Non-precious metal-based hyrdosilylation catalysts exhibiting improved selectivity

Patent metadata

Field	Value
Publication number	US-9782763-B2
Application number	US-201113325250-A
Country	US
Kind code	B2
Filing date	Dec 14, 2011
Priority date	Dec 14, 2011
Publication date	Oct 10, 2017
Grant date	Oct 10, 2017

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.

First claim

What is claimed is:

1. 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 R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group;
each occurrence of R 3 is independently H, C1-C18 alkyl, C1-C18 substituted alkyl, or an inert functional group, wherein R 1 to R 9 , other than hydrogen, optionally contain at least one heteroatom;
each occurrence of R 10 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R 10 optionally contains at least one heteroatom;
optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 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 R 3 a (R 4 O) b SiH (Formula II), Q u T v T p H D w D H x M H y M z (Formula III), R 3 Si(CH 2 ) f (SiR 2 O) e SiR 2 H Formula XX), (RO) 3 Si(CH 2 ) f (SiR 2 O) e SiR 2 H (Formula XXI), and combinations thereof,
wherein Q is SiO 4/2 , T is R′SiO 3/2 , T H is HSiO 3/2 , D is R′ 2 SiO 2/2 , D H is R′HSiO 2/2 , M H is H g R′ 3-g SiO 1/2 , M is R′ 3 SiO 1/2 ,
each occurrence of R 3 , R 4 , R, and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R 3 , R 4 , R, 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 1, 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-pyridinediylκN)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-pyridinediylκN)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.

2. The process of claim 1 comprising the step of removing the complex from the hydrosilylation product by magnetic separation, filtration and/or extraction.

3. The process of claim 1 wherein each occurrence of R 10 is independently

wherein R 1 , R 2 , R 4 , R 5 , and R 6 are as defined in claim 1 .

4. The process of claim 1 wherein R 1 and R 2 are isopropyl groups.

5. The process of claim 1 wherein R 3 is methyl.

6. The process of claim 1 wherein G is Fe.

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

8. The process of claim 7 wherein the support is selected from the group consisting of carbon, silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), dendrimers, and combinations thereof.

9. The process of claim 8 wherein at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 contains a functional group that covalently bonds with the support.

10. The process of claim 1 , wherein each of p, u, v, y, and z is independently from 0 to 10, w and x are independently from 0 to 100, wherein p+x+y equals 1 to 100.

11. The process of claim 1 wherein the silyl hydride has a structure of

wherein in Formula (IV) and Formula (V), each of R 7 , R 8 , and R 9 is independently a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, R 6 is hydrogen, a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, and x is greater than zero and w is greater than or equal to 0.

12. The process of claim 1 wherein the silyl hydride is selected from the group consisting of (CH 3 O) 3 SiH, (C 2 H 5 O) 3 SiH, (CH 3 ) 3 SiOSi(CH 3 ) 2 H, [(CH 3 ) 3 SiO] 2 SiH(CH 3 ), [(CH 3 ) 2 SiO] 3 OSiH(CH 3 ) and [(CH 3 ) 2 SiO] 4 OSiH(CH 3 ).

13. The process of claim 1 wherein the compound containing at least one unsaturated group is selected from the group consisting of R 3 a SiR 12 4-a (Formula XVII), Q u T v T vi p D w D vi x M vi y M z (Formula XVIII), and combinations thereof,
wherein Q is SiO 4/2 , T is R′SiO 3/2 , T vi is R 12 SiO 3/2 , D is R′ 2 SiO 2/2 , D vi is R′R 12 SiO 2/2 , M vi is R 12 g R′ 3-g SiO 1/2 , M is R′ 3 SiO 1/2 ;
R 12 is vinyl;
each occurrence of R 3 and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R 3 and R′ optionally contain at least one heteroatom;
a has a value of from 1 to 3, each g has a value of 1, p is from 0 to 20, u is from 0 to 20, v is from 0 to 20, w is from 0 to 5000, x is from 0 to 5000, y is from 0 to 20, and z is from 0 to 20, provided that v+p+w+x+y equals 1 to 10,000, and at least p, x, or y is greater than zero, and the valences of all of the elements in the compound containing at least one unsaturated group are satisfied.

14. The process of claim 1 wherein the compound containing at least one unsaturated group is selected from the group consisting of 1-octene, trivinyl cyclohexane, styrene, alkyl-capped allyl polyether, N,N-dimethylallylamine, a vinyl siloxane of the Formula (VI), and combinations thereof,
wherein Formula (VI) is

wherein each occurrence of R 11 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.

Assignees

• Weller Keith James
• Atienza Crisita Carmen H
• Boyer Julie
• Chirik Paul
• Delis Johannes G P
• Lewis Kenrick
• Nye Susan A
• Momentive Performance Mat Inc
• Univ Princeton

Inventors

• Weller Keith James
• Atienza Crisita Carmen H
• Boyer Julie
• Chirik Paul
• Delis Johannes G P
• Lewis Kenrick
• Nye Susan A

Classifications

• B01J31/1805 Primary

  the ligands containing nitrogen · CPC title

• B01J2531/842

  Iron · 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

• B01J2531/845

  Cobalt · CPC title