Amide-substituted silicones and methods for their preparation and use

1. An amide-substituted silicone having unit formula:

(R 2 a R 1 3-a SiO 1/2 ) u (R 2 b R 1 2-b SiO 2/2 ) v (R 2 c R 1 1-c SiO 3/2 ) w (R 1 3 SiO 1/2 ) x (R 1 2 SiO 2/2 ) y (R 1 SiO 3/2 ) z (SiO 4/2 ) 1-u-v-w-x-y-z , where a has a value ranging from 0 to 1, b has a value ranging from 0 to 1, c has a value ranging from 0 to 1, (a +b+c) >0,(u+x) has a value ranging from 0 to 0.4,(v+y) has a value ranging from 0.6 to 1,(w+z) has a value ranging from 0 to 0.1, each R 1 is independently a monovalent hydrocarbon group, each R 2 is independently an alkyl group having 5 to 30 carbon atoms or an amide-functional group of formula:

where each R 3 is independently a hydrogen atom, a halogen atom, or a monovalent organic group, provided, however, that at least one R 3 is not hydrogen, each R 4 is independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and each R 5 is independently a group of formula -(CR 3 2 ) r R 1 , where r has a value ranging from 5 to 29, and q has a value ranging from 10 to 29, with the proviso that 1 mole % to 100 mole % of R 2 is the amide-functional group.

2. The amide-substituted silicone of claim 1 having a formula selected from:

or a combination thereof, where m has a value ranging from 4 to 100, n has a value ranging from 0 to 100, p has a value ranging from 1 to 30, s has a value ranging from 0 to 7, t has a value ranging from 1 to 8, and (s+t) has a value ranging from 3 to 8.

3. A method for making an amide-substituted silicone, the method comprising:

1) heating an amine and an aliphatically unsaturated acid, acid anhydride, or acyl chloride at a temperature of at least 200° C. to form an amide,

2) adding a terminal alkene, and

3) hydrosilylation of the amide with a polyorganohydrogensiloxane having at least one silicon bonded hydrogen atom in the presence of a platinum group metal catalyst.

4. The method of claim 3 , where the amine has formula

and the acid has the formula

where each R 1 is independently an unsaturated monovalent hydrocarbon group, where each R 3 is independently a hydrogen atom, a halogen atom, or a monovalent organic group, provided, however, that at least one R 3 is not hydrogen, each R 4 is independently a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and each R 5 is independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or a group of formula -(CR 3 2 ) r R 1 , where r has a value ranging from 5 to 29, and q has a value ranging from 2 to 29.

5. The method of claim 3 , further comprising purifying the amide formed in step 1) before step 2).

6. A method for making an amide-substituted silicone, the method comprising:

1) heating an amine and an aliphatically unsaturated acid, acid anhydride, or acyl chloride at a temperature of at least 200° C. to form an amide, and

2) hydrosilylation of the amide with a polyorganohydrogensiloxane having at least one silicon bonded hydrogen atom in the presence of a platinum group metal catalyst, where the amine has formula

and the acid has the formula

where each R 1 is independently an unsaturated monovalent hydrocarbon group, where each R 3 is independently a hydrogen atom, a halogen atom, or a monovalent organic group, provided, however, that at least one R 3 is not hydrogen, each R 4 is independently a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and each R 5 is independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, or a group of formula -(CR 3 2 ) r R 1 , where r has a value ranging from 5 to 29, and q has a value ranging from 2 to 29, and where the polyorganohydrogensiloxane has unit formula:

(H a R 1 3-a SiO 1/2 ) u (H b R 1 2-b SiO 2/2 ) v (H c R 1 1-c SiO 3/2 ) w (R 1 3 SiO 1/2 ) x (R 1 2 SiO 2/2 ) y (R 1 SiO 3/2 ) z (SiO 4/2 ) 1-u-v-w-x-y-z , where a has a value ranging from 0 to 1, b has a value ranging from 0 to 1, c has a value ranging from 0 to 1,(a+b+c)>0, (u+x) has a value ranging from 0 to 0.4, (v+y) has a value ranging from 0.6 to 1, (w+z) has a value ranging from 0 to 0.1, and each R 1 is independently a monovalent hydrocarbon group.

7. The method of claim 6 , where the polyorganohydrogensiloxane containing has a formula selected from:

or a combination thereof, where m has a value ranging from 4 to 100, n has a value ranging from 0 to 100, p has a value ranging from 1 to 30, s has a value ranging from 0 to 7, t has a have a value ranging from 1 to 8; and (s+t) has a value ranging from 3 to 8.