High selectivity epoxysilicone-cross-linked polyimide membranes for gas separations

Patent metadata

Field	Value
Publication number	US-9480954-B2
Application number	US-201514661591-A
Country	US
Kind code	B2
Filing date	Mar 18, 2015
Priority date	Mar 18, 2015
Publication date	Nov 1, 2016
Grant date	Nov 1, 2016

Abstract

The present invention provides a high selectivity epoxysilicone-cross-linked polyimide membrane comprising a polyimide polymer with hydroxyl functional groups cross-linked with epoxy functional groups on epoxysilicone polymer. The present invention also provides a process for separating at least one gas from a mixture of gases using the high selectivity epoxysilicone-cross-linked polyimide membrane. The process comprises providing the high selectivity epoxysilicone-cross-linked polyimide membrane which is permeable to the at least one gas; contacting the mixture on one side of the membrane to cause the at least one gas to permeate the membrane; and removing from the opposite side of the membrane a permeate gas composition comprising a portion of the at least one gas which permeated the high selectivity epoxysilicone-cross-linked polyimide membrane.

First claim

The invention claimed is:

1. An epoxysilicone-cross-linked polyimide membrane comprising an epoxysilicone-cross-linked polyimide polymer wherein said epoxysilicone-cross-linked polyimide polymer comprises a plurality of repeating units of formula (I), wherein formula (I) is

wherein R is selected from the group consisting of
MD x D E y Q z T u D Rf j D A k D P l (D′(CH(R′)CH 2 O) m ) n D B p M,
M E D x D E y Q z T u D Rf j D A k D P l (D′(CH(R′)CH 2 O) m ) n D B p M E ,
M E D x D E y Q z T u D Rf j D A k D P l (D′(CH(R′)CH 2 O) m ) n D B p M,
and mixtures thereof; wherein
M=(CH 3 ) 3 SiO 1/2 ,
M E =

D=(CH 3 ) 2 SiO 2/2 ,
D′=(CH 3 ) 3 SiO 2/2 ,
D E =

D Rf =(CF 3 CH 2 CH 2 )(CH 3 )SiO 2/2 ,
D A =((HO)(C 2 H 3 )C 6 H 9 (CH 2 ) 2 (CH 3 )SiO 2/2 ,
D P =((HO)(C 6 H 4 )(CH 2 ) 3 )(CH 3 )SiO 2/2 ,
D B =((C 6 H 5 COO)(HO)(C 6 H 9 )(CH 2 ) 2 )(CH 3 )SiO 2/2 ,
Q=SiO 4/2 ,
T=(CH 3 ) 3 SiO 3/2 ,
wherein R′ is selected from the group consisting of hydrogen, methyl, and ethyl, and wherein j, k, l, m, n, p, x, y, z, and u are positive integers and j, k, l, n, p, u, and z may be zero; wherein X 1 and X 2 are selected from the group consisting of

and mixtures thereof, respectively; X 1 and X 2 are the same or different from each other; wherein Y 1 is selected from the group consisting of

and mixtures thereof,
Y 2 is selected from the group consisting of

and mixtures thereof, R″ is selected from the group consisting of

and mixtures thereof, and R′″ is selected from the group consisting of —H, COCH 3 , and mixtures thereof; and wherein a, b, and c are independent integers from 1 to 500.

2. The epoxysilicone-cross-linked polyimide membrane of claim 1 wherein in formula (I), X 1 and X 2 are selected from the group consisting of

and mixtures thereof, respectively; and X 1 and X 2 are the same or different from each other.

3. The epoxysilicone-cross-linked polyimide membrane of claim 1 wherein in formula (I), Y 2 is

wherein R′″ is selected from the group consisting of —H, COCH 3 , and mixtures thereof.

4. The epoxysilicone-cross-linked polyimide membrane of claim 1 wherein in formula (I), R is selected from the group consisting of MD x D E y M, M E D x D E y M E , M E D x D E y M, and mixtures thereof; wherein
M=(CH 3 ) 3 SiO 1/2 ,
M E =

D=(CH 3 ) 2 SiO 2/2 ,
D E =

wherein x and y are positive integers.

