DE4343566A1 - Stereo-rigid metallocene used in olefin] polymerisation - Google Patents

Abstract

Stereo-rigid metallocenes (Mc) contain at least two opt. substd. cyclopentadienyl (Cp) ligands linked together via a mono- or poly-cyclic ring system which forms a condensed ring system with at least one of the Cp gps.. Also claimed are (i) a supported and/or prepolymerised catalyst component contg. Mc; and (ii) a process for the prodn. of polyolefins by (co)polymerisation of olefins in presence of a catalyst contg. Mc cpd(s)..

Description

The present invention relates to a stereorigid metallocene compound, the Ligands are connected in a special way. The invention Compound can advantageously be used as a catalyst component in the manufacture of Polyolefins are used.

From the literature is the production of polyolefins with soluble Metallocene compounds in combination with aluminoxanes or others Cocatalysts which, due to their Lewis acidity, convert the neutral metallocene into one Can convert and stabilize cation, known.

When using soluble metallocene compounds based on Bis (cyclopentadienyl) zirconium dialkyl or dihalide in combination with oligomeric aluminoxanes give atactic polymers which, because of their technically unbalanced and insufficient product properties only from are of little importance.

Derivatives of zirconocene dichloride in which the two are substituted Cyclopentadienyl groups via a methyl, ethylene or a Dimethylsilylene bridge can be connected due to their conformative rigidity as catalysts for the isospecific polymerization of Olefins can be used (Chem. Lett. 1989, pp. 1853-1856 or EP-A 0 316 155). Metallocenes with (substituted) are of particular importance Indenyl residues as ligands for the production of highly isotactic polymers with high Crystallinity and high melting point (EP 485 823, EP 530 647).

Of great interest, however, are products whose profile of properties lie between these two extremes.

The task was to provide a catalyst system that the Production of polymers with reduced crystallinity, increased Impact strength, increased transparency, high fluidity Processing temperature, low molecular weight and reduced melting point enables.

The present invention thus relates to a stereorigid metallocene compound, the ligands are at least two substituted or unsubstituted Cyclopentadienyl groups has a mono- or polycyclic Ring system are interconnected, characterized in that at least one cyclopentadienyl group on the mono- or polycyclic Ring system is fused.

A cyclopentadienyl group is preferably located as a substituent on the mono- or polycyclic ring system, while another cyclopenta dienyl group is fused to the mono- or polycyclic ring system.

The mono- or polycyclic ring system can be aromatic, aliphatic or mixed aromatic and aliphatic and can also carry substituents. It preferably has at least six ring atoms.

Fused cyclopentadienyl groups are simple (e.g. via the 1,2- or 1,3- Position of the cyclopentadienyl ring) or multiple times (e.g. via the 1,2,3- or 1,2,3,4-position of the cyclopentadienyl ring) fused, preferably simply fused.  

Compounds of the formula I are preferred

wherein
M¹ is a metal from group IIIb, IVb, Vb or VIb of the periodic table,
M² is carbon or silicon,
R¹ and R² are the same or different and are a hydrogen atom, a C₁-C₁₀ alkyl, a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl ,, a C₆-C₂₅ aryloxy, a C₂-C₁₀ alkenyl -, a C₁-C₄₀-arylalkyl, a C₇-Cyl-arylalkenyl, an OH group or a halogen atom, or R¹ and R² together with the atoms connecting them form a ring system,
R³, R⁴, R⁵, R⁷, R⁸ and R⁹ are identical or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl group which may be halogenated, a C₆-C₂₀ aryl group, a -NR¹⁴₂-, -OSiR¹⁴₃-, -SiR¹⁴₃- or -PR¹⁴₂ radical, wherein R¹⁴ is a halogen atom, a C₁-C₁₀ alkyl group or a C₆-C₁₀ aryl group, or two or more adjacent radicals R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ together form a ring system with the atoms connecting them,
R¹⁰ is a hydrogen atom, a C₁-C₂₀ alkyl, a C₁-C₁₀ alkoxy, a C₆-C₂₀ aryl, a C₆-C₂₀ aryloxy, a C₂-C₁₂ alkenyl, a C₇-C₄₀ arylalkyl -, a C₇-C₄₀-alkylaryl, or a C₈-C₄₀-arylalkenyl group, each of which can carry radicals -NR¹⁴₃, SR¹⁴₂-, -OSiR¹⁴₃, wherein R¹⁴ represents a halogen atom, a C₁-C₁₀ alkyl group or a C₆-C₁₀- Is aryl group, R¹¹

where n is an integer from 1 to 8,
X is O, = NR¹⁴, = CO, = PR¹⁴, = P (O) R¹⁴, = SO, = SO₂ or -S-, wherein R¹⁴ is a halogen atom, a C₁-C₁₀ alkyl group or a C₆-C₁₀ aryl group ,
R¹⁵ and R¹⁶ are the same or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl, a C₁-C₁₀ fluoroalkyl, a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl, a C₆-C₁₀- Fluoroaryl, a C₆-C₁₀ aryloxy- 'a C₂-C₁₀ alkenyl, a C₇-C₄₀ arylalkyl, a C₇-C₄₀ alkylaryl, a C₈-C₄₀ arylalkenyl group, or two radicals R¹⁵, two radicals R¹⁶, or R¹⁵ and R¹⁶ each form one or more rings with the atoms connecting them, and M³ is silicon, germanium or tin,
R¹² and R¹³ are the same or different, and a hydrogen atom, a C₁-C₂₀ alkyl, a C₁-C₁₀ alkoxy, a C₆-C₂₀ aryl, a C₆-C₂₀ aryloxy, a C₂-C₁₂ alkenyl -, A C₇-C Ar-arylalkyl, a C₇-C₄₀-alkylaryl, or a C₈-C₄₀-arylalkenyl group, each of the radicals -NR¹⁴₃, -SR¹⁴₂, -OSiR¹⁴₃, wherein R¹⁴ is a halogen atom, a C₁-C₁₀ alkyl group or is a C₆-C₁₀ aryl group, or can carry halogen,
R²³ are identical or different are a hydrogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl, a C₆-C₂₅ aryloxy, a C₂-C₁₀ alkenyl, a C₇-C₄₀ -Arylalkyl-, a C₇-C₄₀-arylalkenyl group or a halogen atom, or one or both radicals R²³ are connected to one or both radicals R¹⁵ and R¹⁶, and m is an integer from 0 to 24, in the event that R¹¹ is CH₂, at least one of the radicals R³, R⁴, R⁶, R⁷ and R⁹ is not hydrogen.

For compounds of formula I it is preferred that
M¹ is zirconium or hafnium, in particular zirconium,
R¹ and R² are the same and represent a C₁-C₃ alkyl group or a halogen atom, especially chlorine,
R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are the same or different and are a hydrogen atom, a C₁-C₁₀ alkyl group or a C₆-C₂₄ aryl group, or two or more adjacent radicals together with the atoms connecting them are aromatic or form an aliphatic hydrocarbon ring system,
R¹⁰ is a hydrogen atom, a C₆-C₂₄ aryl group or a C₁-C₁₀ alkyl group, in particular a C₁-C₄ alkyl group,
R¹¹

is, where n is an integer from 1 to 8, in particular from 2 to 4, R¹⁵ and R¹⁶ are identical or different and are hydrogen or a C₁-C₁₀ alkyl group, or two radicals R¹⁵, two radicals R¹⁶, or R¹⁵ and R¹⁶ together with the atoms connecting them form a hydrocarbon ring system,
M² is carbon,
R¹² and R¹³ are the same or different and are a hydrogen atom, a C₁-C₁₀ alkyl group, especially a C₁-C₄ alkyl group, or a C₆-C₁₀ aryl group and m = 0.

