Crosslinked Organic-Inorganic Hybrid Membranes and Their Use in Gas Separation

• US 20090299015A1
• Filed: 06/02/2008
• Published: 12/03/2009
• Est. Priority Date: 06/02/2008
• Status: Active Grant

• Current Assignee: UOP Llc (Honeywell International Inc.)
• Original Assignee: UOP Llc (Honeywell International Inc.)
• Inventors: Liu, Chunqing, Wilson, Stephen T., Kulprathipanja, Santi
• Granted Patent: US 7,790,803 B2
• Time in Patent Office: Days
• US Class Current: 525/418
• CPC Class Codes: B01D 2257/102 Nitrogen
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 67/0079 Manufacture of membranes comprising organic and inorganic components
• CPC Class Codes: B01D 67/00793 Dispersing a component, e.g. as particles or powder, in another component
• CPC Class Codes: B01D 71/00 Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
• CPC Class Codes: B01D 71/16 Cellulose acetate
• CPC Class Codes: B01D 71/52 Polyethers
• CPC Class Codes: B01D 71/5211 Polyethylene glycol or polyethyleneoxide
• CPC Class Codes: B01D 71/70 Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
• CPC Class Codes: B01D 71/702 Polysilsesquioxanes or combination of silica with bridging organosilane groups
• CPC Class Codes: C08B 7/00 Preparation of cellulose esters of both organic and inorganic acids rendering cellulose suitable for esterification C08B1/02
• CPC Class Codes: C08G 2650/58 Ethylene oxide or propylene oxide copolymers, e.g. pluronics
• CPC Class Codes: C08G 65/33306 acyclic
• CPC Class Codes: C08G 65/33351 acyclic
• CPC Class Codes: C08G 65/336 containing silicon
• CPC Class Codes: C08L 1/20 Esters of both organic acids and inorganic acids
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y02P 20/151 Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The present invention is for crosslinked membranes and in particular for crosslinked poly(ethylene oxide)-cellulose acetate-silsesquioxane (PEO-CA-Si) organic-inorganic hybrid membranes and their use in gas separation. These crosslinked PEO-CA-Si membranes were prepared by in-situ sol-gel co-condensation of crosslinkable PEO-organotrialkoxysilane and CA-organotrialkoxysilane polymers in the presence of acetic acid catalyst during the formation of membranes. The crosslinkable PEO- and CA-organotrialkoxysilane polymers were synthesized via the reaction between the hydroxyl groups on PEO (or on CA) and the isocyanate on organotrialkoxysilane to form urethane linkages under mild conditions. The crosslinked PEO-CA-Si membranes exhibited both increased selectivity of CO₂/N₂ and CO₂ permeability as compared to a CA membrane, suggesting that these membranes are very promising for gas separations such as CO₂/N₂ separation.

Claims

1. A crosslinked organic-inorganic hybrid polymer made from at least two different precursor organic polymers having hydroxyl, amino, epoxy, isocyanato, or dianhydride groups and crosslinked with an organosilicon alkoxide crosslinking agent.

2. The crosslinked organic-inorganic hybrid polymer of claim 1 wherein said precursor organic polymer is selected from the group consisting of poly(ethylene oxide) (PEO), cellulose acetate (CA), poly(propylene oxide) (PPO), co-block-poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO), tri-block-poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminepropyl ether) (PAPE), dendritic PEO, and hyperbranched amine-terminated PEO.

3. The crosslinked organic-inorganic hybrid polymer of claim 2 wherein one of said precursor polymers is cellulose acetate.

4. The crosslinked organic-inorganic hybrid polymer of claim 1 wherein said organosilicon alkoxide crosslinking agent comprises

5. The crosslinked organic-inorganic hybrid polymer of claim 1 wherein one of said precursor polymers is cellulose acetate and at least one of said precursor polymers is selected from the group consisting of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), co-block-poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO), tri-block-poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (PAPE), dendritic PEO, and hyperbranched amine-terminated PEO.

6. The crosslinked organic-inorganic hybrid polymer of claim 5 wherein one of said precursor polymers is cellulose acetate and at least two of said precursor polymers are selected from the group consisting of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), co-block-poly(ethylene oxide)-poly(propylene oxide)s (PEO-PPO), tri-block-poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminepropyl ether) (PAPE), dendritic PEO, and hyperbranched amine-terminated PEO.

7. The crosslinked organic-inorganic hybrid polymer of claim 2 wherein one of said precursor polymers is cellulose acetate and one of said precursor polymers is poly(ethylene oxide).

