Ester modified cross-linked silicone compositions

1. A composition comprising a polymer having branched silicone substituted by at least one alkylcarbonylalkyl group and by at least one alkylcarboxy group, and cross-linked with an alkenyl functional cross-linker, wherein an average number of alkylcarboxyalkyl substitutions per silicone is between 1 and 60 and an average number of crosslinks between branched silicones is between 1 and 30.

2. The composition of claim 1 , wherein the average number of alkylcarboxyalkyl substitutions per silicone is between 1 and 15.

3. The composition of claim 1 , wherein the average number of crosslinks between branched silicones is between 1 and 15.

4. The composition of claim 1 , wherein the polymer is prepared by a method comprising reacting:

(a) a Si—H functional compound of formula (I):

M H a M b D H c D d T H e T f Q g   (I)

wherein:

M H =R 1 R 2 HSiO 1/2 ;

M=R 3 R 4 R 5 SiO 1/2 ;

D H =R 6 HSiO 2/2 ;

D=R 7 R 8 SiO 2/2 ;

T H HSiO 3/2 ;

T=R 9 SiO 3/2 ; and

Q=SiO 4/2 ;

wherein

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently an aliphatic, aromatic, or fluoro monovalent hydrocarbon having from 1 to 60 carbon atoms; and

a, b, c, d, e, f, and g are independently zero or a positive integer, such that 2≤a+b+c+d+e+f+g≤6000 and when a′+c′+e′=2, a+c+e>2 and wherein e+f+g≥1;

(b) a carboxy functional olefin of formula (II):

wherein

R′ is a combination of R 1 and —Si(R a ) 3 , wherein R 1 is a C 1 -C 60 monovalent hydrocarbon and R a is an aliphatic, aromatic, or fluoro monovalent hydrocarbon; and

n is 0≤n≤30; and

(c) a silicone based alkenyl functional cross-linker of formula (III) and/or a non-silicone based alkenyl functional cross-linker of formula (IV):

M 1 a′ M 2 b′ D 1 c′ D 2 d′ T 1 e′ T 2 f′ Q g′   (III)

wherein:

M 1 =R 10 R 11 R 12 SiO 1/2 ;

M 2 =R 13 R 14 R 15 SiO 1/2 O;

D 1 =R 16 R 17 SiO 2/2 ;

D 2 =R 18 R 19 SiO 2/2 ;

T 1 =R 20 SiO 3/2 ;

T 2 =R 21 SiO 3/2 ; and

Q=SiO 4/2 ;

wherein

R 11 , R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 , and R 21 , are independently an aliphatic, aromatic, or fluoro monovalent hydrocarbon having from 1 to 60 carbon atoms;

R 10 , R 16 , and R 20 are each a monovalent radical containing at least one terminal olefin bond; a′, b′, c′, d′, e′, f′, and g′ are independently zero or a positive integer, such that 2≤a′+b′+c′+d′+e′+f+g′≤6000 and when a+c+e=2, a′+c′+e′>2; and

Z is —(CHR 22 ) m — or —(CH 2 CHR 23 O) k —, wherein m and k are positive integers, such that 1≤m≤60 and 1≤k≤500, and R 22 and R 23 are independently hydrogen or monovalent hydrocarbon having from 1 to 60 carbon atoms.

5. The composition of claim 4 , wherein the one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is a C 1 -C 20 monovalent hydrocarbon.

6. The composition of claim 4 , wherein a, b, c, d, e, f, and g are 2≤a+b+c+d+e+f+g: ≤4000.

7. The composition of claim 4 , wherein one or more of R 11 , R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 , and R 21 is a C 1 -C 30 monovalent hydrocarbon.

8. The composition of claim 4 , wherein one or more of R 11 , R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 , and R 21 is an aromatic monovalent hydrocarbon.

9. The composition of claim 4 , wherein one or more of R 11 , R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 , and R 21 is a fluoro monovalent hydrocarbon.

