Granted Patent B2

US 8,637,626 · App. 13/302,448 · Granted Jan 28, 2014

Abstract

Claims (89)

1. A complex of Formula (I)

wherein:

G is Mn, Fe, Ni, or Co;

each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 30 and R 31 is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein optionally each of R 1 to R 9 , R 30 and R 31 may independently contain at least one heteroatom;

optionally any two of R 3 , R 7 , R 8 , R 9 , R 30 , and R 31 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;

L 1 and L 2 each is a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, C2-C18 alkenyl or C2-C18 alkynyl, or L 1 -L 2 together is one of the following:

wherein each occurrence of R 10 , R 11 , R 13 , R 14 , R 15 and R 16 is independently hydrogen, C1-C18 alkyl, C2-C18 alkenyl, or C2-C18 alkynyl, wherein R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, optionally contain at least one heteroatom, and R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, are optionally substituted;

each occurrence of R 12 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C2-C18 alkenyl, C2-C18 substituted alkenyl, C2-C18 alkynyl, C2-C18 substituted alkynyl, aryl, substituted aryl, wherein R 12 optionally contains at least one heteroatom;

optionally any two of R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 taken together form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 17 and R 18 is independently alkyl, substituted alkyl, aryl, or substituted aryl, wherein each of R 17 and R 18 optionally contains at least one heteroatom, and wherein R 17 and R 18 taken together optionally form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 19 and R 20 is independently a covalent bond that connects Si and C, an alkyl, substituted alkyl, or a heteroatom, wherein R 19 and R 20 optionally contain at least one heteroatom;

wherein L 1 -L 2 bonds with G through unsaturated sites S 1 and S 2 .

2. A complex according to Formula (I) of claim 1 wherein each occurrence of R 1 and R 2 is independently hydrogen or a methyl group.

3. A complex according to Formula (I) of claim 1 wherein R 5 is hydrogen, a methyl, ethyl, n-propyl or isopropyl group.

4. A complex according to Formula (I) of claim 1 wherein R 3 is methyl.

5. A complex according to Formula (I) of claim 1 wherein R 4 and R 6 are hydrogen.

6. A complex according to Formula (I) of claim 1 wherein R 7 to R 9 , R 30 and R 31 are hydrogen.

7. A complex according to Formula (I) of claim 1 wherein each of L 1 and L 2 is independently —CH 2 SiR 60 3 , each occurrence of R 60 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl.

8. A complex according to Formula (I) of claim 1 wherein L 1 -L 2 is selected from the group consisting of butadienes, 1,5-cyclooctadienes, dicyclopentadienes, norbornadienes, trivinylcyclohexane, tetramethyltetravinylcyclotetrasiloxane, and divinyl tetramethyl disiloxane.

9. A complex according to Formula (I) of claim 1 wherein G is Fe.

10. A complex according to Formula (I) of claim 1 wherein the complex is immobilized on a support.

11. The complex of claim 10 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.

12. The complex of claim 10 wherein at least one of R 7 , R 8 , R 9 , R 30 and R 31 contains a functional group that covalently bonds with the support.

13. 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 according to 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;

each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 30 and R 31 is independently hydrogen, an inert functional group, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein optionally each of R 1 to R 9 , R 30 and R 31 may independently contain at least one heteroatom;

optionally any two of R 3 , R 7 , R 8 , R 9 , R 30 , and R 31 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;

L 1 and L 2 each is a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, C2-C18 alkenyl or C2-C18 alkynyl, or

L 1 -L 2 together is one of the following:

wherein each occurrence of R 10 , R 11 , R 13 , R 14 , R 15 and R 16 is independently hydrogen, C1-C18 alkyl, C2-C18 alkenyl, or C2-C18 alkynyl, wherein R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, optionally contain at least one heteroatom, and R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, are optionally substituted;

each occurrence of R 12 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C2-C18 alkenyl, C2-C18 substituted alkenyl, C2-C18 alkynyl, C2-C18 substituted alkynyl, aryl, substituted aryl, wherein R 12 optionally contains at least one heteroatom;

optionally any two of R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 taken together form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 17 and R 18 is independently alkyl, substituted alkyl, aryl, or substituted aryl, wherein each of R 17 and R 18 optionally contains at least one heteroatom, and wherein R 17 and R 18 taken together optionally form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 19 and R 20 is independently a covalent bond that connects Si and C, an alkyl, substituted alkyl, or a heteroatom, wherein R 19 and R 20 optionally contain at least one heteroatom;

wherein L 1 -L 2 bonds with G through unsaturated sites S 1 and S 2 ,

wherein the silyl hydride is Q u T v T p H D w D H x M H y M z , 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′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, wherein R′ optionally contains at least one heteroatom, g has a value of from 0 to 3, each of p, u, v, y and z is independently from 0 to 20, w and x are independently from 0 to 1000, provided that p +x +y equals 1 to 3000, and the valences of the all the elements in the silyl hydride are satisfied;

wherein the compound containing an unsaturated group is selected from the group consisting of an alkyne, a C2-C18 olefin, an unsaturated aryl ether, a vinyl-functional silane, and combinations thereof.

