IP Library Granted Patent US 9,845,380
Granted Patent B2
US 9,845,380 · App. 14/982,386 · Granted Dec 19, 2017

Ionic polyimide materials and methods of use

Inventors: Jason Edward Bara (Tuscaloosa, AL); Matthew S. Shannon (Northport, AL); John David Roveda, Jr. (Mobile, AL); David A. Wallace (Brentwood, TN); Max Simon Mittenthal (Tuscaloosa, AL)
Assignee: The Board of Trustees of The University of Alabama
C08G73/1085B01D53/228B01D71/64B01J20/262B01J20/264B01J20/28033C08G73/0616C08G73/1039C08G73/1067C08K5/3445B01D53/1475B01D53/1493B01D2252/30B01D2257/504Y02C10/10Y02P20/152
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Quick Facts
Patent No.
US 9,845,380
App. No.
14/982,386
Granted
Dec 19, 2017
Kind
B2
Abstract

Disclosed are compositions and methods of preparing ionic polyimides. Also disclosed are methods to tune the properties of the ionic polyimide by designing the components of the ionic polyimide. Additionally, disclosed herein is a composition comprising an ionic polyimide. Also disclosed herein is a composition comprising an ionic polyimide and an ionic liquid. The disclosed compositions can be utilized to capture gases.

Claims (52)

1. A composition, comprising an ionic polyimide having the formula:

wherein,

Y is selected from the group consisting of null, hydrogen, halogen, hydroxyl, carbonyl, O, S, SO 2 , cyano, C(CF 3 ) 2 , substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;

Z is selected from the group consisting of CH, CH 2 , carbonyl, O, S, SO 2 , cyano, C(CF 3 ) 2 , substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;

L 1 and L 2 are selected from the group consisting of branched and unbranched alkyl, alkenyl, and alkynyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, and mixture thereof;

Q is an ionized heteroaryl;

A is an anion; and

n is an integer from 1 to 100,000.

2. The composition of claim 1 , wherein Q is selected from the group consisting of substituted or unsubstituted pyrazolium, substituted or unsubstituted pyridinium, substituted or unsubstituted pyrazinium, substituted or unsubstituted pyrimidinium, substituted or unsubstituted pryidazinium, substituted or unsubstituted piperidinium, substituted or unsubstituted pyrrolidinium, substituted or unsubstituted indolizinium, substituted or unsubstituted isoindolium, substituted or unsubstituted indolium, substituted or unsubstituted indazolium, substituted or unsubstituted imidazolium, substituted or unsubstituted oxazolium, substituted or unsubstituted triazolium, substituted or unsubstituted tetrazolium, substituted or unsubstituted thiazolium, substituted or unsubstituted purinium, substituted or unsubstituted isoquinolinium, substituted or unsubstituted quinolinium, substituted or unsubstituted phthalazinium, substituted or unsubstituted quinooxalinium, substituted or unsubstituted phenazinium, and substituted or unsubstituted morpholininium.

3. The composition of claim 1 , wherein Q is substituted with a functional group selected from the group consisting of alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, and thiol.

4. The composition of claim 1 , wherein Q is imidazolium.

5. The composition of claim 1 , wherein A is selected from the group consisting of chloride, bromide, iodide, nitrate, dicyanamide, acetate, bis(trifluoromethane)sulfonamide, hexafluorophosphate, tetrafluoroborate, sulfate, phosphate, tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride, thiocyanide, mesylate, triflate, and tosylate.

6. The composition of claim 1 , wherein Y and Z together with the atoms to which they are attached form a substituted or unsubstituted triptycene.

7. The composition of claim 1 , wherein the ionic polyimide is selected from the group consisting of:

wherein n is an integer from 1 to 100,000.

8. The composition of claim 1 , wherein n is an integer from 10 to 5,000.

9. The composition of claim 1 , further comprising an ionic liquid having the formula:

wherein,

R 1 , R 2 , R 3 , R 4 , and R 5 are, independent of one another, selected from the group consisting of hydrogen, branched or unbranched C 1-12 alkyl, branched or unbranched C 2-12 alkenyl, and branched or unbranched C 2-12 alkynyl; and

A 1 is an anion.

10. The composition of claim 9 , wherein A and A 1 are independently selected from the group consisting of chloride, bromide, iodide, nitrate, dicyanamide, acetate, bis(trifluoromethane)sulfonamide, hexafluorophosphate, tetrafluoroborate, sulfate, phosphate, tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride, thiocyanide, mesylate, triflate, and tosylate.

11. The composition of claim 9 , wherein the ionic liquid is 1-ethyl-3-methylimidazolium bis(trifluoromethane)sulfonamide.

12. The composition of claim 11 , wherein the ionic polyimide is selected from the group consisting of:

wherein n is an integer from 1 to 100,000.

