Non-precious metal-based hyrdosilylation catalysts exhibiting improved selectivity
View Patent ↗Disclosed herein is the use of manganese, iron, cobalt, or nickel complexes containing tridentate pyridine di-imine ligands as hydrosilylation catalysts. These complexes are effective for efficiently catalyzing hydrosilylation reactions, as well as offering improved selectivity and yield over existing catalyst systems.
1. A process for the hydrosilylation of a composition containing a silyl hydride and a compound containing at least one unsaturated group, the process comprising: (i) contacting the composition with a complex of Formula (I), optionally in the presence of a solvent, to cause the silyl hydride to react with the compound containing at least one unsaturated group to produce a hydrosilylation product containing said complex, and (ii) optionally removing the complex from the hydrosilylation product,
wherein the complex of Formula (I) is:
wherein:
G is Mn, Fe, Ni, or Co;
x is 0 or 1;
each occurrence of R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group;
each occurrence of R 3 is independently H, C1-C18 alkyl, C1-C18 substituted alkyl, or an inert functional group, wherein R 1 to R 9 , other than hydrogen, optionally contain at least one heteroatom;
each occurrence of R 10 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R 10 optionally contains at least one heteroatom;
optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;
wherein the silyl hydride is selected from the group consisting of R 3 a (R 4 O) b SiH (Formula II), Q u T v T p H D w D H x M H y M z (Formula III), R 3 Si(CH 2 ) f (SiR 2 O) e SiR 2 H Formula XX), (RO) 3 Si(CH 2 ) f (SiR 2 O) e SiR 2 H (Formula XXI), and combinations thereof,
wherein Q is SiO 4/2 , T is R′SiO 3/2 , T H is HSiO 3/2 , D is R′ 2 SiO 2/2 , D H is R′HSiO 2/2 , M H is H g R′ 3-g SiO 1/2 , M is R′ 3 SiO 1/2 ,
each occurrence of R 3 , R 4 , R, and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R 3 , R 4 , R, and R′ optionally contain at least one heteroatom;
a and b are integers 0 to 3, with the proviso that a+b=3, f has a value of 1 to 8, e has a value of 1 to 11, each g has a value of 1, p is from 0 to 20, u is from 0 to 20, v is from 0 to 20, w is from 0 to 1000, x is from 0 to 1000, y is from 0 to 20, and z is from 0 to 20, provided that p+x+y equals 1 to 3000, and the valences of all of the elements in the silyl hydride are satisfied;
wherein the compound containing at least one unsaturated group is selected from the group consisting of an alkyne, a C2-C18 olefin, a cycloalkene, an unsaturated cycloalkane, an unsaturated cycloalkene, an unsaturated cycloalkyl epoxide, an unsaturated alkyl epoxide, a terminally unsaturated amine, an unsaturated aromatic hydrocarbon, an alkyl-capped allyl polyether, an unsaturated aryl ether, a vinyl-functionalized silane, a vinyl-functionalized silicone, a terminally unsaturated acrylate or methyl acrylate, a terminally unsaturated polyurethane polymer, and combinations thereof,
with the proviso that
when the complex of Formula (I) is iron, bis(dinitrogen)[N,N′-[(2,6-pyridinediylκN)diethylidyne]bis[2,6-bis(1-methylethyl)benzenamine-κN]]-, (SP-5-13)-coordination compound and the silyl hydride is triethylsilane, the compound containing at least one unsaturated group cannot be an alkyl-capped allyl polyether or styrene; and
when the complex of Formula (I) is iron, bis(dinitrogen)[N,N′-[(2,6-pyridinediylκN)diethylidyne]bis[2,6-bis(1-methylethyl)benzenamine-κN]]-, (SP-5-13)-coordination compound and the silyl hydride is methylbis(trimethylsilyloxy)silane, the compound containing at least one unsaturated group cannot be an alkyl-capped allyl polyether.
2. The process of claim 1 comprising the step of removing the complex from the hydrosilylation product by magnetic separation, filtration and/or extraction.
3. The process of claim 1 wherein each occurrence of R 10 is independently
wherein R 1 , R 2 , R 4 , R 5 , and R 6 are as defined in claim 1 .
4. The process of claim 1 wherein R 1 and R 2 are isopropyl groups.
5. The process of claim 1 wherein R 3 is methyl.
6. The process of claim 1 wherein G is Fe.
7. The process of claim 1 wherein the complex is immobilized on a support.
8. The process of claim 7 wherein the support is selected from the group consisting of carbon, silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), dendrimers, and combinations thereof.
9. The process 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 contains a functional group that covalently bonds with the support.
10. The process of claim 1 , wherein each of p, u, v, y, and z is independently from 0 to 10, w and x are independently from 0 to 100, wherein p+x+y equals 1 to 100.
11. The process of claim 1 wherein the silyl hydride has a structure of
wherein in Formula (IV) and Formula (V), each of R 7 , R 8 , and R 9 is independently a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, R 6 is hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, and x is greater than zero and w is greater than or equal to 0.
12. The process of claim 1 wherein the silyl hydride is selected from the group consisting of (CH 3 O) 3 SiH, (C 2 H 5 O) 3 SiH, (CH 3 ) 3 SiOSi(CH 3 ) 2 H, [(CH 3 ) 3 SiO] 2 SiH(CH 3 ), [(CH 3 ) 2 SiO] 3 OSiH(CH 3 ) and [(CH 3 ) 2 SiO] 4 OSiH(CH 3 ).
13. The process of claim 1 wherein the compound containing at least one unsaturated group is selected from the group consisting of R 3 a SiR 12 4-a (Formula XVII), Q u T v T vi p D w D vi x M vi y M z (Formula XVIII), and combinations thereof,
wherein Q is SiO 4/2 , T is R′SiO 3/2 , T vi is R 12 SiO 3/2 , D is R′ 2 SiO 2/2 , D vi is R′R 12 SiO 2/2 , M vi is R 12 g R′ 3-g SiO 1/2 , M is R′ 3 SiO 1/2 ;
R 12 is vinyl;
each occurrence of R 3 and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R 3 and R′ optionally contain at least one heteroatom;
a has a value of from 1 to 3, each g has a value of 1, p is from 0 to 20, u is from 0 to 20, v is from 0 to 20, w is from 0 to 5000, x is from 0 to 5000, y is from 0 to 20, and z is from 0 to 20, provided that v+p+w+x+y equals 1 to 10,000, and at least p, x, or y is greater than zero, and the valences of all of the elements in the compound containing at least one unsaturated group are satisfied.
14. The process of claim 1 wherein the compound containing at least one unsaturated group is selected from the group consisting of 1-octene, trivinyl cyclohexane, styrene, alkyl-capped allyl polyether, N,N-dimethylallylamine, a vinyl siloxane of the Formula (VI), and combinations thereof,
wherein Formula (VI) is
wherein each occurrence of R 11 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.