11c , R 11d , R 21a , R 21b , R 21c , R 21d , R 31a , R 31b , R 31c , and R 31d are each independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl;
R 12a , R 12b , R 12c , R 12d , R 22a , R 22b , R 22c , R 22d , R 32a , R 32b , R 32c , and R 32d are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl;
R 13a , R 13b , R 14a , and R 14b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl,
R 23a , R 23b , R 24a , and R 24b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl, provided that one of R 23a , R 23b , R 24a and R 24b is absent, the remaining three are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl, and the ring having the absent R 23a , R 23b , R 24a , or R 24b is uncharged;
R 33a , R 33b , R 34a , and R 34b are each independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl;
R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl;
X 11 , X 21 , and X 31 are each independently selected from the group consisting of absent, C 1-6 alkylene, C 1-6 haloalkylene, arylene, and heteroarylene; and
a, b, and c are mole percentages, wherein
a is from 0 mole percent to 45 mole percent,
b+c is 55 mole percent to 100 mole percent,
b and c are each more than 0 percent, and
a+b+c=100%.

12. The polymer of claim 11 , having Formula (VIIIa)

wherein:
R 11a , R 11b , R 11c , R 11d , R 21a , R 21b , R 21c , R 21d , R 31a , R 31b , R 31c , and R 31d are each independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl;
R 12a , R 12c , R 22a , R 22c , R 32a , and R 32c are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl;
R 13a , R 13b , R 14a , and R 14b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl, provided that two of R 13a , R 13b , R 14a , and R 14b are absent, and the remaining two are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl,
R 23a , R 23b , R 24a , and R 24b are each independently selected from absent, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl, provided that one of R 23a , R 23b , R 24a and R 24b is absent, and the remaining three are present and independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl, and the ring having the absent R 23a , R 23b , R 24a , or R 24b is uncharged;
R 33a , R 33b , R 34a , and R 34b are each independently selected from C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl;
R 15a , R 15b , R 15c , R 15d , R 15e , R 15f , R 25a , R 25b , R 25c , R 25d , R 25e , R 25f , R 35a , R 35b , R 35c , R 35d , R 35e , and R 35f are each independently selected from H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy, C 1-6 haloalkoxy, halo, aryl, and heteroaryl;
X 11 , X 21 , and X 31 are each independently selected from the group consisting of absent, C 1-6 alkylene, C 1-6 haloalkylene, arylene, and heteroarylene; and
a, b, and c are mole percentages, wherein
a is from 0 mole percent to 45 mole percent,
b+c is 55 mole percent to 100 mole percent,
b and c are each more than 0 percent, and
a+b+c=100%.

13. The polymer according to claim 11 , wherein R 11a , R 11

Assignees

• Univ Fraser Simon

Inventors

• Holdcroft Steven
• Wright Andrew

Classifications

• C08G73/18 Primary

  Polybenzimidazoles · CPC title

• C08J2379/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• C08J5/2256

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

• C25B13/08

  based on organic materials · CPC title

• H01M4/8668

  Binders · CPC title