Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation
View Patent ↗Disclosed herein are cobalt complexes containing pyridine di-imine ligands and chelating alkenyl-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 2 , R 3 , R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, wherein one or more of R 1 -R 5 and R 8 -R 14 , other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl or a substituted C6-C18 aryl, wherein one or both R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 vicinal to one another, R 1 -R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, with the proviso that R 5 -R 6 and R 1 -R 7 are not taken to form a terpyridine ring; and Z is O, NR 15 , or CR 16 R 17 , wherein R 15 , R 16 , and R 17 is independently hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, a C6-C18 aryl, or a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, and one or more of R 15 , R 16 , and R 17 optionally contain at least one heteroatom.
2. The complex of claim 1 , wherein Z is O, and R 8 and R 9 are independently chosen from a C1-C4 alkyl or a C6-C10 aryl.
3. The complex of claim 1 , wherein Z is O, and R 8 and R 9 are independently chosen from methyl or phenyl.
4. The complex of claim 1 , wherein R 6 and R 7 are independently chosen from a C1-C8 linear, branched, or cyclic alkyl, a C6-C18 aryl, or a substituted C6-C18 aryl.
5. The complex of claim 1 , wherein R 6 and/or R 7 comprise an aryl of the formula:
wherein each occurrence of R 18 , R 19 , R 20 , R 21 , and R 22 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, wherein one or more of R 18 -R 22 , other than hydrogen, optionally contain at least one heteroatom.
6. The complex of claim 5 , wherein R 18 , R 20 , and R 22 are a C1-C4 alkyl, and R 19 and R 21 are hydrogen.
7. The complex of claim 1 , wherein the complex is of the formula:
or
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 , and/or R 7 comprises a functional group that covalently bonds with the support.
11. A process for producing a dehydrogenatively 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 dehydrogenatively silylated product, wherein the catalyst is a complex of the Formula (I) or an adduct thereof:
wherein each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, wherein one or more of R 1 -R 5 and R 8 -R 14 , other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl or a substituted C6-C18 aryl, wherein one or both R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 vicinal to one another, R 1 -R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, with the proviso that R 5 -R 6 and R 1 -R 7 are not taken to form a terpyridine ring; and Z is O, NR 15 , or CR 16 R 17 , wherein R 15 , R 16 , and R 17 is independently hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, a C6-C18 aryl, or a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, and one or more of R 15 , R 16 , and R 17 optionally contains at least one heteroatom.
12. The process of claim 11 , wherein one or both of R 6 and R 7 comprise an aryl of the formula:
wherein each occurrence of R 18 , R 19 , R 20 , R 21 , and R 22 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, wherein one or more of R 18 -R 22 , other than hydrogen, optionally contain at least one heteroatom.
13. The process of claim 12 wherein R 18 and R 22 are independently methyl, ethyl or isopropyl groups and R 3 is hydrogen or methyl.
14. The process of claim 12 wherein R 18 , R 20 , and R 22 are each methyl.
15. The process of claim 12 wherein R 1 and R 5 are independently methyl or phenyl groups.
16. The process of claim 12 wherein R 2 , R 3 , and R 4 are hydrogen.
17. The process of claim 11 , wherein the catalyst is chosen from a complex of the formula:
or
or a combination of two or more thereof.
18. The process of claim 11 further comprising removing the complex and/or derivatives thereof from the dehydrogenative silylated product.
19. The process of claim 11 , wherein the dehydrogenatively silylated product comprises a silane or siloxane containing a silyl group and an unsaturated group.
20. The process of claim 19 , wherein the unsaturated group is in the alpha or beta position relative to the silyl group.
21. The process of claim 11 , wherein the molar ratio of the unsaturated group in said component (a) relative to the silylhydride functional group in said component (b) is equal to 2:1 or greater.
22. The process of claim 11 , wherein the dehydrogenatively silylated product contains two or more terminal silyl groups derived from component (b).
23. The process of claim 11 , wherein said component (a) is a mono-unsaturated compound.
24. The process of claim 11 , wherein said component (a) is selected from the group consisting of an alkyne or an 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-functionalized silane and/or silicone; an unsaturated fatty acid; an unsaturated ester; or a combination 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 −40° C. to 200° C.
29. The process of claim 11 , wherein the silylated product comprises an anti-Markovnikov addition product, a Markovnkiov addition product, or a combination thereof.
30. A composition produced by the process of claim 11 , wherein the composition contains the catalyst or derivatives thereof.
31. The composition of claim 30 comprising at least one component chosen from a silane, a silicone fluid, a crosslinked silicone, or a combination of two or more thereof.
