Crosslinked polymer compositions, gas separation membranes of such crosslinked polymer compositions, methods of making such membranes, and methods of separating gases using such membranes

Patent metadata

Field	Value
Publication number	US-9533254-B2
Application number	US-201414530108-A
Country	US
Kind code	B2
Filing date	Oct 31, 2014
Priority date	Nov 1, 2013
Publication date	Jan 3, 2017
Grant date	Jan 3, 2017

Abstract

Gas separation membrane compositions including at least one crosslinked polymer, gas separation membranes made of such compositions, methods for making such gas separation membranes, and methods of using such membranes to separate gases are described. In one embodiment, the crosslinked polymer includes polyarylene ethers (PAE).

First claim

The invention claimed is:

1. A composition for a gas separation membrane, wherein the composition comprises at least one crosslinked polymer having the structure of formula (I):
-(A-O—B—O) n —  (I)

wherein in formula (I):
A is selected from the group consisting of:
—Ar 1 -Q-Ar 2 —, —Ar 1 —, and —Ar 1 —Ar 2 —

B is selected from the group consisting of:
—Ar 1 ′-Q′-Ar 2 ′—, —Ar 1 ′—, and —Ar 1 ′—Ar 2 ′—;

Ar 1 , Ar 2 , Ar 1 ′, and Ar 2 ′ are each independently a bivalent C 5 -C 24 arylene or a bivalent C 5 -C 24 heterocyclic ring, and wherein the arylene or heterocyclic ring is independently optionally substituted with at least one R 1 group;
each occurrence of R 1 is independently selected from the group consisting of H, halo, —CN, —SO 3 H or a salt thereof, —CO 2 H or a salt thereof, —C 1 -C 10 alkyl, —C 1 -C 10 alkoxy, —C 1 -C 10 haloalkyl, —C 1 -C 10 haloalkoxy, phenyl, and cyclohexyl, wherein the alkyl, phenyl, and cyclohexyl groups are optionally substituted; or two or more R 1 groups may be joined together to form a ring; or two R 1 groups may be covalently bonded to Y;
Y is selected from the group consisting of —O—, —S—, —C(═O), —CH(OH)—, —S(═O) 2 —, —Si(CH 3 ) 2 —, —(CH 2 ) p —, —(CF 2 ) q —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, and —C(═O)NR 1 —;
Q and Q′ are each independently selected from the group consisting of —O—, —S—, —C(═O), —CH(OH)—, —S(═O) 2 —, —Si(CH 3 ) 2 —, —(CH 2 ) p —, —(CF 2 ) q —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —C(R 1 )(R 1 )—, C(═O)NH—, —P(═O)C 6 H 5 —, —C(CH 3 )(CF 3 )—, —C(═O)C 6 H 4 C(═O)—, —C(R 1 )(R 1 )—C 6 H 4 —C(R 1 )(R 1 )—, -phenyl- (C 1 -C 6 )alkyl, -phenyl-(C 1 -C 6 )haloalkyl, phenyl, cycloalkyl, and heterocyclyl, wherein the phenyl, cycloalkyl, and heterocyclyl groups are optionally substituted; or the two R 1 groups in —C(R 1 )(R 1 ) may be joined together to form a ring, wherein the ring is optionally substituted;
p is an integer from 1 to 10; and
q is an integer from 1 to 10;
wherein at least one occurrence of Ar 1 , Ar 2 , Ar 1 ′, or Ar 2 ′ is substituted with an R 1 group comprising a benzylic hydrogen, and at least one occurrence of Q or Q′ includes a UV activator, wherein the UV activator is a carbonyl group.

2. The composition of claim 1 , wherein the at least one occurrence of Ar 1 , Ar 2 , Ar 1 ′, or Ar 2 ′ substituted with an R 1 group comprising a benzylic hydrogen, and the at least one occurrence of Q or Q′ including a UV activator are on the same polymer.

3. The composition of claim 1 , wherein A is —Ar 1 -Q-Ar 2 — and B is —Ar 1 ′-Q′-Ar 2 ′—.

4. The composition of claim 1 , wherein Ar 1 , Ar 2 , Ar 1 ′ and Ar 2 ′ are each phenyl, further wherein each phenyl is independently optionally substituted with 1-2 R 1 groups.

5. The composition of claim 1 , wherein the polymer comprises at least one crosslink formed via a reaction between a benzylic hydrogen and a Q or Q′ carbonyl group.