Compounds of the formula I in which
M¹ is zirconium,
R¹ and R² are the same and represent a halogen atom, especially chlorine,
R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are the same or different and are hydrogen or a C₁-C₄ alkyl group, or R⁸ and R⁹ and R³ and R⁴ and / or R⁶ and R⁶ together with the atoms connecting them an aromatic Form hydrocarbon ring system, in particular a six-membered ring, which in turn can be substituted,
M² is a carbon atom,
R¹⁰ is a C₁-C₆ alkyl group, especially methyl,
R¹¹ is -CH₂-CH₂-,
R¹² and R¹³ are the same or different and represent a methyl or phenyl group and m = 0.

Examples of metallocene compounds according to the invention are:
[4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] - dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η ⁵-4,5,6,7-tetrahydroindenyl)] dichlorohafnium,
[4- (η⁵-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] - dichlorotitanium,
[4- (η⁶-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4 (η⁵-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] - dichlorotitan,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-3′-tert-butyl-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-3′-tert-butyl-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydro indenyl)] dichlorotitanium,
[4- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydro indenyl)] dichlorozirconium,
[4- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetra hydroindenyl)] dichlorotitanium,
[4- (η⁵-3′tert.Butyl-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,6,7-tetra hydroindenyl)] dichlorozirconium,
[4- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetra hydroindenyl)] dichlorotitanium,
[4- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetra hydroindenyl)] dichlorozirconium,
[4- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetra hydroindenyl)] dichlorotitanium,
[4- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetra hydroindenyl)] dichlorozirconium,
[4- (η⁵-indenyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-indenyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-indenyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-indenyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-indenyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-indenyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-indenyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-indenyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-indenyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-indenyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η ⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium,
[4- (η⁵-3′-methylcyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-3′-methylcyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-3-methylcyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-3′-methylcyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-3′-methylcyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydro indenyl)] dichlorotitanium,
[4- (η⁵-3′-methylcyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydro indenyl)] dichlorozirconium,
[4- (η⁵-3′-methylcyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetra hydroindenyl)] dichlorotitanium,
[4- (η⁵-3′-methylcyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetra hydroindenyl)] dichlorozirconium,
[4- (η⁵-3′-methylcyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydro indenyl)] dichlorotitanium,
[4- (η⁵-3′-methylcyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydro indenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-2-methyl-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-2-methyl-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-2-methyl-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-2-methyl-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-2-methyl-4,5,6,7-tetrahydro indenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-2-methyl-4,5,6,7-tetrahydro indenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-2-methyl-4,5,6,7-tetra hydroindenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-2-methyl-4,5,6,7-tetra hydroindenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-2-methyl-4,5,6,7-tetrahydro indenyl)] dichlorotitanium,
[4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl - (η⁵-2-methyl-4,5,6,7-tetrahydro indenyl)] dichlorozirconium,
[4- (η⁵-3-methylcyclopentadienyl) -4,7,7-trimethyl- (η⁵-2-methyl-4,5,6,7-tetra hydroindenyl)] dichlorotitanium,
[4- (η⁵-3-methylcyclopentadienyl) -4,7,7-trimethyl- (η⁵-2-methyl-4, 5,6,7-tetra hydroindenyl)] dichlorozirconium,
[4- (η⁵-3′-methylcyclopentadienyl) -4,7,7-triphenyl- (η⁵-2-methyl-4,5,6,7-tetra hydroindenyl)] dichlorotitanium,
[4- (η⁵-3-methylcyclopentadienyl) -4,7,7-triphenyl- (η⁵-2-methyl-4,5,6,7-tetra hydroindenyl)] dichlorozirconium,
[4- (η⁵-3'-methylcyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-2-methyl-4,5,6,7-tetra hydroindenyl)] dichlorotitanium,
[4- (η⁵-3 ′ -methylcyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-2-methyl-4,5,6,7-tetra hydroindenyl)] dichlorozirconium,
[4- (η⁵-3'-methylcyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-3-methyl-4-5,6,7-tetra hydroindenyl)] dichlorotitanium,
[4- (η⁵-3'-methylcyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-2-methyl-4-5-6,7-tetra hydroindenyl)] dichlorozirconium,
[4- (η⁵-3′-methylcyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-2-methyl-4,5,6,7-tetra hydroindenyl)] dichlorotitanium,
[4- (η⁵-3'-methylcyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-2-methyl-4,5,6,7-tetra hydroindenyl)] dichlorozirconium,
[4- (η⁵-fluorenyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-fluorenyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-fluorenyl) -4,7,7-triphenyl- (η⁵-4, 5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-fluorenyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-fluorenyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-fluorenyl) -4, 7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-fluorenyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-fluorenyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] [4- (η⁵-fluorenyl) -4,7-dimethyl-7- butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[4- (η⁵-fluorenyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl-4,5,6,7,10,11,12,13-octahydro-5, -6-benzoindenyl)] - dichlorozirconium,
[5- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5-η⁵-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5-η⁵-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5-η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-3-tert-butyl-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] - dichlorotitanium,
[5- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-3'-tert-butyl-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-indenyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-indenyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-indenyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-indenyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-indenyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-lndenyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-indenyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-indenyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-indenyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-indenyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium,
[5- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium,
[5- (η⁵-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium,
[5- (η⁵-cyclopentadienyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium,
[5- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium,
[5- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium,
[5- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-naphthyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium,
[5- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-naphthyl - (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium,
[5- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorotitanium,
[5- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7-tetrahydrofluorenyl)] dichlorozirconium,
[5- (η⁵-fluorenyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-fluorenyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-fluorenyl) -4,7,7-triphenyl- (η⁵-4,5,6,7tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-fluorenyl) -4,7,7-triphenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium,
[5- (η⁵-fluorenyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium,
[5- (η⁵-fluorenyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorozirconium.

The naming of the above-mentioned compounds according to the invention is intended based on the compound [4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7- tetrahydroindenyl)] dichlorozirconium:

