Porous or non-porous substrate coated with a polymeric composition having hydrophilic functional groups and process

1. An article having a hydrophilic surface formed from a substrate comprising a fluorine-containing polymer having the surface of the substrate contacted with and modified with a crosslinked fluorocarbon polymeric composition which is crosslinked with fluorinated crosslinking groups and which has hydrophilic functional groups, said crosslinked fluorocarbon polymeric composition being derived from an uncrosslinked fluorocarbon polymeric composition containing a functional group selected from the group consisting of a sulfonyl halide, a carbonyl halide, a group that can be converted to a sulfonyl halide and a group that can be converted to a carbonylhalide; wherein the crosslinked fluorocarbon polymeric composition having hydrophilic functional groups has the formula:

covalently bonded through the R f groups each to a CY group of a fluorocarbon polymeric composition of the formula:

wherein A is a polymeric group derived from at least one fluorine-containing polymerizable monomer, n is an integer that can be 0, 1 or greater than 1, m is an integer of at least 1 and Y is hydrogen or halogen wherein at least one Y is a fluorine; T is a carbonyl or sulfonyl group; R f is a C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, wherein the R f groups can be the same or different; Z+ is a proton or an organic or an inorganic cation; t can be 0 or 1; L is C, CH or N; E′ is -TR f ″T- or —R f ′—; G is R f ′T- or R; R f ′ is C 1 –C 20 linear, cyclic or branched fluoroalkyl radical optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group; R f ″ is C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, optionally connected to another chain or the fluorocarbon polymeric composition having hydrophilic functional groups and R is hydrogen or a substituted or unsubstituted alkyl or aryl group.

2. An article having a hydrophilic surface formed from a substrate comprising a fluorine-containing polymer having the surface of the substrate contacted with and modified with a crosslinked fluorocarbon polymeric composition which is crosslinked with fluorinated crosslinking groups and which has hydrophilic functional groups, said crosslinked fluorocarbon polymeric composition being derived from an uncrosslinked fluorocarbon polymeric composition containing a functional group selected from the group consisting of a sulfonyl halide, a carbonyl halide, a group that can be converted to a sulfonyl halide and a group that can be converted to a carbonylhalide; wherein the crosslinked fluorocarbon polymeric composition having hydrophilic functional groups has the formula:

covalently bonded through the R f groups, each to a CY group of a fluorocarbon polymeric composition of the formula:

wherein A is a polymeric group derived from at least one fluorine-containing polymerizable monomer, n is an integer that can be 0, 1 or greater than 1; m is an integer of at least 1 and Y is hydrogen or halogen wherein at least one Y is a fluorine; T is a carbonyl or sulfonyl group; R f is a C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, wherein the R f groups can be the same or different; R f ″ and R f ′″ can be the same or different and can be a C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, optionally connected to another chain of the fluorocarbon polymeric composition having hydrophilic functional groups; Z+ is a proton or an organic or an inorganic cation; and t can be 0 to 1.

3. The article of any one of claims 1 or 2 wherein A is selected from the group consisting of vinyl fluoride, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoro(alkylvinyl ether, and tetrafluoroethylene.

4. The article of claim 3 wherein the substrate is porous and the article is porous.

5. The article claim 3 wherein the substrate is porous and the article is non-porous.

6. The article of claim 3 wherein the substrate is non-porous and the article is non-porous.

7. An article having a hydrophilic surface formed from a substrate comprising a fluorine-containing polymer having the surface of the substrate contacted with and modified with a crosslinked fluorocarbon polymeric composition which is crosslinked with fluorinated crosslinking groups and which has hydrophilic functional groups, said crosslinked fluorocarbon polymeric composition being derived from an uncrosslinked fluorocarbon polymeric composition containing a functional group selected from the group consisting of a sulfonyl halide, a carbonyl halide, a group that can be converted to a sulfonyl halide and a group that can be converted to a carbonylhalide; wherein the crosslinked fluorocarbon polymeric composition having hydrophilic functional groups has the formula:

covalently bonded through the R f groups each to a CY group of a fluorocarbon polymeric composition of the formula:

wherein A is a polymeric group derived from at least one fluorine-containing polymerizable monomer, n is an integer that can be 0, 1 or greater than 1; m is an integer of at least 1 and Y is a hydrogen or halogen wherein at least one Y is a fluorine; T is a carbonyl or sulfonyl group; R f is a C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, wherein the R f groups can be the same or different; Z + is a proton or an organic or an inorganic cation; t can be 0 or 1; R f ″ is C 1 –C 20 linear, cyclic or branched fluoroalkyl radical optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, optionally connected to another chain of the fluorocarbon composition having hydrophilic functional groups.