8. A crosslinked poly(ethylene oxide)-cellulose acetate-silsesquioxane organic-inorganic hybrid polymer.

9. A process of making a crosslinked organic-inorganic hybrid polymer comprising preparing at least two crosslinkable precursor polymers by reacting a first precursor polymer with an organosilicon crosslinking agent to produce a first crosslinkable precursor polymer and separately reacting a second precursor polymer with said organosilicon crosslinking agent to produce a second crosslinkable precursor polymer followed by reacting said first crosslinkable precursor polymer with said second precursor polymer together with a crosslinking catalyst to produce said crosslinked organic-inorganic hybrid polymer.

10. The process of claim 9 wherein said first precursor polymer and said second precursor polymer comprise different polymers and are each selected from the group consisting of poly(ethylene oxide) (PEO), cellulose acetate (CA), poly(propylene oxide) (PPO), co-block-poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO), tri-block-poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminepropyl ether) (PAPE), dendritic PEO, and hyperbranched amine-terminated PEO.

11. The process of claim 9 wherein said first crosslinkable precursor polymer and said second precursor polymer are reacted by sol-gel polymerization.

12. The process of claim 9 wherein said first precursor polymer comprises cellulose acetate.

13. The process of claim 9 wherein said organosilicon alkoxide crosslinking agent comprises

14. The process of claim 9 wherein one of said precursor polymers is cellulose acetate and at least one of said precursor polymers is selected from the group consisting of poly(ethylene oxide)s (PEO), poly(propylene oxide) (PPO), co-block-poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO), tri-block-poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminepropyl ether) (PAPE), dendritic PEO, and hyperbranched amine-terminated PEO.

15. The process of claim 9 wherein one of said precursor polymers is cellulose acetate and at least two of said precursor polymers are selected from the group consisting of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), co-block-poly(ethylene oxide)-poly(propylene oxide)s (PEO-PPO), tri-block-poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminepropyl ether) (PAPE), dendritic PEO, and hyperbranched amine-terminated PEO.

16. The process of claim 9 wherein one of said precursor polymers is cellulose acetate and one of said precursor polymers is poly(ethylene oxide).

17. A crosslinked organic-inorganic hybrid polymer membrane comprising a crosslinked organic-inorganic hybrid polymer made from at least two different precursor organic polymers having hydroxyl, amino, epoxy, isocyanato, or dianhydride groups and crosslinked with an organosilicon alkoxide crosslinking agent.

18. The crosslinked organic-inorganic hybrid polymer membrane of claim 17 wherein said precursor organic polymer is selected from the group consisting of poly(ethylene oxide) (PEO), cellulose acetate (CA), poly(propylene oxide) (PPO), co-block-poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO), tri-block-poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminepropyl ether) (PAPE), dendritic PEO, and hyperbranched amine-terminated PEO.

19. The crosslinked organic-inorganic hybrid polymer membrane of claim 17 wherein one of said precursor polymers is cellulose acetate.

20. The crosslinked organic-inorganic hybrid polymer membrane of claim 17 wherein said organosilicon alkoxide crosslinking agent comprises

21. The crosslinked organic-inorganic hybrid polymer membrane of claim 17 wherein one of said precursor polymers is cellulose acetate and at least one of said precursor polymers is selected from the group consisting of poly(ethylene oxide)s (PEO), poly(propylene oxide) (PPO), co-block-poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO), tri-block-poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminepropyl ether) (PAPE), dendritic PEO, and hyperbranched amine-terminated PEO.

22. The crosslinked organic-inorganic hybrid polymer membrane of claim 17 wherein one of said precursor polymers is cellulose acetate and at least two of said precursor polymers are selected from the group consisting of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), co-block-poly(ethylene oxide)-poly(propylene oxide)s (PEO-PPO), tri-block-poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) (PPO-PEO-PPO), poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminepropyl ether) (PAPE), dendritic PEO, and hyperbranched amine-terminated PEO.

23. The crosslinked organic-inorganic hybrid polymer membrane of claim 17 wherein one of said precursor polymers is cellulose acetate and one of said precursor polymers is poly(ethylene oxide).

24. The crosslinked organic-inorganic hybrid polymer membrane of claim 17 that is used to separate a gas mixture selected from the group consisting of carbon dioxide and nitrogen;

olefins and paraffins;

carbon dioxide and methane;

aromatics and non-aromatics;

water and methane;

sulfur dioxide and nitrogen, hydrogen sulfide and methane;

ammonia and methane;

hydrogen sulfide and nitrogen;

hydrogen sulfide and hydrogen, oxygenates and hydrocarbon, nitrogenates and hydrocarbon, and sulfur compounds and hydrocarbon.