Semipermeable thin-film membranes comprising siloxane, alkoxysilyl and aryloxysilyl oligomers and copolymers
First Claim
1. A semipermeable membrane comprising the polycondensation reaction product of two complementary polyfunctional compounds, at least one of which is selected from a group consisting essentially of siloxanes, alkoxysilanes, and aryloxysilanes, each of said complementary polyfunctional compounds having at least two functional groups selected from a member of Group A or Group B:
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space="preserve" listing-type="tabular">______________________________________ Group A Group B ______________________________________ --COX --NHR.sub.h --SO.sub.2 X --OH --NCO --SH --POXR.sub.o --NR.sub.h COX ______________________________________ where X is halide;
Ro is selected from alkyloxy and substituted alkyloxy containing 1 to 18 carbons in the carbon chain, alkyl and substituted alkyl containing from 1 to 18 carbons in the carbon chain,cycloakyl, substituted cycloalkyl, and substituted heterocycloalkyl, aryl and substituted aryl;
Rh is selected from hydrogen and Ro ;
provided that when said at least two functional groups are selected from group A for one of said complementary polyfunctional compounds, said at least two functional groups are selected from group B for the other of said complementary polyfunctional compounds, and vice-versa; and
further provided that when at least one of said complementary polyfunctional compounds is a siloxane and the functional group from group A is --NCO, the functional group from group B is not --NHRh.
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Abstract
Novel semiperimeable membranes and thin film composite (TFC) gas separation membranes useful in the separation of oxygen, nitrogen, hydrogen, water vapor, methane, carbon dioxide, hydrogen sulfide, lower hydrocarbons, and other gases are disclosed. The novel semipermeable membranes comprise the polycondensation reaction product of two complementary polyfunctional compounds, each having at least two functional groups that are mutually reactive in a condensation polymerization reaction, and at least one of which is selected from siloxanes, alkoxsilyls and aryloxysilyls. The TFC membrane comprises a microporous polymeric support, the surface of which has the novel semipermeable film formed thereon, preferably by interfacial polymerization.
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Citations
32 Claims
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1. A semipermeable membrane comprising the polycondensation reaction product of two complementary polyfunctional compounds, at least one of which is selected from a group consisting essentially of siloxanes, alkoxysilanes, and aryloxysilanes, each of said complementary polyfunctional compounds having at least two functional groups selected from a member of Group A or Group B:
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space="preserve" listing-type="tabular">______________________________________ Group A Group B ______________________________________ --COX --NHR.sub.h --SO.sub.2 X --OH --NCO --SH --POXR.sub.o --NR.sub.h COX ______________________________________where X is halide;
Ro is selected from alkyloxy and substituted alkyloxy containing 1 to 18 carbons in the carbon chain, alkyl and substituted alkyl containing from 1 to 18 carbons in the carbon chain,cycloakyl, substituted cycloalkyl, and substituted heterocycloalkyl, aryl and substituted aryl;
Rh is selected from hydrogen and Ro ;
provided that when said at least two functional groups are selected from group A for one of said complementary polyfunctional compounds, said at least two functional groups are selected from group B for the other of said complementary polyfunctional compounds, and vice-versa; and
further provided that when at least one of said complementary polyfunctional compounds is a siloxane and the functional group from group A is --NCO, the functional group from group B is not --NHRh. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10)
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10. The membrane of claim 1 wherein at least one of said complementary polyfunctional compounds is an alkoxysilyl or aryloxysilyl of the structure ##STR9## where R is aryl or alkyl containing up to 10 carbon atoms;
- g and h are numbers selected from 0 and integers from 1 to 12; and
j is an integer from 1 to 20.