8. The article of claim 7 wherein A is selected from the group consisting of vinyl fluoride, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifuoroethylene, perfluoro(alkylvinyl ether), and tetrafluoromethylene.

9. The article of any one of claims 7 or 8 wherein the substrate is porous and the article is porous.

10. The article of any one of claims 7 or 8 wherein the substrate is porous and the article is non-porous.

11. The article of any one of claims 7 or 8 wherein the substrate is non-porous and the article is non-porous.

12. An article having a hydrophilic surface formed from a substrate comprising a fluorine-containing polymer having the surface of the substrate contacted with and modified with a crosslinked fluorocarbon polymeric composition which is crosslinked with fluorinated crosslinking groups and which has hydrophilic functional groups, said crosslinked fluorocarbon polymeric composition being derived from an uncrosslinked fluorocarbon polymeric composition containing a functional group selected from the group consisting of a sulfonyl halide, a carbonyl halide, a group that can be converted to a sulfonyl halide and a group that can be converted to a carbonylhalide; wherein the crosslinked fluorocarbon polymeric composition having hydrophilic functional groups has the formula:

—[R f ] t -T-CH 2 -T-R f ″-T-CH 2 -T-[R f ] t —

which is covalently bonded through the R f groups, each to a CY group of a fluorocarbon polymeric composition of the formula:

wherein A is a polymeric group derived from at least one fluorine-containing polymerizable monomer, n is an integer that can be 0, 1 or greater than 1, m is an integer of at least 1 and Y is hydrogen or halogen wherein at least one Y is a fluorine; T is a carbonyl or sulfonyl group; R f is a C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, wherein the R f groups can be the same or different; t can be 0 or 1; and R f ″ is C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group; optionally connected to another chain of the fluorocarbon polymeric composition having hydrophilic functional groups.

13. The article of claim 12 wherein A is selected from the group consisting of vinyl fluoride, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluorethylene, perfluoro(alkylvinyl ether), and tetrafluoroethylene.

14. An article having a hydrophilic surface formed of a substrate comprising a fluorine containing a polymer having its surface contacted with and modified with a crosslinked fluorocarbon polymeric composition having hydrophilic functional groups of the formula:

—[R f ] t -T-N(R)R f ″N(R)-T-[R f ] t —

which is covalently bonded through the R f groups, each to a CY group of a fluorocarbon polymeric composition of the formula:

wherein A is a polymeric group derived from at least one fluorine-containing polymerizable monomer, n is an integer that can be 0, 1 or greater than 1, m is an integer of at least 1 and Y is hydrogen or halogen wherein at least one Y is a fluorine; T is a carbonyl or sulfonyl group; R f is a C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, wherein the R f groups can be the same or different; t can be 0 or 1, and R is hydrogen or a sustituted or unsustituted alkyl or aryl group, and R f ″ is C 1 –C 20 linear, cyclic or branched fluoroalkyl radical optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group; optionally connected to another chain of the fluorocarbon polymeric composition having hydrophilic functional groups selected from the group consisting of a sulfonyl halide, a carbonyl halide, a group that can be converted to a sulfonyl halide and a group that can be converted to a carbonyl halide.

15. The article of claim 14 wherein A is selected from the group consisting of vinyl fluoride, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoro(alkylvinyl ether), and tetrafluoroethylene.

16. The article of any one of claims 12 , 13 , 14 or 15 wherein the substrate is porous and the article is porous.

17. The article of any one of claims 12 , 13 , 14 or 15 wherein the substrate is porous and the article is non-porous.

18. The article of any one of claims 12 , 13 , 14 or 15 wherein the substrate is non-porous and the article is non-porous.

19. An article having a hydrophilic surface formed from a substrate comprising a fluorine-containing polymer having its surface contacted with and modified with a branched fluorocarbon polymer having a branch chain of the formula selected from the group consisting of:

which is covalently bonded through the R f groups, each to a CY group of a fluorocarbon polymeric composition of the formula:

wherein A is a polymeric group derived from at least one fluorine-containing polymerizable monomer, n is an integer that can be 0, 1 or greater than 1, m is an integer of at least 1 and Y is hydrogen or halogen wherein at least one Y is a fluorine; T is a carbonyl or sulfonyl group; R f is a C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, wherein the R f groups can be the same or different; Z+ is a proton or an organic or an inorganic cationt, and R is hydrogen or a sustituted or unsustituted alkyl or aryl group; t can be 0 or 1 and R f ′ is C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, optionally connected to another chain or the fluorocarbon polymeric composition having hydrophilic functional groups, said branched fluorocarbon polymeric composition being derived from an uncrosslinked fluorocarbon polymeric composition containing a functional group selected from the group consisting of a sulfonyl halide, a carbanyl halide, a group that can be converted to a sulfonyl halide and a group that can be converted to a carbonyl halide.