The following compounds are named according to the IUPAC nomenclature.
[η⁵-9- (η⁵-cyclopentadienyl) tricyclo [6.1.1.0 ^2.6 ] deca-2,5-dienyl] dichlorotitanium,
[η⁵-9- (η⁵-cyclopentadienyl) tricyclo [6.1.1.0 ^2.6 ] deca-2,5-dienyl] dichlorozirconium,
[η⁵-7-methyl-9- (η⁵-cyclopentadienyl) tricyclo [6.1.1.0 ^2.6 ] deca-2,5-dienyl] dichlorotitanium,
[η⁵-7-methyl-9- (η⁵-cyclopentadienyl) tricyclo [6.1.1.0 ^2.6 ] deca-2,5-dienyl] dichlorozirconium,
[η⁵-9-methyl-9- (η⁵-cyclopentadienyl) tricyclo [6.1.1.0 ^2.6 ] deca-2,5-dienyl) dichlorotitanium,
[η⁵-9-methyl-9- (η⁵-cyclopentadienyl) tricyclo [6.1.1.0 ^2.6 ] deca-2,5-dienyl] dichlorozirconium,
[η⁵-10- (η⁵-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ] deca-2,5-dienyl] dichlorotitanium,
[η⁵-10- (η⁵-cyclopentadienyl) tricyclo [5.2.1.0 ^2,6 ) deca-2,5-dienyl] dichlorozirconium,
[η⁵-10-methyl-10- (η⁵-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ) deca-2,5-dienyl] dichlorotitanium,
[η⁵-10-methyl-10- (η⁵-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ] deca-2,5-dienyl] dichlorozirconium,
[η⁵-9- (η⁵-cyclopentadienyl) tricyclo [5.2.2.0 ^2,6 ] undeca-2,5-dienyl] dichlorotitanium,
[η⁵-9- (η⁵-cyclopentadienyl) tricyclo [5.2.2.0 ^2,6 ) undeca-2,5-dienyl] dichlorozirconium,
[η⁵-9-methy-9- (η⁵-cyclopentadienyl) tricyclo [5.2.2.0 ^2.6 ] undeca-2,5-dienyl) dichlorotitanium,
[η⁵-9-methy-9- (η⁵-cyclopentadienyl) tricyclo [5.2.2.0 ^2.6 ) undeca-2,5-dienyl] dichlorozirconium,
[η⁵-10- (η⁵-3′-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ) deca-2,5-dienyl] dichlorotitanium,
[η⁵-10- (η⁵-3′-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ) deca-2,5-dienyl] dichlorozirconium,
[η⁵-10-methyl-10- (η⁵-3′-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ] deca-2,5-dienyl] dichlorotitanium,
[η⁵-10-methyl-10- (η⁵-3′-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ] deca-2,5-dienyl] dichlorozirconium,
[η⁵-4-methyl-10- (η⁵-3′-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2.8 ] deca-2,5-dienyl] dichlorotitanium,
[η⁵-4-methyl-10- (η⁵-3′-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ] deca-2,5-dienyl] dichlorozirconium,
[η⁵-4,10-dimethyl-10- (η⁵-3′-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ] deca-2,5-dienyl] dichlorotitanium,
[η⁵-4,10-dimethyl-10- (η⁵-3′-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ] deca-2,5-dienyl] dichlorozirconium,
[η⁵-5-methyl-10- (η⁵-3'-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2,6 -e] deca-2,5-dienyl]. dichlorotitan,
[η⁵-5-methyl-10- (η⁵-3′-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ] deca-2,5-dienyl] dichlorozirconium,
[η⁵-5,10-dimethyl-10- (η⁵-3′-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ] deca-2,5-dienyl] dichlorotitanium,
[η⁵-5,10-dimethyl-10- (η⁵-3'-methyl-cyclopentadienyl) tricyclo [5.2.1.0 ^2.6 ] deca-2,5-dienyl] dichlorozirconium.

The production of the metallocenes according to the invention is intended to be carried out by the following Reaction scheme illustrated using metallocenes of formula I. in which m = O. M⁴ is a metal from main group Ia, IIa or IIIa.

The bisful veins of formula II are made from diketones (Chem. Ber. 114, 1226 (1181 ibid 109, 3426 (1976); ibid 107, 2453 (1974)] and ketoaldehyden prepared by methods known from the literature (J.Org. Chem. 57 (1992) 2504; ibid, 49 (1984) 1849; Chimia, 46 (1992) 377).  

The conversion of the bisfulven II to the ligand system of structure III takes place by reaction with a metal-organic compound (such as Methyl lithium, butyllithium, phenyllithium) or Grignard reagents.

The salts of structure III can be added directly to the corresponding dianion Compounds of structure V by deprotonation with, for example Butyllithium are implemented.

The hydrolysis of compound III leads to the formation of the biscyclopentadiene Compound IV, which is obtained as a mixture of constitutional isomers and can be cleaned chromatographically. By double deprotonation of IV with, for example, butyllithium becomes the dianion compound of structure V educated.

The conversion to the bridged metallocenes of the formula VI and the Isolation of the desired complexes is known in principle. For this, the Dianion of structure V in an inert solvent with the corresponding Metal halide such as B. implemented zirconium tetrachloride.

The metallocenes of structure VI can also be obtained directly from the bisfulvenes Structure II can be synthesized without isolation of the intermediates.

Suitable solvents are aliphatic or aromatic solvents, such as for example hexane or toluene, ethereal solvents such as Tetrahydrofuran or diethyl ether or halogenated hydrocarbons, such as for example methylene chloride or halogenated aromatic Hydrocarbons such as o-dichlorobenzene.

The biscyclopentadienyl compounds of the formula IV, in which at least one of the radicals R³ to Re or R⁷ to R⁹ is a hydrogen atom, by Methods known from the literature for the fulvene of structure IVa implemented  become. This is illustrated by the reaction scheme below become.

By reacting the Fulva IVa with organometallic compounds Formula R¹⁹M⁵ (where R¹⁹ = R¹³, the same or different; M⁵ = M⁴, the same or different) leads to the formation of the monoanion compound IIIa. The usage of two equivalent R¹⁹M⁴ leads directly to the formation of the dianion compound Va

The salts of structure IIIa can be added directly to the corresponding dianion Compounds of structure Va by deprotonation with, for example Butyllithium are implemented. Implementation to the bridged Metallocenes of the formula I take place in accordance with the reaction from V to VI.

Another way of representing the compounds of the invention consists in the implementation of mono- or polycyclic ring systems which are fused to a cyclopentadienyl group, and this mono- or polycyclic ring systems carry functional groups that act as leaving groups can serve in substitution reactions (such as bromide or Tosylate) with, for example, cyclopentadienyl or indyl lithium compounds.

The present invention also relates to a method for producing a Olefin polymer by polymerization or copolymerization of at least one Olefins in the presence of a catalyst which is at least one stereorigid Metallocene compound as a transition metal compound and at least one Contains cocatalyst, the stereorigid metallocene compound as ligand at least two substituted or unsubstituted cyclopentadienyl groups has one another via a mono- or polycyclic ring system  are connected, characterized in that at least one cyclopenta dienyl group is fused to the mono- or polycyclic ring system.

Preference is given to olefins of the formula Ra-CH = CH-Rb, in which R ^b and R ^{b are} identical or different and denote a hydrogen atom or a hydrocarbon radical having 1 to 20 C atoms, in particular 1 to 10 C atoms, or Ra and R ^b can form one or more rings with the atoms connecting them, polymerized or copolymerized. Examples of such olefins are ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene. In particular, propylene or ethylene are polymerized.

The polymerization or copolymerization is preferred at one temperature from -60 to 200 ° C, particularly preferably 30 to 80 ° C, performed. The pressure is preferably 0.5 to 100 bar, in particular 5 to 64 bar. The Polymerization can be carried out continuously or batchwise, in one or more stages Solution, in suspension or in the gas phase.

The metallocenes according to the invention are highly active catalyst components for olefin polymerization. Depending on the substitution pattern of the ligands the metallocenes according to the invention are obtained as a mixture of isomers. The Metallocenes are preferably used isomerically pure. The use of the Racemats is sufficient in most cases.

However, the pure enantiomer can also be used in the (+) - or (-) - Shape. An optically active polymer can be produced with the pure enantiomers. However, the configuration isomeric forms of Metallocenes, since the polymerization-active center (the metal atom) in these Compounds a polymer with different properties. For certain Applications such as soft molded articles can do this be desirable.  

Mixtures of two or more metallocenes can also be used become. This allows polyolefins with wider or multimodal Molecular weight distribution can be obtained.

A metallocene and a are preferably used in the process according to the invention Cocatalyst used. An aluminoxane is preferred as the cocatalyst used, which is preferably the formula VIIa for the linear type and / or has the formula VIIb for the cyclic type

wherein in the formulas VIIa and VIIb, the radicals R²⁰ are the same or different and a C₁-C₆ alkyl group, a C₆-C₁₈ aryl group, benzyl or hydrogen mean, and p is an integer from 2 to 50, preferably 10 to 35.