10. A method for preparing a polymer having branched silicone comprising reacting:

(a) a Si—H functional compound of formula (I):

M H a M b D H c D d T H e T f Q g   (I)

wherein:

M H =R 1 R 2 HSiO 1/2 ;

M=R 3 R 4 R 5 SiO 1/2 ;

D H =R 6 HSiO 2/2 ;

D=R 7 R 8 SiO 2/2 ;

T H =HSiO 3/2 ;

T=R 9 SiO 3/2 ; and

Q=SiO 4/2 ;

wherein

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently an aliphatic, aromatic, or fluoro monovalent hydrocarbon having from 1 to 60 carbon atoms; and

a, b, c, d, e, f, and g are independently zero or a positive integer, such that 2≤a+b+c+d+e+f+g≤6000 and when a′+c′+e′=2, a+c+e>2 and wherein e+f+g≥1;

(b) a carboxy functional olefin of formula (II):

wherein

R′ is a combination of R 1 and —Si(R a ) 3 , wherein R 1 is an aliphatic, aromatic, or fluoro monovalent hydrocarbon having from 1 to 60 carbon atoms and R a is an aliphatic, aromatic, or fluoro monovalent hydrocarbon, and;

n is 0≤n≤30; and

(c) a silicone based alkenyl functional cross-linker of formula (III) and/or a non-silicone based alkenyl functional cross-linker of formula (IV):

M 1 a′ ,M 2 b′ D 1 c′ D 2 d′ T 1 e′ T 2 f′ Q g′

wherein:

M 1 =R 10 R 11 R 12 SiO 1/2 ;

M 2 =R 13 R 14 R 15 SiO 1/2 ;

D 1 =R 16 R 17 SiO 2/2 ;

D 2 =R 18 R 19 SiO 2/2 ;

T 1 =R 20 SiO 3/2 ;

T 2 =R 21 SiO 3/2 ; and

Q=SiO 4/2 ;

wherein

R 11 , R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 , and R 21 , are independently an aliphatic, aromatic, or fluoro monovalent hydrocarbon having from 1 to 60 carbon atoms;

R 10 , R 16 , R 20 and are each a monovalent radical containing at least one terminal olefin bond;

a′, b′, c′, d′, e′, f′, and g′ are independently zero or a positive integer, such that 2≤a′+b′+c′+d′+e′+f+g′≤6000 and when a+c+e=2, a′+c′+e′>2;

Z is —(CHR 22 ) m — or —(CH 2 CHR 23 O) k —, wherein m and k are positive integers, such that 1≤m≤60 and 1≤k≤500, and R 22 and R 23 are independently hydrogen or monovalent hydrocarbon having from 1 to 60 carbon atoms; and

wherein an average number of crosslinks between branched silicones is between 1 and 30.

11. The method of claim 10 , wherein one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is a C 1 -C 20 monovalent hydrocarbon.

12. The method of claim 10 , wherein one or more R 11 , R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 , and R 21 is a C 1 -C 60 monovalent hydrocarbon.

13. The method of claim 10 , wherein the reaction between the Si—H compound of formula (I), the carboxy functional olefin of formula (II) and the alkenyl functional cross-linker of formula (III) and/or (IV) occurs in the presence of at least one precious metal catalyst selected from the group consisting of a rhodium, ruthenium, palladium, osmium, iridium, iron and platinum catalyst.

14. A personal care composition comprising:

(a) the composition of claim 1 ; and

(b) one or more personal care components.

15. The composition of claim 4 , wherein the method further comprises deprotecting the silyl protected carboxylic acid.

16. The method of claim 10 , wherein the method further comprises deprotecting the silyl protected carboxylic acid.

17. The composition of claim 4 , wherein a=12; b, c, d, e, and f=0; and g=10.

18. The composition of claim 4 , wherein a=3; b, c, d, e, and g=0; and f=1.