Metallocenes and catalysts for olefin-polymerisation

• US 6,451,724 B1
• Filed: 07/08/1999
• Issued: 09/17/2002
• Est. Priority Date: 11/12/1997
• Status: Expired due to Term

• Current Assignee: Basell Technology Company BV (Lyondellbasell Industries NV)
• Original Assignee: Basell Technology Company BV (Lyondellbasell Industries NV)
• Inventors: Bagrov, Vladimir V., Nifantʼev, Ilya E.
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): HARLAN, ROBERT D
• Application Number:
  US09/341,438
• Time in Patent Office: 1,167 Days
• Field of Search: 526/160, 526/943, 526/161, 526/127, 502/152, 556/52
• US Class Current: 502/103
• CPC Class Codes: C07D 209/70 containing carbocyclic rings other than six-membered
• CPC Class Codes: C07F 17/00 Metallocenes
• CPC Class Codes: C07F 9/65683 the ring phosphorus atom being part of a phosphine
• 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 110/02 Ethene
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 210/08 Butenes
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/08 Low density, i.e. < 0.91 g/cm3
• CPC Class Codes: C08F 2500/15 Isotactic
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/20 Activation energy or enthalpy
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

A class of metallocenes of formula (I): (ZR¹_m)_n(Cp)(A)_rML_pL′_q(I) wherein (ZR¹_m)_n, is a divalent group bridging Cp and A, Cp is a heterocyclic cyclopentadienyl group of formula (II) or (II′), wherein one of X or Y is a single bond, the other being an heteroatom; R² and R³ are hydrogen, halogen or a hydrocarbon radical, optionally containing heteroatoms; R⁴ is halogen or an hydrocarbon radical, optionally containing heteroatoms; the group A is a cyclopentadienyl derivative or is equal to Cp; M is Ti, Zr or Hf; m is 1 or 2; n ranges from 0 to 4; r is 0 or 1; p and q range from 0 to 3; and a ranges from 0 to 4. Moreover, are disclosed catalyst systems containing these metallocenes, useful in the polymerization of olefins.

Claims

1. A metallocene of formula (I):

2. The metallocene according to claim 1, wherein (ZR¹_m)_n is selected from the group consisting of CR¹₂, SiR¹₂, GeR¹₂, NR¹, PR¹, and (CR¹₂)₂.

3. The metallocene according to claim 2, wherein (ZR¹_m)_n is SI(CH₃)₂, SiPh₂, CH₂, (CH₂)₂, or C(CH₃)₂.

4. The metallocene according to claim 1, wherein Cp corresponds to formula (IIIa) or formula (IIIb):

wherein the substituents R⁵, the same or different from each other, are selected from the group consisting of halogen, linear or branched, saturated or unsaturated C₁-C₂₀ alkyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, C₇-C₂₀ alkylaryl, C₇-C₂₀ arylalkyl, —

OR⁶, —

OCOR⁶, —

SR⁶, —

NR⁶₂, and —

PR⁶₂; and

b is an integer ranging from 0 to 4.

5. The metallocence according to claim 4, wherein Cp is selected from the group consisting of 5,10-dihydroindeno[1,2-bi]indol-10-yl, N-methyl-5,10-dihydroindeno [1,2-b]indol-10-yl, N-phenyl-5,10-dihydroindeno[1,2-b]indol-10-yl, 5,6- dihydroindeno[2,1-b]indol-6-yl, N-methyl-5,6-dihydroindeno[2,1-b]indol-6-yl, N-ally-5,6- dihydroindeno[2,1-b]indol-6-yl, and N-phenyl-5,6-dihydroindeno [2,1-b]indol-6-yl.

6. The metallocene according to claim 4, wherein A corresponds to formula (IIIa) or (IIIb).

7. The metallocene according to claim 6 wherein the metallocene is methylen-bis(N-methyl-5,6-dihydroindeno[2,1-b]indol-6-yl)zirconium dichloride or dimethyl.

8. The metallocene according to claim 1, wherein A is selected from the group consisting of cyclopentadienyl, 4-t-butyl-cyclopentadienyl, 4-adamanthyl- cyclopentadienyl, idenyl, and tetrahydroindenyl.

9. The metallocene according to claim 1, wherein M is Ti, Zr, or Hf.

10. The metallocene according to claim 1, wherein L is halogen or R⁶.

11. A bridged ligand of formula (IV):

12. The bridged ligand according to claim 11, wherein (ZR¹_m)_n is selected from the group consisting of Si(CH₃)₂, SiPh₂, CH₂, (CH₂)₂, and C(CH₃)₂.

13. The bridged ligand according to claim 11, wherein Cp corresponds to formula (IIIa) or (IIIb):

wherein the substituents R⁵, the same or different from each other, are selected from the group consisting of halogen, linear or branched, saturated or unsaturated C₁-C₂₀ alkyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, C₇-C₂₀ alkylaryl, C₇-C₂₀ arylalkyl, —

OR⁶, —

OCOR⁶, —

SR⁶, —

NR⁶₂, and —

PR⁶₂; and

b is an integer ranging from 0 to 4.

14. The bridged ligand according to claim 13, wherein Cp is selected from the group consisting of N-methy-5,10-dihydroindeno[1,2-b]indolyl, N-phenyl-5,10- dihydroindeno[1,2-b]indolyl, N-allyl-5,10-dihydroindeno[1,2-b]indole, N-methyl-5,6- dihydroindeno[2,1-b]indole, N-phenyl-5,6-dihydroindeno[2,1-b]indole, and N-allyl-5,6- dihydroindeno[21,-b]indole.

15. The bridged ligand according to claim 11, wherein A corresponds to formula (IIIa) or (IIIb):

wherein the substitutes R⁵, the same or different from each other, are selected from the group consisting of halogen, linear or branched, saturated or unsaturated C₁-C₂₀ alkyl, C₃-C₂₀ cycloalkyl, C₆-C₂₀ aryl, C₇-C₂₀ alkylaryl, C₇-C₂₀ arylalkyl, —

OR⁶, —

OCOR⁶, —

SR⁶, —

NR⁶₂, and —

PR⁶₂; and

b is an integer ranging from 0 to 4.

16. The bridged ligand according to claim 15, wherein the bridged ligand is 6- [N-methyl-5,6-dihydroindeno[2,1-b]indol-6-yl)methyl]-N-methyl-5,6- dihydroindeno[2,1-b]indole.