Imidazoles and imidazolium cations with exceptional alkaline stability

Patent metadata

Field	Value
Publication number	US-11242432-B2
Application number	US-201615566595-A
Country	US
Kind code	B2
Filing date	Apr 14, 2016
Priority date	Apr 14, 2015
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

The invention provides: imidazole and imidazolium compounds of formulas (I) and (II):

polymers containing a plurality of imidazolium-containing repeating units of formula (III′):

and membranes and devices comprising the polymers. Also provided are methods of making the inventive compounds and polymers.

First claim

The invention claimed is:

1. A polymer comprising a plurality of imidazolium-containing repeating units represented by a structural formula selected from

wherein:
R 2′ is selected from C 1 -C 6 alkyl or R 2 ;
R 2 is phenyl substituted with 0 to 3 substituents R 6 each independently selected from C 1 -C 3 alkyl;
R 3′ is selected from hydrogen, methyl, or R 3 ;
R 3 is selected from C 2 -C 16 hydrocarbyl;
R 4 and R 5 each is independently selected from C 1 -C 16 hydrocarbyl, or, taken together, R 4 and R 5 , together with the carbon atoms to which they are attached, form a ring selected from benzene, cyclooctene or norbornene;
X − is a counterion;
wavy lines indicate points of attachment to adjacent repeating units of the polymer;
and
Z is C 1 -C 8 hydrocarbyl, wherein one carbon atom of the C 1 -C 8 hydrocarbyl may optionally be replaced by O.

2. A polymer according to claim 1 , wherein
R 2′ is R 2 ; and
R 3′ is R 3 .

3. A polymer according to claim 1 , wherein R 3′ is R 3 ; and R 3 is selected from C 2 -C 12 hydrocarbyl.

4. A polymer according to claim 1 , comprising a plurality of imidazolium-containing repeating units represented by a structural formula selected from

wherein:
m is 0 or 1; and
when m is 0 Z 1A is C 1 -C 8 hydrocarbyl and when m is 1 Z 1A is C 1 -C 6 hydrocarbyl.

5. A polymer according to claim 4 , wherein:
R 2′ is R 2 ; and
R 3′ is R 3 .

6. A polymer according to claim 4 , wherein Z 1a is —(CH 2 ) p —(Ph) q —(CH 2 ) r —, wherein: p is 1-6; q is 0 or 1; and r is 1-6.

7. A polymer according to claim 1 , comprising a plurality of imidazolium-containing repeating units represented by a structural formula selected from:

wherein:
m is 0 or 1; and
when m is 0 n is 1-8 and when m is 1 n is 1-6.

8. A polymer according to claim 7 , wherein:
R 2′ is R 2 ; and
R 3′ is R 3 .

9. A polymer according to claim 1 in the form of a membrane.

10. A polymer according to claim 1 , wherein R 2′ is R 2 ; and R 2 is a moiety of formula:

wherein:
represents the point of attachment to the imidazolium ring; and
R 6a , R 6b , and R 6c each is independently selected from hydrogen or C 1 -C 3 alkyl.

11. A polymer according to claim 10 , wherein R 3′ is R 3 ; R 3 is n-butyl; R 6a and R 6c are methyl; R 6b is hydrogen; and R 4 and R 5 each is independently selected from phenyl or methyl.

12. A polymer according to claim 1 , wherein R 4 and R 5 each is independently selected from phenyl or C 1 -C 3 alkyl.

13. A polymer according to claim 1 , wherein X − is selected from halide, bicarbonate, carbonate, nitrate, cyanide, or carboxylate.

14. A polymer according to claim 1 , wherein X − is a halide.

15. A polymer according to claim 1 , comprising a plurality of repeating units having a structure selected from:

wherein
X − is selected from hydroxide, a halide, bicarbonate, nitrate, cyanide, a carboxylate, or a C 1 -C 4 alkoxide; and
represents a point of attachment to adjacent repeating units of the polymer.

16. A polymer according to claim 1 , wherein the polymer has the following structure:

wherein
n′ is 0.05 to 1.0.

17. A polymer according to claim 1 , wherein the polymer has the following structure:

wherein
n′ is 0.05 to 1.0.

18. A fuel cell comprising a polymer according to claim 1 , an anode, and a cathode.

19. A polymer according to claim 1 , wherein:
R 2′ is selected from C 1 -C 6 unsubstituted alkyl or R 2 ;
R 2 is phenyl substituted with 0 to 3 substituents R 6 each independently selected from unsubstituted C 1 -C 3 alkyl;
R 3′ is selected from hydrogen, methyl, or R 3 ;
R 3 is selected from C 2 -C 16 unsubstituted alkyl;
R 4 and R 5 each is independently selected from C 1 -C 16 unsubstituted alkyl, or, taken together, R 4 and R 5 , together with the carbon atoms to which they are attached, form a ring selected from unsubstituted benzene, unsubstituted cyclooctene or unsubstituted norbornene.

Assignees

• Univ Cornell

Inventors

• Coates Geoffrey W
• Hugar Kristina M

Classifications

• H01M50/414

  Synthetic resins, e.g. thermoplastics or thermosetting resins · CPC title

• B01D71/44

  Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42 · CPC title

• C08F8/30

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title

• C08L71/02

  Polyalkylene oxides · CPC title

• C08J5/2231

  based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds · CPC title