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US 2013/0158281 A1Published application
Non-precious Metal-based Hyrdosilylation Catalysts Exhibiting Improved Selectivity
AssigneesPrinceton University, Momentive Performance Materials Inc.
InventorsKeith James Weller, Crisita Carmen H. Atienza, Julie Boyer, Paul Chirik, Johannes G.P. Delis, Kenrick Lewis, Susan A. Nye
Life of this patent
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Abstract
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.
Claims34
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 R1, R2, R4, R5, R6, R7, R8 and R9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group;
- each occurrence of R3 is independently H, C1-C18 alkyl, C1-C18 substituted alkyl, or an inert functional group, wherein R1 to R9, other than hydrogen, optionally contain at least one heteroatom;
- each occurrence of R10 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R10 optionally contains at least one heteroatom;
- optionally any two of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 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 R3a(R4O)bSiH (Formula II), QuTvTpHDwDHxMHyMz (Formula III), R3Si(CH2)f(SiR20)eSiR2H (Formula XX), (RO)3Si(CH2)f(SiR2O)eSiR2H (Formula XXI), and combinations thereof,
- wherein Q is SiO4/2, T is R′SiO3/2, TH is HSiO3/2, D is R′2SiO2/2, DH is R′HSiO2/2, MH is HgR′3-gSiO1/2, M is R′3SiO1/2,
- each occurrence of R3, R4 and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R3, R4 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 from 1 to 3, 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-pyridinediyl κN)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-pyridinediyl κN)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.
15 more elements
A process for selectively producing a mono-hydrosilylated product from a composition containing a 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 R1, R2, R4, R5, R6, R7, R8 and R9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group;
- each occurrence of R3 is independently H, C1-C18 alkyl, C1-C18 substituted alkyl, or an inert functional group, wherein R1 to R9, other than hydrogen, optionally contain at least one heteroatom;
- each occurrence of R10 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R10 optionally contains at least one heteroatom;
- each occurrence of R15 is aryl or substituted aryl;
- optionally any two of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 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)
- E1[(CH2)βCR1═CH2]α, (Formula VII)
- R2γE2[(CH2)βCR1═CH2]α, (Formula VIII)
- wherein
- E1 is a divalent or polyvalent aliphatic or aromatic cyclic hydrocarbon group containing from 3 to 25 carbon atoms, or a divalent or polyvalent aliphatic 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;
- E2 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 R1 and R2 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).
17 more elements
A process for selectively producing a mono-hydrosilylated product from 1,2,4-trivinylcyclohexane and a 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 R1, R2, R4, R5, R6, R7, R8 and R9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group;
- each occurrence of R3 is independently H, C1-C18 alkyl, C1-C18 substituted alkyl, or an inert functional group, wherein R1 to R9, other than hydrogen, optionally contain at least one heteroatom;
- each occurrence of R10 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R10 optionally contains at least one heteroatom;
- each occurrence of R15 is aryl or substituted aryl;
- optionally any two of R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 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);
- and
- wherein the silyl group from the silyl hydride is selectively added to the 4 position of the 1,2,4-trivinylcyclohexane.
9 more elements
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 R1, R2, R4, R5, R6, R7, R8 and R9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group;
- each occurrence of R15 is aryl or substituted aryl;
- R1, R2, R4, R5, R6, R7, R8, R9, and R15, other than hydrogen, optionally contain at least one heteroatom;
- each occurrence of R10 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R10 optionally contains at least one heteroatom;
- optionally any two of R1, R2, R15, R4, R5, R6, R7, R8, R9 and R10 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 (R4O)3SiH (Formula XXII), each occurrence of R4 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, and R4 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.
9 more elements
Dependencies are inferred from the claim text.