5. The epoxysilicone-cross-linked polyimide membrane of claim 1 is in a form selected from an asymmetric integrally skinned membrane, a thin film composite (TFC) membrane or a hollow fiber membrane.

6. The epoxysilicone-cross-linked polyimide membrane of claim 5 wherein the thin film composite comprises a thin nonporous selective separation layer comprising an epoxysilicone-cross-linked polyimide polymer and a porous nonselective mechanical support layer made from a material different from the epoxysilicone-cross-linked polyimide polymer.

7. The epoxysilicone-cross-linked polyimide membrane of claim 6 wherein the porous nonselective mechanical support layer comprises a polymer selected from the group consisting of polysulfones, sulfonated polysulfones, polyethersulfones, sulfonated polyethersulfones, polyethers, polyetherimides, cellulosic polymers, polyamides, polyimides, polyether ketones, and mixtures thereof.

8. The epoxysilicone-cross-linked polyimide membrane of claim 1 wherein the polyimide polymer comprises poly(2,2′-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride-3,3′-dihydroxy-4,4′-diamino-biphenyl-3,3′-diacetoxy-4,4′-diamino-biphenyl), poly(2,2′-bis-(3,4-dicarboxyphenyl)hexatluoropropane dianhydride-3,3′-dihydroxy-4,4′-diamino-biphenyl-3,3′-diacetoxy-4,4′-diamino-biphenyl-3,5-diaminobenzoic acid).

9. The epoxysilicone-cross-linked polyimide membrane of claim 1 wherein in formula (I), Y 1 is selected from the group consisting of

and mixtures thereof.

10. The epoxysilicone-cross-linked polyimide membrane of claim 1 wherein in formula (I), X 1 is

11. A process for separating at least one gas from a mixture of gases using an epoxysilicone-cross-linked polyimide membrane comprising an epoxysilicone-cross-linked polyimide polymer wherein said epoxysilicone-cross-linked polyimide polymer comprises a plurality of repeating units of formula (I), wherein formula (I) represented by a chemical structure

wherein R is selected from the group consisting of
MD x D E y Q z T u D Rf j D A k D P l (D′(CH(R′)CH 2 O) m ) n D B p M,
M E D x D E y Q z T u D Rf j D A k D P l (D′(CH(R′)CH 2 O) m ) n D B p M E ,
M E D x D E y Q z T u D Rf j D A k D P l (D′(CH(R′)CH 2 O) m ) n D B p M,
and mixtures thereof; wherein
M=(CH 3 ) 3 SiO 1/2 ,
M E =

D=(CH 3 ) 2 SiO 2/2 ,
D′=(CH 3 ) 3 SiO 2/2 ,
D E =

D Rf =(CF 3 CH 2 CH 2 )(CH 3 )SiO 2/2 ,
D A =((HO)(C 2 H 3 )C 6 H 9 (CH 2 ) 2 (CH 3 )SiO 2/2 ,
D P =((HO)(C 6 H 4 )(CH 2 ) 3 )(CH 3 )SiO 2/2 ,
D B =((C 6 H 5 COO)(HO)(C 6 H 9 )(CH 2 ) 2 )(CH 3 )SiO 2/2 ,
Q=SiO 4/2 ,
T=(CH 3 ) 3 SiO 3/2 ,
wherein R′ is selected from the group consisting of hydrogen, methyl, and ethyl, and wherein j, k, l, m, n, p, x, y, z, and u are positive integers and j, k, l, n, p, u, and z may be zero; wherein X 1 and X 2 are selected from the group consisting of

and mixtures thereof, respectively; X 1 and X 2 are the same or different from each other; wherein Y 1 is selected from the group consisting of

and mixtures thereof; Y 2 is selected from the group consisting of

Assignees

• Uop Llc

Inventors

• Liu Chunqing
• Tran Howie Q

Classifications

• B01D53/228

  characterised by specific membranes · CPC title

• B01D2053/224

  with hollow fibres · CPC title

• B01D69/088

  Co-extrusion; Co-spinning · CPC title

• B01D69/125 Primary

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

• B01D71/80 Primary

  Block polymers · CPC title