Methods of making high fluorine content fluoro-silicone copolymers
View Patent ↗A method of producing silicone copolymers having fluorinated repeat units (D units) wherein the fluorine content of the copolymer is above about thirty-seven (37) weight percent.
1. A method for producing a fluorosilicone composition comprising the steps of:
(a) reacting a perfluoro alpha olefin with a substituted hydrogen di-halo-silane to produce a first reaction product;
(b) reacting said first reaction product with a primary or secondary amine to produce a second reaction product;
(c) reacting said second reaction product with a fluorine containing silanol terminated siloxane to produce a fluorosilicone composition said fluorosilicone composition comprising M, D and D′ units having the formula:
M a D b D′ c
with:
M=R 1 R 2 R 3 SiO 1/2 ,
where R 1 and R 2 are each independently selected from the group of C1 to C40 monovalent hydrocarbon radicals and R 3 is selected from the group consisting of C1 to C40 monovalent hydrocarbon radicals, C2 to C40 monovalent alkenyl hydrocarbon radicals, hydrogen, hydroxyl, C3 to C16 fluorine substituted monovalent hydrocarbon radicals and R 11 R 12 N where R 11 is selected from the group C1 to C10 monovalent hydrocarbon radicals and R12 is selected from the group C1 to C10 monovalent hydrocarbon radicals and hydrogen;
D=R 4 R 5 SiO 2/2 ,
where R 4 is selected from the group consisting of C1 to C40 monovalent hydrocarbon radicals, C2 to C40 monovalent alkenyl hydrocarbon radicals and C3 to C7 fluorine substituted monovalent hydrocarbon radicals and R 5 is selected from the group of C3 to C7 fluorine substituted monovalent hydrocarbon radicals; and
D′=R 6 R 7 SiO 2/2 ,
where R 6 is selected from the group consisting of C1 to C40 monovalent hydrocarbon radicals and C6 to C16 fluorine substituted monovalent hydrocarbon radicals and R 7 is selected from the group of C6 to C16 fluorine substituted monovalent hydrocarbon radicals, where the subscripts a, b and c are non-zero and positive, a is at least 2 and c is at least 2.
2. The method of claim 1 wherein said fluorosilicone has a weight percent fluorine content in excess of about 37.5 weight percent.
3. The method of claim 1 wherein said fluorosilicone has a weight percent fluorine content in excess of about 45.0 weight percent.
4. The method of claim 1 wherein said fluorosilicone has a weight percent fluorine content in excess of about 50.0 weight percent.
5. The method of claim 1 where R 4 is methyl.
6. The method of claim 1 where R 5 is trifluoropropyl.
7. The method of claim 1 where R 6 is methyl.
8. The method of claim 1 where R 7 is (C n F 2n+1 )CH 2 CH 2 ) with n ranging from 4 to 14.
9. The method of claim 8 where n is 8.
10. The method of claim 9 where R 4 is methyl.
11. The method of claim 10 where R 5 is trifluoropropyl.
12. The method of claim 11 where R 6 is methyl.
13. The method of claim 12 wherein said fluorosilicone has a weight percent fluorine content in excess of about 37.5 weight percent.
14. The method of claim 12 wherein said fluorosilicone has a weight percent fluorine content in excess of about 45.0 weight percent.
15. The method of claim 12 wherein said fluorosilicone has a weight percent fluorine content in excess of about 50.0 weight percent.