- g and h are numbers selected from 0 and integers from 1 to 12; and
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11. A thin-film composite separation membrane comprising a microporous polymeric support having a thin polymeric semipermeable film formed on the surface of said support, said film comprising the polycondensation reaction product of two complementary polyfunctional compounds, at least one of which is selected from a group consisting essentially of siloxanes, alkoxysilanes, and aryloxysilanes, each of said complelemtary polyfunctional compounds having at least two functional groups selected from a member of Group A or Group B:
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space="preserve" listing-type="tabular">______________________________________ Group A Group B ______________________________________ --COX --NHR.sub.h --SO.sub.2 X --OH --NCO --SH --POXR.sub.o --NR.sub.h COX ______________________________________where X is halide;
Ro is selected from alkyloxy and substituted alkyloxy containing 1 to 18 carbons in the carbon chain, alkyl and substituted alkyl containing from 1 to 18 carbons in the carbon chain, cycloakyl, substituted cycloalkyl, and substituted heterocycloalkyl, aryl and substituted aryl;
Rh is selected from hydrogen and Ro ;
provided that when said at least two functional groups are selected from group A for one of said complementary polyfunctional compounds, said at least two functional groups are selected from group B for the other of said complementary polyfunctional compounds, and vice-versa; and
further provided that when at least one of said complementary polyfunctional compounds is a siloxane and the functional group from group A is --NCO, the functional group from group B is not --NHRh. - View Dependent Claims (12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32)
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17. The thin-film composite membrane of claim 16 wherein F is an amine, F'"'"' is selected from --COX and --NCO, m is 2 and n averages from 5 to 75.
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18. The thin-film composite membrane of claim 17 wherein F is --OH.
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19. The thin-film composite membrane of claim 11 wherein the support is selected from sheets and hollow fibers.
- 20. The thin-film composite separation membrane of claim 11 wherein at least one of said complementary polyfunctional compounds is an alkoxysilyl or aryloxysilyl of the structure
- space="preserve" listing-type="equation">F--CH.sub.2).sub.a (M).sub.c (CH.sub.2).sub.b F
where F is selected from members of Group A or Group B;
M is selected from Y or Z or combinations thereof;
a and b are numbers selected from 0 and integers from 1 to 12;
c is an integer from 1 to 20;
Y is of the structure ##STR11## Z is of the structure ##STR12## R is aryl or alkyl containing up to 10 carbon atoms; and
d, e, and f are numbers selected from 0 and integers from 1 to 12.
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21. The thin-film composite separation membrane of claim 11 wherein at least one of said complementary polyfunctional compounds is an alkoxy-silyl or aryloxy-silyl of the structure ##STR13## where R is aryl or alkyl containing up to 10 carbon atoms;
- g and h are numbers selected from 0 and integers from 1 to 12; and
j is an integer from 1 to 20.
- g and h are numbers selected from 0 and integers from 1 to 12; and
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22. A method for the separation of oxygen and nitrogen comprising splitting a feed stream containing oxygen and nitrogen with the thin-film composite separation membrane of claims 11, 15, 20, or 21 into an oxygen-rich permeate stream and a nitrogen-rich residue
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23. A method for the separation of hydrogen and nitrogen comprising splitting a feed stream containing hydrogen and nitrogen with the thin-film composite separation membrane of claims 11, 15, 20 or 21 into an hydrogen-rich permeate stream and a nitrogen-rich residue stream.
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24. A method for the separation of carbon dioxide and a hydrocarbon mixture comprising alkanes and alkenes containing one to four carbon atoms, the method comprising splitting a feed gas stream containing carbon dioxide and said hydrocarbon mixture with the thin-film composite separation membrane of claims 11, 15, 20 or 21 into a carbon dioxide-rich permeate stream and a hydrocarbon mixture-rich residue stream.
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25. The method of claim 24 wherein said hydrocarbon mixture is predominantly methane.
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26. A method for the separation of hydrogen and a hydrocarbon mixture comprising alkanes and alkenes containing one to four carbon atoms, the method comprising splitting a feed stream containing hydrogen and said hydrocarbon mixture with the thin-film composite separation membrane of claims 11, 15, 20 or 21 into a hydrogen-rich permeate stream and a hydrocarbon mixture-rich residue stream.
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27. The method of claim 26 wherein said hydrocarbon mixture is predominantly methane.
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28. A method for the separation of hydrogen sulfide and a hydrocarbon mixture comprising alkanes and alkenes containing one to four carbon atoms, the method comprising splitting a feed stream containing hydrogen sulfide and said hydrocarbon mixture with the thin-film composite separation membrane of claims 11, 15, 20 or 21 into a hydrogen sulfide-rich permeate stream and a hydrocarbon mixture-rich residue stream.
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29. The method of claim 28 wherein said hydrocarbon mixture is predominantly methane.
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30. A method for the separation of water vapor and a gas comprising splitting a gaseous feed stream containing water vapor with the thin-film composite separation membrane of claims 11, 15, 20 or 21 into a water vapor-rich permeate stream and a water vapor-poor residue stream.
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31. The method of claim 30 wherein said gaseous feed stream comprises air.
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32. The method of claim 30 wherein said gaseous feed stream comprises methane.
Specification