14. The process of claim 13 comprising the step of removing the complex from the hydrosilylation product by magnetic separation and/or filtration.

15. The process of claim 13 wherein in connection with Formula (I), each of L 1 and L 2 is independently —CH 2 SiR 60 3 , each occurrence of R 60 is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl.

16. 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 according to 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;

each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 30 and R 31 is independently hydrogen, an inert functional group, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein optionally each of R 1 to R 9 , R 30 and R 31 may independently contain at least one heteroatom;

optionally any two of R 3 , R 7 , R 8 , R 9 , R 30 , and R 31 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;

L 1 and L 2 each is a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, C2-C18 alkenyl or C2-C18 alkynyl, or

L 1 -L 2 together is one of the following:

wherein each occurrence of R 10 , R 11 , R 13 , R 14 , R 15 and R 16 is independently hydrogen, C1-C18 alkyl, C2-C18 alkenyl, or C2-C18 alkynyl, wherein R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, optionally contain at least one heteroatom, and R 10 , R 11 , R 13 , R 14 , R 15 and R 16 , other than hydrogen, are optionally substituted;

each occurrence of R 12 is independently C1-C18 alkyl, C1-C18 substituted alkyl, C2-C18 alkenyl, C2-C18 substituted alkenyl, C2-C18 alkynyl, C2-C18 substituted alkynyl, aryl, substituted aryl, wherein R 12 optionally contains at least one heteroatom;

optionally any two of R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 taken together form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 17 and R 18 is independently alkyl, substituted alkyl, aryl, or substituted aryl, wherein each of R 17 and R 18 optionally contains at least one heteroatom, and wherein R 17 and R 18 taken together optionally form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure;

each occurrence of R 19 and R 20 is independently a covalent bond that connects Si and C, an alkyl, substituted alkyl, or a heteroatom, wherein R 19 and R 20 optionally contain at least one heteroatom;

wherein L 1 -L 2 bonds with G through unsaturated sites S 1 and S 2 ,

wherein the silyl hydride is selected from the group consisting of R a SiH 4-a , (RO) a SiH 4-a , HSiR a (OR) 3-a , and combinations thereof, wherein each occurrence of R is independently C1-C18 alkyl, C1-C18 substituted alkyl, ary, or substituted aryl, wherein R optionally contains at least one heteroatom, each occurrence of a independently has a value of from 1 to 3;

wherein the compound containing an unsaturated group is selected from the group consisting of an alkyl-capped allyl polyether, a vinyl functionalized alkyl-capped allyl or methallyl polyether, an alkyne, an unsaturated cycloalkyl epoxide, a terminally unsaturated acrylate or methyl acrylate, an unsaturated aryl ether, an unsaturated aromatic hydrocarbon, an unsaturated cycloalkane, a vinyl-functionalized polymer, a vinyl-functionalized silane, a vinyl-functionalized silicone, and combinations thereof.

17. The process of claim 16 comprising the step of removing the complex from the hydrosilylation product by magnetic separation and/or filtration.

18. A process for the hydrosilylation of a composition containing a silyl hydride and a compound containing at least one unsaturated group comprising (i) providing a complex according to Formula (II); (ii) contacting the complex, optionally in the presence of a solvent, with an activator shortly before, simultaneously or after contacting the complex with the composition, 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/or derivatives thereof, and (iii) optionally removing the complex and/or derivatives thereof from the hydrosilylation product

wherein the complex of formula (II) is

wherein:

G is Mn, Fe, Ni, or Co;

each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 30 and R 31 is independently hydrogen, an inert functional group, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein optionally each of R 1 to R 9 , R 30 and R 31 may independently contain at least one heteroatom;

optionally any two of R 3 , R 7 , R 8 , R 9 , R 30 , and R 31 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;

wherein X is an anion;

wherein the silyl hydride is Q u T v T p H D w D H x M H y M z ,

wherein Q is SiO 4/2 , T is R′ SiO 3/2 , T H is HSiO 3/2 , D is R ′ 2 Si 0 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′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, wherein R′ optionally contains at least one heteroatom, g has a value of from 0 to 3, each of p, u, v, y and z is independently from 0 to 20, w and x are independently from 0 to 1000, provided that p+x+y equals 1 to 3000, and the valences of the all the elements in the silyl hydride are satisfied,

wherein the compound containing an unsaturated group is selected from an alkyne, a C2-C18 olefin, an unsaturated aryl ether, a vinyl-functional silane, and combinations thereof.

