Fluorocarbon-grafted polysiloxanes

1. A composition comprising a polymer prepared by contacting a polyfluoroalkyl sulfonyl halide of formula I

R f —R 1 —SO 2 X  I

wherein

R f is a straight or branched perfluoroalkyl group having from about 2 to about 20 carbon atoms,

R 1 is a divalent linking group C k H 2k wherein k is 0 to about 20, and

X is halogen,

with a silane compound of Formula II, III or IV

(E-(O) q ) 3 Si—O—(Si(R 2 ) 2 —O) m —[Si(R 3 —NHR 4 )(R 2 )O] n —Si—((O) q -E) 3   Formula II

HR 4 N—R 3 —Si(R 2 ) 2 —O—[Si(R 2 ) 2 —O] m —[Si(R 3 —NHR 4 )(R 2 )O] n —Si(R 2 ) 2 —R 3 —NHR 4   Formula III

HR 4 N—R 3 —Si(R 2 ) 2 —O—[Si(R 2 ) 2 —O] m —Si—((O) q -E) 3   Formula IV

wherein

each R 2 is independently a C 1 to C 8 alkyl,

each R 3 is independently a divalent group containing carbon, oxygen, and optionally nitrogen, with proviso that R 3 does not contain sulfur,

each R 4 is independently H or C 1 to C 8 alkyl,

each E is independently a C 1 to C 8 branched or linear alkyl,

each q is independently zero or 1,

m is a positive integer, and n is independently a positive integer, such that n/(m+n) is a positive fraction having a value up to about 0.7, and the polymer viscosity is less than or equal to 10000 mPas under a shear rate of 0.1 s −1 at a temperature of 20° C.;

wherein the sulfonylhalide is of the formula F(CF 2 ) p CH 2 CH 2 SO 2 X and p is from about 2 to about 20, and mixtures thereof.

2. The composition of claim 1 wherein the sulfonylhalide is of the formula F(CF 2 ) p CH 2 CH 2 SO 2 X wherein p is from about 2 to about 20, and mixtures thereof.

3. The composition of claim 1 wherein R f is a perfluoroalkyl group having from about 4 to about 16 carbon atoms.

4. The composition of claim 1 wherein the silane compound is a compound of Formula II

(E-(O) q ) 3 Si—O—(Si(R 2 ) 2 —O) m —[Si(R 3 —NHR 4 )(R 2 )O] n —Si—((O) q -E) 3

wherein R 2 , R 3 , R 4 , E, q, m and n are as defined in claim 1 .

5. The composition of claim 1 having a viscosity of from about 500 to about 5000 mPas under a shear rate of 0.1 s −1 at a temperature of 20 C.

6. The composition of claim 1 in the form of a dispersion or solution.

7. A process for the preparation of a perfluoroalkylsulfonamide-grafted poly(alkylsiloxane) comprising contacting a polyfluoroalkyl sulfonyl halide of formula I

R f —R 1 —SO 2 X  I

wherein

R f is a straight or branched perfluoroalkyl group having from about 2 to about 20 carbon atoms,

R 1 is a divalent linking group C k H 2k wherein k is 0 to about 20, and

X is halogen,

with a silane compound of Formula II, III or IV

(E-(O) q ) 3 Si—O—(Si(R 2 ) 2 —O) m —[Si(R 3 —NHR 4 )(R 2 )O] n —Si—((O) q -E) 3   Formula II

HR 4 N—R 3 —Si(R 2 ) 2 —O—[Si(R 2 ) 2 —O] m —[Si(R 3 —NHR 4 )(R 2 )O] n —Si(R 2 ) 2 —R 3 —NHR 4   Formula III

HR 4 N—R 3 —Si(R 2 ) 2 —O—[Si(R 2 ) 2 —O] m —Si—((O) q -E) 3   Formula IV

wherein

each R 2 is independently a C 1 to C 8 alkyl,

each R 3 is independently a divalent group containing carbon, oxygen, and optionally at least one of nitrogen, and sulfur,

each R 4 is independently H or C 1 to C 8 alkyl,

each E is independently a C 1 to C 8 branched or linear alkyl,

each q is independently zero or 1,

m is a positive integer, and n is independently a positive integer, such that n/(m+n) is a positive fraction having a value up to about 0.7, and the polymer viscosity is less than or equal to 10000 mPas under a shear rate of 0.1 s −1 at a temperature of 20° C.

