DE4344708A1 - Multi:nuclear metallocenes with more than one central atom - Google Patents

Abstract

Multinuclear metallocenes of formula (I) are new: M<1> = Gp. IVb, Vb or VIb metal; X = H, 1-10C alkyl or alkoxy, 6-10C aryl or aryloxy, 2-10C alkenyl, 7-40C aralkyl or alkaryl, 8-40C aralkenyl, OH, halo or pseudohalogen; L, L' = pi-ligand or other electron donor; k = 2 if B = M<2>, C; k = 2 or more if B = or ; R<1> = divalent hydrocarbon-contg. gp.; R<2> = H, halo or hydrocarbon-contg. gp.; R<3> = trivalent hydrocarbon-contg. residue; M<2> = Si, Ge or Sn; n = k; m = k - 1. Also claimed is a process for the prepn. of (I) (see below). Also claimed is a catalyst system contg. cpd(s). (I) and cocatalyst(s); the system can be supported and/or prepolymerised. Also claimed is a process for the prodn. of olefin polymers by polymerisation of olefin(s) in the presence of this catalyst system, and moulded prods. contg. such olefin polymers.

Description

The present invention relates to metallocenes that have more than one Contain central atom and very advantageous as catalyst components in the Production of polyolefins, especially those with high stereoregularity, high molecular weight and good grain morphology, can be 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.

Soluble metallocene compounds based on bis (cyclopentadienyl) zircon dialkyl or dihalide in combination with oligomeric aluminoxanes can Polymerize ethylene with good activity and propylene with moderate activity. You get Polyethylene with a narrow molecular weight distribution and medium molecular weight. That on polypropylene produced in this way is atactic and has a very low level Molar mass.

The production of isotactic polypropylene is possible with the help of the Ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride together with an aluminoxane in a suspension polymerization (EP 185 918). The Polymer has a narrow molar mass distribution. The disadvantage of this procedure is that at technically relevant polymerization temperatures only polymers with very low molecular weight can be produced.  

There was also a special pre-activation method of the metallocene with described an aluminoxane, which leads to a considerable increase in Activity of the catalyst system and to a significant improvement in Grain morphology of the polymer leads (EP 30 24 24). The pre-activation increases however, the molar mass is not essential.

Furthermore, catalysts are based on Ethylene bisindenyl hafnium dichloride and ethylene bis (4,5,6,7-tetrahydro-1- known indenyl) hafnium dichloride and methylaluminoxane, with which by Suspension polymerization of higher molecular weight polypropylenes can be produced can (J. Am. Chem. Soc. (1987), 109, 6544). Under technically relevant Polymerization conditions, however, is the grain morphology of those so produced Polymers unsatisfactory and the activity of those used Catalyst systems comparatively low. These systems also exhibit high catalyst costs, so that these systems are inexpensive Polymerization is not possible.

A significant increase in the molecular weight could be achieved by using Metallocenes can be achieved in which those fixed by a bridge aromatic n-ligands in the 2-position (EP 48 58 23) or in 2- and 4-position (EP 53 06 47) bear substituents. These metallocenes with in 2- or 2- and 4-position to the bridge substituted ligands are in this regard already very powerful at 70 ° C polymerization temperature, nevertheless the achievable molar masses at technically relevant polymerization temperatures (e.g. 70 ° C) for some technical applications such as the Production of polymers for tubes and large hollow bodies as well as special fibers still too low.

Metallocenes with two substituted cyclopentadienyl π ligands such as Dimethylsilanediyl (2-methyl-4-t-butyl-1-cyclopentadienyl) ₂ZrCl₂ were also proposed as polymerization catalysts (Angew. Chem. 102 (1990) 339). However, these systems are convincing in terms of achievable  Polymer molecular weights, stereospecificity or polymer melting point in no way, moreover, their polymerization activity is very low and the necessary Separation of the ex-synthesis meso and rac forms - only with the rac Mold is highly isotactic polyolefin - very difficult. Furthermore, the meso form in approximately the same amount as the rac form, which means that approx. half of the chemicals used must be disposed of and only that Half of the product is usable.

EP 544 308 describes catalysts with two different π ligands about isopropylidene (4-methyl-1-cyclopentadienyl) (3-t-butyl-1-indenyl) ZrCl₂- proposed that due to their asymmetry a priori do not have a meso shape and thus circumvent the rac / meso separation problem, the deficits regarding However, polymer properties and catalyst activity could not be solved become.

From work by Ewen et al. (J. Am. Chem. Soc. 110 (1988) 6255) also catalysts with two different π ligands such as Isopropylidene (cyclopentadienyl) (fluorenyl) ZrCl₂ known. These connections however, produce syndiotactic polyolefins. The production of isotactic Polyolefins are therefore not possible.

From EP 528041 binuclear metallocenes are known which can be used for the production low molecular weight syndiotactic polymers.

Another disadvantage when using soluble (homogeneous) metallocene Methylaluminoxane catalyst systems in processes in which the formed Polymer accumulates as a solid, is the formation of strong deposits Reactor walls and stirrers. These deposits are caused by agglomeration of the Polymer particles if the metallocene, or aluminoxane, or both dissolved in the Suspension medium are available. Such coatings in the reactor systems must be removed regularly as these quickly become significant strengths  reach, have high strength and heat exchange to Prevent coolant.

Metallocenes can be supported to avoid reactor coatings. Methods for this are known (EP 92 107 331.8). Due to technical reasons it would be advantageous for the additional process step of the support dispense.

The task was therefore to provide a catalyst system in its presence, especially in the case of technically relevant polymerizations temperatures with high stereoselectivity and high polymerization activity High molecular weight polyolefins can be produced.

Furthermore, the task was to find a catalyst system that without Support avoids the formation of deposits on the reactor walls.

