Non-precious metal-based hyrdosilylation catalysts exhibiting improved selectivity
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 selectively producing a mono-hydrosilylated product from a composition containing a tertiary silyl hydride and a polyunsaturated compound comprising contacting the composition with a complex of Formula (I) or Formula (XIX) to cause the silyl hydride to react with the polyunsaturated compound such that hydrosilylation occurs selectively at one unsaturated group of the unsaturated compound thereby producing the mono-hydrosilylated product,
wherein Formula (I) and Formula (XIX) are:
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;
each occurrence of R 15 is aryl or substituted aryl;
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 polyunsaturated compound is represented by Formula (VII) or Formula (VIII)
E 1 [(CH 2 ) β CR 1 ═CH 2 ] α , (Formula VII)
R 2 γ E 2 [(CH 2 ) β CR 1 ═CH 2 ] α , (Formula VIII)
wherein
E 1 is a divalent or polyvalent aliphatic cyclic hydrocarbon group or aromatic cyclic hydrocarbon group containing from 3 to 25 carbon atoms, or a divalent or polyvalent aliphatic heterocyclic hydrocarbon or aromatic heterocyclic hydrocarbon containing from 3 to 25 carbon atoms, wherein the heteroatom is selected from the group consisting of oxygen, nitrogen, silicon and sulfur;
E 2 is a divalent or polyvalent cyclic silicone group containing from 3 to 8 silicon atoms and from 3 to 8 oxygen atoms;
each occurrence of R 1 and R 2 is independently a hydrogen or a hydrocarbon group containing from 1 to 8 carbon atoms;
each occurrence of α, β and γ is independently an integer, wherein α is 2 to 6; β is 0 to 6; and γ is 0 to 4;
wherein the molar ratio of the Si-H functional groups in the silyl hydride to the alkenyl functional groups in the unsaturated compound is between about (0.5/α) and about (1.1/α); and the tertiary silyl hydride is selected from Formula II, Formula IV, Formula V, or a combination thereof
R 3 a (R 4 O) b SiH (Formula II),
wherein R 3 , R 4 , R 7 , R 8 , and R 9 is each 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, x and w are independently greater than or equal to 0, a and b are integers 0 to 3, with the proviso that a+b=3, and x is greater than or equal to 0.
2. The process of claim 1 wherein the molar ratio of the Si-H functional groups in the silyl hydride to the alkenyl functional groups in the unsaturated compound is about 1/α.
3. The process of claim 1 wherein the unsaturated compound is selected from the group consisting of trivinyl cyclohexanes, tetravinylcyclobutane, trivinyltrimethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, triallylcyanurate, and triallylisocyanurate.
4. The process of claim 1 wherein the unsaturated compound is trivinylcyclohexane.
5. 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 ).
6. 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 .
7. The process of claim 1 wherein the complex is immobilized on a support.
8. The process of claim 1 , wherein the silylhydride is of the formula
R 3 a (R 4 O) b SiH (Formula II).
9. A process for selectively producing a mono-hydrosilylated product from 1,2,4-trivinylcyclohexane and a tertiary silyl hydride comprising reacting the trivinylcyclohexane with the silyl hydride in the presence of a complex of Formula (I) or Formula (XIX),
wherein Formula (I) and Formula (XIX) are:
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;
each occurrence of R 15 is aryl or substituted aryl;
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 molar ratio of the Si-H functional groups in the silyl hydride to the alkenyl functional groups in the 1,2,4-trivinylcyclohexane is between about (0.5/3) and about (1.1/3);
wherein the silyl group from the silyl hydride is selectively added to the 4 position of the 1,2,4-trivinylcyclohexane; and
the tertiary silyl hydride is selected from Formula II, Formula IV, Formula V, or a combination thereof
R 3 a (R 4 O) b SiH (Formula II),
wherein R 3 , R 4 , R 7 , R 8 , and R 9 is each 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, x and w are independently greater than or equal to 0, a and b are integers 0 to 3, with the proviso that a+b=3, and x is greater than or equal to 0.
10. The process of claim 9 wherein the silyl hydride is triethoxysilane.
11. The process of claim 9 wherein the silyl hydride is bis(trimethylsiloxy)methylsilane.
12. The process of claim 9 wherein the trivinylcyclohexane is a mixture of trivinylcyclohexane stereoisomers.
13. The process of claim 9 wherein the trivinylcyclohexane is trivinylcyclohexane isomer A and/or trivinylcyclohexane isomer B, wherein isomer A and isomer B have structure Formulae (XV) and (XVI):
14. 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 (XIX), 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 (XIX) 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 15 is aryl or substituted aryl;
R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 15 , 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 15 , 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 (R 4 O) 3 SiH (Formula XXII), each occurrence of R 4 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, and R 4 optionally contains at least one heteroatom;
wherein the compound containing at least one unsaturated group is selected from the group consisting of a terminally unsaturated amine, an unsaturated aromatic hydrocarbon, an unsaturated cycloalkane, and combinations thereof.