RU2147587C1 - Metallocenes, method of preparing thereof, catalyst system, method of preparing polyolefins, and molded polymeric product - Google Patents

Abstract

FIELD: chemical industry. SUBSTANCE: described are new polynuclear metallocene compounds of formula I:

wherein M¹ is metal of IV b group of the Periodic Table; X is halogen atom; L and L′ are the same or different and denote substituted cyclopentadienyl optionally substituted indoenyl and unsubstituted fluorhenyl; B is group of formula (a) wherein R¹ is divalent hydrocarbon bridge group, R² residues are the same and denote C₁-C₄ alkyl group; M² is silicon. Also described are method of preparing said compounds, catalyst system comprising thereof, method of preparing polyolefins, and molded polymeric product. EFFECT: more efficient preparation method. 11 cl, 22 ex

Description

 The present invention relates to new metallocenes that contain more than one central atom and can be used preferably as catalyst components for the production of polyolefins, in particular polyolefins with high stereoregularity, high molecular weight and good particle morphology.

 It is known from the literature that polyolefins are prepared using soluble metallocene compounds in combination with aluminoxanes or other cocatalysts that can convert a neutral metallocene into a cation and stabilize it.

 Soluble metallocene compounds based on bis [cyclopentadienyl] zirconium dialkyl, respectively, dihalide, in combination with oligomeric aluminoxanes exhibit good activity in the polymerization of ethylene, and moderate activity in the polymerization of propylene. A polyethylene with a narrow molecular weight distribution and an average molecular weight is obtained. The resulting polypropylene is atactic and has a very low molecular weight.

 Isotactic polypropylene is obtained using ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride together with aluminoxane by suspension polymerization [EP 185918]. The polymer has a narrow molecular weight distribution. The disadvantage of this method is to obtain polymers with a very low molecular weight.

 A known method of pre-activation of metallocene using alumoxane, which leads to a significant increase in the activity of the catalytic system and to a distinct improvement in the morphology of polymer particles [EP 302424]. However, preactivation does not increase molecular weight.

 Known catalysts based on ethylene bisindenyl hafnium dichloride and ethylene bis (4,5,6,7-tetrahydro-1-indenyl) hafnium dichloride and methylaluminoxane, by which higher molecular weight polypropylenes can be obtained by suspension polymerization (J. Am.Chem.Soc . (1987), 109, 6544). However, the morphology of the particles of the obtained polymers is unsatisfactory and the activity of the used catalytic systems is relatively insignificant, while the cost of these systems is very high.

 A distinct increase in molecular weight can be achieved through the use of metallocenes containing substituents in indenyl ligands at position 2 (EP 485822) or at positions 2 and 4 (EP 530647).

 The molecular weight can be further increased by the use of indenyl ligands with substituents at positions 2, 4 and 6 (EP 545303), as well as by aromatic π-ligands of the 4,5-benzoindenyl type (EP 549900).

 In the case of stereospecific polymerization of prochiral monomers, for example propylene, in the presence of metallocene catalysts, the disadvantage is the relatively low isotacticity (stereoregularity), which in the case of isotactic polypropylene corresponds to low melting points. The use of metallocenes with substituents at position 2 and 4, and especially rac.-dimethylsilyl bis (2-methyl-4-isopropyl-indenyl) zirconium dichloride in combination with methylaluminoxane in the case of propylene, gives a polymer with high isotacticity and high melting point (EP 530647 ) A further increase in melting points is achieved through the use of 4-aryl-substituted bisindenyl systems (EP 576970).

 Of course, there are also applications where low melting points are desired.

 When using soluble metallocenemethylaluminoxane catalyst systems in processes in which the polymer is precipitated as a solid, the disadvantage is the formation of large deposits on the walls of the reactor and the mixer. These deposits are formed due to the agglomeration of polymer particles when the metallocene or alumoxane, or both, are dissolved in a suspension medium. Such deposits in reactors must be regularly removed, since they quickly reach a significant thickness, have high strength and prevent heat exchange with the cooling medium.

