Acrylate cross linked silicone copolymer networks
View Patent ↗The compositions of the present invention comprise silicone copolymers, terpolymers and higher order polymers that comprise 1) polyether substituted structural units and 2) epoxy or oxirane structural units that are reacted with acrylate species to produce cross linked silicones comprising polyether substituted structural units and acrylate cross links. The cross linked polymers of the present invention are self-emulsifying and may be either water swellable or oil swellable.
1. A silicone composition comprising the reaction product of:
a) M a M H b-h-k M PE h M E k D c D H d-i-l D PE i D E l T e T H f-j-m T PE j T E m Q g ;
b) a stoichiometric or super-stoichiometric quantity of acrylate where
M=R 1 R 2 R 3 SiO 1/2 ;
M H =R 4 R 5 HSiO 1/2 ;
M PE =R 4 R 5 (—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 1/2 ;
M E =R 4 R 5 (—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 1/2
D=R 6 R 7 SiO 2/2 ; and
D H =R 8 HSiO 2/2
D PE =R 8 (—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 2/2
D E =R 8 (—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 2/2 ;
T=R 19 SiO 3/2 ;
T H =HSiO 3/2 ;
T PE =(—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 3/2 ;
T E =(—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 3/2 ; and
Q=SiO 4/2 ;
where R 1 , R 2 , R 3 , R 4 , R5 , R 6 , R 7 , R 8 and R 19 are each independently selected from the group of monovalent hydrocarbon radicals having from 1 to 60 carbon atoms;
R 9 is H or a 1 to 6 carbon atom alkyl group; R 10 is a divalent alkyl radical of 1 to 6 carbons;
R 11 is selected from the group of divalent radicals consisting of —C 2 H 4 O—, —C 3 H 6 O—, and —C 4 H 8 O—; R 12 is H, a monofunctional hydrocarbon radical of 1 to 6 carbons, or acetyl; R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from the group of hydrogen and monovalent hydrocarbon radicals having from one to sixty carbon atoms, Q t is a di- or trivalent hydrocarbon radical having from one to sixty carbon atoms, Q s is a divalent hydrocarbon radical having from one to sixty carbon atoms subject to the limitation that when Q t is trivalent R 14 is absent and R 16 and R 18 may be either cis- or trans- to each other;
the subscript a may be zero or positive subject to the limitation that when the subscript a is zero, b must be positive;
the subscript b may be zero or positive subject to the limitation that when b is zero, the subscript a must be positive;
the subscript c is positive and has a value ranging from about 5 to about 1,000;
the subscript d is positive and has a value ranging from about 3 to about 400;
the subscript e is zero or positive and has a value ranging from 0 to about 50;
the subscript f is zero or positive and has a value ranging from 0 to about 30;
the subscript g is zero or positive and has a value ranging from 0 to about 20;
the subscript h is zero or positive and has a value ranging from 0 to about 2 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript i is zero or positive and has a value ranging from 0 to about 200 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript j is zero or positive and has a value ranging from 0 to about 30 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript k is zero or positive and has a value ranging from 0 to about 2 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript l is zero or positive and has a value ranging from 0 to about 200 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript m is zero or positive and has a value ranging from 0 to about 30 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript n is zero or one;
the subscript o is zero or one;
the subscript p is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript q is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript r is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript s is zero or one;
the subscript t is zero or one; and
c) a free radical initiator wherein the reaction product is swellable.
