Complexes of mid-transition metals and unsaturated nitrogenous ligands as single-site catalysts

• US 20020058583A1
• Filed: 12/17/2001
• Published: 05/16/2002
• Est. Priority Date: 10/06/1999
• Status: Active Grant

• Current Assignee: Christopher D. Tagge, Robert B. Wilson Jr
• Original Assignee: Christopher D. Tagge, Robert B. Wilson Jr
• Inventors: Wilson, Robert B. Jr., Tagge, Christopher D.
• Granted Patent: US 6,841,676 B2
• Time in Patent Office: Days
• US Class Current: 502/103
• CPC Class Codes: C07C 251/12 being acyclic
• CPC Class Codes: C07D 213/53 Nitrogen atoms
• CPC Class Codes: C07D 241/12 with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• CPC Class Codes: C07F 11/005 compounds without a metal-carbon linkage
• CPC Class Codes: C07F 7/003 without C-Metal linkages
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 4/64013 NN
• CPC Class Codes: C08F 4/69034 NN
• CPC Class Codes: C08F 4/69043 NO

Abstract

Novel compounds are provided which are useful as catalysts, particularly in the polymerization of addition polymerizable monomers such as olefinic or vinyl monomers. The compounds are complexes of a mid-transition metal coordinated to at least two ligands, at least one of which is an unsaturated nitrogenous ligand. Depending on ligand substitution, stereospecific catalysts can be provided, including isospecific catalysts and syndiospecific catalysts. Catalyst systems containing the novel compounds in combination with a catalyst activator are provided as well, as are methods of using the novel compounds in the preparation of polyolefins.

Claims

1. A compound having the structural formula L¹[MQ¹Q²]L² in which M is a mid-transition metal selected from the group consisting of Nb, Ta, Mo, W, Mn and Re, Q¹ and Q² are each a univalent radical, and L¹ and L² are ligands coordinated to M, wherein each of L¹ and L² contains a first coordinating atom that is a nitrogen atom contained within a C═

N group, and a second coordinating atom that is either a second nitrogen atom, optionally present in a second C═

N group, or an oxygen, sulfur or phosphorus atom.

2. The compound of claim 1, wherein, in each of L¹ and L², the second coordinating atom is a second nitrogen atom.

3. The compound of claim 2, wherein, in each of L¹ and L², the second nitrogen atom is present in a second C═

N group.

4. The compound of claim 3, wherein L¹ and L² are identical.

5. The compound of claim 4, wherein the first nitrogen atom in each of L¹ and L² is bound to a first substituent R_S, and the second nitrogen atom in each of L¹ and L² is bound to a second substituent R_L, wherein the difference in steric bulk between R_S and R_L is sufficient to result in isospecificity when the compound is used as a polymerization catalyst.

6. The compound of claim 3, wherein L¹ and L² are different.

7. The compound of claim 6, wherein the first and second nitrogen atoms in the ligand L¹ are bound to a first substituent R_S, and the first and second nitrogen atoms in the ligand L² are bound to a second substituent R_L, wherein the difference in steric bulk between R_S and R_L is sufficient to result in syndiospecificity when the compound is used as a polymerization catalyst.

8. The compound of claim 1, wherein the compound has a positive charge +y and is associated with y/z anions each bearing a negative charge −

z.

9. The compound of claim 8, wherein y and z are independently integers in the range of 1 to 4 inclusive.

10. The compound of claim 9, wherein y and z are independently 1 or 2.

11. The compound of claim 8, wherein the anions are selected from the group consisting of halide and pseudohalide.

13. The compound of claim 12, wherein the compound has a positive charge +y and is associated with y/z anions each bearing a negative charge −

z.

14. The compound of claim 13, wherein y and z are independently integers in the range of 1 to 4 inclusive.

15. The compound of claim 14, wherein y and z are independently 1 or 2.

16. The compound of claim 12, wherein the anions are selected from the group consisting of halide and pseudohalide.

17. The compound of claim 12, having the structure of formula (II)

18. The compound of claim 17, wherein the compound has a positive charge +y and is associated with y/z anions each bearing a negative charge −

z.

