Dehydrogenative silylation, hydrosilylation and crosslinking using pyridinediimine cobalt carboxylate catalysts
A process for producing a silylated product comprises 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, to produce a dehydrogenative silylated product, a hydrosilylated product, or a combination of a dehydrogenative silylated product and a hydrosilylated product, wherein the catalyst is chosen from a pyridine diimine cobalt dicarboxylate complex or a cobalt carboxylate compound, and the process is conducted without pre-activating the catalyst via a reducing agent and/or without an initiator or promoter compound. The present catalysts have been found to be active in the presence of the silyl hydride employed in the silylation reaction.
1. A process for producing a silylated product comprises 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, to produce a dehydrogenative silylated product, a hydrosilylated product, or a combination of a dehydrogenative silylated product and a hydrosilylated product, wherein the catalyst is a complex of the Formula (I) or an adduct thereof; Formula (II), or a combination of two or more thereof:
wherein each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently chosen from hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, where R 1 -R 5 , other than hydrogen, may optionally contain at least one heteroatom;
each occurrence of R 6 and R 7 is independently chosen from a C1-C18 alkyl, a C1-C18 substituted alkyl, an aryl, or a substituted aryl, where R 6 and R 7 may optionally contain at least one heteroatom;
optionally any two neighboring groups of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, optionally containing one or more heteroatoms; and
R 8 and R 9 is each independently, chosen from an alkyl or aryl group optionally containing at least one heteroatom, or R 8 and R 9 are connected so as to form a dicarboxylate chelating group; and
the carboxylate is derived from substituted or unsubstituted, straight-chain, branched or cyclic aliphatic carboxylic acid, dicarboxylic acid, or aromatic carboxylic acid, and which optionally contains one or more heteroatoms chosen from O, N, S, P, Si, F, Cl, Br, I, or a combination of two or more thereof;
wherein the mixture is free of a separate reducing agent and a promoter.
2. The process of claim 1 , wherein R 8 and R 9 are each chosen from a C1-C18 alkyl.
3. The process of claim 1 , wherein R 8 and R 9 are each CH 3 , 3-heptyl, or C(CH3) 3 .
4. The process of claim 1 , wherein R 6 and R 7 are independently chosen from a C1-C10 alkyl.
5. The process of claim 1 , wherein R 6 and R 7 are each methyl, ethyl, or cyclohexyl.
6. The process of claim 1 , wherein R 1 -R 7 and R 5 -R 6 taken together form a 5-membered heterocyclic ring structure or a 6-membered heterocyclic ring structure with the imine nitrogen.
7. The process of claim 6 , wherein the ring structure further comprises one or more heteroatoms other than the imine nitrogen.
8. The process of claim 7 , wherein the catalyst comprises a compound chosen from:
or a combination of two or more thereof.
9. The process of claim 1 , wherein the catalyst is chosen from:
10. The process of claim 1 , wherein the Co(carboxylate) 2 is chosen from Co(acetate) 2 .4H 2 O, anhydrous Co(acetate) 2 , Co(2-ethylhexanoate) 2 , or a combination of two or more thereof.
11. The process of claim 1 , wherein component (a) is chosen from an olefin, a cycloalkene, an unsaturated polyether, a vinyl-functional alkyl-capped allyl or methallyl polyether, an alkyl-capped terminally unsaturated amine, an alkyne, a terminally unsaturated acrylate or methacrylate, an unsaturated aryl ether, a vinyl-functionalized polymer or oligomer, a vinyl-functionalized silane, a vinyl-functionalized silicone, an unsaturated fatty acid, an unsaturated ester, or a combination of two or more thereof.