It has been found that this problem can be solved by Metallocene compound that contains more than one central atom and as ligands a substituted or unsubstituted cyclopentadienyl group and one has substituted or unsubstituted indenyl group.

Because of their chemical structure, the inventive Metallocenes do not have a meso form that can be separated in an expensive manner would have to, since only atactic polyolefin can be produced with meso molds. In addition, it is with the proposed metallocene catalyst concept possible by combining a few different π ligands inexpensive to manufacture range of polymerization catalysts for to provide different polymerization and product requirements.

Surprisingly, it was further found that the inventive Metallocenes are used to produce polyolefins with only a small amount extractable portion.  

The present invention thus relates to a multinuclear metallocene compound of formula I.

wherein
M¹ are identical or different and are a metal from group IVb, Vb or VIb of the periodic table,
X are the same or different and are hydrogen, a C₁-C₁₀ alkyl, a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl, a C₆-C₁₀ aryloxy, a C₂-C₁₀ alkenyl, a C₇ Mean -C₄₀-arylalkyl, a C₇-C₄₀-alkylaryl, a C₈-C₄-arylalkenyl, an OH group, a halogen atom or pseudohalogen,
the radicals R¹, R², R³ and R⁴ are the same or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl group which may be halogenated, a C₈-C₄₀-aryl, C₇-C₄₀-arylalkyl, a C₇- C₄₀-alkylaryl, a C₂-C₁₀ alkenyl, C₈-C₄₀ arylalkenyl group, a -NR¹¹₂-, -SR¹¹-, -OSiR¹¹₃-, -SiR¹¹₃- or -PR¹¹₂ radical, wherein R¹¹ is the same or different and one Is C₁- C₁₀ alkyl group or a C₆-C₁₀ aryl group,
R⁵ to R¹⁰ 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-, C₇-C₄₀-arylalkyl-, a C₇-C₄₀-alkylaryl-, a C₂-C₁₀ alkenyl, C₈-C₄₀ arylalkenyl group, an -NR¹¹₂-, -SR¹¹-, -OSiR¹¹₃-, -SiR¹¹₃- or -PR¹¹₂ radical, wherein R¹¹ is the same or different and a C₁-C₁₀ alkyl group or is a C₆-C₁₀ aryl group or two or more adjacent radicals R⁵ and R⁶, or R⁷, R⁸, R⁹ and R¹⁰ together with the atoms connecting them form a ring system,
k is 2 if B

and k is an integer <1 if B

where R¹² are the same or different and represent a double-bonded hydrocarbon-containing bridge,
the radicals R¹³ are the same or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl, a C₁-C₁₀ fluoroalkyl-₁ a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl, a C₆-C₁₀ Fluoroaryl, a C₆-C₁₀ aryloxy, a C₂-C₁₀ alkenyl, a C₇-C₂ alkylaryl, a C₇-C₄₀ alkylaryl, a C₈-C₄₀ arylalkenyl group,
R¹⁴ is a three-membered hydrocarbon radical, and n is k and m is k-1 and
M² is silicon, germanium or tin.

M¹ are the same or different and are preferably a metal from group IVb, for example titanium, zirconium, hafnium.

The radicals X are identical or different and denote a hydrogen atom, a C₁-C₁₀-, preferably C₁-C₄-alkyl group, a C₁-C₁₀-, preferably C₁-C₃ alkoxy group, a C₆-C₁₀-, preferably C₈-aryl group, a C₆-C₁₀-, preferably C₈-C₆ aryloxy group, a C₂-C₁₀-, preferably C₂-C₆- Alkenyl group, a C₇-C₄₀, preferably C₇-C₁₆ arylalkyl group, a C₇-C₄₀-, preferably C₇-C₁₆-alkylaryl group, a C₈-C₄₀-, preferably C₈-C₁₂ arylalkenyl group, or a halogen atom, preferably chlorine.

The radicals R¹ to R¹⁰ are the same or different and mean one Hydrogen atom, a halogen atom, preferably fluorine, chlorine or bromine, a C₁-C₁₀-, preferably C₁-C₆-alkyl group, which can be halogenated, a C₆-C₂₀-, preferably C₆-C₁₆-aryl group, a - NR¹¹₂-, -SR¹¹-, -OSiR¹¹₃-, -SiR¹¹₃- or -PR¹¹₂ radical, where R¹¹ is a C₁-C₁₀-, preferably C₁-C₄- Alkyl group or a C₆-C₂₀, preferably C₆-C₁₀ aryl group can be. Two or more adjacent radicals R⁵ and R⁶ or R⁷, R⁸, R⁹ and R¹⁰ can together with the atoms connecting them an aromatic or Form aliphatic ring system, preferably aromatic or aliphatic Six rings.  

B is

wherein R¹² are the same or different and a double-bonded hydrocarbon-containing bridge, preferably a double-bonded C₁-C₄₀ alkyl, C₁-C₁₀ fluoroalkyl, C₆-C₁₀ aryl, C₆-C₁₀ fluoroaryl, C₇-C₂, alkylaryl, C- Are C₂₀-arylalkyl, C₁-C₁₀ alkoxy, C₆-C₁₀ aryloxy, C₂-C₁₀ alkenyl or C₈-C₂₀ arylalkenyl,
the radicals R¹³ 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 Are fluoroaryl, a C₆-C₁₀ aryloxy, a C₂-C₁₀ alkenyl, a C₇-C₂₀ alkylaryl, a C₇-C₄₀ alkylaryl, a C₈-C₄₀ arylalkenyl group and R¹⁴ is a three-membered hydrocarbon radical, preferably a hydrocarbon radical, particularly preferably a trivalent C₇-C₄₀-alkyl, C₁-C₄₀-alkylaryl, C₆-C₄₀-arylalkyl, C₂-C₄₀-alkenyl or C oder-C₄₀-arylalkenyl group, n is k and m is k Is -1 and M² is silicon, germanium or tin.