 To prevent the formation of deposits in the reactor, metallocenes can be applied onto carriers (EP 578838). It is preferable to abandon the additional step of applying to the carrier. Binuclear metallocenes are known from EP 528041 which are suitable for the preparation of low molecular weight syndiotactic polymers.

 The objective of the invention is a catalytic system that allows to obtain polymers with a very high molecular weight and, in the case of stereospecific polymerization of prochiral monomers, polymers with high stereoregularity and with high yield.

 The task is also the development of a catalytic system to prevent the formation of deposits on the walls of the reactor.

 It has been shown that metallocenes that contain more than one central atom and have a special bridging compound are suitable catalysts that do not have the disadvantages known from the prior art.

 Further, it was unexpectedly shown that the metallocenes according to the invention are preferably suitable for the production of isotactic polyolefins with only a small extractable fraction.

где M¹ обозначает металл группы IVб Периодической системы элементов,
X обозначает атом галогена,
L и L¹ являются одинаковыми или разными и обозначают π-лиганд, выбранный из группы, включающей замещенный циклопентадиенил, необязательно замещенный инденил и незамещенный флуоренил;
k=2;
B обозначает

причем R¹ обозначает двухвалентную углеводородсодержащую мостиковую группу;
остатки R² являются одинаковыми и обозначают углеводородсодержащий остаток, представляющий собой C₁-C₄-алкильную группу;
M² обозначает кремний.Thus, the present invention relates to a multicore metallocene compound of the formula (1):

where M ¹ denotes a metal of group IVb of the Periodic system of elements,
X is a halogen atom,
L and L ¹ are the same or different and denote a π ligand selected from the group consisting of substituted cyclopentadienyl, optionally substituted indenyl and unsubstituted fluorenyl;
k is 2;
B stands for

wherein R ¹ is a divalent hydrocarbon-containing bridging group;
R ² residues are the same and represent a hydrocarbon-containing residue representing a C ₁ -C ₄ alkyl group;
M ² is silicon.

 It should be clarified that each “free” valency of structural element B is associated with one of the ligands L or L '.

Examples of L and L 'are:
cyclopentadienyl, tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl tert. -butylcyclopentadienyl, tert.-butylcyclopentadienyl, isopropylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, trimethylethylcyclopentadienyl, phenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 3-methylindenyl, 3-methylthenyl -phenyl-indenyl, 2-ethyl-4-phenyl-indenyl, 2-methyl-4-naphthyl-indenyl, 2-methyl-4-isopropyl-indenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl , 2-methyl-α - acenaphthindenyl, 2-methyl-4,6-diisopropylindenyl, fluorenyl, 4-methylfluorenyl or 2,7-di- PET butilfluorenil.

где M¹ обозначает металл группы IVб Периодической системы элементов;
X обозначает атом галогена;
остатки R⁵, R⁶, R⁷ и R⁸ являются одинаковыми или разными и обозначают атом водорода, C₁-C₁₀ - алкильную группу, C₆-C₂₀ - арильную группу или два соседних остатка;
R⁷ и R⁸ вместе со связывающими их атомами образуют ароматическую циклическую систему;
R⁹ - R¹⁴ являются одинаковыми или разными и обозначают атом водорода, C₁-C₁₀ - алкильную группу, C₆-C₂₀ - арильную группу или два соседних остатка R⁹ и R¹⁰ вместе со связывающими их атомами образуют ароматическую циклическую систему;
k обозначает целое число, равное 2;
B обозначает

причем R¹ обозначает двухвалентную линейную C₁-C₆ - алкильную группу, в особенности 1,2 - этилен или 1,6-гексилен; и остатки R² являются одинаковыми и обозначают C₁-C₄ - алкильную группу;
M² обозначает кремний.Preferred multicore metallocene compounds corresponding to the formula (II):

