Highly crosslinked hybrid polyimide-silsesquioxane membranes

Patent metadata

Field	Value
Publication number	US-10052592-B2
Application number	US-201414915454-A
Country	US
Kind code	B2
Filing date	Sep 2, 2014
Priority date	Sep 2, 2013
Publication date	Aug 21, 2018
Grant date	Aug 21, 2018

Abstract

Gaseous molecules, such as H 2 , CO 2 and CH 4 , can be separated using a hybrid organic-inorganic polyimide network membrane, wherein the polyimide contains bis-imide units of formula 1 (formula 1), wherein A represents an organic moiety having 2-22 carbon atoms; or corresponding tris-imide groups, wherein a nitrogen atom of two or more of said bis-imide units is linked to a group Q of a polyhedral oligomeric silsesquioxane (POSS) group of formula 3 Q m R (2n-m) Si 2n O 3n .xH 2 O 3 wherein Q is C p H q bound to a silicon atom, R is hydrogen, hydroxy or C 1 -C 4 alkyl, alkoxy, hydroxyalkyl, aminoalkyl or ammonioalkyl, bound to a silicon atom, m is from 2 up to 2n, n is from 2 up to 6, p=1 to 6; q=2(p−r) with r=0, 1, 2<p; and x is from 0 to 2n−1.

First claim

The invention claimed is:

1. A process of producing a hybrid organic-inorganic polyimide membrane having a thickness of 500 nm or less, wherein the polyimide is a network of alternating (a) bis-imide and/or tris-imide units and (b) polyhedral oligomeric silsesquioxane (POSS) groups, comprising:
(i) contacting a solution of a POSS polyamine having the following formula
(H 2 NQ) m R (2n-m) Si 2n O 3n

or its acid-addition salt in a polar solvent,
wherein
Q is C p H q bound to a silicon atom,
R is hydrogen, hydroxy or C 1 -C 4 alkyl, alkoxy, hydroxyalkyl, aminoalkyl or optionally N-alkylated ammonioalkyl, bound to a silicon atom,
m is from 2 up to 2n,
n is from 2 up to 6,
p=1 to 6,
q=2(p−r) with r=0 to 4 and r<p; and
x is from 0 to 2n−1,
with a solution of a organic dianhydride of the following formula or its corresponding trianhydride,

in an organic solvent which is immiscible with said polar solvent, to produce a polymer layer;
(ii) drying and heating the polymer layer to a temperature of at least 180° C.

2. The process according to claim 1 , wherein the polar solvent comprises water.

3. A method for separating gaseous molecules from a gas mixture, comprising subjecting a gas mixture to a membrane produced by a process according to claim 1 .

4. The method according to claim 3 , wherein hydrogen is separated from a gas mixture comprising at least one gas selected from carbon dioxide, carbon monoxide, methane, nitrogen and hydrogen sulphide.

5. The method according to claim 4 , wherein the gas mixture comprises carbon dioxide or methane.

6. The method according to claim 5 , wherein the gas mixture has a temperature between 50 and 300° C.

7. The method according to claim 5 , wherein the gas mixture has a pressure between 5 and 100 bar.

8. The method according to claim 3 , wherein carbon dioxide is separated from a gas mixture comprising methane or nitrogen.

9. The process according to claim 1 , wherein the organic solvent is selected from C 5 -C 10 aliphatic, alicyclic or aromatic hydrocarbons.

10. The process according to claim 1 , wherein A is selected from ethylene, ethylidene, optionally substituted alicyclic and aromatic ring systems, and combinations of two or three of said ring systems, optionally linked by C 1 -C 4 alkylidene or halo-alkylidene, ether, carbonyl, sulfide or sulfone bonds.

11. The process according to claim 1 , wherein the dianhydrides are selected from the dianhydrides of tetracarboxylic acids of ethylene, alkanes, cycloalkanes, heterocycloalkanes, aromatic, heteroaromatic and polyaromatic ring groups and their hydrogenated and/or halogenated analogues.

12. The process according to claim 1 , wherein A represents a ring system selected from benzene, naphthalene, phenalene, anthracene, phenanthrene, biphenyl, biphenylene, triphenylene, fluorene, diphenyl ether, diphenyl sulfide and diphenyl sulfone, benzophenone, diphenyl C 1 -C 4 alkanes, dibenzofuran, xanthenes, diphenoxybenzene, terphenyl, and their hydrogenated and/or halogenated analogues.

13. The process according to claim 12 , wherein the ring system is selected from benzene, naphthalene, biphenyl, biphenylene, fluorene, diphenyl ether, diphenyl C 1 -C 3 alkanes, and their hydrogenated and/or halogenated analogues.

14. The process according to claim 13 , wherein the ring system is selected from benzene, biphenyl, and hexafluoro-2,2-diphenylpropane.

15. The process according to claim 1 , wherein the bis-imide units to silicon atoms are in a molar ratio between 0.25 and 0.5.

16. The process according to claim 1 , wherein the membrane has a thickness between 20 and 500 nm.

17. The process according to claim 1 , wherein the membrane has a hydrogen to nitrogen and/or a hydrogen to methane selectivity of at least 5:1 up to a temperature of at least 300° C.

18. The process according to claim 17 , wherein the membrane has a hydrogen to nitrogen and/or a hydrogen to methane selectivity of at least 10:1 up to a temperature of at least 300° C.

19. The process according to claim 1 , wherein the membrane has a nitrogen permeance at 200° C. of at least 0.6×10 −9 mol·m −2 ·s −1 ·Pa −1 .

20. The process according to claim 18 , wherein the membrane has a nitrogen permeance at 200° C. of at least 68×10 −9 mol·m −2 ·s −1 ·Pa −1 .

21. The process according to claim 1 , further comprising providing a support.

22. The process according to claim 21 , wherein the support is a mesoporous or microporous ceramic support, or an organic polymeric support, or a porous metallic support.

Assignees

• Univ Twente

Inventors

• Benes Nieck Edwin
• Raaijmakers Michiel Jozef Thomas

Classifications

• B01D2257/7025

  Methane · CPC title

• B01D2257/504

  Carbon dioxide · CPC title

• B01D2257/108

  Hydrogen · CPC title

• B01D69/02

  characterised by their properties · CPC title

• B01D67/0006

  by chemical reactions (in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125) · CPC title