Dehydrogenative silylation, hydrosilylation and crosslinking using cobalt catalysts

Patent metadata

Field	Value
Publication number	US-9371340-B2
Application number	US-201414547696-A
Country	US
Kind code	B2
Filing date	Nov 19, 2014
Priority date	Aug 16, 2012
Publication date	Jun 21, 2016
Grant date	Jun 21, 2016

Abstract

Disclosed herein are cobalt complexes containing terdentate pyridine di-imine ligands and their use as efficient and selective dehydrogenative silylation, hydrosilylation, and crosslinking catalysts.

First claim

What is claimed is:

1. A process for producing a silylated product comprising 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;

wherein each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, R 1 -R 5 , other than hydrogen, optionally contain at least one heteroatom;
each occurrence of R 6 and R 7 is independently a C1-C18 alkyl, a C1-C18 substituted alkyl, an aryl, or a substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom;
optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and
L is CH 2 SiR 8 3 where each occurrence of R 8 is independently a C1-10 alkyl or an aryl group, where R 8 optionally contains at least one heteroatom.

2. The process of claim 1 , wherein R 8 is CH 3 .

3. The process of claim 1 , wherein R 6 and R 7 are independently chosen from a C1-C10 alkyl.

4. The process of claim 3 , wherein R 6 and R 7 are each methyl.

5. The process of claim 3 , wherein R 6 and R 7 are each ethyl.

6. The process of claim 3 , wherein R 6 and R 7 are each cyclohexyl.

7. The process of claim 1 , wherein R 8 is methyl; R 6 and R 7 are independently chosen from a C1-C10 alkyl, and R 2 , R 3 , and R 4 are each hydrogen.

8. The process of claim 1 , wherein the catalyst is chosen from:

or a combination of two or more thereof.

9. 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.

10. 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 ) 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.

11. The process of claim 1 , wherein component (a) is chosen from N,N-dimethylallyl amine, allyloxy-substituted polyethers, 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 (VI),

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.

12. 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 x M H y M z , R 3 Si(CH 2 R) x SiOSiR 2 (OSiR 2 ) y 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 1 to 11, 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 , an 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; x is 1-8, and y is 0-10.

13. The process of claim 1 , wherein the catalyst is present in an amount of from 0.01 mole percent to 10 mole percent based on the molar quantity of the unsaturated compound to be reacted.

14. The process of claim 1 , wherein the process is conducted at a temperature of between about 0° C. and about 300° C.

15. The process of claim 1 , wherein the complex is immobilized on a support.

16. The complex of claim 15 , wherein the support is chosen from carbon, silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), sulfonated polystyrene, or a combination of two or more thereof.

17. A process for producing a hydrosilylated product comprising 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, in order to produce the dehydrogenative silylated product, and/or hydrosilylated product wherein the catalyst is a complex of the Formula (I) or an adduct thereof;

wherein each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, wherein R 1 -R 5 , other than hydrogen, optionally contain at least one heteroatom;
each occurrence of R 6 and R 7 is independently a C1-C18 alkyl, a C1-C18 substituted alkyl, an aryl, a substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom;
optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated,

Assignees

• Momentive Performance Mat Inc
• Univ Princeton

Inventors

• Diao Tianning
• Chirik Paul J
• Roy Aroop Kumar
• Lewis Kenrick
• Nye Susan
• Weller Keith J
• Delis Johannes G P
• Yu Renyuan

Classifications

• B01J2531/845

  Cobalt · CPC title

• B01J2531/0244

  Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds · CPC title

• C07F7/0829 Primary

  Hydrosilylation reactions · CPC title

• C07F15/065

  without a metal-carbon linkage · CPC title

• C07F7/0838

  Compounds with one or more Si-O-Si sequences (compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21) · CPC title