The radicals R²⁰ are preferably the same and are methyl, isobutyl, phenyl or Benzyl, particularly preferably methyl.

If the radicals R²⁰ are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, with hydrogen or isobutyl being preferred 0.01-40% (number of residues R²⁰) are included.

The aluminoxane can be made in various ways by known methods getting produced. For example, one of the methods is that a  Aluminum hydrocarbon compound and / or a hydrido aluminum carbon hydrogen compound with water (gaseous, solid, liquid or bound. for example as water of crystallization) in an inert solvent (such as for example toluene) is implemented. To produce an aluminoxane with various radicals R²⁰ are, for example, according to the desired Composition two different aluminum trialkyls reacted with water.

Regardless of the type of manufacture, all aluminoxane solutions are one changing content of unreacted aluminum starting compound, which in free form or as an adduct, together.

It is possible to use the metallocene in the polymerization reaction with a cocatalyst, in particular to preactivate aluminoxane. Thereby the polymerization activity is significantly increased and the grain morphology improved. The preactivation of the transition metal compound is in solution performed. The metallocene is preferably in a solution of Aluminoxane dissolved in an inert hydrocarbon. As an inert Hydrocarbon is an aliphatic or aromatic Hydrocarbon. Toluene is preferably used.

The concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total amount of solution. The metallocene can be used in the same concentration, but it is preferably used in an amount of 10 ^-4 -1 mol per mol of aluminoxane. The preactivation is 5 minutes to 60 hours, preferably 5 to 60 minutes. One works at a temperature of -78 to 100 ° C, preferably 0 to 70 ° C.

A prepolymerization can be carried out using the metallocene. For Prepolymerization is preferably the (or one of) in the polymerization olefin (s) used.  

The metallocene can also be applied to a support. Suitable Carrier materials are, for example, silica gels, aluminum oxides, solid Aluminoxan or other inorganic carrier materials such as Magnesium chloride. A suitable carrier material is also a polyolefin powder in finely divided form.

Preferably the cocatalyst, e.g. B. aluminoxane, on a support such as for example silica gels, aluminum oxides, solid aluminoxane, others inorganic carrier materials or a polyolefin powder in finely divided Mold applied and then implemented with the metallocene.

Oxides which can be used as inorganic carriers are: flame pyrolytic by burning element halides in one Oxyhydrogen flame were generated, or as silica gels in certain grain sizes Distributions and grain shapes can be produced.

The preparation of the supported cocatalyst can, for example, as in EP 92 107 331.8 described in the following manner in a stainless steel Explosion-proof design with a pumping system from Pressure level 60 bar, with inert gas supply, temperature control through jacket cooling and the second in the cooling circuit via a heat exchanger on the pump system respectively. The pump system sucks the reactor contents through a connection in the Reactor bottom with a pump and pushes it into a mixer and through a riser pipe back into the reactor via a heat exchanger. The mixer is designed so that there is a narrow pipe cross-section in the inlet, where there is an increased flow velocity, and in its Turbulence zone axially and against the direction of flow a thin feed line is guided, through which - clocked - a defined amount of water each 40 bar argon can be fed. The reaction is checked via a sampler on the pump circuit.

In principle, however, other reactors are also suitable.  

In the reactor described above with 16 dm³ volume 5 dm³ Decane submitted under inert conditions. 0.5 dm³ (= 5.2 mol) trimethylalumini to be added at 25 ° C. Then 250 g of silica gel SD 3216-30 (Grace AG), which previously dried at 120 ° C in an argon fluid bed were metered into the reactor through a solids funnel and with the aid of Stirrer and the pumping system distributed homogeneously. A total of 76.5 g of water are in portions of 0.1 cm³ for 3.25 h every 15 s placed in the reactor. The pressure coming from the argon and the evolving gases, is kept constant at 10 bar by a pressure control valve. After all the water has been introduced, the pumping system switched off and stirring continued at 25 ° C for 5 h.

The supported cocatalyst produced in this way is called a 10% Suspension used in n-decane. The aluminum content is 1.06 mmol Al per cm³ suspension. The isolated solid contains 31% by weight of aluminum Suspension medium contains 0.1% by weight of aluminum.

Further possibilities for the production of a supported cocatalyst are in EP 92 107331.8.

Thereafter, the metallocene according to the invention is on the supported Cocatalyst applied by the dissolved metallocene with the supported Co-catalyst is stirred. The solvent is removed and by a Replaces hydrocarbon in which both cocatalyst and that Metallocene are insoluble.

The reaction to the supported catalyst system takes place at one temperature from -20 ° to + 120 ° C, preferably 0-100 ° C, particularly preferably at 150 to 40 ° C. The metallocene is supported with the cocatalyst in the manner implemented that the cocatalyst as a suspension with 1 to 40 wt .-%, preferably with 5 to 20 wt .-% in an aliphatic, inert Suspension agents such as n-decane, hexane, heptane, diesel oil with a solution of the  Metallocens in an inert solvent such as toluene, hexane, heptane, Dichloromethane or with the finely ground solid of the metallocene is brought together. Conversely, a solution of the metallocene be reacted with the solid of the cocatalyst.

The implementation takes place by intensive mixing, for example by Stirring at a molar Al / M¹ ratio of 100/1 to 10000/1, preferably from 100/1 to 3000/1 and a reaction time from 5 to 120 minutes, preferably 10 to 60 minutes, particularly preferably 10 to 30 minutes under inert conditions.

In the course of the reaction time for the production of the supported catalyst system occur in particular when using the metallocenes according to the invention with absorption maxima in the visible range changes in the color of the Reaction mixture on whose course the progress of the reaction lets track.

After the reaction time has elapsed, the supernatant solution is separated off, for example by filtration or decanting. The remaining solid is 1 to 5 times with an inert suspending agent such as toluene, n-decane, Hexane, diesel oil, dichloromethane to remove soluble components in the formed catalyst, especially for the removal of unreacted and with soluble metallocene, washed.

The supported catalyst system thus produced can be dried in vacuo resuspended as a powder or solvent and as Suspension in one of the aforementioned inert suspending agents in the Polymerization system be metered.  

According to the invention, instead of or in addition to an aluminoxane, compounds of the formulas R²¹ _x NH _4-x BR²²₄, R²¹ _x PH _4-x BR²²₄, R²¹₃CBR²²₄, BR²²₃ can be used as suitable cocatalysts. In these formulas, x is a number from 1 to 4, preferably 3, the radicals R²¹ are identical or different, preferably the same, and mean C₁-C₁₀-alkyl, C₆-C₁₈-aryl or two radicals R²¹ form together with the atom connecting them a ring, and the radicals R²² are the same or different, preferably the same, and are C₆-C₁₈ aryl, which may be substituted by alkyl, haloalkyl or fluorine.

In particular, R²¹ is ethyl, propyl, butyl or phenyl and R²² is phenyl, Pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (see EP 277 003, EP 277 004 and EP 426 638).

When using the above-mentioned cocatalysts, the actual one exists (Active) polymerization catalyst from the reaction product of metallocene and one of the compounds mentioned. Therefore, this is first Reaction product preferably outside of the polymerization reactor in one separate step using a suitable solvent.

In principle, any compound is suitable as a cocatalyst according to the invention convert the neutral metallocene into a cation due to its Lewis acidity and can stabilize it ("unstable coordination") Cocatalyst or the anion formed from it no further reactions with enter the metallocene cation formed (cf. EP 427 697).

