Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation
View Patent ↗Disclosed herein are cobalt complexes containing terpyridine ligands and chelating alkene-modified silyl ligands, and their use as hydrosilylation and/or dehydrogenative silylation and crosslinking catalysts. The cobalt complexes also exhibit adequate air stability for handling and manipulation.
1. A complex of the formula:
wherein each occurrence of R 1 -R 18 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R 1 -R 18 , other than hydrogen, optionally contain at least one heteroatom; optionally any two of R 1 -R 11 vicinal to one another, R 4 -R 5 , and/or R 7 -R 8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and Z is O, NR 19 , or CR 20 R 21 , wherein R 19 , R 20 , and R 21 is independently hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, where one or more of R 19 , R 20 , and R 21 optionally contains at least one heteroatom.
2. The complex of claim 1 , wherein Z is O.
3. The complex of claim 2 , wherein R 12 and R 13 is independently chosen from a C1-C8 linear, branched or cyclic alkyl or a C6-C18 aryl.
4. The complex of claim 2 , wherein R 12 and R 13 are methyl, and R 14 -R 18 are hydrogen.
5. The complex of claim 2 , wherein R 12 and R 13 are phenyl, and R 14 -R 18 are hydrogen.
6. The complex of claim 1 , wherein the complex is of the formula:
7. The complex of claim 1 , wherein the complex is of the formula:
8. The complex of claim 1 , wherein the complex is immobilized on a support.
9. The complex of claim 8 , wherein the support is chosen from carbon, silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), sulfonated polystyrene, or a combination of two or more thereof.
10. The complex of claim 8 , wherein at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and/or R 11 comprises a functional group that covalently bonds with the support.
11. A process for producing a silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in order to produce the silylated product, wherein the catalyst is a complex of the Formula (I) or an adduct thereof:
wherein each occurrence of R 1 -R 18 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R 1 -R 18 , other than hydrogen, optionally contain at least one heteroatom; optionally any two of R 1 -R 11 vicinal to one another, R 4 -R 5 , and/or R 7 -R 8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and Z is O, NR 19 , or CR 20 R 21 , wherein R 19 , R 20 , and R 21 is independently hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, where one or more of R 19 , R 20 , and R 21 optionally contains at least one heteroatom.
12. The process of claim 11 , wherein Z is O.
13. The process of claim 12 , wherein R 12 and R 13 is independently chosen from a C1-C8 linear branched or cyclic alkyl or a C6-C18 aryl.
14. The process of claim 12 , wherein R 12 and R 13 are methyl, and R 14 -R 18 are hydrogen.
15. The process of claim 12 , wherein R 12 and R 13 are phenyl, and R 14 -R 18 are hydrogen.
16. The process of claim 11 , wherein the complex is of the formula:
17. The process of claim 11 , wherein the complex is of the formula:
18. The process of claim 11 , further comprising removing the complex and/or derivatives thereof from the silylated product.
19. The process of claim 11 , wherein the silylated product comprises a hydrosilylation product.
20. The process of claim 11 , wherein the silylated product comprises a dehydrogenatively silylated product.
21. The process of claim 11 , wherein the silylated product comprises a mixture of (d) a hydrosilylation product, and (e) a dehydrogenative silylated product.
22. The process of claim 21 , wherein the hydrosilylated product comprises 50.1% to 99.9% of the silylation product.
23. The process of claim 20 , wherein the dehydrogenatively silylated product comprises a silane or siloxane containing a silyl group and an unsaturated group, and the unsaturated group is in the alpha or beta position relative to the silyl group.
24. The process of claim 11 , wherein the unsaturated compound (a) is chosen from a linear or branched olefin; a cycloalkene; an alkyl-capped allyl polyether; a vinyl-functional alkyl-capped allyl or methallyl polyether; an alkyl-capped terminally unsaturated amine; an alkyne; terminally unsaturated acrylate or methacrylate; unsaturated aryl ether; vinyl-functionalized polymer or oligomer; vinyl-functionalized and/or terminally-unsaturated alkenyl-functional silane; and/or silicone; an unsaturated fatty acid; an unsaturated ester; or combinations of two or more thereof.