2. The composition of claim 1 wherein said silicone composition is self-emulsifying.
3. The composition of claim 1 wherein said silicone composition may be swollen by a solvent.
4. The composition of claim 3 wherein said solvent is water.
5. The composition of claim 3 wherein said solvent is a silicone or an oil.
6. The composition of claim 3 wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
7. The composition of claim 4 wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
8. The composition of claim 5 wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
9. The composition of claim 7 where R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 is vinylcyclohexene oxide.
10. The composition of claim 8 where R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 is vinylcyclohexene oxide.
11. An aqueous emulsion where the discontinuous phase comprises water and the continuous phase comprises a silicone composition comprising the reaction product of:
c) M a M H b-h-k M PE h M E k D c D H d-i-l D PE i D E l T e T H f-j-m T PE j T E m Q g ;
d) a stoichiometric or super-stoichiometric quantity of acrylate where
M=R 1 R 2 R 3 SiO 1/2 ;
M H =R 4 R 5 HSiO 1/2 ;
M PE =R 4 R 5 (—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 1/2 ;
M E =R 4 R 5 (—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 1/2
D=R 6 R 7 SiO 2/2 ; and
D H =R 8 HSiO 2/2
D PE =R 8 (—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 2/2
D E =R 8 (—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 2/2 ;
T=R 19 SiO 3/2 ;
T H =HSiO 3/2 ;
T PE =(—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 3/2 ;
T E =(—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 3/2 ; and
Q=SiO 4/2 ;
where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each independently selected from the group of monovalent hydrocarbon radicals having from 1 to 60 carbon atoms;
R 9 is H or a 1 to 6 carbon atom alkyl group; R 10 is a divalent alkyl radical of 1 to 6 carbons;
R 11 is selected from the group of divalent radicals consisting of —C 2 H 4 O—, —C 3 H 6 O—, and C 4 H 8 O—; R 12 is H, a monofunctional hydrocarbon radical of 1 to 6 carbons, or acetyl; R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from the group of hydrogen and monovalent hydrocarbon radicals having from one to sixty carbon atoms, Q t is a di- or trivalent hydrocarbon radical having from one to sixty carbon atoms, Q s is a divalent hydrocarbon radical having from one to sixty carbon atoms subject to the limitation that when Q t is trivalent R 14 is absent and where R 16 and R 18 may be either cis- or trans- to each other;
the subscript a may be zero or positive subject to the limitation that when the subscript a is zero, b must be positive;
the subscript b may be zero or positive subject to the limitation that when b is zero, the subscript a must be positive;
the subscript c is positive and has a value ranging from about 5 to about 1,000;
the subscript d is positive and has a value ranging from about 3 to about 400;
the subscript e is zero or positive and has a value ranging from 0 to about 50;
the subscript f is zero or positive and has a value ranging from 0 to about 30;
the subscript g is zero or positive and has a value ranging from 0 to about 20;
the subscript h is zero or positive and has a value ranging from 0 to about 2 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript i is zero or positive and has a value ranging from 0 to about 200 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript j is zero or positive and has a value ranging from 0 to about 30 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript k is zero or positive and has a value ranging from 0 to about 2 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript l is zero or positive and has a value ranging from 0 to about 200 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript m is zero or positive and has a value ranging from 0 to about 30 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript n is zero or one;
the subscript o is zero or one;
the subscript p is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript q is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript r is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript s is zero or one;
the subscript t is zero or one; and
c) a free radical initiator.
12. The composition of claim 11 wherein said silicone composition is self-emulsifying.
13. The composition of claim 11 wherein said silicone composition may be swollen by a solvent.
14. The composition of claim 13 wherein said solvent is water.
15. The composition of claim 13 wherein said solvent is a silicone or an oil.
16. The composition of claim 13 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
17. The composition of claim 14 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
18. The composition of claim 15 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
19. The composition of claim 17 where R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 is vinylcyclohexene oxide.
20. The composition of claim 18 where R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 is vinylcyclohexene oxide.
21. A composition comprising an aqueous emulsion where the continuous phase comprises water and the discontinuous phase comprises the reaction product of:
a) M a M H b-h-k M PE h M E k D c D H d-i-l D PE i D E l T e T H f-j-m T PE j T E m Q g ;
b) a stoichiometric or super-stoichiometric quantity of acrylate where
M=R 1 R 2 R 3 SiO 1/2 ;
M H =R 4 R 5 HSiO 1/2 ;
M PE =R 4 R 5 (—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 1/2 ;
M E =R 4 R 5 (—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 1/2
D=R 6 R 7 SiO 2/2 ; and
D H =R 8 HSiO 2/2
D PE =R 8 (—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 2/2
D E =R 8 (—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 2/2 ;
T=R 19 SiO 3/2 ;
T H =HSiO 3/2 ;
T PE =(—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 3/2 ;
T E =(—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 3/2 ; and
Q=SiO 4/2 ;
where R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each independently selected from the group of monovalent hydrocarbon radicals having from 1 to 60 carbon atoms;
R 9 is H or a 1 to 6 carbon atom alkyl group; R 10 is a divalent alkyl radical of 1 to 6 carbons;
R 11 is selected from the group of divalent radicals consisting of —C 2 H 4 O—, —C 3 H 6 O—, and —C 4 H 8 O—; R 12 is H, a monofunctional hydrocarbon radical of 1 to 6 carbons, or acetyl; R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from the group of hydrogen and monovalent hydrocarbon radicals having from one to sixty carbon atoms, Q t is a di- or trivalent hydrocarbon radical having from one to sixty carbon atoms, Q s is a divalent hydrocarbon radical having from one to sixty carbon atoms subject to the limitation that when Q t is trivalent R 14 is absent and where R 16 and R 18 may be either cis- or trans- to each other;
the subscript a may be zero or positive subject to the limitation that when the subscript a is zero, b must be positive;
the subscript b may be zero or positive subject to the limitation that when b is zero, the subscript a must be positive;
the subscript c is positive and has a value ranging from about 5 to about 1,000;
the subscript d is positive and has a value ranging from about 3 to about 400;
the subscript e is zero or positive and has a value ranging from 0 to about 50;
the subscript f is zero or positive and has a value ranging from 0 to about 30;
the subscript g is zero or positive and has a value ranging from 0 to about 20;
the subscript h is zero or positive and has a value ranging from 0 to about 2 subject to the limitation that the sum of the subscripts h, I and j is positive;
the subscript i is zero or positive and has a value ranging from 0 to about 200 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript j is zero or positive and has a value ranging from 0 to about 30 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript k is zero or positive and has a value ranging from 0 to about 2 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript l is zero or positive and has a value ranging from 0 to about 200 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript m is zero or positive and has a value ranging from 0 to about 30 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript n is zero or one;
the subscript o is zero or one;
the subscript p is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript q is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript r is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript s is zero or one;
the subscript t is zero or one; and
c) a free radical initiator.