Cleaning is required to remove catalyst poisons present in the olefin with an aluminum alkyl, for example trimethyl aluminum or Triethyl aluminum advantageous. This cleaning can be done both in Polymerization system itself, or the olefin is added in before brought the polymerization system into contact with the Al compound and then separated again.  

As a molecular weight regulator and / or to increase the activity, if required, hydrogen added. The total pressure in Polymerization system is preferably 0.5 to 100 bar. Especially polymerization in the technically particularly interesting is preferred Pressure range from 5 to 64 bar.

The metallocene is used in a concentration, based on the transition metal, of preferably 10 ^-3 to 10 ^-8 , preferably 10 ^-4 to 10 ^-7 mol of transition metal per dm³ of solvent or per dm³ of reactor volume. The aluminoxane is used in a concentration of 10 ^-5 to 10 ^-1 mol, preferably 10 ^-4 to 10 ^-2 mol per dm³ solvent or per dm³ reactor volume. The other cocatalysts mentioned are used in approximately equimolar amounts to the metallocene. In principle, however, higher concentrations are also possible.

If the polymerization as a suspension or solution polymerization is carried out, becomes a customary for the Ziegler low pressure process inert solvent used. For example, one works in an aliphatic or cycloaliphatic hydrocarbon; as such, for example Propane, butane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane, called. A gasoline or hydrogenated diesel oil fraction can also be used become. Toluene can also be used. Is preferred in the liquid monomer polymerized.

If inert solvents are used, the monomers become gaseous or metered in liquid.

The duration of the polymerization is arbitrary, because according to the invention catalyst system using only a small time-dependent drop in the Shows polymerization activity.  

Before adding the catalyst, especially the supported one Catalyst system (from a metallocene according to the invention and a supported cocatalyst or from an inventive Metallocene and an organoaluminum compound on one Polyolefin powder in finely divided form), can also be another Aluminum alkyl compound such as trimethyl aluminum, Triethyl aluminum, triisobutyl aluminum, trioctyl aluminum or Isoprenyl aluminum for inerting the polymerization system (e.g. to separate existing catalyst poisons in the olefin) into the reactor become. This is in a concentration of 100 to 0.01 mmol Al per kg Reactor contents added to the polymerization system. To be favoured Triisobutyl aluminum and triethyl aluminum in a concentration of 10 to 0.1 mmol Al per kg reactor content. This allows the synthesis of a supported catalyst system, the molar Al / M¹ ratio chosen small become.

Basically, however, the use of other substances for the catalysis of Polymerization reaction not required, i. that is, the systems of the invention can be used as sole catalysts for olefin polymerization become.

The metallocenes according to the invention are suitable for the production of polymers with reduced crystallinity, increased impact strength, increased transparency, high fluidity at processing temperature, low molecular weight and reduced melting point.

The main application of such polymers is plasticizer and Lubricant formulations, hot melt adhesive applications, coatings, Seals, insulation, pouring compounds or sound insulation materials.

The following examples serve to explain the invention in more detail.  

General information: Production and handling of organometallic Connections were made in the absence of air and moisture under argon Protection (Schlenk technology). All required solvents were checked before use by boiling over a suitable desiccant for several hours and followed by absolute distillation under argon.

The production of the diketones and Ketoaldehyde was carried out according to methods known from the literature. Cyclopentadiene and Methylcyclopentadiene was obtained by cracking the dimers and at Stored at -35 ° C.

The Al / CH₃ ratio in the aluminoxane was determined by Decompose the sample with H₂SO₄ and determine the volume of the resulting hydrolysis gases under normal conditions as well as complexometric titration of the aluminum in the then dissolved sample Schwarzenbach.

The compounds were determined by 1 H-NMR, 13 C-NMR and IR spectroscopy characterized.

A. Presentation of the bisful vein II example 1 Synthesis of 2,5-bis (2,4-cyclopentadien-1-ylidene) hexane

According to a modified reaction procedure [a], 11.0 g (96.3 mmol) of 2.5 hexanedione and 12.7 g (193 mmol) of freshly cracked cyclopentadiene are dissolved in 60 ml of methanol, cooled to 0 ° C. and at 8.60 g (121 mmol) of pyrrolidine were added. After stirring at 0 ° C. for 90 min, the reaction solution is hydrolyzed with 5 ml of glacial acetic acid and 50 ml of water, extracted twice with 70 ml of diethyl ether each time and the combined organic phases are washed with saturated sodium chloride solution. It is dried over magnesium sulfate and, after removing the solvent in vacuo, 18.0 g (89%) of the difulven is obtained as an orange-red oily residue.
[a] = MS Erickson, JM Cronan, JG Garcia, ML McLaughlin, J. Org. Chem. 57 (1992) 2504-2508.
KJ Stone, RD Little, J. Org. Chem. 49 (1984) 1849-1853.

B. Synthesis of the Bridged Biscyclopentad ienyl Anions, V Example 2 Synthesis of 4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7- tetrahydroindenyl)] dilithium

To a solution of 10.0 g (47.5 mmol) of 2,5-bis (2,4-cyclopentadien-1- ylidene) hexane in 150 ml of diethyl ether, 62.4 ml (99.8 mmol) of one ethereal 1.60 M methyl lithium solution at 0 ° C with vigorous stirring slowly added dropwise. The mixture is allowed to warm to room temperature and is obtained 24 hours stirring a beige precipitate. After frits and repeated washing with pentane gives 13.2 g (89%) of the di  Lithium salt as a beige powder, which with a molar equivalent of diethyl ether is coordinated.

Example 3 Synthesis of 4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-phenyl- (η⁵-4,5,6,7- tetrahydroindenyl) dilithium

An ethereal phenyllithium solution (83.4 ml, 74.3 mol, 0.89 M Diethyl ether solution) at 0 ° C to a solution of 7.10 g (33.7 mmol) Difulven (Example 1) was added dropwise in 100 ml of diethyl ether. It starts after approx To precipitate a beige precipitate for 5 minutes. Allow to room temperature heat and stir for a further 12 hours at 25 ° C. After fritting, repeated washing with pentane and drying in an oil pump vacuum the dilithium salt as a beige, very hydrolysis-sensitive powder in 82% Yield (10.3 g).

Example 4 Synthesis of 4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7- tetrahydroindenyl) dilithium

A solution of 15.0 g (71.3 mmol) Difulven (Example 1), dissolved in 100 ml Diethyl ether is cooled to -30 ° C and slowly with vigorous stirring 94 ml (150 mmol) of a 1.60 M solution of n-butyllithium in hexane were added. A lemon-yellow precipitate forms. Allow to room temperature heat and stir to complete the reaction 24 hours. Then the precipitate is filtered off, several times with Washed pentane and dried in an oil pump vacuum. 23.0 g are obtained (91%) of the dilithium salt as a beige, very hydrolysis-sensitive powder which is coordinated with a molar equivalent of diethyl ether.  

C. Synthesis of the Bridged Cyclopentadienes IV Example 5 Synthesis of 7-cyclopentadienyl-4,4,7-trimethyl-4,5,6,7-tetrahydro-1H-indene

To a suspension of 7.35 g (23.5 mmol) of the dilithium salt (Example 2) in 50 ml of diethyl ether is added dropwise at 0 ° C to 50 ml of degassed water added. The beige suspension disappears immediately and you get one clear, orange diethyl ether phase. Then you separate the phases in the Separating funnel, the aqueous phase is extracted twice with 25 ml each Diethyl ether and washes the combined organic phases with 20 ml of one saturated sodium chloride solution. After drying over magnesium sulfate and removing the solvent in vacuo 5.1 g (96%) of Isolate the hydrolyzed product as an orange-red oil.