13. The composition of claim 9 , wherein n is an integer from 10 to 5,000.

14. A method for capturing carbon dioxide from a gas stream, comprising:

feeding the gas stream through a membrane, wherein the membrane comprises an ionic polyimide having the following structure:

wherein,

Y is selected from the group consisting of null, hydrogen, halogen, hydroxyl, carbonyl, O, S, SO 2 , cyano, C(CF 3 ) 2 , substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted triptycene, and substituted or unsubstituted heteroaryl;

Z is selected from the group consisting of CH, CH 2 , carbonyl, O, S, SO 2 , cyano, C(CF 3 ) 2 , substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted triptycene, and substituted or unsubstituted heteroaryl;

L 1 and L 2 are selected from the group consisting of branched and unbranched alkyl, alkenyl, and alkynyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, and mixture thereof;

Q is an ionized heteroaryl;

A is an anion; and

n is an integer from 1 to 100,000.

15. The method of claim 14 , wherein Q is selected from the group consisting of substituted or unsubstituted pyrazolium, substituted or unsubstituted pyridinium, substituted or unsubstituted pyrazinium, substituted or unsubstituted pyrimidinium, substituted or unsubstituted pryidazinium, substituted or unsubstituted piperidinium, substituted or unsubstituted pyrrolidinium, substituted or unsubstituted indolizinium, substituted or unsubstituted isoindolium, substituted or unsubstituted indolium, substituted or unsubstituted indazolium, substituted or unsubstituted imidazolium, substituted or unsubstituted oxazolium, substituted or unsubstituted triazolium, substituted or unsubstituted tetrazolium, substituted or unsubstituted thiazolium, substituted or unsubstituted purinium, substituted or unsubstituted isoquinolinium, substituted or unsubstituted quinolinium, substituted or unsubstituted phthalazinium, substituted or unsubstituted quinooxalinium, substituted or unsubstituted phenazinium, and substituted or unsubstituted morpholininium.

16. The method of claim 14 , wherein Q is substituted with a functional group selected from the group consisting of alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, and thiol.

17. The method of claim 14 , wherein Q is imidazolium.

18. The method of claim 14 , wherein A is selected from the group consisting of chloride, bromide, iodide, nitrate, dicyanamide, acetate, bis(trifluoromethane)sulfonamide, hexafluorophosphate, tetrafluoroborate, sulfate, phosphate, tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride, thiocyanide, mesylate, triflate, and tosylate.

19. The method of claim 14 , wherein Y and together with the atoms to which they are attached form a substituted or unsubstituted triptycene.

20. The method of claim 14 , wherein the ionic polyimide is selected from the group consisting of:

wherein n is an integer from 1 to 100,000.

21. The method of claim 14 , wherein n is an integer from 10 to 5,000.

22. The method of claim 14 , wherein the membrane further comprises an ionic liquid having the formula:

wherein,

R 1 , R 2 , R 3 , R 4 , and R 5 are, independently of each other, selected from the group consisting of hydrogen and branched and unbranched alkyl, alkenyl, and alkynyl groups having 1 to 12 carbon atoms; and

A 1 is an anion.

23. The method of claim 22 , wherein A and A 1 are independently selected from the group consisting of chloride, bromide, iodide, nitrate, dicyanamide, acetate, bis(trifluoromethane)sulfonamide, hexafluorophosphate, tetrafluoroborate, sulfate, phosphate, tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride, thiocyanide, mesylate, triflate, and tosylate.

24. The method of claim 22 , wherein the ionic liquid is 1-ethyl-3-methylimidazolium bis(trifluoromethane)sulfonamide.

25. The method of claim 24 , wherein the ionic polyimide is selected from the group consisting of:

wherein n is an integer from 1 to 100,000.

26. The method of claim 22 , wherein n is an integer from 10 to 5,000.

27. The method of claim 14 , wherein the gas stream is a flue gas or post-combustion stream.

Assignments (3)
CONFIRMATORY LICENSE Recorded Mar 28, 2016
From: UNIVERSITY OF ALABAMA, TUSCALOOSA
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 038275/0172 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 15, 2016
From: MITTENTHAL, MAX SIMON
To: THE BOARD OF TRUSTEES OF THE UNIVERSITY OF ALABAMA
Reel/Frame 037987/0760 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 30, 2015
From: BARA, JASON EDWARD; SHANNON, MATTHEW S.; ROVEDA, JOHN DAVID; WALLACE, DAVID A.
To: THE BOARD OF TRUSTEES OF THE UNIVERSITY OF ALABAMA
Reel/Frame 037384/0802 →
Continuity (2)
Provisional Application 62098068 · Dec 30, 2014
Related Publication 20160185909A1 · Jun 30, 2016