12. The process of claim 1 , wherein component (a) is chosen from a compound of the formula:
R 10 (OCH 2 CH 2 ) z (OCH 2 CHR 11 ) w —OR 12 ;
R 12 O(CHR 11 CH 2 O) w (CH 2 CH 2 O) z —CR 13 2 —C≡C—CR 13 2 —(OCH 2 CH 2 ) z (OCH 2 CHR 11 ) w R 12 ;
H 2 C═CR 11 CH 2 O(CH 2 CH 2 O) z (CH 2 CHR 11 O) w CH 2 CR 13 ═CH 2 ;
or a combination of two or more thereof, wherein R 10 is chosen from an unsaturated organic group containing from 2 to 10 carbon atoms; R 12 is chosen from hydrogen, a vinyl group, or a polyether capping group of from 1 to 8 carbon atoms; each occurrence of R 11 is independently chosen from a monovalent hydrocarbon group having 1-20 carbon atoms, an aryl group, an alkaryl, an aralkyl, a cycloalkyl group; each occurrence of R 13 is independently chosen from hydrogen, a monovalent hydrocarbon group having 1-20 carbon atoms, an aryl group, an alkaryl group, an aralkyl group, or a cycloalkyl group; each occurrence of z is 0 to 100 inclusive; and, each occurrence of w is 0 to 100 inclusive.
13. The process of claim 1 , wherein component (a) is chosen from N,N-dimethylallyl amine, allyloxy-substituted polyethers, allyl glycidyl ether, 1,2-epoxy-4-vinylcyclohexane, propylene, 1-butene, 1-hexene, styrene, vinylnorbornane, 5-vinyl-norbornene, 1-octadecene, cyclopentene, cyclohexene, norbornene, 3-hexene, isobutylene, 3-methyl-1-octene, polybutadiene, polyisoprene, EPDM, oleic acid, linoleic acid, methyl oleate, a vinyl siloxane of the Formula IX,
or a combination of two or more thereof, wherein each occurrence of R 14 is independently a C1-C18 alkyl, C1-C18 substituted alkyl, vinyl, aryl, or a substituted aryl, and n is greater than or equal to zero.
14. The process of claim 1 , wherein component (b) is chosen from a compound of the formula R a SiH 4-a , (RO) a SiH 4-a , HSiR a (OR) 3-a , R 3 Si(CH 2 ) f (SiR 2 O) k SiR 2 H, (RO) 3 Si(CH 2 ) f (SiR 2 O) k SiR 2 H, Q u T v T p H D w D H y M H y M z , R 3 Si(CH 2 ) h SiOSiR 2 (OSiR 2 ) j OSiR 2 H, or combinations of two or more thereof where each occurrence of R is independently a C1-C18 alkyl, a C1-C18 substituted alkyl, wherein R optionally contains at least one heteroatom, each occurrence of a independently has a value from 0 to 3, f has a value of 1 to 8, k has a value of 0 to 3000, each of p, u, v, y and z independently has a value from 0 to 20, w and x are from 0 to 3000, provided that p+x+y equals 1 to 1000 and the valences of the all the elements in the silyl hydride are satisfied, M represents a monofunctional group of formula R′ 3 SiO 1/2 , D represents a difunctional group of formula R′ 2 SiO 2/2 , T represents a trifunctional group of formula R′SiO 3/2 , Q represents a tetrafunctional group of formula SiO 4/2 , and M H represents HR′ 2 SiO 1/2 T H represents HSiO 3/2 , and D H represents R′HSiO 2/2 ; each occurrence of R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, wherein R′ optionally contains at least one heteroatom; h is 1-8, and j is 0-10.
15. The process of claim 1 , wherein the catalyst is present in an amount of from 0.001 mole percent to 10 mole percent based on the molar quantity of the unsaturated compound to be reacted.
16. The process of claim 1 , wherein the process is conducted at a temperature of between about 0° C. and about 300° C.
17. The process of claim 1 , wherein the process is conducted at a temperature of between about 60° C. and about 100° C.
18. The process of claim 9 , wherein the process is conducted at a temperature of between about 60° C. and about 100° C., and the catalyst comprises a catalyst of Formula (III).
19. The process of claim 1 , wherein the molar ratio of component (a) to component (b) is from about 5:1 to 1:4.
20. The process of claim 1 , wherein the molar ratio of component (a) to component (b) is from about 2:1 to about 1:1.
21. The process of claim 1 , wherein the catalyst is immobilized on a support chosen from carbon, silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), sulfonated polystyrene, or a combination of two or more thereof.