22. The composition of claim 21 wherein said silicone composition is self-emulsifying.
23. The composition of claim 21 wherein said silicone composition may be swollen by a solvent.
24. The composition of claim 23 wherein said solvent is water.
25. The composition of claim 23 wherein said solvent is a silicone or an oil.
26. The composition of claim 23 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
27. The composition of claim 24 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
28. The composition of claim 25 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
29. The composition of claim 27 where R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 is vinylcyclohexene oxide.
30. The composition of claim 28 where R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 is vinylcyclohexene oxide.
31. A composition comprising a non-aqueous emulsions where the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the reaction product of:
a) M a M H b-h-k M PE h M E k D c D H d-i-l D PE i D E l T e T H f-j-m T PE j T E m Q g ;
b) a stoichiometric or super-stoichiometric quantity of acrylate where
M=R 1 R 2 R 3 SiO 1/2 ;
M H =R 4 R 5 HSiO 1/2 ;
M PE =R 4 R 5 (—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 1/2 ;
M E =R 4 R 5 (—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 1/2
D=R 6 R 7 SiO 2/2 ; and
D H =R 8 HSiO 2/2
D PE =R 8 (—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 2/2
D E =R 8 (—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 2/2 ;
T=R 19 SiO 3/2 ;
T H =HSiO 3/2 ;
T PE =(—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 3/2 ;
T E =(—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 3/2 ; and
Q=SiO 4/2 ;
where R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each independently selected from the group of monovalent hydrocarbon radicals having from 1 to 60 carbon atoms;
R 9 is H or a 1 to 6 carbon atom alkyl group; R 10 is a divalent alkyl radical of 1 to 6 carbons;
R 11 is selected from the group of divalent radicals consisting of —C 2 H 4 O—, —C 3 H 6 O—, and —C 4 H 8 O—; R 12 is H, a monofunctional hydrocarbon radical of 1 to 6 carbons, or acetyl; R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from the group of hydrogen and monovalent hydrocarbon radicals having from one to sixty carbon atoms, Q t is a di- or trivalent hydrocarbon radical having from one to sixty carbon atoms, Q s is a divalent hydrocarbon radical having from one to sixty carbon atoms subject to the limitation that when Q t is trivalent R 14 is absent and where R 16 and R 18 may be either cis- or trans- to each other;
the subscript a may be zero or positive subject to the limitation that when the subscript a is zero, b must be positive;
the subscript b may be zero or positive subject to the limitation that when b is zero, the subscript a must be positive;
the subscript c is positive and has a value ranging from about 5 to about 1,000;
the subscript d is positive and has a value ranging from about 3 to about 400;
the subscript e is zero or positive and has a value ranging from 0 to about 50;
the subscript f is zero or positive and has a value ranging from 0 to about 30;
the subscript g is zero or positive and has a value ranging from 0 to about 20;
the subscript h is zero or positive and has a value ranging from 0 to about 2 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript i is zero or positive and has a value ranging from 0 to about 200 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript j is zero or positive and has a value ranging from 0 to about 30 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript k is zero or positive and has a value ranging from 0 to about 2 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript l is zero or positive and has a value ranging from 0 to about 200 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript m is zero or positive and has a value ranging from 0 to about 30 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript n is zero or one;
the subscript o is zero or one;
the subscript p is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript q is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript r is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript s is zero or one;
the subscript t is zero or one; and
c) a free radical initiator.
