Fluorinated nanoporous molecular sieve membranes for efficient gas separation
A crosslinked microporous membrane (crosslinked polymer) composition useful in gas separation, the membrane comprising: (i) an aromatic polymer containing a multiplicity of benzene rings; and (ii) a multiplicity of fluorinated aromatic moieties, each fluorinated aromatic moiety containing at least two separate methylene (—CH 2 —) linkages connected to benzene rings on the aromatic polymer; wherein the cross-linked microporous membrane possesses micropores having a pore size of up to 2 nm. Also described are methods for producing the crosslinked polymer and a microporous carbon material produced by pyrolysis of the crosslinked polymer membrane. Also described are methods for using the crosslinked polymer and microporous carbon material for gas or liquid separation, filtration, or purification.
1. A crosslinked microporous membrane composition useful in gas separation, the membrane comprising:
(i) an aromatic polymer containing a multiplicity of benzene rings; and
(ii) a multiplicity of fluorinated aromatic moieties, each fluorinated aromatic moiety containing at least two separate methylene (—CH 2 —) linkages connected to benzene rings on the aromatic polymer;
wherein the cross-linked microporous membrane possesses micropores having a pore size of up to 2 nm.
2. The membrane composition of claim 1 , wherein said aromatic polymer is non-fluorinated.
3. The membrane composition of claim 1 , wherein said aromatic polymer comprises polystyrene or a copolymer thereof.
4. The membrane composition of claim 1 , wherein said aromatic polymer comprises a block copolymer of polystyrene and polybutadiene.
5. The membrane composition of claim 1 , wherein at least a portion of said micropores are ultra-micropores having a size of less than 1 nm.
6. The membrane composition of claim 1 , wherein at least a portion of said micropores are ultra-micropores having a size of no more than 0.5 nm.
7. The membrane composition of claim 1 , wherein at least a portion of said fluorinated aromatic moieties are bivalent.
8. The membrane composition of claim 1 , wherein at least a portion of said fluorinated aromatic moieties are trivalent.
9. The membrane composition of claim 1 , wherein at least a portion of said fluorinated aromatic moieties have the following structure:
wherein R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of hydrogen atom (H), fluorine atom (F), and hydrocarbon groups (R) containing one to twelve carbon atoms, optionally substituted with fluorine; wherein R 1 and R 2 are optionally interconnected, and/or R 3 and R 4 are optionally interconnected; and wherein at least 50% of hydrogen atoms bound to aromatic rings in the structure of Formula (1) are substituted with fluorine atoms.
10. The membrane composition of claim 1 , wherein at least a portion of said fluorinated aromatic moieties have the following structure:
wherein R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are independently selected from the group consisting of hydrogen atom (H), fluorine atom (F), and hydrocarbon groups (R) containing one to twelve carbon atoms, optionally substituted with fluorine; wherein R 5 and R 6 are optionally interconnected, and/or R 7 and R 8 are optionally interconnected; and/or R 9 and R 10 are optionally interconnected; and/or R 11 and R 12 are optionally interconnected; and wherein at least 50% of hydrogen atoms bound to aromatic rings in the structure of Formula (2) are substituted with fluorine atoms.
11. The membrane composition of claim 1 , wherein at least a portion of said fluorinated aromatic moieties have the following structure:
wherein R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 are independently selected from the group consisting of hydrogen atom (H), fluorine atom (F), and hydrocarbon groups (R) containing one to twelve carbon atoms, optionally substituted with fluorine; wherein R 13 and R 14 are optionally interconnected, and/or R 14 and R 15 are optionally interconnected; and/or R 16 and R 17 are optionally interconnected; and/or R 17 and R 18 are optionally interconnected; and wherein at least 50% of hydrogen atoms bound to aromatic rings in the structure of Formula (3) are substituted with fluorine atoms.
12. The membrane composition of claim 1 , wherein at least a portion of said fluorinated aromatic moieties have the following structure:
wherein R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 are independently selected from the group consisting of hydrogen atom (H), fluorine atom (F), and hydrocarbon groups (R) containing one to twelve carbon atoms, optionally substituted with fluorine; wherein R 19 and R 20 are optionally interconnected, and/or R 20 and R 21 are optionally interconnected; and/or R 21 and R 22 are optionally interconnected; and/or R 23 and R 24 are optionally interconnected; and/or R 24 and R 25 are optionally interconnected; and/or R 25 and R 26 are optionally interconnected; and wherein at least 50% of hydrogen atoms bound to aromatic rings in the structure of Formula (4) are substituted with fluorine atoms.
13. The membrane composition of claim 1 , wherein at least a portion of said fluorinated aromatic moieties have the following structure:
wherein R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , and R 38 are independently selected from the group consisting of hydrogen atom (H), fluorine atom (F), and hydrocarbon groups (R) containing one to twelve carbon atoms, optionally substituted with fluorine; wherein R 27 and R 28 are optionally interconnected, and/or R 29 and R 30 are optionally interconnected; and/or R 31 and R 32 are optionally interconnected; and/or R 33 and R 34 are optionally interconnected; and/or R 35 and R 36 are optionally interconnected; and/or R 37 and R 38 are optionally interconnected; and wherein at least 50% of hydrogen atoms bound to aromatic rings in the structure of Formula (5) are substituted with fluorine atoms.
14. The membrane composition of claim 1 , wherein the membrane has a thickness of no more than 100 microns.
15. The membrane composition of claim 1 , wherein the membrane has a fluorine content of at least 20 wt %.
16. A method for at least partially separating carbon dioxide gas from a carbon dioxide-containing mixture of gases, the method comprising passing the carbon dioxide-containing mixture of gases through a crosslinked polymer microporous membrane, wherein gas exiting the microporous polymer membrane has an increased carbon dioxide concentration relative to the initial carbon dioxide-containing mixture of gases not passed through the microporous polymer membrane;
wherein said crosslinked microporous membrane comprises:
(i) an aromatic polymer containing a multiplicity of benzene rings;
(ii) a multiplicity of fluorinated aromatic moieties, each fluorinated aromatic moiety containing at least two separate methylene (—CH 2 —) linkages connected to benzene rings on the aromatic polymer;
wherein the cross-linked microporous membrane possesses micropores having a pore size of up to 2 nm.
17. The method of claim 16 , wherein the carbon dioxide-containing mixture of gases comprises carbon dioxide and nitrogen, and the method achieves a carbon dioxide to nitrogen selectivity of at least 10.
18. The method of claim 16 , wherein said aromatic polymer comprises polystyrene or a copolymer thereof.
19. The method of claim 16 , wherein said aromatic polymer comprises a block copolymer of polystyrene and polybutadiene.
20. The method of claim 16 , wherein at least a portion of said micropores are ultra-micropores having a size of less than 1 nm.
21. The method of claim 16 , wherein the membrane has a thickness of no more than 100 microns.
22. The method of claim 16 , wherein the membrane has a fluorine content of at least 20 wt %.