Granted Patent B2

US 8,927,674 · App. 13/966,568 · Granted Jan 6, 2015

Abstract

Claims (104)

1. A process for producing a dehydrogenatively 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 dehydrogenatively silylated product, 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, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 1 -R 5 , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 6 and R 7 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom;

optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and

L is hydroxyl, chloride, bromide, or a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl group, an alkaryl group, an aralkyl group, —H, SiR 3 where R is an alkyl, aryl, or siloxanyl group, or component (a) wherein L optionally contains at least one heteroatom.

2. A process for producing a dehydrogenatively 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 dehydrogenatively silylated product, wherein the catalyst is a complex selected from the group consisting of Formula (IV), Formula (V), Formula (VI), Formula (VII), or an adduct thereof

wherein R is an alkyl, aryl, or siloxanyl group.

3. The process of claim 1 further comprising removing the complex and/or derivatives thereof from the dehydrogenative silylated product.

4. The process of claim 1 wherein the dehydrogenatively silylated product comprises a silane or siloxane containing a silyl group and an unsaturated group.

5. The process of claim 4 , wherein the unsaturated group is in the alpha or beta position relative to the silyl group.

6. The process of claim 1 wherein the molar ratio of the unsaturated group in said component (a) relative to the silylhydride functional group in said component (b) is less than equal to 1:1.

7. The process of claim 6 wherein the silane or siloxane of the dehydrogenatively silylated product contains one silyl group derived from component (b).

8. The process of claim 6 wherein the dehydrogenatively silylated product contains two or more terminal silyl groups derived from component (b).

9. The process of claim 6 , wherein said process produces an α,ω-substituted alkane or alkene diol from a parent α,ω-bis(silyl) substituted alkane or alkene.

10. The process of claim 1 wherein the molar ratio of the unsaturated group in said component (a) relative to the silylhydride functional group in said component (b) is greater than 1:1.

11. The process of claim 10 wherein the silane or siloxane contains two or more silyl groups derived from component (b).

12. The process of claim 1 wherein said component (a) is a mono-unsaturated compound.

13. The process of claim 1 wherein said component (a) is selected from the group consisting of an 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, terminally unsaturated acrylate or methacrylate, unsaturated aryl ether, vinyl-functionalized polymer or oligomer, vinyl-functionalized silane, vinyl-functionalized silicone, unsaturated fatty acids, unsaturated esters, and combinations thereof.

14. The process of claim 13 wherein said component (a) is selected from the group consisting of N,N-dimethylallyl amine, allyloxy-substituted polyethers, cyclohexene, linear alpha olefins, internal olefins, branched olefins, unsaturated polyolefins, a vinyl siloxane of the Formula (XII), and combinations thereof, wherein Formula (XII) is

wherein each occurrence of R 8 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.

15. The process of claim 1 wherein said component (b) is selected from the group consisting of R a SiH 4-a , (RO) a SiH 4-a , HSiR a (OR) 3-a , R 3 Si(CH 2 ) j (SiR 20 ) k SiR 2 H, (RO) 3 Si(CH 2 ) f (SiR 20 ) 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 HR′ 2 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.

16. The process of claim 15 , 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.

17. The process of claim 1 wherein said component (b) has one of the following structures:

wherein each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 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, x and w are independently greater than or equal to 0 (x is at least equal to 1 for Formula X), and a and b are integers from 0 to 3 provided that a+b=3.

18. The process of claim 1 wherein at least one of R 6 and R 7 is

wherein each occurrence of R 8 , R 9 , R 10 , R 11 , and R 12 is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 8 -R 12 , other than hydrogen, optionally contain at least one heteroatom.

19. The process of claim 18 wherein R 8 and R 12 are independently methyl, ethyl or isopropyl groups and R 10 is hydrogen or methyl.

20. The process of claim 19 wherein R 8 , R 10 , and R 12 are each methyl.

21. The process of claim 1 wherein R 1 and R 5 are independently methyl or phenyl groups.

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

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

24. The process of claim 23 wherein the support is selected from the group consisting of carbon, silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), sulfonated polystyrene, dendrimers, and combinations thereof.

25. The process of claim 23 wherein at least one of R 1 to R 7 contains a functional group that covalently bonds with the support.

26. The process of claim 1 wherein the catalyst is generated in-situ by contacting a 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, wherein the catalyst precursor is represented by structural Formula (VIII)

wherein

each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 1 -R 5 , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 6 and R 7 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom;

optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and

X is an anion selected from the group consisting of 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 alkylene group, and R 50 is a C1-C10 hydrocarbyl group;

and wherein the activator is a reducing agent or an alkylating agent selected from the group consisting of NaHBEt 3 , CH 3 Li, DIBAL-H, LiHMDS, MeMgBr, EtMgCl, and combinations thereof.

27. The process of claim 1 wherein the reaction is conducted under an inert atmosphere.

28. The process of claim 1 wherein the reaction is conducted in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combinations thereof.

29. The process of claim 1 wherein the reaction is carried out at a temperature of −40° C. to 200° C.

30. A composition produced by the process of claim 1 , wherein the composition contains the catalyst or derivatives thereof.

31. The composition of claim 30 comprising at least one component selected from the group consisting of silanes, silicone fluids and crosslinked silicones.

32. A compound of Formula (II)

wherein

each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 1 -R 5 , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 6 and R 7 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; and

optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure.

33. A process for producing a dehydrogenatively 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 dehydrogenatively silylated product, wherein the catalyst is a complex of the Formula (III) or an adduct or salt thereof;

wherein

each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 1 -R 5 , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 6 and R 7 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom;

optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and

Y is a neutral ligand optionally containing at least one heteroatom;

and wherein Formula III is a neutral, cationic, or anionic complex.

