Granted Patent B2

US 8,765,987 · App. 13/302,236 · Granted Jul 1, 2014

Abstract

Claims (72)

1. A process for the hydrosilylation of a reaction mixture containing a silyl hydride and a compound containing at least one unsaturated group, the process comprising:

(i) providing a catalyst precursor being a complex having a structural formula according to Formula (I), Formula (II), or Formula (III);

(ii) activating the catalyst precursor by contacting the catalyst precursor with an activator in the presence of a liquid medium containing at least one component selected from the group consisting of a solvent, the silyl hydride, the compound containing at least one unsaturated group, and combinations thereof, thereby providing an activated catalyst;

(iii) reacting the silyl hydride, selected from the group consisting of R 3 SiH, (RO) 3 SiH, 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 , 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 and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R and R′ optionally contain at least one heteroatom, each occurrence of a independently has a value from 1 to 3, f has a value of 1 to 8, k has a value of 1 to 11, g has a value of from 1 to 3, 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 the all the elements in the silyl hydride are satisfied and the compound containing at least one unsaturated group in the presence of the activated catalyst to produce a hydrosilylation product containing the activated catalyst or derivatives thereof,

wherein step (ii) is conducted shortly before, or at the same time as, step (iii); and

(iv) optionally removing the activated catalyst or derivatives thereof,

wherein Formula (I), Formula (II) and Formula (III) are:

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 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert group, wherein any two of R 1 -R 3 , R 3 -R 7 , R 3 -R 9 , R 14 -R 15 and R 17 -R 18 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, wherein R 2 to R 9 , and R 11 to R 24 other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 10 is C1-C18 alkyl group or C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R 10 optionally contains at least one heteroatom; and

X is an anion.

2. The process of claim 1 wherein the activator is a reducing agent having a reduction potential of >−0.6 v versus ferrocene in the presence of nitrogen.

3. The process of claim 2 wherein the reducing agent is selected from the group consisting of sodium naphthalenide, Mg(butadiene).2THF, NaEt 3 BH, LiEt 3 BH, Mg (Anthracenide).3THF, diisobutylaluminum hydride, and combinations thereof.

4. The process of claim 1 wherein X is F − , Cl − , Br − , I − , CF 3 R 40 SO 3 − or R 50 COO − , wherein R 40 is a covalent bond or a C1-C6 alkyl group, and R 50 is a C1-C10 hydrocarbyl group.

5. The process of claim 1 wherein the complex according to Formula (I), Formula (II) or Formula (III) is immobilized on a support.

6. The process of claim 5 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.

7. The process of claim 5 wherein at least one of R 1 to R 9 or R 11 to R 24 contains a functional group that covalently bonds with the support.

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

9. The process of claim 1 , 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, a terminally unsaturated amine, an alkyne, a C2-C40 olefin, 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.

10. The process of claim 1 , 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 (IV),

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   Formula (V) or

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 (VI),

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 hydrogen, 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 R 5 is vinyl, or a polyether capping group of from 1 to 8 carbon atoms, each occurrence of z is 0 to 100 inclusive, and each occurrence of w is 0 to 100 inclusive.

11. A process for selectively producing a mono-hydrosilylated product from a reaction mixture containing a silyl hydride and a polyunsaturated compound, the process comprising:

(i) providing a catalyst precursor being a complex having a structural formula according to Formula (I), Formula (II), or Formula (III);

(ii) activating the catalyst precursor by contacting the catalyst precursor with an activator in the presence of a liquid medium containing at least one component selected from the group consisting of a solvent, the silyl hydride, the polyunsaturated compound, and combinations thereof, thereby providing an activated catalyst;

(iii) reacting the silyl hydride, selected from the group consisting of R 3 SiH, (RO) 3 SiH, 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 , 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 and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R and R′ optionally contain at least one heteroatom, each occurrence of a independently has a value from 1 to 3, f has a value of 1 to 8, k has a value of 1 to 11, g has a value of from 1 to 3, 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 the elements in the silyl hydride are satisfied and the polyunsaturated compound in the presence of the activated catalyst such that hydrosilylation occurs selectively at one unsaturated group of the polyunsaturated compound, thereby producing the mono-hydrosilylated product containing the activated catalyst or derivatives thereof;

wherein step (ii) is conducted shortly before, or at the same time as, step (iii); and

(iv) optionally removing the activated catalyst or derivatives thereof,

wherein Formula (I), Formula (II) and Formula (III) are:

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 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert group, wherein any two of R 1 -R 3 , R 3 -R 7 , R 3 -R 9 , R 14 -R 15 and R 17 -R 18 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, wherein R 2 to R 9 , and R 11 to R 24 other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 10 is C1-C18 alkyl group or C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R 10 optionally contains at least one heteroatom; and

X is an anion;

wherein the polyunsaturated compound is represented by Formula (X) or Formula (XI)

E 1 [(CH 2 ) β CR 1 ═CH 2 ] α ,  (Formula X)