Example 6 Preparation of 7-cyclopentadienyl-4,7-dimethyl-7-phenyl-4,5,6,7-tetrahydro- 1H-inden

A yellow suspension of 3.64 g (9.72 mmol) of the cooled to 0 ° C. Dilithium salt (Example 3) in 50 ml of diethyl ether is added by slow addition hydrolyzed by 20 ml of degassed water. The suspension disappears and you get an orange, clear reaction solution. After going twice extracted with 20 ml of diethyl ether, the combined organic Phases washed several times with saturated aqueous sodium chloride solution and dried over magnesium sulfate. By subsequently removing the Solvent in vacuum, the hydrolyzed product can be used as an orange oil Isolate in 94% yield (2.62 g).  

Example 7 Preparation of 7-cyclopentadienyl-4,7-dimethyl-7-butyl-4,5,6,7-tetrahydro-1H- in the

A yellow suspension of 5.00 g (17.33 mmol) of the cooled to 0 ° C. Dilithium salt (Example 4) in 50 ml of diethyl ether is added by slow addition hydrolyzed by 20 ml of degassed water. The suspension disappears and you get an orange, clear reaction solution. After going twice extracted with 20 ml of diethyl ether, the combined organic Phases washed several times with saturated aqueous sodium chloride solution and dried over magnesium sulfate. By subsequently removing the The hydrolyzed product can be used as a solvent in a vacuum Isolate orange oil in 96% yield (4.59 g).

D. Synthesis of the bridged cyclopentadiene-fulvene ligands IVa by subsequent introduction of substituents Example 8 Synthesis of 7- (3-isopropylidene-cyclopenta-1,4-dienyl) -4,4,7-trimethyl-4,5,6,7- tetrahydro-1H-indene

7.70 g (34.0 mmol) of the cyclopentadienyltetrahydroindenyl (Example 5) dissolved in 70 ml of methanol and cooled to 0 ° C. Then the orange-red reaction solution in succession with 2.96 g (51.0 mmol) of acetone and 4.83 g (68.0 mmol) of pyrrolidine were added. After stirring for 5 hours at 0 ° C to complete the reaction for 2 hours at room temperature Stir before stopping the reaction by adding 4 ml of glacial acetic acid. The red, clear reaction solution is hydrolyzed with 200 ml of water and the yellow Suspension extracted 3 times with 50 ml of diethyl ether. After repeated Wash the combined organic phases with saturated aqueous  Sodium chloride solution and drying over magnesium sulfate you get that Fulven as an orange-red waxy residue in a yield of 88% (8.00 g).

E. Synthesis of Dianion Complexes Va Example 9 Synthesis of 4- [3-tBu- (η⁵-cyclopentadienyl)] - 4,7,7-trimethyl- (η⁵- tetrahydroindenyl) dilithium

In the reaction of the tetrahydroindenylfulven (Example 8) with an ethereal Methyl lithium solution (2 equivalents) at 0 ° C is obtained after just a few Seconds of intense yellow precipitation. They are left for another 12 hours Room temperature stirring and obtained after frying, washing with pentane and Dry the dilithium salt in an oil pump vacuum without further ado Characterization is directly implemented further.

F. Synthesis of Metallocenes of Formula I. Example 10 Synthesis of 4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7- tetrahydroindenyl)] dichlorozirconium

To a suspension of 9.58 g (30.7 mmol) cooled to -78 ° C. Dilithium compound (Example 2) in 200 ml of toluene are 7.50 g (32.2 mmol) Zirconium tetrachloride was added in portions within 10 minutes. To The precipitate is fritted off and stirred for 50 hours at room temperature the orange-colored filtrate was evaporated to dryness in vacuo. After repeated Washing with pentane gives 4.38 g of the zirconocene dichloride as orange-yellow powder in a raw yield of 37%.  

For cleaning, the orange-yellow powder is washed in with pentane for several days a circulation frit extracted, after removing the solvent in Oil pump vacuum 1.70 g (14%) of the zirconocene dichloride as a yellow powder received, m.p .: 223 ° C (dec., DSC).

Example 11 Synthesis of 4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7- tetrahydroindenyl) dichlorotitan

A suspension of 5.46 g (17.5 mmol) of the dilithium etherate (Example 2) in 200 ml of toluene is cooled to -78 ° C and 3.3 g (17.5 mmol) Titanium tetrachloride added. The reaction solution immediately turns dark red. The mixture is stirred at room temperature for 30 hours and insoluble is fritted and evaporates the dark red toluene phase to dryness in an oil pump vacuum. To repeated washing with pentane gives 1.85 g of the titanocene dichloride as a brown beige powder. The crude product is then mixed with pentane Circulation frit extracted for several days, taking the titanocene dichloride after removal of the solvent as a brown solid in 13% yield (780 mg); Mp .: 259 ° C (dec., DSD).

Example 12 Synthesis of [4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7- tetrahydroindenyl)] dichlorozirconium from 2,5-bis (2,4-cyclopentadiene-1- ylidene) hexane

To a solution of 10.0 g (47-5 mmol) 2,5-bis (2,4-cyclopentadien-1- ylidene) hexane (Example 1) in 150 ml of toluene, 62.4 ml (99.8 mmol) are one ethereal 1.60 M methyl lithium solution at 0 ° C with vigorous stirring slowly admitted. After the addition has ended, the mixture is left to stand for 24 hours Stir room temperature, then cool to -30 ° C and give 9.32 g  (40 mmol) zirconium tetrachloride. After stirring for 30 hours Room temperature is filtered off from the LiCl and the filtrate in vacuo Dry evaporated. After washing several times with pentane, 4.02 g is obtained (26%) of the zirconium dichloride.

Example 13 Synthesis of both diastereomers of 4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7- phenyl (η⁵-4,5,6,7-tetrahydroindenyl) dichlorozirconium

A cooled to -78 ° C suspension of 4.37 g (11.7 mmol) of Dilithium salt (Example 3) in 200 ml of toluene is mixed with 2.72 g (11.7 mmol) Zirconium tetrachloride added in portions. Allow to room temperature warm and stir in the orange suspension for a further 20 hours 20 ° C. After filtering off the solvent from the filtrate in Oil pump vacuum removed and the orange-red, oily residue by intensive Stir powdered in 20 ml of pentane. Then you get after removal of the pentane in vacuo 2.64 g (50%) of the zirconocene dichloride as yellow-orange powder. Using the 1 H-NMR spectrum of the crude product, this can be done Estimate the diastereomer ratio of 8: 1.

Example 14 Synthesis of both diastereomers of 4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7- butyl- (η⁵-4,5,6,7-tetrahydroindenyl) dichlorozirconium

A suspension of 7.80 g (22.0 mmol) of the dilithium salt (Example 4) in 200 ml of toluene is cooled to -78 ° C and with 5.10 g (22.0 mmol) Zirconium tetrachloride added in portions. Allow to room temperature warm and stir the yellow-orange suspension for a further 48 hours. After that fries from the insoluble and removes the solvent in the  Oil pump vacuum. The red-orange oil is mixed with intensive stirring Pentane pulverized, the zirconocene dichloride in a crude yield of 30% (2.72 g).