34. The process of claim 33 further comprising removing the complex and/or derivatives thereof from the dehydrogenatively silylated product.

35. The process of claim 33 wherein the dehydrogenatively silylated product comprises a silane or siloxane containing a silyl group and an unsaturated group.

36. The process of claim 35 , wherein the unsaturated group is in the alpha or beta position relative to the silyl group.

37. The process of claim 33 wherein the molar ratio of the unsaturated group in said component (a) relative to the silylhydride functional group in said component (b) is less than 1:1.

38. The process of claim 37 wherein the silane or siloxane of the dehydrogenatively silylated product contains one silyl group derived from component (b).

39. The process of claim 33 wherein the molar ratio of the unsaturated group in said component (a) relative to the silylhydride functional group in said component (b) is equal to or greater than 1:1.

40. The process of claim 39 wherein the silane or siloxane contains two or more silyl groups derived from component (b).

41. The process of claim 33 wherein said component (a) is a mono-unsaturated compound.

42. The process of claim 33 wherein said component (a) is selected from the group consisting of an 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, terminally unsaturated acrylate or methacrylate, unsaturated aryl ether, vinyl-functionalized polymer or oligomer, vinyl-functionalized silane, vinyl-functionalized silicone, unsaturated fatty acids, unsaturated esters, and combinations thereof.

43. The process of claim 33 , wherein Y is selected from the group consisting of dinitrogen (N 2 ), phosphines, CO, nitrosyls, olefins, amines, ethers, and combinations thereof.

44. The process of claim 43 , wherein Y is selected from the group consisting of PH 3 , PMe 3 , CO, NO, ethylene, THF, and NH 3 .

45. The process of claim 42 wherein said component (a) is selected from the group consisting of N,N-dimethylallyl amine, allyloxy-substituted polyethers, cyclohexene, linear alpha olefins, internal olefins, branched olefins, unsaturated polyolefins, a vinyl siloxane of the Formula (XII), and combinations thereof, wherein Formula (XII) is

wherein each occurrence of R 8 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.

46. The process of claim 33 wherein said component (b) is selected from the group consisting of R a SiH 4-a , (RO) a SiH 4-a , HSiR a (OR) 3-a , R 3 Si(CH 2 ) j (SiR 20 ) k SiR 2 H, (RO) 3 Si(CH 2 ) f (SiR 20 ) k SiR 2 H, Q a 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 HR′ 2 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.

47. The process of claim 46 , 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.

48. The process of claim 33 wherein said component (b) has one of the following structures:

wherein each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 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, x and w are independently greater than or equal to 0 (x is at least equal to 1 for Formula X), and a and b are integers from 0 to 3 provided that a +b=3.

49. The process of claim 33 wherein at least one of R 6 and R 7 is

wherein each occurrence of R 8 , R 9 , R 10 , R 11 , and R 12 is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 8 -R 12 , other than hydrogen, optionally contain at least one heteroatom.

50. The process of claim 49 wherein R 8 and R 12 are independently methyl, ethyl or isopropyl groups and R 10 is hydrogen or methyl.

51. The process of claim 50 wherein R 8 , R 10 , and R 12 are each methyl.

52. The process of claim 33 wherein R 1 and R 5 are independently methyl or phenyl groups.

53. The process of claim 33 wherein R 2 , R 3 and R 4 are hydrogen.

54. The process of claim 33 wherein the complex is immobilized on a support.

55. The process of claim 54 wherein the support is selected from the group consisting of carbon, silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), sulfonated polystyrene, dendrimers, and combinations thereof.

56. The process of claim 55 wherein at least one of R 1 to R 7 contains a functional group that covalently bonds with the support.

57. The process of claim 33 wherein the catalyst is generated in-situ by contacting a 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, wherein the catalyst precursor is represented by structural Formula (VIII)

wherein

each occurrence of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 1 -R 5 , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 6 and R 7 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom;

optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and

X is an anion selected from the group consisting of 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 alkylene group, and R 50 is a C1-C10 hydrocarbyl group;

and wherein the activator is a reducing agent or an alkylating agent selected from the group consisting of NaHBEt 3 , CH 3 Li, DIBAL-H, LiHMDS, MeMgBr, EtMgCl, and combinations thereof.

58. The process of claim 33 wherein the reaction is conducted under an inert atmosphere.

59. The process of claim 33 wherein the reaction is conducted in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combinations thereof.

60. The process of claim 33 wherein the reaction is carried out at a temperature of −40° C. to 200° C.

61. A process for producing a crosslinked material, comprising reacting a mixture comprising (a) a silyl-hydride containing polymer, (b) a mono-unsaturated olefin or an unsaturated polyolefin, or combinations thereof and (c) a catalyst, optionally in the presence of a solvent, in order to produce the crosslinked material, 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, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert substituent, wherein R 1 -R 5 , other than hydrogen, optionally contain at least one heteroatom;

each occurrence of R 6 and R 7 is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom;

optionally any two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 vicinal to one another taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and

L is hydroxyl, chloride, bromide, or a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl group, an alkaryl group, an aralkyl group, —H, SiR 3 where R is an alkyl, aryl, or siloxanyl group, or component (a) wherein L optionally contains at least one heteroatom.

62. The process of claim 61 wherein the reaction is conducted under an inert atmosphere.

63. The process of claim 61 wherein the reaction is conducted in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combinations thereof.

64. The process of claim 61 wherein the reaction is carried out at a temperature of −40° C. to 200° C.

65. The process of claim 1 , further comprising adding additional unsaturated compound (a) and silyl hydride (b), and repeating said reacting step in the presence of the original charge of said catalyst (c) to produce additional dehydrogenatively silylated product.

Assignments (18)