19. The process of claim 18 wherein the activator is a reducing agent having a reduction potential more negative than −0.6 v versus ferrocene.

20. The process of claim 18 wherein the activator is selected from sodium naphthalenide, Mg(butadiene) ●2THF, NaEt 3 BH, Mg(Anthracenide) ●3THF, diisobutylaluminium hydride, and combinations thereof.

21. A process for the hydrosilylation of a composition containing a silyl hydride and a compound containing at least one unsaturated group comprising (i) providing a complex according to Formula (II); (ii) contacting the complex, optionally in the presence of a solvent, with an activator shortly before, simultaneously or after contacting the complex with the composition, 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/or derivatives thereof, and (iii) optionally removing the complex and/or derivatives thereof from the hydrosilylation product

wherein the complex of formula (II) is

wherein:

G is Mn, Fe, Ni, or Co;

each occurrence of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 30 and R 31 is independently hydrogen, an inert functional group, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein optionally each of R 1 to R 9 , R 30 and R 31 may independently contain at least one heteroatom;

optionally any two of R 3 , R 7 , R 8 , R 9 , R 30 , and R 31 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure;

wherein X is an anion;

wherein the silyl hydride is selected from the group consisting of R a SiH 4-a , (RO) a SiH 4-a , HSiR a (OR) 3-a , and combinations thereof, wherein each occurrence of R is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, wherein R optionally contains at least one heteroatom, each occurrence of a independently has a value of from 1 to 3,

wherein the compound containing an unsaturated group is selected from the group consisting of an alkyl-capped allyl polyether, a vinyl functionalized alkyl-capped allyl or methallyl polyether, an alkyne, an unsaturated cycloalkyl epoxide, a terminally unsaturated acrylate or methyl acrylate, an unsaturated aryl ether, an unsaturated aromatic hydrocarbon, an unsaturated cycloalkane, a vinyl-functionalized polymer, a vinyl-functionalized silane, a vinyl-functionalized silicone, and combinations thereof.

22. The process of claim 16 , wherein the compound containing an unsaturated group is a polyoxyalkylene having the generic formula:

R 1 (OCH 2 CH 2 ) z (OCH 2 CHR 3 ) w —OR 2 ,  Formula (III)

R 2 O(CHR 3 CH 2 O) w (CH 2 CH 2 O) z —CR 4 2 —C≡CR 4 2 —(OCH 2 CH 2 ) z (OCH 2 CHR 3 ) w R 5 or   Formula (IV)

H 2 C═CR 4 CH 2 O(CH 2 OCH 2 ) z (CH 2 OCHR 3 ) w CH 2 CR 4 ═CH 2   Formula (V)

wherein each occurrence of R 1 is an unsaturated organic group containing from 2 to 10 carbon atoms, each occurrence of R 2 is independently vinyl, or a polyether capping group of from 1 to 8 carbon atoms, each occurrence of R 3 and R 4 are independently monovalent hydrocarbon groups, each occurrence of z is 0 to 100 inclusive, each occurrence of R 5 is independently hydrogen, vinyl, or a polyether capping group of from 1 to 8 carbon atoms, and each occurrence of w is 0 to 100 inclusive.

23. The process of claim 21 , wherein the compound containing an unsaturated group is a polyoxyalkylene having the generic formula:

R 1 (OCH 2 CH 2 ) z (OCH 2 CHR 3 ) w —OR 2 ,  Formula (III)

R 2 O(CHR 3 CH 2 O) w (CH 2 CH 2 O) z —CR 4 2 —C≡C—CR 4 2 —(OCH 2 CH 2 ) z (OCH 2 CHR 3 ) w R 5   or Formula (IV)

H 2 C═CR 4 CH 2 O(CH 2 OCH 2 ) z (CH 2 OCHR 3 ) w CH 2 CR 4 ═CH 2   Formula (V)

wherein each occurrence of R 1 is an unsaturated organic group containing from 2 to 10 carbon atoms, each occurrence of R 2 is independently vinyl, or a polyether capping group of from 1 to 8 carbon atoms, each occurrence of R 3 and R 4 are independently monovalent hydrocarbon groups, each occurrence of z is 0 to 100 inclusive, each occurrence of R 5 is independently hydrogen, vinyl, or a polyether capping group of from 1 to 8 carbon atoms, and each occurrence of w is 0 to 100 inclusive.

Assignments (20)