Semipermeable thin-film membranes comprising siloxane, alkoxysilyl and aryloxysilyl oligomers and copolymers

Claim 2

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: ______________________________________ 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; R o 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; R h is selected from hydrogen and R o ; 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 --NHR h .

Claim 3

The membrane of claim 1 wherein the polycondensation is by interfacial polymerization.

Claim 4

The membrane of claim 1 wherein the Group A at least two functional groups are --COX and the Group B at least two functional groups are --NHR h .

Claim 5

The membrane of claim 1 wherein the Group A at least two functional groups are --COX and the Group B at least two functional groups are --OH.

Claim 6

The membrane of claim 1 wherein the Group A at least two functional groups are --NCO and the Group B at least two functional groups are --OH.

Claim 7

The membrane of claim 1 wherein at least one of said complementary polyfunctional compounds is a siloxane of the structure ##STR6## where F' is selected from members of Group A and Group B R is lower alkyl, halogen-substituted lower alkyl, and aryl; R' and R" are hydrogen or lower alkyl; and m and n are zero or integers up to 500.

Claim 8

The membrane of claim 6 wherein F' on one of said complementary polyfunctional compounds is an amine; F' on the other of said complementary polyfunctional compounds is --COX; m is 2 and n averages from 5 to 75.

Claim 9

The membrane of claim 7 wherein F' on the other of said complementary polyfunctional compounds is --OH.

Claim 10

The membrane of claim 1 wherein at least one of said complementary polyfunctional compounds is an alkoxysilyl or aryloxysilyl of the structure 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 ##STR7## Z is of the structure ##STR8## 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.

Claim 11

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.

Claim 12

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: ______________________________________ 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; R o 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; R h is selected from hydrogen and R o ; 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 --NHR h .

Claim 13

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: ______________________________________ 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; R o 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; R h is selected from hydrogen and R o ; 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 --NHR h .

Claim 14

The thin-film composite membrane of claim 11 wherein the polycondensation is by interfacial polymerization.

Claim 15

The thin-film composite membrane of claim 11 wherein the Group A at least two functional groups are --COX and the Group B at least two functional groups are --NHR h .

Claim 16

The thin-film composite membrane of claim 11 wherein the Group A at least two functional groups are --COX and the Group B at least two functional groups are --OH.

Claim 17

The thin-film composite membrane of claim 11 wherein the Group A at least two functional groups are --NCO and the Group B at least two functional groups are --OH.

Claim 18

The thin-film composite membrane of claim 11 wherein said support is selected from the group consisting essentially of polyethylene, polypropylene, polytetrafluoroethylene, cellulose acetate, cellulose triacetate, cellulose butyrate, regenerated cellulose, polysulfone, polyethersulfone, polyamide, polyetheramide, and polyvinylidene fluoride, one of said complementary polyfunctional compounds is of the formula F--R.sub.1 --F where R 1 is selected from alkylene, substituted alkylene, cycloalkylene, substituted cycloalkylene, arylene, substituted arylene, heterocycloalkylene and substituted heterocycloalkylene; and the other of said complementary polyfunctional compounds is a siloxane of the structure ##STR10## where F and F' are selected from members of Group A and Group B; R is lower alkyl, halogen-substituted lower alkyl, and aryl; R' and R" are hydrogen or lower alkyl; and m and n are zero or integers up to 500.

Claim 19

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.

Claim 20

The thin-film composite membrane of claim 17 wherein F is --OH.

Claim 21

The thin-film composite membrane of claim 11 wherein the support is selected from sheets and hollow fibers.

Claim 22

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 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.

Claim 23

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.

Claim 27

The method of claim 24 wherein said hydrocarbon mixture is predominantly methane.

Claim 29

The method of claim 26 wherein said hydrocarbon mixture is predominantly methane.

Claim 31

The method of claim 28 wherein said hydrocarbon mixture is predominantly methane.

Claim 33

The method of claim 30 wherein said gaseous feed stream comprises air.

Claim 34

The method of claim 30 wherein said gaseous feed stream comprises methane.