US 11,052,383 B2
Non-precious metal-based hyrdosilylation catalysts exhibiting improved selectivity
Keith James Weller, Rensselear, NY (US); Crista Carmen H. Atienza, Houston, TX (US); Julie Boyer, Columbia, MD (US); Paul Chirik, Princeton, NJ (US); Johannes G. P. Delis, Bergen op Zoom (NL); Kenrick Lewis, Flushing, NY (US); and Susan A. Nye, Feura Bush, NY (US)
Assigned to MOMENTIVE PERFORMANCE MATERIALS INC., Waterford, NY (US); and PRINCETON UNIVERSITY, Princeton, NJ (US)
Filed by Momentive Performance Materials Inc., Waterford, NY (US); and PRINCETON UNIVERSITY, Princeton, NJ (US)
Filed on Sep. 26, 2017, as Appl. No. 15/715,324.
Application 15/715,324 is a continuation of application No. 13/325,250, filed on Dec. 14, 2011, granted, now 9,782,763.
Prior Publication US 2018/0015449 A1, Jan. 18, 2018
This patent is subject to a terminal disclaimer.
Int. Cl. B01J 31/18 (2006.01)
CPC B01J 31/1805 (2013.01) [B01J 2231/323 (2013.01); B01J 2531/0244 (2013.01); B01J 2531/72 (2013.01); B01J 2531/842 (2013.01); B01J 2531/845 (2013.01); B01J 2531/847 (2013.01)] 14 Claims
 
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:

OG Complex Work Unit Chemistry
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 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;
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); and the tertiary silyl hydride is selected from Formula II, Formula IV, Formula V, or a combination thereof
R3a(R4O)bSiH  (Formula II),

OG Complex Work Unit Chemistry
wherein R3, R4, R7, R8, and R9 is each independently a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, R6 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.