Highly selective polynorbornene homopolymer membranes for natural gas upgrading

Patent metadata

Field	Value
Publication number	US-9896527-B2
Application number	US-201615057894-A
Country	US
Kind code	B2
Filing date	Mar 1, 2016
Priority date	Mar 1, 2016
Publication date	Feb 20, 2018
Grant date	Feb 20, 2018

Abstract

Embodiments for a crosslinked alkoxysilyl polynorbornene homopolymer and methods of making crosslinked alkoxysilyl polynorbornene homopolymer are provided, where the method comprises polymerizing through addition polymerization or ring opening metathesis polymerization a norbornene monomer comprising an alkoxysilyl moiety in the presence of a catalyst to produce an alkoxysilyl modified polynorbornene homopolymer, and producing a crosslinked alkoxysilyl polynorbornene homopolymer through sol-gel initiated crosslinking of the alkoxysilyl modified polynorbornene homopolymer at ambient conditions, or acid-catalyzed conditions.

First claim

What is claimed is:

1. A method of making a crosslinked alkoxysilyl polynorbornene homopolymer comprising:
polymerizing a norbornene monomer comprising at least one alkoxysilyl moiety in the presence of a catalyst to produce an alkoxysilyl modified polynorbornene homopolymer, and
producing a crosslinked alkoxysilyl polynorbornene homopolymer through sol-gel initiated crosslinking of the alkoxysilyl modified polynorbornene homopolymer at ambient conditions, acid-catalyzed, or base-catalyzed conditions.

2. The method of claim 1 , where the polymerizing step comprises an addition polymerization process, which utilizes a transition metal catalyst.

3. The method of claim 2 , where the transition metal catalyst comprises a palladium metallocene derivative catalyst.

4. The method of claim 3 , further comprising a trityl borate, a phosphine, or combinations thereof.

5. The method of claim 1 , where the polymerizing step comprises a ring opening metathesis polymerizing (ROMP) process, which utilizes a Grubbs 1 st Generation catalyst, or any later generation of Grubbs catalyst.

6. The method of claim 1 , where the alkoxysilyl moiety includes from one to eighteen alkoxy groups.

7. The method of claim 1 , where the crosslinked alkoxysilyl polynorbornene homopolymer has either of the following structures:

where R1 is an alkyl, an alkoxy, or alkoxysiloxane, R2 is an alkyl, an alkoxy, or alkoxysiloxane, R3 is an alkyl, an alkoxy, or alkoxysiloxane, and n is at least one, where at least one of R1, R2, and R3, is an alkoxy or alkoxysiloxane.

8. The method of claim 7 where at least two of R1, R2, and R3 is an alkoxy or an alkoxysiloxane, where at least two alkoxys are the same or a different moiety.

9. The method of claim 1 where the norbornene monomer comprises methyldiethoxysilylnorbornene, dimethylethoxysilylnorbornene, or triethoxysilylnorbornene.

10. The method claim 1 , where the sol-gel initiated crosslinking involves hydrolysis in water or exposure to the atmosphere.

11. The method claim 10 , where the sol-gel initiated crosslinking is acid or base catalyzed.

12. The method of claim 1 , where the degree of cross-linking is measured by gel content, and has about 10% to about 100% by weight gel content.

13. A formulation comprising a crosslinked alkoxysilyl polynorbornene homopolymer having either of the following structures:

where R1 is an alkyl, an alkoxy, or alkoxysiloxane, R2 is an alkyl, an alkoxy, or alkoxysiloxane, R3 is an alkyl, an alkoxy, or alkoxysiloxane, and n is at least one, where at least one of R1, R2, and R3, is an alkoxy or alkoxysiloxane; and
where the cross-linking is characterized by 10% to 100% by weight gel content.

14. The formulation according to claim 13 where the crosslinked alkoxysilyl polynorbornene homopolymer includes at least a first chain packing region and a second chain packing region, where the first chain packing region is defined by a first interchain distance and the second chain packing region is defined by a second interchain distance, the first interchain distance being smaller than the second interchain distance, where the first interchain distance and second interchain distance are calculated from Bragg's Law for angle peaks measured by Wide Angle X-ray diffraction (WAXRD).

15. The formulation according to claim 14 , further comprising a third packing region defined by a third interchain distance, the third interchain distance being larger than the first interchain distance and second interchain distance, where the third interchain distance is calculated from Bragg's Law for angle peaks measured by WAXRD.

16. The formulation according to claim 15 , further comprising a fourth packing region defined by a fourth interchain distance, the fourth interchain distance being smaller than the first, second, and third interchain distances, where the fourth interchain distance is calculated from Bragg's Law for angle peaks measured by WAXRD.

17. The formulation according to claim 13 , where the crosslinked alkoxysilyl polynorbornene homopolymer comprises a molecular weight distribution (MWD) from 1 to 3, where MWD is defined as M w /M n with M w being a weight average molecular weight and M n being a number average molecular weight.

18. A natural gas separation membrane comprising the formulation of claim 13 .

Assignees

• Saudi Arabian Oil Co

Inventors

• Sundell Benjamin J
• Lawrence Iii John A

Classifications

• C08J2365/00

  Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08J2307/00 - C08J2357/00, C08J2361/00 take precedence); Derivatives of such polymers · CPC title

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C08G2261/76

  crosslinking · CPC title

• B01D53/228

  characterised by specific membranes · CPC title

• B01D2256/245

  Methane · CPC title