If B

k is preferably an integer from 2 to 100,000, particularly preferably 2 to 20, especially 2.

Preferably B is

wherein the radicals R¹² are the same or different and are a divalent C₁-C₁₀, preferably C₁-C₆ alkyl group, which may be linear or branched, in particular 1,2-ethanediyl, 1,3-propanediyl, 1,4-butanediyl, 1,6-hexanediyl, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,6-hexylene, a C₆- C₁₀-, preferably C₆-aryl group, especially 1,4-phenylene, a C₆ -C₁₀- fluoroaryl, preferably C₆-fluoroaryl, a C₇-C₂₀-alkylaryl, preferably C₇-C₁₂-alkylaryl, especially p-xylylene, m-xylylene, o- xylylene, a C₇-C₂₀-arylalkyl, preferably C₇-C₁₂- Arylalkyl group, a C₁-C₁₀ alkoxy, preferably C₁-C₆ alkoxy group, a C₂-C₁₀ alkenyl, preferably C₂-C₆ alkenyl group, a C₈-C₂₀ arylalkenyl, preferably C₈- C₁₈ arylalkenyl group,
the radicals R¹³ are the same or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀, preferably C₁-C₄ alkyl group, especially methyl group, a C₁-C₁₀ fluoroalkyl, preferably CF₃ group, a C₆-C₂₀, preferably C₆ -C₁₀ aryl, a C₆-C₁₀ fluoroaryl, preferably pentafluorophenyl group, a C₁-C₁₀, preferably C₁-C₄ alkoxy group, especially methoxy group, a C₂-C₁₀, preferably C₂-C₄ alkenyl group, a C₇-C₄₀ -, preferably C₇-C₁₀-arylalkyl group, a C₈-C₄₀-, preferably C₈-C₁ ₂-arylalkenyl group, a C₇-C₄₀-, preferably C₇-C₁₂-alkylaryl group and n is k and m is k-1, and
M² is silicon, germanium or tin, preferably silicon or germanium, in particular silicon.

For compounds of the formula I it is particularly preferred that M¹ are the same or different zirconium or hafnium, the radicals X are the same and represent a C₁-C₄ alkyl group, a C₇-C₁₀ alkylaryl group or a halogen atom,
R¹ to R¹⁰ are the same or different and are hydrogen or a C₁-C₁₀ alkyl group, a C₆-C₁₀ aryl group or an SiR¹¹₃ radical in which R¹¹ is a C₁-C₁₀ alkyl group, or two or more adjacent radicals R⁵ and R⁶ or R⁷, R⁸, R⁹ and R¹⁰ together with the atoms connecting them form an aromatic or aliphatic ring system, k is 2,
B

where M² is silicon and
the radicals R¹³ are the same or different and are hydrogen, a C₁-C₄-alkyl group or a C₆-C₁₀-aryl group and R¹² are the same or different and a divalent linear or branched C₁-C₆-alkyl group in particular 1,2-ethylene, 1, 3-propylene, 1,4-butylene or 1,6-hexylene.

Particularly preferred are compounds of the formula I in which M¹ is zirconium, the radicals X are the same and are methyl, benzyl or chlorine, the radicals R¹ to R⁴ are the same or different and are hydrogen, a C₁-C₄- alkyl, a C₆- Aryl group or a SiR¹¹₃ radical, in which R¹¹ is a C₁-C₄ alkyl group,
R⁵ and R⁶ are identical or different and form hydrogen, a C₁-C₄ alkyl group, a SiR¹¹₃ radical or together form an aliphatic or aromatic substituted or unsubstituted 6-ring, R⁷ to R¹⁰ are identical or different and hydrogen, a C₁-C₁₀- Mean alkyl group or C₁-C₁₀ aryl group or adjacent radicals together with the atoms connecting them form an aromatic substituted or unsubstituted six-membered ring,
B

where M² is silicon,
and the radicals R¹³ are the same and represent a C₁-C₄ alkyl group and R¹² represent a divalent C₁-C₆ alkyl group, in particular 1,2-ethylene or 1,6-hexylene.

Preferred compounds of the formula I are those in which the indenyl group in 2-, 2,3-, 2,4-, 3,5-, 2,6-, 2,4,6-, 2,4,5-, 2,4,5,6- or 2,5, 6 position to Bridge is substituted or two or more adjacent radicals R⁷, R⁸, R⁹ and R¹⁰ together with the atoms connecting them form a ring system, or represents a fluorenyl group which is in 2-, 2.7-, 3-, 3.6-, 4-, 4.5-, 1-, 1.8-, 1,3,6,8-, or 2,4,5,7-position is substituted, and the cyclopentadienyl group is substituted in the 2-, 2,3- or 2,3,5-position, the substituents are preferably C₁-C₁₀ alkyl or C₆-C₁₀ aryl radicals.

Compounds are preferred for the production of isotactic polyolefins of formula I used, in which the residues of the indenyl group in 2- and 3- Do not form a ring system in relation to the bridge (R⁵ and R⁶). Particularly preferred are compounds of formula I in which the indenyl group in 2-, 2,4-, 2,6-, 2,4,6-, 2,4,5-, 2,4,5,6- and 2,5,6-position is substituted, the Substituents are preferably C₁-C₁₀ alkyl or C₆-C₁₀ aryl radicals, or two or several adjacent radicals R⁷, R⁸, R⁹ and R¹⁰ together with them connecting atoms form a ring system.