6. The composition of claim 1 , wherein the polymer has the structure of formula (II):

wherein in formula (II):
each occurrence of T 1 , T 2 , T 3 , and T 4 is independently selected from the group consisting of H, halo, —CN, —SO 3 H or a salt thereof, and —C 1 -C 10 alkyl;
Q and Q′ are each independently selected from the group consisting of —O—, —S—, —C(═O), —CH(OH)—, —S(═O) 2 —, —Si(CH 3 ) 2 —, —(CH 2 ) p —, —(CF 2 ) q —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —C(R 1 )(R 1 )—, C(═O)NH—, —P(═O)C 6 H 5 —, —C(CH 3 )(CF 3 )—, —C(═O)C 6 H 4 C(═O)—, —C(R 1 )(R 1 )—C 6 H 4 —C(R 1 )(R 1 )—, -phenyl- (C 1 -C 6 )alkyl, -phenyl-(C 1 -C 6 )haloalkyl, phenyl, cycloalkyl, and heterocyclyl, wherein the phenyl, cycloalkyl, and heterocyclyl groups are optionally substituted; or the two R 1 groups in —C(R 1 )(R 1 ) may be joined together to form a ring, wherein the ring is optionally substituted;
a is an integer from 0 to 4;
b is an integer from 0 to 4;
c is an integer from 0 to 4;
d is an integer from 0 to 4;
p is an integer from 1 to 10; and
q is an integer from 1 to 10
wherein at least one occurrence of T 1 , T 2 , T 3 , or T 4 comprises a benzylic hydrogen, and at least one occurrence of Q or Q′ includes a carbonyl group.

7. The composition of claim 6 , wherein Q and Q′ are selected from the group consisting of: (a) Q is —C(CH 3 ) 2 — and Q′ is —C(═O)—; (b) Q is —C(CH 3 ) 2 — and Q′ is —C(═O)C 6 H 4 C(═O)—; (d) Q is —C(CH 3 ) 2 —C 6 H 4 —C(CH 3 ) 2 — and Q′ is —C(═O)—; and (e) Q is —C(CF 3 )(C 6 H 4 )— and Q′ is —C(═O)—.

8. The composition of claim 1 , wherein the polymer has a structure selected from the group consisting of: the structure of formula (III):

the structure of formula (IV):

the structure of formula (V):

the structure of formula (VI):

 and
the structure of formula (VII):

9. A composition for a gas separation membrane, wherein the composition comprises a crosslinked copolymer comprising structural units (A-O) and (B—O), wherein
A is selected from the group consisting of:
—Ar 1 -Q-Ar 2 —, —Ar 1 —, and —Ar 1 —Ar 2 —;

B is selected from the group consisting of:
—Ar 1 ′-Q′-Ar 2 ′—, —Ar 1 ′—, and —Ar 1 ′—Ar 2 ′—;

Ar 1 , Ar 2 , Ar 1 ′, and Ar 2 ′ are each independently a bivalent C 5 -C 24 arylene or a bivalent C 5 -C 24 heterocyclic ring, and wherein the arylene or heterocyclic ring is independently optionally substituted with at least one R 1 group
each occurrence of R 1 is independently selected from the group consisting of H, halo, —CN, —SO 3 H or a salt thereof, —CO 2 H or a salt thereof, —C 1 -C 10 alkyl, —C 1 -C 10 alkoxy, —C 1 -C 10 haloalkyl, —C 1 -C 10 haloalkoxy, phenyl, and cyclohexyl, wherein the alkyl, phenyl, and cyclohexyl groups are optionally substituted; or two or more R 1 groups may be joined together to form a ring; or two R 1 groups may be covalently bonded to Y;
Y is selected from the group consisting of —O—, —S—, —C(═O), —CH(OH)—, —S(═O) 2 —, —Si(CH 3 ) 2 —, —(CH 2 ) p —, —(CF 2 ) q —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 — and —C(═O)NR 1 —;
Q and Q′ are each independently selected from the group consisting of —O—, —S—, —C(═O), —CH(OH)—, —S(═O) 2 —, —Si(CH 3 ) 2 —, —(CH 2 ) p —, —(CF 2 ) q —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —C(R 1 )(R 1 ) —, C(═O)NH—, —P(═O)C 6 H 5 —, —C(CH 3 )(CF 3 )—, —C(═O)C 6 H 4 C(═O)—, —C(R 1 )(R 1 ) —C 6 H 4 —C(R 1 )(R 1 )—, - phenyl-(C 1 -C 6 )alkyl, -phenyl-(C 1 -C 6 )haloalkyl, phenyl, cycloalkyl, and heterocyclyl, wherein the phenyl, cycloalkyl, and heterocyclyl groups are optionally substituted; or the two R 1 groups in —C(R 1 )(R 1 ) may be joined together to form a ring, wherein the ring is optionally substituted;
p is an integer from 1 to 10; and
q is an integer from 1 to 10
wherein at least one occurrence of Ar 1 , Ar 2 , Ar 1 ′, or Ar 2 ′ is substituted with an R 1 group comprising a benzylic hydrogen, and at least one occurrence of Q or Q′ includes a activator, wherein the UV activator is a carbonyl group.

10. The composition of claim 9 , further comprising the structural unit (D-O), wherein D is selected from the group consisting of:
—Ar 1 ″-Q″-Ar 2 ″—, —Ar 1 ″—, and —Ar 1 ″—Ar 2 ″—;

wherein Ar 1 ″ and Ar 2 ″

Assignees

• Virginia Tech Intellectual Properties Inc
• Univ Texas
• Kraft Colleen

Inventors

• Mcgrath James
• Chen Yu
• Guo Rulian
• Freeman Benny

Classifications

• B01D2323/345

  UV-treatment · CPC title

• B01D71/80

  Block polymers · CPC title

• B01D2053/221

  Devices · CPC title

• B01D2323/30

  Cross-linking · CPC title

• B01D53/228 Primary

  characterised by specific membranes · CPC title