Composites comprising novel RTIL-based polymers, and methods of making and using same

Patent metadata

Field	Value
Publication number	US-9687840-B2
Application number	US-201314413772-A
Country	US
Kind code	B2
Filing date	Jul 9, 2013
Priority date	Jul 9, 2012
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

The invention includes compositions comprising curable imidazolium-functionalized poly(room-temperature ionic liquid) copolymers and homopolymers. The invention further includes methods of preparing and using the compositions of the invention. The invention further includes novel methods of preparing thin, supported, room-temperature ionic liquid-containing polymeric films on a porous support. In certain embodiments, the methods of the invention avoid the use of a gutter layer, which greatly reduces the overall gas permeance and selectivity of the composite membrane. In other embodiments, the films of the invention have increased gas selectivity and permeance over films prepared using methods described in the prior art.

First claim

What is claimed is:

1. A composition comprising a curable imidazolium-functionalized poly(room temperature ionic liquid) (poly(RTIL)) copolymer, the copolymer comprising a plurality of imidazolium-functionalized monomeric units, wherein
(100λ(1−p))% of the monomeric units comprise a side-chain imidazolium group substituted with a curable group,
(100×p) % of the monomeric units comprise a side-chain imidazolium group substituted with a non-curable group, and
0<p<1,

the copolymer having formula (I),

wherein:
A is H, alkyl or substituted alkyl;
n ranges from 2 to 100,000;
W is the side chain selected from the group consisting of:

wherein in (II):
R is C 1 -C 6 alkylene, C 2 -C 6 alkenylene or C 2 -C 6 alkynylene, wherein R is optionally substituted;
R 1 is NH or O;
each occurrence of Y is independently selected from the group consisting of H, alkyl, benzyl, phenyl, hydroxyl, nitro, halo, —(CH 2 CH 2 O) m A and —O(CH 2 CH 2 O) m A, wherein m is an integer ranging from 1 to 20, wherein each Y is independently optionally substituted;
X − 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, sulfonate, and any combinations thereof;
in (100×(1−p)) % of the monomeric units, Z is the curable group selected from the group comprising vinyl, 1,3-butadienyl, (1,3-butadienyl)-(C 1 -C 6 alkylene), styrenyl, CH 2 ═C(A)C(═O)R; (oxiran-2-yl)-R; and any combinations thereof; and
in (100×p) % of the monomeric units, Z is the non-curable group selected from the group consisting of H, alkyl, benzyl, phenyl, and oligo(ethylene glycol).

2. The composition of claim 1 , wherein 0<p<0.8.

3. The composition of claim 1 , wherein formula (I) is:

4. The composition of claim 1 , wherein formula (II) is:

5. The composition of claim 1 , wherein the composition is at least partially cured.

6. The composition of claim 1 , further comprising at least one component selected from the group consisting of an imidazolium-functionalized RTIL, polymerization initiator, and imidazolium-based RTIL monomer.

7. The composition of claim 6 , wherein at least 50 wt % of the RTIL-containing material in the composition corresponds to the imidazolium-functionalized RTIL.

8. The composition of claim 1 , wherein the composition is embedded within a porous support membrane or deposited as a layer on the surface of a porous support membrane.

9. The composition of claim 8 , wherein the composition is at least partially cured after being embedded within the porous support membrane or deposited as a layer on the surface of the porous support membrane.

10. A method of processing a given gas mixture comprising a first gas component and a second gas component, the method comprising:
(i) providing a membrane or film comprising at least one composition selected from the group consisting of:
(a) a composition comprising a curable imidazolium-functionalized poly(RTIL) copolymer comprising a plurality of imidazolium-functionalized monomeric units, wherein (100×(1−p))% of the monomeric units comprise a side-chain imidazolium group substituted with a curable group, (100×p) % of the monomeric units comprise a side-chain imidazolium group substituted with a non-curable group, and 0<p<1,
the copolymer having formula (I),

 wherein:
A is H, alkyl or substituted alkyl;
n ranges from 2 to 100,000;
W is the side chain selected from the group consisting of:

wherein in (II):
 R is C 1 -C 6 alkylene, C 2 -C 6 alkenylene or C 2 -C 6 alkynylene, wherein R is optionally substituted;
 R 1 is NH or O;
 each occurrence of Y is independently selected from the group consisting of H, alkyl, benzyl, phenyl, hydroxyl, nitro, halo, —(CH 2 CH 2 O) m A and —O(CH 2 CH 2 O) m A, wherein m is an integer ranging from 1 to 20, wherein each Y is independently optionally substituted;
 X − 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, sulfonate, and any combinations thereof;
 in (100×(1−p)) % of the monomeric units, Z is the curable group selected from the group comprising vinyl, 1,3-butadienyl, (1,3-butadienyl)-(C 1 -C 6 alkylene), styrenyl, CH 2 ═C(A)C(═O)R; (oxiran-2-yl)-R; and any combinations thereof; and
 in (100×p) % of the monomeric units, Z is the non-curable group selected from the group consisting of H, alkyl, benzyl, phenyl, and oligo(ethylene glycol); and,

(b) a composition comprising a RTIL, a step-growth imidazolium-based RTIL monomer and an amine-containing monomer;
wherein the step-growth imidazolium-based RTIL monomer comprises a compound of formula (IV):

wherein X − is an anion; each occurrence of Z 3 is independently C 1 -C 20 alkylene, wherein one or more methylene groups are optionally replaced with —O—; and each occurrence of Z 2 is independently selected from the group consisting of H, alkyl, alkenyl, alkynyl, and aryl groups having 1 to 20 carbon atoms,

wherein the at least one composition is at least partially cured,
further wherein the membrane or film comprises a feed side and a permeate side, and-is selectively permeable to the first gas component over the second gas component;

(ii) contacting the given gas mixture with the feed side of the membrane or film; and
(iii) applying a pressure difference across the membrane or film;
whereby the gas mixture isolated at the permeate side of the membrane or film is enriched for the first gas component over the second gas component as compared to the given gas mixture.

11. The method of claim 10 , wherein the first gas component comprises carbon dioxide (CO 2 ) and the second gas component comprises methane (CH 4 ), hydrogen (H 2 ), or nitrogen gas (N 2 ).

12. The method of claim 10 , wherein providing the membrane or film comprises embedding the composition within the pores of a solid porous support and optionally curing the composition at least partially.

13. The method of claim 10 , wherein the membrane or film forms a layer on the surface of a solid porous support.

14. A composition comprising a RTIL, a step-growth imidazolium-based RTIL monomer and an amine-containing monomer, wherein the step-growth imidazolium-based RTIL monomer comprises a compound of formula (IV):

wherein X − is an anion; each occurrence of Z 3 is independently C 1 -C 20 alkylene, wherein one or more m

Assignees

• Univ Colorado Regents

Inventors

• Gin Douglas
• Carlisle Trevor
• Noble Richard
• Nicodemus Garret
• Mcdanel William
• Cowan Matthew

Classifications

• B01D71/34

  Polyvinylidene fluoride · CPC title

• C08F112/32

  containing two or more rings · CPC title

• C08F112/26

  Nitrogen · CPC title

• C08F12/26

  Nitrogen · CPC title

• B01D2323/46

  Impregnation · CPC title