The following nomenclature applies to the place of substitution:

Preferred indenyl groups are:
1-indenyl, 2-alkyl-4-aryl-1-indenyl, 2,4-dialkyl-1-indenyl, 2,4-diaryl-1-indenyl, 2,4,6-trialkyl-1-indenyl, 1- alkyl-α-acenaphth-1-indenyl, 1-alkyl-4,5-benzo-1-indenyl, 2,5-dialkyl-1-indenyl, 2,5,6-trialkyl-1-indenyl, 2,4, 5-trialkyl-1-indenyl, 2-alkyl-1-indenyl, 2-aryl-1-indenyl, 2,6-dialkyl-4-aryl-1-indenyl, 2-alkyl-5-aryl-1-indenyl, 2-alkyl-5,6-diaryl-1-indenyl, 2-alkyl-4,5-diaryl-1-indenyl, 2-alkyl-4,6-diaryl-1-indenyl, fluorenyl, 2,7-dialkyl- fluorenyl, or 4-alkylfluorenyl.

Preferred cyclopentadienyl groups are:
2-alkyl-1-cyclopentadienyl, 2,4-dialkyl-1-cyclopentadienyl, 2,4,5-trialkyl-1-cyclopentadienyl, 2-Si (trialkyl) -1-cyclopentadienyl, 2-Si (trialkyl) -4- alkyl-1-cyclopentadienyl, 2-Si (trialkyl) -4,5-dialkyl-1-cyclopentadienyl, 2-alkyl-4-aryl-1-cyclopentadienyl, 2,5-alkyl-4-aryl-1-cyclopentadienyl, 2 , 4-alkyl-5-aryl-1-cyclopentadienyl, 2-aryl-1-cyclopentadienyl, 2-aryl-4-alkyl-1-cyclopentadienyl, 2-aryl-4,5-alkyl-1-cyclopentadienyl or 2-alkyl -4,5-aryl-1-cyclopentadienyl.

The following examples are intended to explain the compounds described in general formula I in more detail. However, they do not claim to be complete:
1,6- {bis [methylsilyl- (fluorenyl) (cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (indenyl) (cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (fluorenyl) (3-methyl-cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (indenyl) (3-methyl-cyclopentadienyl) zirconium dichloride-id]} hexane,
1,6- {bis [methylsilyl- (fluorenyl) (3-isopropyl-cyclopentadienyl) zirconium di-chloride]} hexane,
1,6- {bis [methylsilyl- (indenyl) (3-isopropyl-cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (2,7-di-tert-butyl-fluorenyl) (cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (2-methyl-indenyl) (cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (4-phenyl-indenyl) (cyclopentadienyl) zirconium dichloride-id]} hexane,
1,6- {bis [methylsilyl- (2-methyl-4-phenylindenyl) (2,3,5-trimethyl-cyclopentadienyl) zirconium clichloride]} hexane,
1,6- {bis [methylsilyl- (fluorenyl) (3-phenyl-cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (indenyl) (3-phenyl-cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (2-methyl-4,5-benzo-indenyl) (cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (2-methyl-4,6-diisopropyl-indenyl) (cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (2-methyl-4- (1-naphthyl-indenyl) (cyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (2-ethyl-4-phenyl-indenyl) (cyclopentadienyl) zirconium mdichloride]} hexane,
1,6- {bis [methylsilyl- (2-methyl-4,5-benzo-indenyl) (2,3,5-trimethvl-cyclope-ntadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (2-methyl-4,6-diisoprapyl-indenyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (2-methyl-4- (1-naphthyl-indenyl) (2,3,5-trimethyl-cyc-lopentadienyl) zirconium dichloride]} hexane,
1,6- {bis [methylsilyl- (2-ethyl-4-phenyl-indenyl) (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride]} hexane,
1,2- {bis [methylsilyl- (fluorenyl) (cyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (indenyl) (cyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (fluorenyl) (3-methyl-cyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (indenyl) (3-methyl-cyclopentadienyl) zirconium dichloride-id]} ethane,
1,2- {bis [methylsilyl- (fluorenyl) (3-isopropyl-cyclopentadienyl) zirconium di-chloride]} ethane,
1,2- {bis [methylsilyl- (indenyl) (3-isopropyl-cyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (2,7-di-tert-butyl-fluorenyl) (cyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (2-methyl-indenyl) (cyclopentadienyl) zirconium dichloride-id]} ethane,
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (cyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (4-phenyl-indenyl) (cyclopentadienyl) zirconium dichloride-id]} ethane,
1,2- {bis [methylsilyl- (2-methyl-4-phenylindenyl) (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (fluorenyl) (3-phenyl-cyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (indenyl) (3-phenylcyclopentadienyl) zirconium dichloride] ethane,
1,2- {bis [methylsilyl- (2-methyl-4,5-benzo-indenyl) (cyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (2-methyl-4,6-diisopropyl-indenyl) (cyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (2-methyl-4- (1-naphthyl-indenyl) (cyclopentadienyl) zirconium dichloride]) ethane,
1,2- {bis [methylsilyl- (2-ethyl-4-phenyl-indenyl) (cyclopentadienyl) zirconium mdichloride]} ethane,
1,2- {bis [methylsilyl- (2-methyl-4,5-benzo-indenyl) (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (2-methyl-4,6-diisopropyl-indenyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride]} ethane,
1,2- {bis [methylsilyl- (2-methyl-4- (1-naphthyl-indenyl) (2,3,5-trimethyl-cyc-lopentadienyl) zirconium dichloride]) ethane,
1,2- {bis [methylsilyl- (2-ethyl-4-phenyl-indenyl) (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride]} ethane,
1,4-disilacyclohexane-1,4-diylidene [(fluorenyl) (cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(indenyl) (cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(fluorenyl) (3-methyl-cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(indenyl) (3-methyl-cyclopentadieny-l) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(fluorenyl) (3-isopropyl-cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(indenyl) (3-isopropyl-cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(2,7-di-tert-butyl-fluorenyl) (cyc-lopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-indenyl) (cyclopentadieny-l) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenyl-indenyl) (cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(4-phenyl-indenyl) (cyclopentadieny-l) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenylindenyl) (2,3,5-t-rimethyl cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(fluorenyl) (3-phenyl-cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(indenyl) (3-phenyl-cyclopentadieny-l) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4,5-benzo-indenyl) (cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4,6-diisopropyl-indenyl) - (cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4- (1-naphthyl-indenyl) (c-yclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(2-ethyl-4-phenyl-indenyl) (cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4,5-benzo-indenyl) (2,3,5 - trimethyl cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane 1,4-diylidene [(2-methyl-4,6-diisopropyl-indenyl) (- 2,3,5-trimethyl cyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4- (1-naphthyl-indenyl) (2-, 3,5-trimethylcyclopentadienyl) zirconium dichloride],
1,4-disilacyclohexane-1,4-diylidene [(2-ethyl-4-phenyl-indenyl) (2,3,5-t-rimethyl cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(fluorenyl) (cyclopen-tadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(indenyl) (cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(fluorenyl) (3-methyl-cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,1-diylidene [(indenyl) (3-methyl-cy-clopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(fluorenyl) (3-isopropyl cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(indenyl) (3-isopropy-l-cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2,7-di-tert-butyl-fluorenyl) - (cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-indenyl) (c-yclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenyl-i-ndenyl) - (cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(4-phenyl-indenyl) (c-vclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenylin-denyl) (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(fluorenyl) (3-phenyl - cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(indenyl) (3-phenyl-c-yclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4,5-benzo-indenyl) - (cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4,6-diisopropyl-indenyl) - (cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4- (1-naphthyl-indenyl) - (cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-ethyl-4-phenyl-in-denyl) - (cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4,5-benzo-indenyl) - (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4,6-diisopropyl-indenyl) - (2,3,5-trimethylcyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4- (1-naphthyl-indenyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride],
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-ethyl-4-phenyl-in-denyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride].

