Dialkyl cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation

Patent metadata

Field	Value
Publication number	US-2017190722-A1
Application number	US-201515309453-A
Country	US
Kind code	A1
Filing date	May 7, 2015
Priority date	May 8, 2014
Publication date	Jul 6, 2017
Grant date	—

Abstract

Disclosed herein are dialkyl cobalt complexes containing pyridine di-imine ligands and their use as catalysts for hydrosilylation, dehydrogenative silylation, and/or crosslinking processes.

First claim

1 . A process comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride and/or siloxyhydride containing at least one SiH functional group, and (c) a catalyst to produce a silylated product chosen from a hydrosilylated product, a dehydrogenatively silylated product, or a combination of two or more thereof, 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, C1-C18 alkyl, a C1-C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, wherein one or more of 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, and/or an alkoxy, wherein one or both of R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 -R 7 vicinal to one another, R 1 -R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, with the proviso that R 1 -R 7 and R 5 -R 6 are not taken to form a terpyridine ring; and R 8 and R 9 are independently chosen from a C1-C18 alkyl, a C1-C18 substituted alkyl, and R 8 and R 9 optionally contain one or more heteroatoms that may be substituted with aryl groups.

2 . The process of claim 1 , wherein R 8 and R 9 independently comprise an alkylsilyl group.

3 . The process of claim 2 , wherein the alkylsilyl group is trimethylsilylmethyl.

4 . The process of claim 2 , wherein the catalyst is a complex of the Formula (II):

5 . The process of claim 1 , wherein R 1 and R 5 are independently chosen from methyl and ethyl.

6 . The process of claim 1 , wherein R 1 and R 5 are independently chosen from methyl and phenyl.

7 . The process of claim 1 , wherein R 2 , R 3 , and R 4 are hydrogen.

8 . The process of claim 1 , wherein R 1 and R 5 are each methyl.

9 . The process of claim 8 , wherein R 6 and R 7 are each methyl.

10 . The process of claim 8 , wherein R 6 and R 7 are each ethyl.

11 . The process of claim 8 , wherein R 6 and R 7 are each methoxy.

12 . The process of claim 1 , wherein the catalyst is chosen from a complex of Formulas (III)-(VI):

or a combination of two or more thereof.

13 . The process of any of claim 1 , wherein the silylated product comprises a hydrosilylated product.

14 . The process of claim 1 , wherein the silylated product comprises a dehydrogenative silylated product.

15 . The process of claim 1 , wherein the silylated product comprises a mixture of a hydrosilylated product and a dehydrogenative silylated product.

16 . The process of claim 1 , wherein the silyl/siloxy hydride is chosen from one or a combination of compounds of the formulas:
R 10 m SiH p X 4-(m+p) ; and M a M H b D c D H d T e T H f Q g ,
where each R 10 is independently a substituted or unsubstituted aliphatic or aromatic hydrocarbyl group; X is halogen, alkoxy, acyloxy, or silazane; m is 1-3; p is 1-3; M represents a monofunctional group of formula R 11 3 SiO 1/2 ; a D represents a difunctional group of formula R 12 SiO 2/2 ; a T represents a trifunctional group of formula R 13 SiO 3/2 ; Q represents a tetrafunctional group of formula SiO 4/2 ; M H represents HR 14 2 SiO 1/2 , T H represents HSiO 3/2 , and D H group represents R 15 HSiO 2/2 ; each occurrence of R 10-15 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 10-15 optionally and independently 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.

17 . The process of claim 1 , wherein the unsaturated compound (a) is chosen from an unsaturated polyether; a vinyl functionalized alkyl capped allyl or methylallyl polyether; a terminally unsaturated amine; an alkyne; a C2-C45 olefin; an unsaturated epoxide; a terminally unsaturated acrylate or methyl acrylate; an unsaturated aryl ether; an unsaturated aromatic hydrocarbon; unsaturated cycloalkane; a vinyl-functionalized polymer or oligomer; a vinyl-functionalized silane, a vinyl-functionalized silicone, terminally unsaturated alkenyl-functionalized silane and/or silicone; unsaturated fatty acids; unsaturated fatty esters; vinyl-functional synthetic or natural minerals, or a combination of two or more thereof.

18 . The process of claim 1 , wherein the unsaturated compound (a) is chosen from one or more polyethers having the general formula:
R 16 (OCH 2 CH 2 ) z (OCH 2 CHR 17 ) w OR 18 ; and/or R 16 O(CHR 17 CH 2 O) w (CH 2 CH 2 O) z —CR 19 2 —C≡C—CR 19 2 (OCH 2 CH 2 ) z (OCH 2 CHR 17 ) w OR 18

wherein R 16 is chosen from an unsaturated organic group having from 2 to 10 carbon atoms; R 18 is independently chosen from a hydrogen, vinyl, allyl, methallyl, or a polyether capping group of from 1 to 8 carbon atoms, an acyl group, a beta-ketoester group, or a trialkylsilyl group; R 17 and R 19 are independently chosen from hydrogen, a monovalent hydrocarbon group, an aryl group, an alkaryl group, and a cycloalkyl group; each occurrence of z is 0 to 100 inclusive; and each occurrence of w is 0 to 100 inclusive.

19 . The process of claim 1 further comprising removal of the catalyst composition.

20 . The process of claim 19 , wherein removal of the catalyst composition is achieved by filtration.

21 . The process of claim 1 , wherein the reaction is conducted at a temperature of from about −10° C. to about 300° C.

22 . The process of claim 21 , wherein the reaction temperature is 20-100° C.

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

24 . A process for producing a crosslinked material, the process comprising reacting a mixture of (a) a silylhydride containing polymer; (b) a mono-unsaturated olefin, an unsaturated polyolefin, or a combination of two or more thereof; and (c) a catalyst, 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, C1-C18 alkyl, a C1-C18 substituted alkyl, an aryl, a substituted aryl, or an inert substituent, wherein one or more of 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 or C1-C18 substituted alkyl, or alkoxy, wherein one or both of R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 1 -R 7 vicinal to one another, R 1 -R 2 , and/or R 4 -R 5 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, with the proviso that R 1 -R 7 and R 5 -R 6 are not taken to form a terpyridine ring; and, R 8 and R 9

Assignees

• Momentive Performance Mat Inc
• Univ Princeton

Inventors

• Diao Tianning
• Chirik Paul
• Roy Aroop
• Delis Johannes
• Lewis Kenrick

Classifications

• C07F7/0829

  Hydrosilylation reactions · 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

• B01J2231/323

  Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation · CPC title

• B01J31/1608

  the ligands containing silicon · CPC title

• B01J31/1815

  with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine · CPC title