The cleaning is carried out by extracting the raw product with pentane for several days in a circulation frit. The 1 H-NMR spectrum of the fine yellow precipitate has two sets of signals in a 15: 1 ratio. From the yellow siphoned off filtrate you can store a few crystals after storage at -30 ° C isolate. These crystals of diastereomerically pure zirconocene dichloride (pR, 4R, 7R-4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7- tetrahydroindenyl) dichlorozirconium) enable individual signal sets in the ¹H- Assign NMR. The crystals correspond to those from the pentane solution are crystallized, the diastereomer that is least formed. Crystals can also be made from the 1.35 g (14%) of the yellow, fine powder isolate by putting about 100 mg of the powder in a little methylene chloride dissolves and by diffusion of pentane into this solution very slowly can crystallize out. The main product is the other Diastereomer.

Example 15 Synthesis of 4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7-butyl- (η⁵-4,5,6,7- tetrahydroindenyl) dichlorohafnium

To a suspension of 2.00 g (5.64 mmol) cooled to -78 ° C Dilithium salt (Example 4) in 150 ml of toluene are 1.81 g (5.65 mmol) Hafnium tetrachloride added. The orange suspension is left on Warm to room temperature and stir to complete the reaction For 2 days. Then you fry off the insoluble and narrow it orange-red filtrate at the oil pump to dryness. The orange-red residue 30 ml of pentane are added and the mixture is stirred vigorously overnight. After removal of the solvent in vacuo gives the hafnocene dichloride in one Crude product yield of 700 mg (24%) as a beige powder. 1 H NMR  Only one diastereomer can be found in the spectrum of the crude product.

Example 16 Synthesis of both diastereomers of 4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7- buyl- (η⁵-4,5,6,7-tetrahydrindenyl) dichlorotitanium

5.95 g (16.8 mmol) of the dilithium salt (Example 4) is suspended in 120 ml Toluene, the beige suspension changes color when 3.18 g is added (16.8 mmol) titanium tetrachloride immediately dark red at -78 ° C. The suspension will stirred for a further 36 hours at room temperature before removing the precipitate separated and the dark red filtrate to dryness in an oil pump vacuum constricts. Both diastereomers of titanocene dichloride are obtained as brown-red powder in a crude yield of 1.54 g (24%). 1 H NMR The spectrum of the crude product can be seen in the signals of both diastereomers Determine the ratio 8: 1. Extract the brown-red powder with pentane several days in a circulation frit, a brown one falls from the filtrate Precipitation from. It can be seen in the 1 H-NMR spectrum that the Pentane solution contains both isomers in a ratio of 1: 1 (150 mg, 2.3%), while the brown powder (720 mg, 11%) is approximate is diastereomal.

Example 17 Synthesis of {4- [3′-tBu- (η⁵-cyclopentadienyl)] - 4,7,7-trimethyl- (η⁵ tetrahydroindenyl)} dichlorozirconium

A suspension of 2.84 g (7.71 mmol) of the dilithium salt (Example 9) is in 150 ml of toluene suspended and cooled to -78 ° C. After one added in portions 1.79 g (7.71 mmol) of zirconium tetrachloride, can the mixture is warmed to room temperature and stirred for a further 48 hours. Subsequently if one separates from the insoluble, the orange toluene phase in the  Oil pump vacuum and pulverizes the orange-red oil by vigorous stirring in pentane. The regioisomeric zirconocene dichlorides are obtained as orange-yellow powder in a raw yield of 23% (787 mg). 1 H NMR The spectrum of the crude product shows the signals of both diastereomers in the Ratio 1: 1. By extracting the orange-yellow powder with pentane in one Circulation frit gives 370 mg (11%) of the zirconocene dichloride in one 1: 1 ratio.

G. Synthesis of Metallocendialkyl Complexes Example 18 Synthesis of 4- (η⁵-cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7- tetrahydroindenyl) zirconium dimethyl

Based on the literature specification [b] to a suspension of 1.03 g (2.66 mmol) of zirconocene dichloride (Example 10) in 50 ml of diethyl ether, 3.30 ml (5.33 mmol, 1.60 M) of an ethereal methyl lithium Solution slowly added dropwise at -78 ° C. The mixture is allowed to warm up slowly to room temperature in the cooling bath and is stirred for a further 5 hours at room temperature. The solvent is removed in vacuo and the colorless residue is extracted with 3 × 50 ml of pentane. The combined pentane solutions are concentrated and stored at -25 ° C. for crystallization. After removing the solvent and drying in an oil pump vacuum, 700 mg (76%) of zirconocene dimethyl are obtained as a colorless, crystalline powder.
[b] E. Samuel, MD Rausch, J.Am.Chem.Soc. 95 (1973) 6263.

H. Examples of polymerization General experimentation

The cocatalyst becomes methylalumoxane in a 500 ml polymerization reactor submitted, dissolved in 250 ml of toluene and cooled to -50 ° C. With a  Gas inlet pipe is passed through the solution and thus propene condensed, with excess propene via a bubble counter can escape. Once the desired amount of liquid propene is present (approx. 30-35 ml), the inlet tube is closed. The desired polymerization temperature is then set. To After tempering, a solution of the catalyst is added in a little toluene to. After an appropriate reaction time, the reaction is terminated brought about by adding 500 ml of hydrochloric acid methanol, the Excess propene escapes by boiling the solution. The The polymers are isolated by separating the toluene phase and extraction the water / methanol phase with diethyl ether. The combined toluene and Diethyl ether phases are then evaporated to dryness in vacuo.

The test results obtained are listed in the table below:
Propene polymerization with ansa-metallocene / methylaluminoxane catalyst systems, the metallocenes being 4- (η⁵-cyclopentadienyl) -4,7, 7-trimethyl- (η⁵- 4,5,6,7-tetrahydroindenyl)] dichloron zirconium (Example 10), 4 - (η⁵- Cyclopentadienyl) -4,7,7-trimethyl- (η⁵-4,5,6,7-tetrahydroindenyl)] dichlorotitanium (Example 11) and 4- (η⁵-cyclopentadienyl) -4,7-dimethyl-7 -phenyl- (η⁵-4,5,6,7-tetrahydroindenyl) dichlorozirconium (Example 13) were used.

A 10.6% toluene methylaluminoxane solution was always used as the cocatalyst. The activities are calculated according to the following equation:
Activity = gPP / (g [M] · t · p)
gPP = amount of polypropylene in g
g [M] = amount of transition metal in the catalyst
t = duration in h
p = pressure in bar

Claims (7)