19. The compound of claim 18, wherein y and z are independently integers in the range of 1 to 4 inclusive.

20. The compound of claim 19, wherein y and z are independently 1 or 2.

21. The compound of claim 17, wherein the anions are selected from the group consisting of halide and pseudohalide.

22. The compound of claim 17, having the structure of formula (V)

23. The compound of claim 22, wherein R²⁰, R^20a, R²¹, R^21a, R²², R^22a, R²³ and R^23a are hydrido.

24. The compound of claim 22, wherein R²⁰ and R^20a are methyl, and R²¹, R^21a, R²², R^22a, R²³ and R^23a are hydrido.

25. The compound of any one of claims 21, 22 or 23, wherein the compound has a positive charge +y and is associated with y/z anions each bearing a negative charge −

z.

26. The compound of claim 25, wherein y and z are independently integers in the range of 1 to 4 inclusive.

27. The compound of claim 26, wherein y and z are independently 1 or 2.

28. The compound of claim 25, wherein the anions are selected from the group consisting of halide and pseudohalide.

30. A catalyst system comprising the compound of any one of claims 1, 5, 7, 12, 17 or 22 and a catalyst activator effective to produce a catalytically active ionic species when combined with said compound.

31. The catalyst system of claim 30, wherein the catalyst activator is aluminum-containing or boron-containing.

32. The catalyst system of claim 31, wherein the catalyst activator is aluminum-containing.

33. The catalyst system of claim 32, wherein the catalyst activator is an organoaluminum compound.

34. The catalyst system of claim 33, wherein the catalyst activator is an alkyl aluminoxane.

35. The catalyst system of claim 34, wherein the catalyst activator is methyl aluminoxane.

36. The catalyst system of claim 31, wherein the catalyst activator is boron-containing.

37. The catalyst system of claim 36, wherein the catalyst activator is a fluorohydrocarbylboron compound.

38. The catalyst system of claim 37, wherein the catalyst activator is a fluorinated phenylborate.

39. The catalyst system of claim 30, further including an inert polymerization diluent.

40. The catalyst system of claim 39, wherein the diluent is a volatile hydrocarbon solvent.

41. A method for preparing a polymer composition, comprising:

contacting, under polymerization conditions, an addition polymerizable monomer having at least one degree of unsaturation with the catalyst system of claim 30.

42. The method of claim 41, wherein the addition polymerizable monomer is an olefinic or vinyl monomer.

43. The method of claim 42, wherein the addition polymerizable monomer is ethylene.

44. The method of claim 42, wherein the addition polymerizable monomer is propylene.

45. A method for synthesizing an isotactic polyolefin, comprising:

providing an isospecific catalyst comprising the compound of claim 5;

admixing the catalyst with a catalyst activator, to produce a catalyst system; and

contacting, under polymerization conditions, an olefinic monomer CH₂═

CH₂(R) wherein R is other than hydrogen, with the catalyst system.

46. The method of claim 45, wherein R is methyl and the isotactic polyolefin is isotactic polypropylene.

47. A method for synthesizing a syndiotactic polyolefin, comprising:

providing a syndiospecific catalyst comprising the compound of claim 7;

admixing the catalyst with a catalyst activator, to produce a catalyst system; and

contacting, under polymerization conditions, an olefinic monomer CH₂═

CH₂(R) wherein R is other than hydrogen, with the catalyst system.

48. The method of claim 47, wherein R is methyl and the syndiotactic polyolefin is syndiotactic polypropylene.

49. A method for synthesizing linear low density polyethylene (LLDPE), comprising:

providing a catalyst comprising the compound of claim 1;

admixing the catalyst with a catalyst activator, to produce a catalyst system; and

contacting, under polymerization conditions, a mixture of olefinic monomers with the catalyst system, wherein the mixture comprises ethylene and a second olefinic co-monomer CH₂═

CHR, wherein R is a C₄-C₈ alkyl group.

50. The method of claim 49, wherein the second olefinic co-monomer represents approximately 5 mole % to 15 mole % of the mixture.

51. The method of claim 50, wherein the second olefinic co-monomer is selected from the group consisting of 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, and mixtures thereof.

12. A compound having the structure of formula (I)

29. A compound having the structure of formula (III)