20. An article having a hydrophilic surface formed from a substrate comprising a fluorine-containing polymer having a portion of its surface contacted with and modified with a crosslinked fluorocarbon polymeric composition which is crosslinked with fluorinated crosslinking groups and which has hydrophilic functional groups, said crosslinked fluorocarbon polymeric composition being derived from an uncrosslinked fluorocarbon polymeric composition containing a functional group selected from the group consisting of a sulfonyl halide, a carbonyl halide, a group that can be converted to a sulfonyl halide and a group that can be converted to a carbonyl halide; wherein the crosslinked fluorocarbon polymeric composition having hydrophilic functional groups has the formula:

covalently bonded through the R f groups each to a CY group of a fluorocarbon polymeric composition of the formula:

wherein A is a polymeric group derived from at least one fluorine-containing polymerizable monomer, n is an integer that can be 0, 1 or greater than 1, m is an integer of at least 1 and Y is hydrogen or halogen wherein at least one Y is a fluorine; T is a carbonyl or sulfonyl group; R f is a C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, wherein the R f groups can be the same or different; Z + is a proton or an organic or an inorganic cation; t can be 0 or 1; L is C, CH or N; E′ is -TR f ″T- or —R f ′—; G is R f ′T- or R; R f ′ is C 1 –C 20 linear, cyclic or branched fluoroalkyl radical optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group; R f ″ is C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, optionally connected to another chain or the fluorocarbon polymeric composition having hydrophilic functional groups and R is hydrogen or a substituted or unsubstituted alkyl or aryl group.

21. An article having a hydrophilic surface formed from a substrate comprising a fluorine-containing polymer having a portion of its surface contacted with and modified with a crosslinked fluorocarbon polymeric composition which is crosslinked with fluorinated crosslinking groups and which has hydrophilic functional groups, said crosslinked fluorocarbon polymeric composition being derived from an uncrosslinked fluorocarbon polymeric composition containing a functional group selected from the group consisting of a sulfonyl halide, a carbonyl halide, a group that can be converted to a sulfonyl halide and a group that can be converted to a carbonyl halide; wherein the crosslinked fluorocarbon polymeric composition having hydrophilic functional groups has the formula:

is covalently bonded through the R f groups, each to a CY group of a fluorocarbon polymeric composition of the formula:

wherein A is a polymeric group derived from at least one fluorine-containing polymerizable monomer, n is an integer that can be 0, 1 or greater than 1, m is an integer of at least 1 and Y is hydrogen or halogen wherein at least one Y is a fluorine; T is a carbonyl or sulfonyl group; R f is a C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, wherein the R f groups can be the same or different; R f ″ and R f ′″ can be the same or different and can be a C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, optionally connected to another chain of the fluorocarbon polymeric composition having hydrophilic functional groups; Z + is a proton or an organic or an inorganic cation and t can be 1 or 0.

22. An article having hydrophilic functional groups formed from a substrate comprising a fluorine-containing polymer having a portion of its surface contacted with and modified with a branched fluorocarbon polymer having a branch chain of the formula selected from the group consisting of:

which is covalently bonded through the R f group to a CY group of a fluorocarbon polymeric composition of the formula:

wherein A is a polymeric group derived from at least one fluorine-containing polymerizable monomer, n is an integer that can be 0, 1 or greater than 1, m is an integer of at least 1 and Y is hydrogen or halogen wherein at least one Y is a fluorine; T is a carbonyl or sulfonyl group; L′ is C— or CH, L″ is H or -TR f ″; R f is a C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous, hydrogen and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group, R f ′ is C 1 –C 20 linear, cyclic or branched fluoroalkyl group optionally containing one or more oxygen, nitrogen, chlorine, phosphorous hydrogen, and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group; R f ″ is C 1 –C 20 linear, cyclic or branched fluoroalkyl radical optionally containing one or more oxygen, nitrogen, chlorine, hydrogen, phosphorous and/or sulfur atoms and/or one or more sulfonyl or carbonyl groups, or a sulfonyl or carbonyl-containing fluoropolymeric group; Z + is a proton or an organic or an inorganic cation; and t can be 1 or 0 and R is hydrogen or a substituted or unsubstituted alkyl or aryl group said branched fluorocarbon polymer being derived prior to being covalently bonded from a polymer composition containing a functional group selected from the group consisting of a sulfonyl halide, a carbonyl halide, a group tat can be converted to a sulfonyl halide and a group that can be converted to a carbonyl halide.

23. The article of claim 22 wherein the substrate is porous and the article is porous.

24. The article of claim 22 wherein the substrate is porous and the article is non-porous.

25. The article of claim 22 wherein the substrate is non-porous and the article is non-porous.