where M ¹ denotes a metal of group IVb of the Periodic system of elements;
X represents a halogen atom;
residues R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, C ₁ -C ₁₀ is an alkyl group, C ₆ -C ₂₀ is an aryl group or two adjacent residues;
R ⁷ and R ⁸ together with the atoms bonding them form an aromatic ring system;
R ⁹ - R ¹⁴ are the same or different and represent a hydrogen atom, a C ₁ -C ₁₀ is an alkyl group, a C ₆ -C ₂₀ is an aryl group or two adjacent residues R ⁹ and R ¹⁰ together with the atoms connecting them form an aromatic ring system;
k is an integer equal to 2;
B stands for

wherein R ¹ is a divalent linear C ₁ -C ₆ alkyl group, in particular 1,2 ethylene or 1,6-hexylene; and the residues R ² are the same and represent a C ₁ -C ₄ alkyl group;
M ² is silicon.

Most preferably, the multicore metallocene compound of formula II in which M ¹ is zirconium or hafnium.

For the preparation of isotactic polyolefins, compounds of the formula (II) are preferably used, which contain two indenyl groups as ligands. Particularly preferred for this purpose are those compounds of formula (II) wherein the indenyl groups are substituted at 2-, 2,4-, 2,6-, 2,4,6-, 2,4,5-, 2,4,5 , 6- and 2,5,6-position, moreover, in the 2nd position they are preferably substituted with a C ₁ -C ₁₀ - alkyl residue, in the 4-, 5-, 6-positions, respectively, they are substituted by a C ₁ -C _10- -alkyl residues, C ₆ -C ₁₀ -aryl residues or by anelling at the 4,5- or 4,5,6-position. The term "cyclic system" covers substituted and unsubstituted cyclic systems.

Предпочтительными лигандами являются:
1 - инденил; 2 - алкил-4-арил-1-инденил; 2,4-диалкил-1-инденил; 2,4-диарил-1-инденил; 2,4,6-триалкил-1-инденил; 1-алкил-аценафт-1-инденил; 1-алкил-4,5-бензо-1-инденил; 2,5-диалкил-1-инденил; 2,5,6-триалкил-1-инденил; 2,4,5-триалкил-1-инденил; 2-алкил-1-инденил; 2-арил-1-инденил; 2,6-диалкил-4-арил-1-инденил; 2-алкил-5-арил-1-инденил; 2-алкил-5,6-диарил-1-инденил; 2-алкил-4,5-диарил-1-инденил; 2-алкил-4,6-диарил-1-инденил; флуоренил; 2,7-диалкил-флуоренил или 4-алкилфлуоренил; 2-алкил-1-циклопентадиенил; 2,4-диалкил-1-циклопентадиенил; 2,4,5-триалкил-1-циклопентадиенил; 2-Si-(триалкил)-1-циклопентадиенил; 2-Si(триалкил)-4-алкил-1-циклопентадиенил; 2-Si(триалкил)-4,5-диалкил-1-циклопентадиенил; 2-алкил-4-арил-1-циклопентадиенил; 2,5-алкил-4-арил-1-циклопентадиенил; 2,4-алкил-5-арил-1-циклопентадиенил; 2-арил-1-циклопентадиенил; 2-арил-4-алкил-1-циклопентадиенил; 2-арил-4,5-алкил-1-циклопентадиенил или 2-алкил-4,5-арил-1-циклопентадиенил.The following nomenclature is used to indicate a substitution position:

Preferred ligands 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-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; 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 should explain in more detail the compounds corresponding to the general formula (I), however, they do not limit the scope of the invention:
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]} - hexane;
1,6- {bis [methylsilyl- (fluorenyl) (3-isopropyl-cyclopentadienyl) zirconium dichloride]} - 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]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4-phenylindenyl) (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride]} - 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 dichloride]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4,5-benzo-indenyl) (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4,6-diisopropyl-indenyl) (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4-1-naphthyl-indenyl) (2,3,5-trimethyl-cyclopentadienyl) 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]} - ethane;
1,2- {bis [methylsilyl- (fluorenyl) (3-isopropyl-cyclopentadienyl) zirconium dichloride]} - 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]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (cyclopentadienyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (4-phenyl-indenyl) (cyclopentadienyl) zirconium dichloride]} - 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-phenyl-cyclopentadienyl) 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 dichloride]} - 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-trimethyl-cyclopentadienyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-1-naphthyl-indenyl) (2,3,5-trimethyl-cyclopentadienyl) 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-cyclopentadienyl) 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) (cyclopentadienyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-indenyl) (cyclopentadienyl) 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) (cyclopentadienyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenyl-indenyl) (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(fluorenyl) (3-phenyl-cyclopentadienyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(indenyl) (3-phenyl-cyclopentadienyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4,5-benzo-indenyl) (3-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) - (cyclopentadienyl) 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-trimethyl-cyclopentadienyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-ethyl-4-phenyl-indenyl) - (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(fluorenyl) (cyclopentadienyl) 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-9,10-diylidene [(indenyl) (3-methyl-cyclopentadienyl) 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-isopropyl-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) - (cyclopentadienyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenyl-indenyl) - (cyclopentadienyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(4-phenyl-indenyl) - (cyclopentadienyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenyl-indenyl) (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-cyclopentadienyl) 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-indenyl) (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-trimethyl-cyclopentadienyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-ethyl-4-phenyl-indenyl) (2,3,5-trimethyl-cyclopentadienyl) zirconium dichloride];
1,6- {bis [methylsilyl bis (indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl bis (2-methyl-indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl bis (2-methyl-4-phenyl-indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl bis (2-methyl-4,5-benzo-indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl bis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride]} -hexane;
1,6- {bis [methylsilyl bis (2-methyl-4-isopropyl-indenyl) zirconium dichloride]} -hexane;
1,6- {bis [methylsilyl bis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl bis (2-ethyl-indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl bis (2-ethyl-4-phenyl-indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl bis (2-ethyl-4- (1-naphthyl) indenyl) zirconium dichloride]} -hexane;
1,6- {bis [methylsilyl bis (2-ethyl-4-α-acenaphth-indenyl) zirconium dichloride]} -hexane;
1,2- {bis [methylsilyl bis (indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl bis (2-methyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl bis (2-methyl-4-phenyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl bis (2-methyl-4,5-benzo-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl bis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride]} ethane;
1,2- {bis [methylsilyl bis (2-methyl-4-isopropyl-indenyl) zirconium dichloride]} ethane;
1,2- {bis [methylsilyl bis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl bis (2-ethyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl bis (2-ethyl-4-phenyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl bis (2-ethyl-4- (1-naphthyl) indenyl) zirconium dichloride]} ethane;