22. The process of claim 1 , wherein the unsaturated compound (a) is added to a mixture of the silyl hydride (b) and the catalyst (c).
23. The process of claim 1 , wherein the silyl hydride (b) is added to a mixture of the unsaturated compound (a) and the catalyst (c).
24. A process for producing a crosslinked material, comprising reacting a mixture comprising (a) a silyl-hydride containing polymer, (b) a vinyl-substituted siloxane, a vinyl substituted polysiloxane, an unsaturated polyolefin, or combinations thereof and (c) a catalyst, optionally in the presence of a solvent, in order to produce the crosslinked material, of the Formula (I) or an adduct thereof; Formula (II), or a combination of two or more thereof:
wherein each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently chosen from hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, where R 1 -R 5 , other than hydrogen, may optionally contain at least one heteroatom;
each occurrence of R 6 and R 7 is independently chosen from a C1-C18 alkyl, a C1-C18 substituted alkyl, an aryl, or a substituted aryl, where R 6 and R 7 may optionally contain at least one heteroatom;
optionally any two neighboring groups of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, the ring optionally containing one or more heteroatoms;
R 8 and R 9 is each independently, chosen from an alkyl or aryl group optionally containing at least one heteroatom; and
the carboxylate is derived from substituted or unsubstituted, straight-chain, branched or cyclic aliphatic carboxylic acid or aromatic carboxylic acid, and which optionally contains one or more heteroatoms chosen from O, N, S, P, Si, F, Cl, Br, I, or a combination of two or more thereof;
wherein the mixture is free of a reducing agent and a promoter.
25. The process of claim 24 , wherein R 8 and R 9 are each chosen from a C1-C18 alkyl.
26. The process of claim 24 , wherein R 8 and R 9 are each CH 3 , 3-heptyl, or C(CH3) 3 .
27. The process of claim 24 , wherein R 6 and R 7 are independently chosen from a C1-C10 alkyl.
28. The process of claim 24 , wherein R 6 and R 7 are each methyl, ethyl, or cyclohexyl.
29. The process of claim 24 , wherein R 1 -R 7 and R 5 -R 6 taken together form a 5-membered heterocyclic ring structure or a 6-membered heterocyclic ring structure with the imine nitrogen.
30. The process of claim 29 , wherein the ring structure further comprises one or more heteroatoms other than the imine nitrogen.
31. The process of claim 29 , wherein the catalyst comprises a compound chosen from:
or a combination of two or more thereof.
32. The process of claim 24 , wherein the catalyst is chosen from:
33. The process of claim 24 , wherein the Co(carboxylate) 2 is chosen from Co(acetate) 2 .4H 2 O, anhydrous Co(acetate) 2 , Co(2-ethylhexanoate) 2 , or a combination of two or more thereof.
34. The process of claim 24 , wherein component (b) is chosen from an olefin, a cycloalkene, an unsaturated polyether, a vinyl-functional alkyl-capped allyl or methallyl polyether, an alkyl-capped terminally unsaturated amine, an alkyne, a terminally unsaturated acrylate or methacrylate, an unsaturated aryl ether, a vinyl-functionalized polymer or oligomer, a vinyl-functionalized silane, a vinyl-functionalized silicone, an unsaturated fatty acid, an unsaturated ester, or a combination of two or more thereof.
35. The process of claim 24 , wherein the catalyst is present in an amount of from 0.001 mole percent to 10 mole percent based on the molar quantity of the unsaturated compound to be reacted.
36. The process of claim 24 , wherein the process is conducted at a temperature of between about 0° C. and about 300° C.
37. The process of claim 24 , wherein the process is conducted at a temperature of between about 60° C. and about 100° C.
38. The process of claim 24 , wherein the molar ratio of component (a) to component (b) is from about 5:1 to 1:4.
39. The process of claim 24 , wherein the molar ratio of component (a) to component (b) is from about 2:1 to about 1:1.
40. The process of claim 24 , wherein the unsaturated compound (b) is added to a mixture of the silyl hydride (a) and the catalyst (c).
41. The process of claim 24 , wherein the silyl hydride (a) is added to a mixture of the unsaturated compound (b) and the catalyst (c).