The production of the metallocenes according to the invention is intended to be carried out by the following Reaction scheme are illustrated:

The indene derivatives used are commercially available or can be according to processes known from the literature.

The processes for the preparation of the ligand systems and the implementation of the bridged metallocenes of the formula I is known in principle (EP 92 109 988, EP 0 320 762, EP 0 376 154).

For this purpose, an indene derivative of the formulas A1a and / or A1b with a strong Base such as butyllithium or potassium hydride in an inert Deprotonated solvent and with one equivalent of a reagent Formula A2 to the intermediate of formula A3 or one of its isomers implemented, the double bond in the five-membered ring except between C (2) and C (3) can also be between C (1) and C (2). The intermediate of formula A3 is then with a, with a strong base such as Butyllithium or potassium hydride, deprotonated in an inert solvent Cyclopentadiene derivative of the formula A4, in an inert solvent to the Ligand system of the formula A5 implemented, the double bond in the Five rings can also be moved in addition to the way shown.

In principle, the construction of the ligand A5 can also be carried out in reverse by starting with the cyclopentadiene derivative A4.

The ligand system is then made with 2 k equivalents of a strong base such as butyllithium or potassium hydride in an inert solvent deprotonated and with k equivalents of a metal tetrahalide such as for example zirconium tetrachloride in a suitable solvent to A6 implemented. Suitable solvents are aliphatic or aromatic solvents, such as 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. It can also be a Mixture of several metal halides, for example zirconium tetrachloride and  Hafnium tetrachloid can be used. This way you get to polynuclear metallocenes that carry different metals in one molecule.

If necessary, radicals X unlike halogen can enter the metallocene A6 be introduced, e.g. B. by reaction with alkylating agents such as Methyl lithium to obtain those metallocenes of the formula I in which X is not equal to halogen.

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 has at least one polynuclear Contains metallocene and at least one cocatalyst, thereby characterized in that the multinuclear metallocene is a compound of formula I is.

Preference is given to olefins of the formula Ra-CH = CH-R ^b , in which Ra 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 50 to 100 ° C, performed. Of 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 one used in the process according to the invention preferably contains Catalyst a multinuclear metallocene and a cocatalyst. It can  also mixtures of the multinuclear metallocenes according to the invention, for. B. with mononuclear metallocenes are used.

An aluminoxane, particularly preferably a, is preferably used as the cocatalyst Aluminoxane of the formula IIa for the linear type and / or of the formula IIb for the cyclic type used

wherein in the formulas IIa and IIb, the radicals R¹⁵ are the same or different can and a C₁-C₆ alkyl group, a C₆-C₁₈ aryl group, benzyl or Is hydrogen, and p is an integer from 2 to 50, preferably 10 to 35 means.

The radicals R¹⁵ are preferably the same and are methyl, isobutyl, phenyl or Benzyl, particularly preferably methyl.

If the radicals R¹⁵ are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, with hydrogen or isobutyl being preferred contained in a numerical proportion of 0.01 to 40% (the radicals R¹⁵) are.

The processes for the preparation of the aluminoxanes are known (DE 40 04 477).  

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.

The exact spatial structure of the aluminoxanes is not known (A.R. Barron et al., J. Am. Chem. Soc. (1993) 115, 4971). For example, it is conceivable that chains and rings become larger two-dimensional or three-dimensional Connect structures.

It is possible to use the metallocene in the polymerization reaction with a cocatalyst, e.g. B. an aluminoxane of the formula IIa and / or IIb, preactivate. This significantly increases the polymerization activity and improves the grain morphology. The preactivation of the Transition metal compound is made in solution. It is preferred the metallocene in a solution of the aluminoxane in an inert Dissolved hydrocarbon. A suitable hydrocarbon is inert aliphatic or aromatic hydrocarbon. Toluene is preferred used.