1. Stereorigid metallocene compound which has at least two substituted or unsubstituted cyclopentadienyl groups as ligands which are connected to one another via a mono- or polycyclic ring system, characterized in that at least one cyclopentadienyl group is fused to the mono- or polycyclic ring system. 2. Stereorigid metallocene compound according to claim 1, characterized in that the compound has the formula I. wherein
M¹ is a metal from group IIIb, IVb, Vb or VIb of the periodic table,
M² is carbon or silicon,
R¹ and R² are the same or different and represent a hydrogen atom, a C₁-C₁ Alkyl alkyl, a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl, a C₆-C₂₅ aryloxy, a C₂-C₁₀ alkenyl, represent a C₇-C₄₀-arylalkyl, a C₇-C₄₀-arylalkenyl, an OH group or a halogen atom, or R¹ and R² together with the atoms connecting them form a ring system,
R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are the same or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl group, which may be halogenated, a C₆-C₂₀ aryl group, a -NR¹⁴₂-, -OSiR¹⁴₃ -, -SiR¹⁴₃- or -PR¹⁴₂ radical, wherein R¹⁴ is a halogen atom, a C₁-C₁₀ alkyl group or a C₆-C₁₀ aryl group, or two or more adjacent radicals R³, R⁴, R⁶, R⁶, R⁷, R⁸ and R⁹ together with the atoms connecting them form a ring system,
R¹⁰ is a hydrogen atom, a C₁-C₂₀ alkyl, a C₁-C₁₀ alkoxy, a C₆-C₂₀ aryl, a C₆-C₂₀ aryloxy, a C₂-C₁₂ alkenyl, a C₇-C₄₀ arylalkyl -, a C₇-C₄₀-alkylaryl, or a C₈-C₄₀-arylalkenyl group, each of which can carry radicals -NR¹⁴₃, SR¹⁴₂-, -OSiR¹⁴₃, wherein R¹⁴ represents a halogen atom, a C₁-C₁₀ alkyl group or a C₆-C₁₀- Aryl group is
R¹¹ where n is an integer from 1 to 8,
X is O, = NR¹⁴, CO, = PR¹⁴, = P (O) R¹⁴, = SO, = SO₂ or -S-, where R¹⁴ is a halogen atom, a C₁-C₁₀ alkyl group or a C₆-C₁₀ aryl group,
R¹⁵ and R¹⁶ are the same or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl, a C₁-C₁₀ fluoroalkyl, a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl, a C₆-C₁₀- Fluoroaryl, a C₆-C₁₀ aryloxy, a C₂-C₁₀ alkenyl, a C₇-C₄₀ arylalkyl, a C₇-C₄₀ alkylaryl, a C₈-C₄₀ arylalkenyl group, or two radicals R¹⁵, two radicals R¹⁶, or R¹⁵ and R¹⁶ each form one or more rings with the atoms connecting them, and M³ is silicon, germanium or tin,
R¹² and R¹³ are the same or different, and a hydrogen atom, a C₁-C₂₀ alkyl, a C₁-C₁₀ alkoxy, a C₆-C₂₀ aryl, a C₆-C₂₀ aryloxy, a C₂-C₁₂ alkenyl -, A C₇-C Ar-arylalkyl, a C₇-C₄₀-alkylaryl, or a C₈-C₄₀-arylalkenyl group, each of the radicals -NR¹⁴₃, -SR¹⁴₂, -OSiR¹⁴₃, wherein R¹⁴ is a halogen atom, a C₁-C₁₀ alkyl group or is a C₆-C₁₀ aryl group, or can carry halogen,
R²³ are identical or different are a hydrogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl, a C₆-C₂₅ aryloxy, a C₂-C₁₀ alkenyl, a C₇-C₄₀ -Arylalkyl-, a C₇-C₄₀-arylalkenyl group or a halogen atom, or one or at radicals R²³ are connected to one or both radicals R¹⁶ and R¹⁸, and m is an integer from 0 to 24, in the event that R¹¹ is CH₂, at least one of the radicals R³, R⁴, R⁶, R⁷ and R⁹ is not hydrogen. 3. Catalyst component containing at least one stereorigid Metallocene compound according to claim 1 or 2, which is supported and / or is prepolymerized. 4. A process for producing an olefin polymer by polymerization or Copolymerization of at least one olefin in the presence of a catalyst, which is at least one stereorigde metallocene compound Contains transition metal compound and at least one cocatalyst, wherein the stereorigid metallocene compound as ligand at least two has substituted or unsubstituted cyclopentadienyl groups, which about a mono- or polycyclic ring system are connected to each other, thereby characterized in that at least one cyclopentadienyl group is attached to the mono-  or polycyclic ring system is fused. 5. The method according to claim 4, characterized in that the stereorigid metallocene compound is a compound of formula I. wherein
M¹ is a metal from group IIIb, IVb, Vb or VIb of the periodic table,
M² is carbon or silicon,
R¹ and R² are the same or different and represent a hydrogen atom, a C₁-C₁ Alkyl alkyl, a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl, a C₆-C₂₅ aryloxy, a C₂-C₁₀ alkenyl, represent a C₇-C₄₀-arylalkyl, a C₇-C₄₀-arylalkenyl, an OH group or a halogen atom, or R¹ and R² together with the atoms connecting them form a ring system, R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are the same or different and represent a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl group, which may be halogenated, a C₆-C₂₀ aryl group, an -NR¹⁴₂-, -OSiR¹⁴₃-, -SiR¹⁴₃- or -PR¹⁴₂ radical , wherein R¹⁴ is a halogen atom, a C₁-C′₀-alkyl group or a C₆-C₁₀-aryl group, or two or more adjacent radicals R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ together with the atoms connecting them a ring system form,
R¹⁰ is a hydrogen atom, a C₁-C₂₀ alkyl, a C₁-C₁₀ alkoxy, a C₆-C₂₀ aryl, a C₆-C₂₀ aryloxy, a C₂-C₁₂ alkenyl, a C₇-C₄₀ arylalkyl -, a C₇-C₄₀-alkylaryl, or a C₈-C₄₀-arylalkenyl group, each of which can carry radicals -NR¹⁴₃, SR¹⁴₂-, -OSiR¹⁴₃, wherein R¹⁴ represents a halogen atom, a C₁-C₁₀ alkyl group or a C₆-C₁₀- Is aryl group, R¹¹ where n is an integer from 1 to 8,
X is O, = NR¹⁴, CO, = PR¹⁴, = P (O) R¹⁴, = SO, = SO₂ or-S-, where R¹⁴ is a halogen atom, a C₁-C₁₀ alkyl group or a C₆-C₁₀ aryl group, R¹⁵ and R¹⁶ are the same or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl, a C₁-C₁₀ fluoroalkyl, a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl, a C₆-C₁₀- Fluoroaryl, a C₆-C₁₀ aryloxy, a C₂-C₁₀ alkenyl, a C₇-C₄₀ arylalkyl, a C₇-C₄₀ alkylaryl, a C₈-C₄₀ arylalkenyl group, or two radicals R¹⁵, two radicals R¹⁶ , or R¹⁵ and R¹⁶ each form one or more rings with the atoms connecting them, and M³ is silicon, germanium or tin,
R¹² and R¹³ are the same or different, and a hydrogen atom, a C₁-C₂₀ alkyl, a C₁-C₁₀ alkoxy, a C₆-C₂₀ aryl, a C₆-C₂₀ aryloxy, a C₂-C₁₂ alkenyl -, A C₇-C Ar-arylalkyl, a C₇-C₄₀-alkylaryl, or a C₈-C₄₀-arylalkenyl group, each of the radicals -NR¹⁴₃, -SR¹⁴₂, -OSiR¹⁴₃, wherein R¹⁴ is a halogen atom, a C₁-C₁₀ alkyl group or is a C₆-C₁₀ aryl group, or can carry halogen,
R²³ are identical or different are a hydrogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy, a C₁-C₁₀ aryl, a C₆-C₂₆ aryloxy, a C₂-C₁₀ alkenyl, a C₇-C₄₀ -Arylalkyl-, a C₇-C₄₀-arylalkenyl group or a halogen atom, or one or both radicals R²³ are connected to one or both radicals R¹⁵ and R¹⁶, and m is an integer from 0 to 24, in the event that R¹¹ is CH₂, at least one of the radicals R³, R⁴, R⁶, R⁷ and R⁹ is not hydrogen. 6. The method according to claim 4 or 5, characterized in that the stereorigid metallocene compound is supported and / or prepolymerized. 7. The method according to one or more of claims 4, 5 and 6, characterized in that the cocatalyst is an aluminoxane.