8. The process of claim 7 further comprising contacting in the presence of an acid receptor.

9. The process of claim 8 wherein the acid receptor is a tertiary amine or base ion exchange resin.

10. A method of providing oil repellency, water repellency, and stain resistance to substrate surfaces comprising contacting said surface with a polymer prepared by contacting a polyfluoroalkyl sulfonyl halide of formula I

R f —R 1 —SO 2 X  I

wherein

R f is a straight or branched perfluoroalkyl group having from about 2 to about 20 carbon atoms,

R 1 is a divalent linking group C k H 2k wherein k is 0 to about 20, and

X is halogen,

with a silane compound of Formula II, III or IV

(E-(O) q ) 3 Si—O—(Si(R 2 ) 2 —O) m —[Si(R 3 —NHR 4 )(R 2 )O] n —Si—((O) q -E) 3   Formula II

HR 4 N—R 3 —Si(R 2 ) 2 —O—[Si(R 2 ) 2 —O] m —[Si(R 3 —NHR 4 )(R 2 )O] n —Si(R 2 ) 2 —R 3 —NHR 4   Formula III

HR 4 N—R 3 —Si(R 2 ) 2 —O—[Si(R 2 ) 2 —O] m —Si—((O) q -E) 3   Formula IV

wherein

each R 2 is independently a C 1 to C 8 alkyl,

each R 3 is independently a divalent group containing carbon, oxygen, and optionally nitrogen, with proviso that R 3 does not contain sulfur,

each R 4 is independently H or C 1 to C 8 alkyl,

each E is independently a C 1 to C 8 branched or linear alkyl,

each q is independently zero or 1,

m is a positive integer, and n is independently a positive integer, such that n/(m+n) is a positive fraction having a value up to about 0.7, and the polymer viscosity is less than or equal to 10000 mPas under a shear rate of 0.1 s −1 at a temperature of 20° C.;

wherein the sulfonylhalide is of the formula F(CF 2 ) n CH 2 CH 2 SO 2 X and n is from about 2 to about 20, and mixtures thereof.

11. The method of claim 10 wherein the polymer is an aqueous dispersion or solution.

12. The method of claim 11 wherein the dispersion or solution further comprises an epoxysilane or a crosslinking agent.

13. The method of claim 10 wherein the polymer is applied at a concentration of from about 1% to about 10% by weight.

14. The method of claim 10 wherein the amount of polymer deposited on the substrate surface is from about 10 to about 1000 g/m 2 .

15. The method of claim 10 wherein the contacting provides softness to textile and leather substrates.

16. A substrate treated according to the method of claim 10 .

17. A substrate having a surface which has been contacted with a composition of claim 1 .

18. The substrate of claim 16 which is a hard surface selected from the group consisting of mineral, glass, stone, masonry, concrete, unglazed tile, brick, clay, unglazed concrete, granite, limestone, grout, mortar, marble, limestone, statuary, monuments, wood, composites, terrazzo, and gypsum board.

19. The substrate of claim 16 which is a fibrous substrate selected from the group consisting of textile, fiber, nonwoven, paper, leather, fabric, and carpet.

20. A composition comprising a polymer prepared by contacting a polyfluoroalkyl sulfonyl halide of formula I

R f —R 1 —SO 2 X  I

wherein

R f is a straight or branched perfluoroalkyl group having from about 2 to about 20 carbon atoms,

R 1 is a divalent linking group C k H 2k wherein k is 0 to about 20, and

X is halogen,

with a silane compound of Formula III

HR 4 N—R 3 —Si(R 2 ) 2 —O—[Si(R 2 ) 2 —O] m —[Si(R 3 —NHR 4 )(R 2 )O] n —Si(R 2 ) 2 —R 3 —NHR 4   Formula III

wherein

each R 2 is independently a C 1 to C 8 alkyl,

each R 3 is independently a divalent group containing carbon, oxygen, and optionally nitrogen, with proviso that R 3 does not contain sulfur,

each R 4 is independently H or C 1 to C 8 alkyl,

each q is independently zero or 1,

m is a positive integer, and n is independently a positive integer, such that n/(m+n) is a positive fraction having a value up to about 0.7, and the polymer viscosity is less than or equal to 10000 mPas under a shear rate of 0.1 s −1 at a temperature of 20° C.;

wherein the sulfonylhalide is of the formula F(CF 2 ) p CH 2 CH 2 SO 2 X and p is from about 2 to about 20, and mixtures thereof.