The concentration of the aluminoxane in the solution is preferably in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, in each case based 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 to 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.  

To control the grain morphology, the metallocene can also be placed on a support be applied. Suitable carrier materials are, for example, silica gels, Aluminum oxides, solid aluminoxane or other inorganic carrier materials such as magnesium chloride. A suitable carrier material is also a Polyolefin powder in finely divided form. The manufacture of the supported Cocatalyst can, for example, as described in EP 92 107 331.8 be performed.

According to the invention, instead of or in addition to an aluminoxane, compounds of the formulas R¹⁶ _x NH _4-x BR¹⁷₄, R¹⁶ _x PH _4-x BR¹⁷₄, R¹⁶₃CBR¹⁷₄, BR¹⁷₃ can be used as suitable cocatalysts. In these formulas, x is a number from 1 to 4, preferably 3, the radicals R¹⁶ are the same or different, preferably the same, and are C₁-C₁₀-alkyl, C₆-C₁₈-aryl, or 2 radicals R¹⁶ form together with that connecting them Atom is a ring, and the radicals R¹⁷ are the same or different, preferably the same, and are C₆-C₁₈ aryl, which may be substituted by alkyl, haloalkyl or fluorine.

In particular, R¹⁶ represents ethyl, propyl, butyl or phenyl and R¹⁷ represents phenyl, Pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (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"). In addition, the Cocatalyst or the anion formed from it no further reactions with enter the metallocene cation formed (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.

The polymerization or copolymerization is carried out in solution in known manner Suspension or in the gas phase, continuously or discontinuously, one or multi-stage at a temperature of -60 to 200 ° C, preferably 30 to 80 ° C, particularly preferably 50 to 80 ° C, carried out.

Olefins of the formula Ra-CH = CH-R ^b are polymerized or copolymerized. In this formula, Ra and R ^{b are the} same or different and represent a hydrogen atom or an alkyl radical having 1 to 14 carbon atoms. However, Ra and R ^b can also form a ring system with the C atoms connecting them. Examples of such olefins are ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, norbornene or norbornadiene. In particular, propylene and ethylene are polymerized.

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

The metallocene is preferably used in a concentration, based on the transition metal, of 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 preferably 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.

The polyolefins produced by the process according to the invention have particularly important for the production of moldings such as foils, plates or large hollow bodies (e.g. pipes).

With the metallocene compound according to the invention can technically particularly interesting temperature range from 50 to 100 ° C at high Catalyst activities Polymers with very high molecular weight and in the case of prochiral ones Obtain monomers of very high molecular weight and very high stereoregularity become. In particular, high molecular weight isotactic polyolefins be preserved. In addition, in the metallocene according to the invention Complex isomer separation is dispensed with.  

If the metallocene according to the invention has different types of central atoms, one arrives at polyolefins with broad, bi- or polymodal Molar mass distribution.

By combining different ligands, polymers can also be used customized properties can be obtained.

In addition, reactor coatings are used with the metallocene according to the invention avoided without having to be carried out for it.

The following examples are intended to explain the invention in more detail.

All glassware was heated in vacuo and flushed with argon. All Operations were carried out in the absence of moisture and oxygen Schlenk vessels performed. The solvents used were under argon each freshly distilled over Na / K alloy and in Schlenk vessels kept. Dichloromethane was distilled off from CaH₂ under argon.

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.

Toluene soluble methylaluminoxane was used for the examples Suspension polymerization and bulk polymerization with unsupported Metallocene used as a 10 wt .-% toluene solution and contained according to Aluminum determination 36 mg Al / cm³. The average degree of oligomerization according to Freezing point depression in benzene was n = 20. Soluble for the toluene A ratio of Al: CH₃ = 1: 1.55 was determined for methylalumoxane.  

It means:

VZ = viscosity number in cm³ / g
M _w = molar mass weight average in g / mol (determined by gel permeation chromatography)
M _w / M _n = molar mass dispersity
Mp = melting point in ° C (determined with DSC, 20 K / min heating / cooling rate)
II = isotactic index (II = mm + 1/2 mr, determined by 13 C-NMR spectroscopy)
MFI 230/5 = melt index, measured according to DIN 53735 in dg / min

A. 1,6- {bis [methylsilyl- (2,3,5.trimethyl-cyclopentadienyl) (2-methyl-4-phenyl- indenyl) zirconium dichloride]} hexane (1)

To a solution of 15 g (73 mmol) of 2-methyl-7-phenyl-indene in 150 ml of toluene and 8 ml of THF were 27 ml (73 mmol) of a 20% strength at room temperature Solution of butyllithium in toluene was added dropwise over the course of 30 minutes. To complete addition was heated to 80 ° C. for a further 2 hours. Subsequently 11.2 g (36 mmol) of 1,6-bis (methyldichlorosilyl) hexane were in at 0 to 5 ° C. 10 ml of toluene were added dropwise within 2 minutes and at 1.5 hours Stirred room temperature. The solvents were removed and the Residue taken up in toluene and then precipitated LiCl filtered off. A suspension of was added to the filtrate at room temperature 1,2,4-trimethylcyclopentadienyllithium (made by reacting 7.9 g (73 mmol) 1,2,4-trimethylcyclopentadiene in 100 ml toluene and 20 ml THF Room temperature with 27 ml (73 mmol) of a 20% solution of butyllithium in toluene and stir for 1 hour at room temperature) within Added dropwise for 30 minutes and then for 2 hours at room temperature continued stirring. The reaction mixture was mixed with 100 ml of water Phases separated and the organic phase washed with 50 ml of water. The Solvents were removed in vacuo and the residue through  Chromatography on 700 g of silica gel (hexane / AcOEt 5: 1) purified. There were 13.5 g (47%) of the ligand system of compound 1 as a very viscous oil receive.