R 2 γ E 2 [(CH 2 ) β CR 1 ═CH 2 ] α ,  (Formula XI)

wherein

E 1 is a divalent or polyvalent aliphatic or aromatic cyclic hydrocarbon group containing from 3 to 25 carbon atoms, or a divalent or polyvalent aliphatic or aromatic heterocyclic hydrocarbon containing from 3 to 25 carbon atoms, wherein the heteroatom is selected from the group consisting of oxygen, nitrogen, silicon and sulfur;

E 2 is a divalent or polyvalent cyclic silicone group containing from 3 to 8 silicon atoms and from 3 to 8 oxygen atoms;

each occurrence of R 1 and R 2 is independently a hydrogen or a hydrocarbon group containing from 1 to 8 carbon atoms;

each occurrence of α, β and γ is independently an integer, wherein α is 2 to 6; β is 0 to 6; and γ is 0 to 4; and

wherein the molar ratio of the Si—H functional groups in the silyl hydride to the alkenyl functional groups in the unsaturated compound is between about (0.5/α) and about (1.1/α).

12. The process of claim 11 wherein the molar ratio of the Si—H functional groups in the silyl hydride to the alkenyl functional groups in the unsaturated compound is about 1/α.

13. The process of claim 11 wherein the unsaturated compound is selected from the group consisting of trivinylcyclohexanes, tetravinylcyclobutane, trivinyltrimethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, triallylcyanurate, and triallylisocyanurate.

14. The process of claim 11 wherein the unsaturated compound is trivinylcyclohexane.

15. The process of claim 11 wherein the silyl hydride has one of the following structures:

wherein each occurrence of R 3 , R 4 , R 7 , R 8 , and R 9 is independently a C1-C 1-8 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, x and w are independently greater than or equal to 0, a and b are integers from 0 to 3 provided that the a+b=3.

16. The process of claim 11 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 ).

17. The process of claim 11 wherein the activator is a reducing agent having a reduction potential of >−0.6 v versus ferrocene in the presence of nitrogen.

18. The process of claim 17 wherein the reducing agent is selected from the group consisting of sodium naphthalenide, Mg(butadiene).2THF, NaEt 3 BH, LiEt 3 BH, Mg (Anthracenide).3THF, diisobutylaluminum hydride, and combinations thereof.

19. The process of claim 11 wherein X is F − , Cl − , Br − , I − , CF 3 R 40 SO 3 − or R 50 COO − , wherein R 40 is a covalent bond or a C1-C6 alkyl group, and R 50 is a C1-C10 hydrocarbyl group.

20. The process of claim 11 wherein the complex according to Formula (I), Formula (II) or Formula (III) is immobilized on a support.

21. A process for selectively producing a mono-hydrosilylated product from a reaction mixture containing a silyl hydride and 1,2,4-trivinylcyclohexane, the process comprising:

(i) providing a catalyst precursor being a complex having a structural formula according to Formula (I), Formula (II), or Formula (III);

(ii) activating the catalyst precursor by contacting the catalyst precursor with an activator in the presence of a liquid medium containing at least one component selected from the group consisting of a solvent, the silyl hydride, the 1,2,4-trivinylcyclohexane, and combinations thereof, thereby providing an activated catalyst;

(iii) reacting the silyl hydride, selected from the group consisting of R 3 SiH, (RO) 3 SiH, 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 D H y M z , 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 and R′ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R and R′ optionally contain at least one heteroatom, each occurrence of a independently has a value from 1 to 3, f has a value of 1 to 8, k has a value of 1 to 11, g has a value of from 1 to 3, 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 the elements in the silyl hydride are satisfied and the 1,2,4-trivinylcyclohexane in the presence of the activated catalyst such that hydrosilylation occurs selectively at the 4 position of the 1,2,4-trivinylcyclohexane, thereby producing the mono-hydrosilylated product,

wherein step (ii) is conducted shortly before, or at the same time as, step (iii); and

wherein Formula (I), Formula (II) and Formula (III) are:

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 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 is independently H, C1-18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert group, wherein any two of R 1 -R 3 , R 3 -R 7 , R 3 -R 9 , R 14 -R 15 and R 17 -R 18 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure, wherein R 2 to R 9 , and R 11 to R 24 other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 10 is C1-C18 alkyl group or C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R 10 optionally contains at least one heteroatom; and

X is an anion;

wherein the molar ratio of the Si—H functional groups in the silyl hydride to the alkenyl functional groups in the 1,2,4-trivinylcyclohexane is between about (0.5/3) and about (1.1/3).

22. The process of claim 21 wherein the silyl hydride is triethoxysilane.

23. The process of claim 21 wherein the silyl hydride is bis(trimethylsiloxy)methylsilane.

24. The process of claim 21 wherein the 1,2,4-trivinylcyclohexane is a mixture of 1,2,4-trivinylcyclohexane stereoisomers.

25. The process of claim 21 wherein the 1,2,4-trivinylcyclohexane is 1,2,4-trivinylcyclohexane isomer A and/or 1,2,4-trivinylcyclohexane isomer B, wherein isomer A and isomer B have structure Formulae (XIX) and (XX):

Assignments (25)