Polytrialkylgermylpropyne polymers and membranes

Claim 2

A polymer having the general structural formula: ##STR8## wherein R 1 is hydrogen or a C 1 -C 2 alkyl group; R 2 and R 3 are independently linear or branched C 1 -C 6 alkyl groups; R 4 is a linear or branched C 1 -C 12 alkyl or aryl group; X is a C 1 -C 3 alkyl group or phenyl; m is at least 100; and n is 0 or 1.

Claim 3

A polymer in accordance with claim 1 which is formed by polymerizing monomer units having the general structural formula: ##STR9## wherein R 1 is hydrogen or a C 1 -C 2 alkyl group; R 2 and R 3 are independently linear or branched C 1 -C 6 alkyl groups; R 4 is a linear or branched C 1 -C 12 alkyl or aryl group; X is a C 1 -C 3 alkyl group or phenyl; and n is 0 or 1.

Claim 4

A polymer in accordance with claim 1 wherein said polymer is cast into membrane form.

Claim 5

A polymer, cast into membrane form, in accordance with claim 3 which is employed in gas separation, liquid separation, pervaporation or ultrafiltration operations.

Claim 6

A polymer in accordance with claim 1 wherein R 1 , R 2 , R 3 and R 4 are methyl groups and n=0.

Claim 7

A copolymer containing structural units set out in claim 1 which also contains one or more different copolymerizable monomers.

Claim 8

A copolymer in accordance with claim 6 in which the various monomer units comprising the copolymer are arranged in an alternating, block or random configuration.

Claim 9

A copolymer in accordance with claim 7 wherein trialkylsilylacetylene derived monomer units comprise up to about 50% of the total polymer.

Claim 10

A polymer, cast into membrane form in accordance with claim 3 which is subsequently subjected to ultraviolet or electromagnetic treatment.

Claim 11

A polymer, cast into membrane form in accordance with claim 3 which is subsequently subjected to treatment in a plasma field.

Claim 12

A treated, semi-permeable, polymeric membrane having improved selectivity for use in separating components of a feed gas mixture, said membrane comprising a polymer, cast into membrane form, having the general structural formula: ##STR10## wherein R 1 is hydrogen or a C 1 -C 2 alkyl group; R 2 , R 3 and R 4 are independently linear or branched C 1 -C 3 alkyl groups; X is a C 1 -C 3 alkyl group or phenyl; m is at least 100; and n is 0 or 1, which has been treated with a reactive source of fluorine for a time sufficient to modify the membrane such that the O 2 /N 2 selectivity ratio of the membrane is increased by at least 50% over that of the membrane prior to treatment with the reactive fluorine source.

Claim 13

A treated, semi-permeable, polymeric membrane having improved selectivity for use in separating components of a feed gas mixture, said membrane comprising a polymer, cast into membrane form, having the general structural formula: ##STR10## wherein R 1 is hydrogen or a C 1 -C 2 alkyl group; R 2 , R 3 and R 4 are independently linear or branched C 1 -C 3 alkyl groups; X is a C 1 -C 3 alkyl group or phenyl; m is at least 100; and n is 0 or 1, which has been treated with a reactive source of fluorine for a time sufficient to modify the membrane such that the O 2 /N 2 selectivity ratio of the membrane is increased by at least 50% over that of the membrane prior to treatment with the reactive fluorine source.

Claim 14

A treated, semi-permeable, polymeric membrane in accordance with claim 11 wherein the reactive fluorine source is a gas stream containing between 0.01-25% fluorine gas.

Claim 15

A treated, semi-permeable, polymeric membrane in accordance with claim 12 wherein the reactive fluorine source is a gas stream containing between 0.1-2% fluorine gas.

Claim 16

A treated, semi-permeable, polymeric membrane in accordance with claim 11 which has been contacted with a reactive source of fluorine for a period of time between 10 seconds and 24 hours.

Claim 17

A treated, semi-permeable, polymeric membrane in accordance with claim 14 which has been contacted with a reactive source of fluorine for a period of time between 0.5 min and 120 min.

Claim 18

A treated, semi-permeable, polymeric membrane in accordance with claim 11 wherein said polymer cast into membrane form has a structural formula wherein n=0.

Claim 19

A treated, semi-permeable, polymeric membrane in accordance with claim 11 wherein said polymer cast into membrane form has a structural formula wherein R 1 , R 2 and R 3 are CH 3 groups and R 4 is a linear or branched C 1 -C 3 alkyl group.

Claim 20

A treated, semi-permeable, polymeric membrane in accordance with claim 17 wherein said polymer cast into membrane form has a structural formula where in n=0.

Claim 21

A treated, semi-permeable, polymeric membrane in accordance with claim 11 which is employed in gas separation, solvent separation, pervaporation or ultrafiltration operations.

Claim 22

A treated, semi-permeable, polymeric membrane in accordance with claim 11 wherein said polymer cast into membrane form also comprises a trialkylacetylene derived copolymer.

Claim 23

A treated, semi-permeable polymeric membrane in accordance with claim 20 wherein said copolymer is present in a concentration of between 10% to 98%.

Claim 24

A treated, semi-permeable, polymeric membrane in accordance with claim 11 in which the polymer cast into membrane form has the following structural formula: ##STR11## wherein m is at least 100.

Claim 25

A membrane in accordance with claim 11 wherein the polymer is cast into the form of an asymmetric membrane having a thin dense layer over a porous layer.