To a solution of 13 g (16.5 mmol) of the ligand system of compound 1 in 150 ml of diethyl ether were 26 ml (70 mmol) of a 20- % solution of butyllithium in toluene was added dropwise over the course of 30 minutes. After the addition was complete, the mixture was heated under reflux for a further 2 hours Solvent removed in vacuo and the residue with hexane over a G3 Schlenk frit filtered. The tetralithium salt was in vacuo for several hours dried in an oil pump at room temperature and then at -78 ° C a suspension of 7.5 g (32 mmol) of zirconium tetrachloride in 150 ml of CH₂Cl₂ given. The cold bath was removed and 1 hour at room temperature stirred. The reaction mixture was filtered through a G3 Schlenk frit, the residue was extracted with a total of 100 ml of methylene chloride and the combined filtrates largely freed from solvent in vacuo. Of the The residue was washed several times with hexane and then dried. 6.1 g (36%) of compound 1 were obtained as a yellow amorphous solid receive.

1 H-NMR (100 MHz, CDCl₃): 6.9 to 8.0 (m, 18 H, aromatic H and β-IndH), 6.4 (s, 1H, H-Cp), 1.9 to 2.2 (m, 24 H, CH₃-Ind and -Cp), 1.2 to 2.0 (m, 18H, 4CH₂, CH₂Si and CH₃Si).

B. 1,6- {bis [methylsilyl- (3-isopropylcyclopentadienyl) (fluorenyl) zirconium dichloride]} hexane (2)

To a solution of 10 g (60 mmol) of fluorene in 100 ml of toluene and 10 ml Diethyl ether was 22 ml (60 mmol) of a 22% strength at room temperature Solution of butyllithium in toluene was added dropwise over the course of 30 minutes. To complete addition was heated to 80 ° C. for a further 2 hours. Subsequently 7.8 g (30 mmol) of 1,6-bis (methyldichlorosilyl) hexane were added at 0 to 5 ° C.  10 ml of toluene were added dropwise within 2 min and at room temperature for 1 hour stirred. The solvents were removed and the residue in toluene recorded and then filtered out precipitated LiCl. To the filtrate was a suspension of at room temperature Isopropylcyclopentadienyllithium (made by reacting 6.5 g (60 mmol) of isopropylcyclopentadiene in 100 ml of toluene and 10 ml of diethyl ether Room temperature with 22 ml (60 mmol) of a 20% solution of butyllithium in toluene and 1 hour after stirring at room temperature) within Added dropwise for 30 minutes and then for 2 hours at room temperature continued stirring. The reaction mixture was mixed with 100 ml of water Phases separated and the organic phase washed with 50 ml of water. The Solvents were removed in vacuo and the residue through Chromatography on 700 g of silica gel (hexane / methylene chloride 10: 1) purified. It 13.3 (63%) of the ligand system of compound 2 was very viscous Get oil.

To a solution of 13 g (18 mmol) of the ligand system of compound 2 in 150 ml of diethyl ether were 30 ml (80 mmol) of a 20- % solution of butyllithium in toluene was added dropwise over the course of 30 minutes. After the addition was complete, the mixture was heated under reflux for a further 2 hours Solvent removed in vacuo and the residue with hexane over a G3 Schlenk frit filtered. The tetralithium salt was in vacuo for several hours dried in an oil pump at room temperature and then at -78 ° C a suspension of 8.15 g (35 mmol) of zirconium tetrachloride in 150 ml Given methylene chloride. The cold bath was removed and at 1 h Stirred room temperature. The reaction mixture was passed through a G3 Schlenk frit filtered, the residue with a total of 300 ml of methylene chloride extracted and the combined filtrates in vacuo to about 1/3 of their Volume constricted. At -20 ° C, 4.6 g (27%) of Compound 2 as a yellow amorphous solid.  

1 H-NMR (100 MHz, CDCl₃): 7.1 to 8.2 (m, 16 H, aromatic H), 5.5, 5.7, 6.3 (3m, 6H, H-Cp), 2.9 (m, 2H, i-propyl), 1.0 to 2.0 (m, 30 H, 4CH₂, CH₂Si, CH₂Si and CH₃-i-propyl).

Polymerization examples example 1

A dry 16 dm³ reactor was first filled with nitrogen and then flushed with propylene and filled with 10 dm³ of liquid propylene. Then were 30 cm³ toluene methylaluminoxane solution added and the approach at 30 ° C stirred. In parallel, 3.0 mg 1 in 20 cm³ of a toluene Methylaluminoxane solution (23 mmol Al) and by standing for 15 minutes Brought reaction. The solution was then added to the reactor Heat supply heated to the polymerization temperature of 50 ° C (4 K / min) and the polymerization system was kept at 50 ° C for 1 hour by cooling. The polymerization was stopped by adding 20 ml of isopropanol Excess monomer is vented and the polymer is dried in vacuo. It 0.56 kg of polypropylene were obtained. The reactor showed essentially no documents on the inner wall and stirrer.

The catalyst activity was 189 kg (PP) / g (metallocene) _* h; VZ = 449 cm³ / g; Mp = 158 ° C; M _w = 529,500 g / mol; M _w / M _n = 2.2.

Example 2

The polymerization from Example 1 was repeated with the difference that 5.6 mg 2 was used and the polymerization temperature was 70 ° C. It 0.17 kg of rubber-like polypropylene was obtained. The reactor showed in essentially no evidence on the inner wall and stirrer.

