Polysiloxanes and polysiloxane prepolymers with vinyl or epoxy functionality

1. A polysiloxane of general formula I:

wherein

R is a C 2-10 alkenyl, a C 2-10 alkyl with an epoxy group or a C 5 -C 7 cycloalkyl with an epoxy group;

R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, C 1-4 alkyl, C 1-4 fluoroalkyl, optionally substituted phenyl and optionally substituted benzyl;

A is —OH or —NHR 5 , wherein R 5 is hydrogen or a C 1-3 alkyl; and

B is —R 1 -A or —R 6 , wherein R 1 is a linking group having an alkylene group with 2 to 8 carbon atoms wherein the alkylene group optionally includes ether, urethane or ureido linkages; and R 6 is selected from the group consisting of C 1-4 alkyl, optionally substituted phenyl and optionally substituted benzyl; and

m and n are integers with an m:n ratio from 30:1 to 3:1.

2. The polysiloxane of claim 1 wherein R is a C 2 -C 10 alkenyl.

3. The polysiloxane of claim 1 wherein R is a C 2-10 alkyl having at least one epoxy group or a C 5 -C 6 cycloalkyl having at least one epoxy group.

4. The polysiloxane of claim 1 wherein the m:n ratio is from 20:1 to 8:1, and the polysiloxane has a number average molecular weight from 2000 to 10,000.

5. The polysiloxane of claim 1 wherein A is —OH.

6. The polysiloxane of claim 2 wherein R is selected from the group consisting of —CH═CH 2 , —CH 2 —CH═CH 2 , —CH 2 —CH 2 —CH═CH 2 —CH 2 —C 5 H 7 and —CH 2 —C 6 H 9 .

7. The polysiloxane of claim 1 wherein R 1 is independently represented by formula S or formula T,

wherein x is any integer from 1 to 6, y is any integer from 2 to 6, and R a and R b are each independently selected from hydrogen, fluorine or methyl.

8. The polysiloxane of claim 7 wherein R 1 is represented by formula S, x is 3 or 4 and R 2 , R 3 and R 4 are independently selected from methyl, ethyl or phenyl.

9. The polysiloxane of claim 3 wherein R is a C 2 -C 4 alkylepoxy selected from the group consisting of

10. A silicone prepolymer of general formula II:

wherein

R is a C 2-10 alkyl with an epoxy group or a C 5 -C 7 cycloalkyl with an epoxy group;

R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, C 1-4 alkyl, C 1-4 fluoroalkyl, optionally substituted phenyl and optionally substituted benzyl;

m and n are integers with an m:n ratio from 30:1 to 3:1;

R 1 is an alkylene group with 2 to 8 carbon atoms wherein the alkylene group optionally includes ether, urethane or ureido linkages;

D is defined by -U-L-M, wherein U is a urethane or urea link, L is an alkylene group with 2 to 8 carbon atoms wherein the alkylene group optionally includes ether, urethane or ureido linkages, and M is an activated polymerizable group; and

E is defined by —R 1 -D or —R 6 , wherein R 6 is selected from the group consisting of C 1-4 alkyl, optionally substituted phenyl and optionally substituted benzyl.

11. The silicone prepolymer of claim 10 wherein R is a C 2 -C 4 alkylepoxy selected from the group consisting of

12. The silicone prepolymer of claim 10 wherein E is —R 1 -D.

13. The silicone prepolymer of claim 10 with a number average molecular weight from 16,000 to 60,000.

14. A silicone prepolymer of general formula IV:

wherein

R is a C 2-10 alkenyl;

R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, C 1-4 alkyl, C 1-4 fluoroalkyl, optionally substituted phenyl and optionally substituted benzyl;

m and n are integers with an m:n ratio from 30:1 to 3:1;

R 1 is an alkylene group with 2 to 8 carbon atoms wherein the alkylene group optionally includes ether, urethane or ureido linkages;

D is defined by -U-L-M, wherein U is a urethane or urea link, L is an alkylene group with 2 to 8 carbon atoms wherein the alkylene group optionally includes ether, urethane or ureido linkages, and M is an activated polymerizable group; and

E is defined by —R 1 -D or —R 6 , wherein R 6 is selected from the group consisting of C 1-4 alkyl, optionally substituted phenyl or optionally substituted benzyl.

15. The silicone prepolymer of claim 14 wherein R is selected from the group consisting of —CH═CH 2 , —CH 2 —CH═CH 2 , —CH 2 —CH 2 —CH═CH 2 , —CH 2 —C 5 H 7 and —CH 2 —C 6 H 9 .

16. The silicone prepolymer of claim 14 wherein E is —R 1 -D.

17. The prepolymer of claim 14 with a number average molecular weight from 16,000 to 60,000.

18. A polysiloxane prepolymer comprising siloxane segments (HS) and (MH)

(*Dii*Diol*Dii*PS) x (HS)

(*Dii*PS) y (MH)

wherein:

each Dii is independently a diradical residue of a diisocyanate;

each Diol is independently a diradical residue of a diol having 1 to 10 carbon atoms;

each * is independently —NHC(O)NH—, —NHC(O)O— or —OC(O)NH—;

x represents the number of segments (HS) and is at least 2;

y represents the number of segments (MH) and is at least 1; and

each PS is independently a diradical residue of a polysiloxane of formula

wherein

R is a C 2-10 alkenyl, a C 2-10 alkyl with an epoxy group or a C 5 -C 7 cycloalkyl with an epoxy group;

R 1 is a linking group having an alkylene group with 2 to 8 carbon atoms wherein the alkylene group optionally includes ether, urethane or ureido linkages;

R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, C 1-4 alkyl, C 1-4 fluoroalkyl, optionally substituted phenyl and optionally substituted benzyl;

A is —OH or —NHR 5 , wherein R 5 is hydrogen or a C 1-3 alkyl; and

m and n are integers with an m:n ratio from 30:1 to 3:1.

19. The polysiloxane prepolymer of claim 18 wherein R 1 is independently represented by formula S or formula T,

x is any integer from 1 to 6, y is any integer from 2 to 6, and R a and R b are each independently selected from hydrogen, fluorine or methyl.

20. The polysiloxane prepolymer of claim 19 wherein R 1 is represented by formula S, x is 3 or 4 and R 2 , R 3 and R 4 are independently selected from methyl, ethyl or phenyl.