25. The process of claim 11 , wherein the complex is immobilized on a support.
26. The process of claim 11 , wherein the reaction is conducted under an inert atmosphere.
27. The process of claim 11 , wherein the reaction is conducted in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combinations thereof.
28. The process of claim 11 , wherein the reaction is carried out at a temperature of −10° C. to 300° C.
29. A composition produced by the process of claim 11 , wherein the composition contains the catalyst or derivatives thereof.
30. The composition of claim 29 comprising at least one component selected from the group of silanes, silicone fluids, and crosslinked silicones, or a combination of two or more thereof.
31. A process for the hydrosilylation of a composition comprising hydrosilylation reactants (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, the process comprising contacting the composition comprising the hydrosilylation reactants with a complex of the formula:
wherein each occurrence of R 1 -R 18 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R 1 -R 18 , other than hydrogen, optionally contain at least one heteroatom; optionally any two of R 1 -R 11 vicinal to one another, R 4 -R 5 , and/or R 7 -R 8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and Z is O, NR 19 , or CR 20 R 21 , wherein R 19 , R 20 , and R 21 is independently hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, where one or more of R 19 , R 20 , and R 21 optionally contains at least one heteroatom.
32. The process of claim 31 , wherein Z is O, and R 12 and R 13 are independently chosen from a C1-C8 linear, branched or cyclic alkyl and a C6-C18 aryl.
33. The process of claim 31 , wherein Z is O, and R 12 and R 13 are independently chosen from methyl or phenyl.
34. The process according to claim 31 , wherein the hydrosilylation reactants comprise a silane or silicone hydride fluid and an unsaturated substrate.
35. The process according to claim 34 , wherein the hydride fluid is chosen from one or a combination of compounds of the formulas:
R 22 m SiH p X 4-(m+p) ;
M a M H b D c D H d T e T H f Q g ;
R 28 3 Si(CHR 28 ) x SiOSiR 28 2 (OSiR 28 2 ) y OSiR 28 2 H;
R 28 3 Si(CHR 28 ) x SiR 28 2 H
or a combination of two or more thereof, where each R 22 is independently a substituted or unsubstituted aliphatic or aromatic hydrocarbyl group; X is halogen, alkoxy, acyloxy, or silazane; m is 0-3; p is 1-3 with the proviso that m+p≦4 and the tetravalency of silicon is preserved; M represents a monofunctional group of formula R 23 3 SiO 1/2 ; a D represents a difunctional group of formula R 23 2 SiO 2/2 ; a T represents a trifunctional group of formula R 23 SiO 3/2 ; Q represents a tetrafunctional group of formula SiO 4/2 ; M H represents HR 23 2 SiO 1/2 , T H represents HSiO 3/2 , and D H group represents R 23 HSiO 2/2 ; each occurrence of R 23 is independently a C 1 -C 18 alkyl, a C 1 -C 18 substituted alkyl, a C 6 -C 14 aryl or substituted aryl, wherein R 23 optionally contains at least one heteroatom; subscripts a, b, c, d, e, f, and g are such that the molar mass of the compound is between 100 and 100,000 Dalton; each occurrence of R 28 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C6-C14 aryl or substituted aryl; x is 1-8, and y is 0-10.
36. The process according to claim 34 , wherein the unsaturated substrate is chosen from an unsaturated polyether; a vinyl functionalized alkyl capped allyl or methylallyl polyether; a terminally unsaturated amine; an alkyne; a C2-C45 olefin; an unsaturated epoxide; a terminally unsaturated acrylate or methyl acrylate; an unsaturated aryl ether; an unsaturated aromatic hydrocarbon; unsaturated cycloalkane; a vinyl-functionalized polymer or oligomer; a vinyl-functionalized and/or terminally-unsaturated alkenyl-functional silane, and/or silicone, or a combination of two or more thereof.
37. The process of claim 31 , wherein the reaction is conducted at a temperature of from about −10 to about 200° C.
38. The process of claim 31 , wherein the reaction is conducted in a subatmospheric pressure.
39. The process of claim 31 , wherein the reaction is conducted in a supra-atmospheric pressure.
40. The process of claim 31 , wherein the complex is immobilized on a support.
41. The process of claim 20 , wherein the dehydrogenatively silylated product contains two or more terminal silyl groups derived from component (b).