32. The composition of claim 31 wherein said silicone composition is self-emulsifying.
33. The composition of claim 31 wherein said silicone composition may be swollen by a solvent.
34. The composition of claim 33 wherein said solvent is water.
35. The composition of claim 33 wherein said solvent is a silicone or an oil.
36. The composition of claim 33 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
37. The composition of claim 34 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
38. The composition of claim 35 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
39. The composition of claim 37 where R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 is vinylcyclohexene oxide.
40. The composition of claim 38 where R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 is vinylcyclohexene oxide.
41. A composition comprising a non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the reaction product of:
a) M a M H b-h-k M PE h M E k D c D H d-i-l D PE i D E l T e T H f-j-m T PE j T E m Q g ;
b) a stoichiometric or super-stoichiometric quantity of acrylate where
M=R 1 R 2 R 3 SiO 1/2 ;
M H =R 4 R 5 HSiO 1/2 ;
M PE =R 4 R 5 (—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 1/2 ;
M E =R 4 R 5 (—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 1/2
D=R 6 R 7 SiO 2/2 ; and
D H =R 8 HSiO 2/2
D PE =R 8 (—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 2/2
D E =R 8 (—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 2/2 ;
T=R 19 SiO 3/2 ;
T H =HSiO 3/2 ;
T PE =(—CH 2 CH(R 9 )(R 10 ) n O(R 11 ) o (C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r R 12 )SiO 3/2 ;
T E =(—R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 )SiO 3/2 ; and
Q=SiO 4/2 ;
where R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each independently selected from the group of monovalent hydrocarbon radicals having from 1 to 60 carbon atoms;
R 9 is H or a 1 to 6 carbon atom alkyl group; R 10 is a divalent alkyl radical of 1 to 6 carbons;
R 11 is selected from the group of divalent radicals consisting of —C 2 H 4 O—, —C 3 H 6 O—, and —C 4 H 8 O—; R 12 is H, a monofunctional hydrocarbon radical of 1 to 6 carbons, or acetyl; R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from the group of hydrogen and monovalent hydrocarbon radicals having from one to sixty carbon atoms, Q t is a di- or trivalent hydrocarbon radical having from one to sixty carbon atoms, Q s is a divalent hydrocarbon radical having from one to sixty carbon atoms subject to the limitation that when Q t is trivalent R 14 is absent and where R 16 and R 18 may be either cis- or trans- to each other;
the subscript a may be zero or positive subject to the limitation that when the subscript a is zero, b must be positive;
the subscript b may be zero or positive subject to the limitation that when b is zero, the subscript a must be positive;
the subscript c is positive and has a value ranging from about 5 to about 1,000;
the subscript d is positive and has a value ranging from about 3 to about 400;
the subscript e is zero or positive and has a value ranging from 0 to about 50;
the subscript f is zero or positive and has a value ranging from 0 to about 30;
the subscript g is zero or positive and has a value ranging from 0 to about 20;
the subscript h is zero or positive and has a value ranging from 0 to about 2 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript i is zero or positive and has a value ranging from 0 to about 200 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript j is zero or positive and has a value ranging from 0 to about 30 subject to the limitation that the sum of the subscripts h, i and j is positive;
the subscript k is zero or positive and has a value ranging from 0 to about 2 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript l is zero or positive and has a value ranging from 0 to about 200 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript m is zero or positive and has a value ranging from 0 to about 30 subject to the limitation that the sum of the subscripts k, l and m is positive;
the subscript n is zero or one;
the subscript o is zero or one;
the subscript p is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript q is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript r is zero or positive and has a value ranging from 0 to about 100 subject to the limitation that (p+q+r)>0;
the subscript s is zero or one;
the subscript t is zero or one; and
c) a free radical initiator.
42. The composition of claim 41 wherein said silicone composition is self-emulsifying.
43. The composition of claim 41 wherein said silicone composition may be swollen by a solvent.
44. The composition of claim 43 wherein said solvent is water.
45. The composition of claim 43 wherein said solvent is a silicone or an oil.
46. The composition of claim 43 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
47. The composition of claim 44 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
48. The composition of claim 45 wherein R 1 , R 2 , R 3 R 4 , R 5 , R 6 , R 7 , R 8 and R 19 are each methyl.
49. The composition of claim 47 where R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 is vinylcyclohexene oxide.
50. The composition of claim 48 where R 17 R 18 C—CR 16 Q s Q t R 15 (COC)R 13 R 14 is vinylcyclohexene oxide.
51. An oil-in-water emulsion comprising the composition of claim 1 wherein said composition is present in the water phase.
52. A water-in-oil emulsion comprising the composition of claim 1 wherein said composition is present in the water phase.
53. A non-aqueous emulsion where the discontinuous phase comprises a non-aqueous hydroxylic organic solvent and the composition of claim 1 .
54. A non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the composition of claim 1 .