32. A process for producing a crosslinked material, comprising reacting a mixture comprising (a) a silyl-hydride containing polymer, (b) a mono-unsaturated olefin or an unsaturated polyolefin, or combinations thereof and (c) a catalyst, optionally in the presence of a solvent, in order to produce the crosslinked material, wherein the catalyst is a complex of the Formula (I) or an adduct thereof;
wherein each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, wherein one or more of R 1 -R 5 , and R 8 -R 14 other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl or a substituted C6-C18 aryl, wherein one or both R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 vicinal to one another, R 1 -R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, with the proviso that R 5 -R 6 and R 1 -R 7 are not taken to form a terpyridine ring; and Z is O, NR 15 , or CR 16 R 17 , wherein R 15 , R 16 , and R 17 is independently hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, a C6-C18 aryl, or a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, and one or more of R 15 , R 16 , and R 17 optionally contains at least one heteroatom.
33. A process for the hydrosilylation of a composition comprising hydrosilylation reactants chosen from (a) an unsaturated compound containing at least one unsaturated functional group, and (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 2 , R 3 , R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, wherein one or more of R 1 -R 5 , and R 8 -R 14 other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl or a substituted C6-C18 aryl, wherein one or both of R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 vicinal to one another, R 1 -R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure with the proviso that R 5 -R 6 and R 1 -R 7 are not taken to form a terpyridine ring; and Z is O, NR 15 , or CR 16 R 17 , wherein R 15 , R 16 , and R 17 is independently hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, a C6-C18 aryl, or a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, and one or more of R 15 , R 16 , and R 17 optionally contains at least one heteroatom.
34. The process of claim 33 , wherein Z is O, and R 8 and R 9 are independently chosen from a C1-C8 alkyl and C6-C18 aryl.
35. The process of claim 33 , wherein Z is O, and R 8 and R 9 are independently chosen from methyl or phenyl.
36. The process of claim 33 , wherein R 6 and R 7 are independently chosen from a C1-C8 linear, branched, or cyclic alkyl, a C6-C18 aryl, or a substituted C6-C18 aryl.
37. The process of claim 33 , wherein R 6 and R 7 are each methyl.
38. The process of claim 37 , wherein R 2 , R 3 , and R 4 are each hydrogen.
39. The process of claim 37 , wherein R 1 and R 5 are each methyl.
40. The process of claim 33 , wherein the complex is of the formula:
or
or a combination thereof.
41. The process of claim 33 , wherein the complex is immobilized on a support.
42. The process according to claim 33 , wherein the silyl hydride is chosen from one or a combination of compounds of the formulas:
R 23 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 29 3 Si(CH 2 R 29 ) x SiOSiR 29 2 (OSiR 29 2 ) y OSiR 29 2 H;
R 29 3 Si(CHR 29 ) x SiR 29 2 H,
or a combination of two or more thereof, where each R 23 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 the silicon remains tetravalent; M represents a monofunctional group of formula R 24 3 SiO 1/2 ; a D represents a difunctional group of formula R 24 2 SiO 2/2 ; a T represents a trifunctional group of formula R 24 SiO 3/2 ; Q represents a tetrafunctional group of formula SiO 4/2 ; M H represents HR 24 2 SiO 1/2 , T H represents HSiO 3/2 , and D H group represents R 24 HSiO 2/2 ; each occurrence of R 24 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 24 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 29 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C6-C14 aryl or substituted aryl; x is 1-8, and y is 0-10.
43. The process according to claim 33 , wherein the unsaturated compound (a) is chosen from an unsaturated polyether; a vinyl functionalized alkyl capped allyl or methylallyl polyether; a terminally unsaturated amine; an alkyne; a C2-C45 olefins; 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 silane, a vinyl-functionalized silicone, terminally unsaturated alkenyl-functionalized silane and/or silicone or a combination of two or more thereof.
44. The process according to claim 43 , wherein the unsaturated compound (a) is chosen from one or more polyethers having the general formula:
R 25 (OCH 2 CH 2 ) z (OCH 2 CHR 27 ) w —OR 26 ;
and/or
R 26 O(CHR 27 CH 2 O) w (CH 2 CH 2 O) z —CR 28 2 —C≡C—CR 28 2 (OCH 2 CH 2 ) z (OCH 2 CHR 27 ) w R 26
wherein R 25 is chosen from an unsaturated organic group having from 2 to 10 carbon atoms; R 26 is independently chosen from a hydrogen, vinyl, allyl, methallyl, or a polyether capping group of from 1 to 8 carbon atoms, an acyl group, a beta-ketoester group, or a trialkylsilyl group; R 27 and R 28 are independently chosen from hydrogen, a monovalent hydrocarbon group, an aryl group, an alkaryl group, and a cycloalkyl group; a Me or H are preferred for R 27 ; each occurrence of z is 0 to 100 inclusive; and each occurrence of w is 0 to 100 inclusive.
45. The process of claim 33 further comprising removal of the catalyst composition.
46. The process of claim 45 , wherein removal of the catalyst composition is achieved by filtration.
47. The process of claim 33 wherein the reaction is conducted at a temperature of from about −10° C. to about 200° C.
48. The process of claim 33 , wherein the reaction is conducted a subatmospheric pressure.
49. The process of claim 33 , wherein the reaction is conducted in a supra-atmospheric pressure.