The catalyst activity was 30 kg (PP) / g (metallocene) _* h; VZ = 80 cm³ / g; isotactic pentads (13 C-NMR) = 58%.

Claims (6)

1. Multinuclear metallocene compound of the formula I wherein
M¹ are identical or different and are a metal from group IVb, Vb or VIb of the periodic table,
X are the same or different and are hydrogen, a C₁-C₁₀ alkyl, a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl, a C₆-C₁ ₀ aryloxy, a C₂-C₁₀ alkenyl, one C₇-C₄₀-arylalkyl, a C₇-C₄₀-alkylaryl, a C₈-C₄₀-arylalkenyl, an OH group, a halogen atom or pseudohalogen,
the radicals R¹, R², R³ and R⁴ 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, C₇-C₄₀-arylalkyl, a C₇- C₄₀-Alkylaryl-, a C₂- C₁₀-alkenyl, C₈-C₄₀-arylalkenyl group, an -NR¹¹₂-, -SR¹¹-, -OSiR¹¹₃-, - SiR¹¹₃- or -PR¹¹₂ radical, in which R¹¹ is identical or different and one Is C₁-C₁₀ alkyl group or a C₆-C₁₀ aryl group,
R⁵ to R¹⁰ 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, C₇-C₄₀ arylalkyl, a C₇-C₄₀ alkylaryl, one C₂-C₁₀ alkenyl, C₈-C₄₀ arylalkenyl group, an -NR¹¹₂-, -SR¹¹-, -OSiR¹¹₃-, -SiR¹¹₃- or -PR¹¹₂ radical, wherein R¹¹ is the same or different and a C₁-C₁₀ alkyl group or is a C₆-C₁₀ aryl group or two or more adjacent radicals R⁵ and R⁶, or R⁷, R⁸, R⁹ and R¹⁰ together with the atoms connecting them form a ring system,
k is 2 if B and k is an integer <1 if B where R¹² are the same or different and represent a double-bonded hydrocarbon-containing bridge,
the radicals R¹³ 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-C₂₀ alkylaryl, a C₇-C₄₀ alkylaryl, a C₈-C₄₀ arylalkenyl group,
R¹⁴ is a three-membered hydrocarbon radical, and n is k and m is k-1 and
M² is silicon, germanium or tin. 2. A multinuclear metallocene compound according to claim 1, characterized in that M¹ are the same or different zirconium or hafnium, the radicals X are the same and are a C₁-C₄-alkyl group, a C₇-C₁₀-alkylaryl group or a halogen atom, R¹ to R¹⁰ are the same or are different and are hydrogen or a C₁-C₁₀ alkyl group, a C₆-C₁₀ aryl group or a SiR¹¹₃ radical in which R¹¹ is a C₁-C₁₀ alkyl group, or two or more adjacent radicals R⁵ and R⁶ or R⁷, R⁸, R⁹ and R¹⁰ together with the atoms connecting them form an aromatic or aliphatic ring system, k is 2, B where M² is silicon and
the radicals R¹³ are the same or different and are hydrogen, a C₁-C₄ alkyl group or a C₆-C₁₀ aryl group and R¹² are the same or different and are a double-bonded linear or branched C₁-C₆ alkyl group. 3. A process for the preparation of an olefin polymer by polymerization or copolymerization of at least one olefin in the presence of a catalyst which contains at least one polynuclear metallocene and at least one cocatalyst, characterized in that the polynuclear metallocene is a compound of the formula I. wherein
M¹ are identical or different and are a metal from group IVb, Vb or VIb of the periodic table,
X are the same or different and are hydrogen, a C₁-C₁₀ alkyl, a C₁-C₁₀ alkoxy, a C₆-C₁₀ aryl, a C₆-C₁₀ aryloxy, a C₂-C₁₀ alkenyl, a C₇ Mean -C₄₀-arylalkyl, a C₇-C₄₀-alkylaryl, a C₈-C₄₀-arylalkenyl, an OH group, a halogen atom or pseudohalogen,
the radicals R¹, R², R³ and R⁴ 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, C₇-C₄₀-arylalkyl, a C₇- C₄₀-Alkylaryl-, a C₂- C₁₀-alkenyl, C₈-C₄₀-arylalkenyl group, an -NR¹¹₂-, -SR¹¹-, -OSiR¹¹₃-, -SiR¹¹₃- or -PR¹¹₂ radical, in which R¹¹ is the same or different and one Is C₁-C₁₀ alkyl group or a C₆-C₁₀ aryl group,
R⁵ to R¹⁰ 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, C₇-C₄₀ arylalkyl, a C₇-C₄₀ alkylaryl, one C₂-C₁₀ alkenyl, C₈-C₄₀ arylalkenyl group, an -NR¹¹₂-, -SR¹¹-, -OSiR¹¹₃-, -SiR¹¹₃- or -PR¹¹₂ radical, in which R¹ is identical or different and is a C₁-C₁ Alkyl alkyl group or is a C₆-C₁₀ aryl group or two or more adjacent radicals R⁵ and R⁶, or R⁷, R⁸, R⁹ and R¹⁰ together with the atoms connecting them form a ring system,
k is 2 if B and k is an integer <1 if B where R¹² are the same or different and represent a double-bonded hydrocarbon-containing bridge,
the radicals R¹³ 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-C₂₀ alkylaryl, a C₇-C₄₀ alkylaryl, a C₈-C₄₀ arylalkenyl group,
R¹⁴ is a three-membered hydrocarbon radical, and n is k and m is k-1 and
M² is silicon, germanium or tin. 4. The method according to claim 3, characterized in that as Cocatalyst an aluminoxane is used. 5. polyolefin which can be prepared by the process according to claim 3 or 4. 6. Shaped article containing at least one polyolefin according to claim 5.