1,2- {bis [methylsilyl bis (2-ethyl-α-acenaphth-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [ethylsilyl bis (indenyl) zirconium dichloride]} - ethane;
1,2- {bis [ethylsilyl bis (2-methyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [ethylsilyl bis (2-methyl-4-phenyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [ethylsilyl bis (2-methyl-4,5-benzo-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [ethylsilyl bis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride]} ethane;
1,2- {bis [ethylsilyl bis (2-methyl-4-isopropyl-indenyl) zirconium dichloride]} ethane;
1,2- [bis / ethylsilyl bis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride] ethane;
1,2- [bis / ethylsilyl bis (2-ethyl-indenyl) zirconium dichloride] ethane;
1,2- [bis / ethylsilyl bis (2-ethyl-4-phenyl-indenyl) zirconium dichloride] ethane;
1,2- [bis / ethylsilyl bis (2-ethyl-4- (1-naphthyl) indenyl) zirconium dichloride] ethane;
1,2- [bis / ethylsilyl bis (2-ethyl-α-acenaphth-indenyl) zirconium dichloride /] ethane;
1,6- [bis / ethylsilyl bis (indenyl) zirconium dichloride]] -hexane;
1,6- [bis / ethylsilyl bis (2-methyl-indenyl) zirconium dichloride]] -hexane;
1,6- [bis / ethylsilyl bis (2-methyl-4-phenyl-indenyl) zirconium dichloride /] - hexane;
1,6- [bis / ethylsilyl bis (2-methyl-4,5-benzo-indenyl) zirconium dichloride /] -hexane;
1,6- [bis / ethylsilyl bis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride /] -hexane;
1,6- [bis / ethylsilyl bis (2-methyl-4-isopropyl-indenyl) zirconium dichloride] hexane;
1,6- [bis / ethylsilyl bis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride /] - hexane;
1,6- [bis / ethylsilyl bis (2-ethyl-indenyl) zirconium dichloride /] - hexane;
1,6- [bis / ethylsilyl bis (2-ethyl-4-phenyl-indenyl) zirconium dichloride /] -hexane;
1,6- [bis / ethylsilyl bis (2-ethyl-4- (1-naphthyl) indenyl) zirconium dichloride /] - hexane;
1,6- [bis / ethylsilyl bis (2-ethyl-α-acenaphth-indenyl) zirconium dichloride /] - hexane;
1,3- [bis / methylsilyl bis (indenyl) zirconium dichloride /] - propane;
1,3- [bis / methylsilyl bis (2-methyl-indenyl) zirconium dichloride]] propane;
1,3- [bis / methylsilyl bis (2-methyl-4-phenyl-indenyl) zirconium dichloride /] - propane;
1,3- [bis / methylsilyl bis (2-methyl-4,5-benzo-indenyl) zirconium dichloride /] - propane;
1,3- [bis / methylsilyl bis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride /] propane;
1,3- [bis / methylsilyl bis (2-methyl-4-isopropyl-indenyl) zirconium dichloride] propane;
1,3- [bis / methylsilyl bis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride /] - propane;
1,3- [bis / methylsilyl bis (2-ethyl-indenyl) zirconium dichloride] propane;
1,3- [bis / methylsilyl bis (2-ethyl-4-phenyl-indenyl) zirconium dichloride]] propane;
1,3- [bis / methylsilyl bis (2-ethyl-4- (1-naphthyl) indenyl) zirconium dichloride] propane;
1,3- [bis / methylsilyl bis (2-ethyl-α-acenaphth-indenyl) zirconium dichloride] propane;
1,4-disilacyclohexane-1,4-diylidene [bis (indenyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [bis (2-methyl-indenyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene (bis (2-ethyl-indenyl) zirconium dichloride);
1,4-disilacyclohexane-1,4-diylidene (bis (2-methyl-4-phenyl-indenyl) zirconium dichloride);
1,4-disilacyclohexane-1,4-diylidene (bis (2-methyl-4- (1-naphthyl-indenyl) zirconium dichloride);
1,4-disilacyclohexane-1,4-diylidene (bis (2-methyl-4-isopropyl-indenyl) zirconium dichloride);
1,4-disilacyclohexane-1,4-diylidene (bis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride);
1,4-disilacyclohexane-1,4-diylidene (bis (2-methyl-4,5-benzo-indenyl) zirconium dichloride);
1,4-disilacyclohexane-1,4-diylidene (bis (2-ethyl-4-phenyl-indenyl) zirconium dichloride);
1,4-disilacyclohexane-1,4-diylidene (bis (2-methyl-α-acenaphth-indenyl) zirconium dichloride);
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene (bis (indenyl) zirconium dichloride);
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene (bis (2-methyl-indenyl) zirconium dichloride);
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene (bis (2-ethyl-indenyl) zirconium dichloride);
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene (bis (2-methyl-4-phenyl-indenyl) zirconium dichloride);
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene (bis (2-methyl-4- (1-naphthyl-indenyl) zirconium dichloride);
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene (bis (2-methyl-4-isopropyl-indenyl) zirconium dichloride);
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [bis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [bis (2-methyl-4,5-benzo-indenyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [bis (2-ethyl-4-phenyl-indenyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [bis (2-methyl-α-acenaphth-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [bis (indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [bis (2-methyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [bis (2-ethyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [bis (2-methyl-4-phenyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [bis (2-methyl-4- (1-naphthyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [bis (2-methyl-4-isopropyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [bis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [bis (2-methyl-4,5-benzo-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [bis (2-ethyl-4-phenyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [bis (2-methyl-α-acenaphth-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disyl-2,3,5,6-tetraphenyl-benzene-1,4-diylidene [bis (indenyl) zirconium dichloride];