Claim 26

A membrane in accordance with claim 11 wherein the polymer, prior to treatment with a reactive source of fluorine is first coated onto the surface of a porous substrate.

Claim 27

A membrane in accordance with claim 24 wherein the porous substrate is in the form of a flat sheet or hollow fiber prior to being coated.

Claim 28

A membrane in accordance with claim 24 wherein the porous substrate is a polyolefine or polysulfone.

Claim 29

A membrane comprising two or more layers wherein at least one of the layers comprises the membrane structure set out in claim 11.

Claim 30

A process for separating a feed gas mixture containing at least two components having different permeabilities through a membrane, said process comprising bringing said feed gas mixture into contact with a treated, semi-permeable, polymeric membrane comprising a polymer, cast into membrane form, having the general structural formula: ##STR12## wherein R 1 is hydrogen or a C 1 -C 2 alkyl group; R 2 , R 3 and R 4 are independently linear or branched C 1 -C 3 alkyl groups; X is a C 1 -C 3 alkyl group or phenyl; m is at least 100; and n is 0 or 1, which has been treated with a reactive source of fluorine for a time sufficient to modify the membrane such that the O 2 /N 2 selectivity ratio of the membrane is increased by at least 50% over that of the membrane prior to treatment with the reactive fluorine source, to separate the more permeable component as a permeate stream and concentrate the less permeable component as a reject stream.

Claim 31

A process for separating a feed gas mixture containing at least two components having different permeabilities through a membrane, said process comprising bringing said feed gas mixture into contact with a treated, semi-permeable, polymeric membrane comprising a polymer, cast into membrane form, having the general structural formula: ##STR12## wherein R 1 is hydrogen or a C 1 -C 2 alkyl group; R 2 , R 3 and R 4 are independently linear or branched C 1 -C 3 alkyl groups; X is a C 1 -C 3 alkyl group or phenyl; m is at least 100; and n is 0 or 1, which has been treated with a reactive source of fluorine for a time sufficient to modify the membrane such that the O 2 /N 2 selectivity ratio of the membrane is increased by at least 50% over that of the membrane prior to treatment with the reactive fluorine source, to separate the more permeable component as a permeate stream and concentrate the less permeable component as a reject stream.

Claim 32

A process in accordance with claim 28 wherein the reactive fluorine source is a gas stream containing between 0.01-25% fluorine gas.

Claim 33

A process in accordance with claim 29 wherein the reactive fluorine source is a gas stream containing between 0.1-2% fluorine gas.

Claim 34

A process in accordance with claim 28 wherein said treated, semi-permeable, polymeric membrane has been contacted with a reactive source of fluorine for a period of time between 10 seconds and 24 hours.

Claim 35

A process in accordance with claim 31 wherein said treated, semi-permeable, polymeric membrane has been contacted with a reactive source of fluorine for a period of time between 0.5 min and 120 min.

Claim 36

A process in accordance with claim 28 wherein said feed gas mixture is brought into contact with a treated, semi-permeable, polymeric membrane comprising a polymer, cast into membrane form, having a structural formula wherein n=0.

Claim 37

A process in accordance with claim 33 wherein said feed gas mixture is brought into contact with a treated, semi-permeable, polymeric membrane comprising a polymer, cast into membrane form, having a structural formula wherein R 1 , R 2 and R 3 are CH 3 groups and R 4 is a linear or branched C 1 -C 3 alkyl group.

Claim 38

A process in accordance with claim 34 wherein said feed gas mixture is brought into contact with a treated, semi-permeable, polymeric membrane comprising a polymer, cast into membrane form, having the structural formula: ##STR13## wherein m is at least 100.

Claim 39

A process in accordance with claim 28 wherein said polymer, cast into membrane form, also comprises one or more copolymers.

Claim 40

A process in accordance with claim 36 wherein said polymer, cast into membrane form comprises a trialkylacetylene derived copolymer.

Claim 41

A process in accordance with claim 28 wherein the feed gas mixture is selected from the group consisting of: O 2 /N 2 , He/CH 4 , H 2 /CH 4 , H 2 /CO, CO 2 /CH 4 , CO 2 /N 2 , H 2 /N 2 and He/N 2 .

Claim 44

A method in accordance with claim 39 wherein the reactive source of fluorine is a gas stream containing between 0.01-25% fluorine gas.

Claim 45

A method in accordance with claim 40 wherein the polymer in membrane form is treated with a reactive source of fluorine for a period of time between 10 seconds and 24 hours.

Claim 46

A method in accordance with claim 39 wherein the polymer cast into membrane form has the general structural formula wherein R 1 , R 2 and R 3 are CH 3 groups, R 4 is a linear or branched C 1 -C 3 alkyl group and n=0.

Claim 47

A method in accordance with claim 39 wherein the polymer cast into membrane form has the following structural formula: ##STR15## wherein m is at least 100.

Claim 48

A method in accordance with claim 39 wherein said polymer in membrane form is treated with a reactive source of fluorine under ambient conditions of temperature and pressure.

Claim 49

A method in accordance with claim 39 wherein said polymer in membrane form is treated with a reactive source of fluorine at elevated temperatures and in the presence of a plasma field or electromagnetic radiation.

Claim 50

A method in accordance with claim 39 wherein the polymer, cast into membrane form, comprises two or more copolymers.

Claim 51

A method in accordance with claim 46 wherein the polymer, cast into membrane form, comprises a trialkylsilylacetylene derived copolymer.