Curable poly(RTIL)-based mixed-matrix membranes and methods using same

Patent metadata

Field	Value
Publication number	US-11745147-B2
Application number	US-201917058821-A
Country	US
Kind code	B2
Filing date	May 29, 2019
Priority date	May 29, 2018
Publication date	Sep 5, 2023
Grant date	Sep 5, 2023

Abstract

The invention includes compositions and methods for promoting gas mixtures separations, such as a carbon dioxide and methane mixture. The composition of the invention is based on a curable polymerized room-temperature ionic liquid [poly(RTIL)].

First claim

What is claimed is:

1. A composition comprising:
at least one porous solid;
a non-polymerizable room-temperature ionic liquid [RTIL];
a [poly(RTIL)] polymer of Formula (II):

wherein:
A 1 is an RTIL comprising a self-cross-linking group;
A 2 is an RTIL not comprising a self-cross-linking group;
z is an integer ranging from 2 to 25;
x is an integer ranging from 10 to 90; and
n is greater than 0 and less than 1;

wherein each non-polymerizable RTIL is independently a compound of Formula (I):

wherein:
each occurrence of R 1 and R 4 is independently selected from the group consisting of optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally C 2 -C 6 alkynyl, optionally C 1 -C 6 alkoxy, optionally C 1 -C 6 aminoalkyl, optionally C 1 -C 6 haloalkoxy, optionally C 1 -C 6 haloalkyl, optionally substituted aryl, and optionally substituted heteroaryl;
each occurrence of R 2 and R 3 is independently selected from the group consisting of H, optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally C 2 -C 6 alkynyl, optionally C 1 -C 6 alkoxy, optionally C 1 -C 6 aminoalkyl, optionally C 1 -C 6 haloalkoxy, and optionally C 1 -C 6 haloalkyl; and
Y is an anion selected from the group consisting of Tf 2 N − , BF 4 − , N(CN) 2 − , PF 6 − , C(CN) 3 − , B(CN) 4 − , N(SO 2 F) 2 − , TfO − , SbF 6 − , halide, and sulfonate.

2. The composition of claim 1 , wherein the at least one porous solid comprises a nanoporous solid, zeolite, or molecular sieve.

3. The composition of claim 2 , wherein the zeolite comprises a silicoaluminophosphate, an aluminosilicate, a silicate, or an alkali metal aluminosilicate.

4. The composition of claim 1 , wherein the self-cross-linking group is selected from the group consisting of terminal alkene, acrylate, methacrylate, or diene.

5. The composition of claim 1 , wherein the terminal alkene comprises vinyl, halovinyl, vinyl ether, or styrene.

6. The composition of claim 1 , wherein the non-polymerizable RTIL of Formula (I) is a compound of Formula (Ia):

7. The composition of claim 1 , wherein the backbone of the [poly(RTIL)] is derived from reversible addition fragmentation chain transfer (RAFT) polymerization.

8. The composition of claim 1 , wherein
A 1 has the structure of Formula (IV):

and A 2 has the structure of Formula (V):

wherein:
each occurrence of R 2 and R 3 is independently selected from the group consisting of H, optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally C 2 -C 6 alkynyl, optionally C 1 -C 6 alkoxy, optionally C 1 -C 6 aminoalkyl, optionally C 1 -C 6 haloalkoxy, and optionally C 1 -C 6 haloalkyl; and
Y is an anion selected from the group consisting of Tf 2 N − , BF 4 − , N(CN) 2 − , PF 6 − , C(CN) 3 − , B(CN) 4 − , N(SO 2 F) 2 − , TfO − , SbF 6 − , halide, and sulfonate.

9. The composition of claim 8 , wherein
A 1 has the structure of Formula (IVa):

and A 2 has the structure of Formula (Va):

10. The composition of claim 1 , wherein RTILs comprising a self-cross-linking group side chain are about 20 mol % to about 35 mol % of the total RTILs in the poly[RTIL].

11. The composition of claim 1 , wherein the [poly(RTIL)] is about 50% to about 85% of the weight of the composition.

12. The composition of claim 1 , wherein the non-polymerizable RTIL is about 10% to about 35% of the weight of the composition.

13. The composition of claim 1 , wherein the porous solids are about 1% to about 35% of the weight of the composition.

14. The composition of claim 1 , which is at least partially polymerized.

15. The composition of claim 14 , wherein the at least partial polymerization does not require use of any additional cross-linking agent.

16. The composition of claim 1 , wherein the composition is cast on a porous support to form a mixed matrix membrane (MMM).

17. A MMM formed from the composition of claim 1 .

18. The MMM of claim 17 , which has higher permeability for CO 2 than for CH 4 .

19. The MMM of claim 18 , wherein the MMM has CO 2 permeability of about 9 barrers to about 48 barrers.

20. The MMM of claim 17 , wherein the MMM has a carbon dioxide/methane (CO 2 /CH 4 ) gas separation selectivity of about 25:1 to about 47:1.

21. The MMM of claim 17 , where in the MMM is cast on a porous support membrane.

22. A method of selectively separating a first gas component from a gas mixture containing at least a first component and a second gas component,
the method comprising contacting the gas mixture with a surface of the MMM of claim 16 , wherein the first gas component selectively diffuses to the opposite surface of the MMM as compared to second gas component, thus selectively removing the first gas component over the second gas component from the gas mixture.

23. The method of claim 22 , wherein the first gas component is carbon dioxide (CO 2 ) and the second gas component is methane (CH 4 ).

24. A kit comprising the composition of claim 1 or the MMM formed therefrom, and an instructional material, wherein the instructional material comprises instructions for separating a first gas component from a gas mixture containing at least a first component and a second gas component.

Assignees

• Univ Colorado Regents

Inventors

• Gin Douglas L
• Dunn Collin Andrew
• Singh Zoban
• Noble Richard D

Classifications

• B01D71/0281

  Zeolites · CPC title

• B01D69/125

  In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction · CPC title

• Y02C20/40

  of CO2 · CPC title

• B01D69/148 Primary

  Organic/inorganic mixed matrix membranes · CPC title

• B01D53/228 Primary

  characterised by specific membranes · CPC title