1,4-dihydro-1,4-disyl-2,3,5,6-tetraphenyl-benzene-1,4-diylidene [bis (2-methyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disyl-2,3,5,6-tetraphenyl-benzene-1,4-diylidene [bis (2-ethyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disyl-2,3,5,6-tetraphenyl-benzene-1,4-diylidene [bis (2-methyl-4-phenyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disyl-2,3,5,6-tetraphenyl-benzene-1,4-diylidene [bis (2-methyl-4- (1-naphthyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disyl-2,3,5,6-tetraphenyl-benzene-1,4-diylidene [bis (2-methyl-4-isopropyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disyl-2,3,5,6-tetraphenyl-benzene-1,4-diylidene [bis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disyl-2,3,5,6-tetraphenyl-benzene-1,4-diylidene [bis (2-methyl-4,5-benzo-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disyl-2,3,5,6-tetraphenyl-benzene-1,4-diylidene [bis (2-ethyl-4-phenyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disyl-2,3,5,6-tetraphenyl-benzene-1,4-diylidene [bis (2-methyl-α-acenaphth-indenyl) zirconium dichloride];
1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-indenyl) - zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-4,5-benzo-indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-4-isopropyl-indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-ethyl-indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-ethyl-4-phenyl-indenyl) zirconium dichloride]} - hexane;
1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-α-acenaphth-indenyl) zirconium dichloride]} - hexane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) - (indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-4,5-benzo-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-4,5-benzo-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-4-isopropyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-ethyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-ethyl-4-phenyl-indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-ethyl-4- (1-naphthyl) indenyl) zirconium dichloride]} - ethane;
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-α-acenaphth-indenyl) zirconium dichloride]} - ethane;
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenyl-indenyl) (indenyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenyl-indenyl) (2-methyl-indenyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenyl-indenyl) (2-ethyl-indenyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenyl-indenyl) (2-methyl-4- (1-naphthyl-indenyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenyl-indenyl) (2-methyl-4-isopropyl-indenyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenyl-indenyl) (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenyl-indenyl) (2-methyl-4,5-benzo-indenyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenyl-indenyl) (2-ethyl-4-phenyl-indenyl) zirconium dichloride];
1,4-disilacyclohexane-1,4-diylidene [(2-methyl-4-phenyl-indenyl) (2-methyl-α-methyl-acenaphth-indenyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenyl-indenyl) - (indenyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenyl-indenyl) (2-methyl-indenyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenyl-indenyl) (2-ethyl-indenyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenyl-indenyl) (2-methyl-4-isopropyl-indenyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenyl-indenyl) (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenyl-indenyl) (2-methyl-4,5-benzo-indenyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenyl-indenyl) (2-ethyl-4-phenyl-indenyl) zirconium dichloride];
9,10-dihydro-9,10-disilaanthracene-9,10-diylidene [(2-methyl-4-phenyl-indenyl) (2-methyl-α-acenaphth-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [(2-methyl-4-phenyl-indenyl) - (indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [(2-methyl-4-phenyl-indenyl) - (2-methyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [(2-methyl-4-phenyl-indenyl) - (2-ethyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [(2-methyl-4-phenyl-indenyl) - (2-methyl-4- (1-naphthyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [(2-methyl-4-phenyl-indenyl) - (2-methyl-4-isopropyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [(2-methyl-4-phenyl-indenyl) - (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [(2-methyl-4-phenyl-indenyl) - (2-methyl-4,5-benzo-indenyl) zirconium dichloride];
1,4-dihydro-1,4-disyl-benzene-1,4-diylidene [(2-methyl-4-phenyl-indenyl) - (2-ethyl-4-phenyl-indenyl) zirconium dichloride]; and
1,4-dihydro-1,4-disilabenzene-1,4-diylidene [(2-methyl-4-phenyl-indenyl) - (2-methyl-α-acenaphth-indenyl) zirconium dichloride].

