Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation

Patent metadata

Field	Value
Publication number	US-9381506-B2
Application number	US-201414547726-A
Country	US
Kind code	B2
Filing date	Nov 19, 2014
Priority date	Nov 19, 2013
Publication date	Jul 5, 2016
Grant date	Jul 5, 2016

Abstract

Disclosed herein are cobalt terpyridine complexes containing a single ligand coordinated to the cobalt, and their use as hydrosilylation and/or dehydrogenative silylation and crosslinking catalysts. The cobalt complexes also exhibit adequate air stability for handling and manipulation.

First claim

What is claimed is:

1. A complex of the Formula:

wherein each occurrence of R 1 -R 11 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R 1 -R 11 , other than hydrogen, optionally contain at least one heteroatom; optionally any two of R 1 -R 11 vicinal to one another, R 4 -R 5 , and/or R 7 -R 8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L is —C(R 22 ) 2 —Si(R 23 ) 3 where R 22 and R 23 are independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and R 22 and R 23 optionally contain at least one heteroatom.

2. The complex of claim 1 , wherein R 1 -R 11 are hydrogen.

3. The complex of claim 1 , wherein the catalyst is of the formula:

4. The complex of claim 1 , wherein at least one of R 1 -R 11 is chosen from an aryl group or a substituted aryl group.

5. The complex of claim 4 , wherein the substituted aryl group is chosen from tolyl, xylyl, naphthyl, mesityl, aniline, fluorophenyl, or a combination of two or more thereof.

6. The complex of claim 1 , wherein R 1 -R 5 and R 7 -R 11 are hydrogen, and R 6 is chosen from pyrrolidino, flourophenyl, aniline, or mesityl.

7. The complex of claim 1 , wherein the complex is of the formula:

8. 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, in order to produce the silylated product, wherein the catalyst is a complex of the Formula (IV) or an adduct thereof:

wherein each occurrence of R 1 -R 11 is independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R 1 -R 11 , other than hydrogen, optionally contain at least one heteroatom; optionally any two of R 1 -R 11 vicinal to one another, R 4 -R 5 , and/or R 7 -R 8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L is chosen from hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, or an aralkyl group, an alkyl trialkylsilyl, where L optionally contains at least one heteroatom.

9. The process of claim 8 , wherein R 1 -R 11 are hydrogen.

10. The process of claim 8 , wherein L is —C(R 22 ) 2 —Si(R 23 ) 3 where R 22 and R 23 are independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and R 22 and R 23 optionally contain at least one heteroatom.

11. The process of claim 10 , wherein R 1 -R 11 are hydrogen.

12. The process of claim 8 , wherein the catalyst is of the formula:

13. The process of claim 8 , wherein at least one of R 1 -R 11 is chosen from an aryl group or a substituted aryl group.

14. The process of claim 13 , wherein the substituted aryl group is aniline.

15. The process of claim 8 , wherein the complex is of the formula:

16. The process of claim 8 , further comprising removing the complex and/or derivatives thereof from the silylated product.

17. The process of claim 8 , wherein the silylated product comprises a hydrosilylation product.

18. The process of claim 8 , wherein the silylated product comprises a dehydrogenatively silylated product.

19. The process of claim 8 , wherein the silylated product comprises a mixture of (i) a hydrosilylation product, and (ii) a dehydrogenative silylated product.

20. The process of claim 8 , wherein the unsaturated compound (a) is chosen from a linear or branched olefin; a cycloalkene; an alkyl-capped allyl 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 and/or terminally-unsaturated alkenyl-functional silane; and/or silicone; an unsaturated fatty acid; an unsaturated ester; or combinations of two or more thereof.

21. The process of claim 8 , wherein the reaction is conducted under an inert atmosphere.

22. The process of claim 8 , wherein the reaction is carried out at a temperature of
−10° C. to 300° C.

23. The process according to claim 8 , wherein the silyl hydride comprises a hydride fluid chosen from one or a combination of compounds of the formulas:
R 24 m SiH p X 4-(m+p) ;
M a M H b D c D H d T e T H f Q g ;
R 30 3 Si(CHR 30 ) x SiOSiR 30 2 (OSiR 30 2 ) y OSiR 30 2 H,
R 30 3 Si(CHR 30 ) x SiR 30 2 H
where each R 24 is independently a substituted or unsubstituted aliphatic or aromatic hydrocarbyl group; X is halogen, alkoxy, acyloxy, or silazane; m is 0-3; p is 1-3, with the proviso that the tetravalency of silicon is preserved; M represents a monofunctional group of formula R 25 3 SiO 1/2 ; a D represents a difunctional group of formula R 25 2 SiO 2/2 ; a T represents a trifunctional group of formula R 25 SiO 3/2 ; Q represents a tetrafunctional group of formula SiO 4/2 ; M H represents HR 25 2 SiO 1/2 , T H represents HSiO 3/2 , and D H group represents R 25 HSiO 2/2 ; each occurrence of R 25 is independently a C 1 -C 18 alkyl, a C 1 -C 18 substituted alkyl, a C 6 -C 14 aryl or substituted aryl, wherein R 25 optionally contains at least one heteroatom; subscripts a, b, c, d, e, f, and g are such that the molar mass of the compound is between 100 and 100,000 Dalton; each occurrence of R 30 is independently a C1-C18 alkyl, a C1-C18 substituted alkyl, a C6-C14 aryl or substituted aryl; x is 1-8, and y is 0-10.

24. The process of claim 8 , wherein the complex is immobilized on a support.

25. The complex of claim 24 , 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.

26. A composition produced by the process of claim 8 , wherein the composition contains the catalyst or derivatives thereof, and comprises at least one component selected from the group of silanes, silicone fluids, and crosslinked silicones, or a combination of two or more thereof.

Assignees

• Diao Tianning
• Chirik Paul J
• Roy Aroop Kumar
• Lewis Kenrick
• Weller Keith J
• Delis Johannes G P
• Yu Renyuan
• Momentive Performance Mat Inc
• Univ Princeton

Inventors

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

Classifications

• C07F7/1804

  Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896) · 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

• B01J31/2295 Primary

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• B01J31/183

  with more than one complexing nitrogen atom, e.g. phenanthroline · CPC title

• C07F5/025 Primary

  Boronic and borinic acid compounds · CPC title