В случае необходимости в металлоцен А-4 можно вводить остатки X, не обозначающие галоген, например, путем введения во взаимодействие с алкилирующими средствами, как метиллитий, для того, чтобы получить такие металлоцены формулы (I), в которых X не означает галоген.The preparation of metallocenes according to the invention should be clearly illustrated by the following reaction scheme:

If necessary, residues X not representing halogen can be introduced into metallocene A-4, for example, by reacting with alkylating agents such as methyl lithium, in order to obtain metallocenes of formula (I) in which X does not mean halogen.

 Indene derivatives are commercially available or can be obtained by methods known from the literature [European patents NN 567952 and 545304].

 Methods for producing ligand systems and interactions prior to the formation of bridged metallocenes of formula (I) are known in principle [European Patent 574597; European Patent 320762; European patent 376154].

 For this purpose, LH and L'H are deprotonated with a strong base, such as, for example, butyl lithium or potassium hydride in an inert solvent and reacted with a reagent of formula A-2 to obtain a ligand system of formula A-3 or one of its isomers, moreover, the double bond in the five-membered ring, in addition to the position between C (2) and C (3), can also be between C (1) and C (2). The ligand system is then deprotonated with “2k” equivalents of a strong base, such as butyllithium or potassium hydride, in an inert solvent, and reacted with “k” equivalents of a metal tetrahalide, such as zirconium tetrachloride, in a suitable solvent, for receiving A-4. Suitable solvents are aliphatic or aromatic solvents, such as, for example, hexane or toluene; ethers, such as tetrahydrofuran or diethyl ether; or halogenated hydrocarbons, such as methylene chloride; or halogenated aromatic hydrocarbons, such as o-dichlorobenzene. You can also use a mixture of several metal halides, for example, zirconium tetrachloride with hafnium tetrachloride. In this way, multicore metallocenes are obtained that contain various metals in the molecule.

 The present invention also relates to a method for producing polyolefins by polymerizing at least one olefin in the presence of a catalyst that contains at least one multicore metallocene and at least one cocatalyst; The method is characterized in that the multicore metallocene in the catalyst is a compound of formula (I).

The polymerization can be carried out as homopolymerization or as copolymerization. Preferably, homo- or copolymerized olefins of the formula R ^a -CH = CH-R ^b, where R ^a and R ^b are identical or different and represent a hydrogen atom or a hydrocarbon residue with 1-20 C-atoms, in particular 1-10 C-atoms , or R ^a and R ^b together with the atoms bonding them form one or more cycles. Examples of such olefins are 1-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene; styrene; dienes such as 1,3-butadiene or 1,4-hexadiene; and cyclic olefins such as norbornene, tetracyclodecene, norbornadiene or vinyl norbornene. Preferably, in the method according to the invention, ethylene and propylene are homopolymerized, or ethylene is copolymerized with one or more 1-olefins with 3-20 C-atoms, such as propylene, and / or one or more dienes with 4-20 C-atoms, like 1, 3-butadiene. Examples of such copolymers are copolymers of ethylene with propylene and copolymers of ethylene with propylene and 1,4-hexadiene.

 The catalyst used in the method according to the invention preferably contains a multi-core metallocene of formula (I) and a cocatalyst. Mixtures of the multi-core metallocenes according to the invention with single-core metallocenes can also be used. In principle, any such compound which, due to its Lewis acidity, can convert a neutral metallocene to a cation and stabilize it (“labile coordination”) is suitable as a cocatalyst in the process according to the invention. Moreover, the cocatalyst or the anion formed from it should not enter into any further reactions with the formed metallocene cation (European patent 427697). As the cocatalyst, aluminum compounds and / or a boron compound are preferably used.

The boron compound preferably corresponds to the formula R _x ¹⁶ H _4-x BR ₄ ¹⁷ ; R _x ¹⁶ RH _4-x BR ₄ ¹⁷ ; R ₃ ¹⁶ CBR ₄ ¹⁷ or BR ₃ ¹⁷ , where:
"x" denotes the number 1-4, preferably 3;
residues R ¹⁶ are the same or different, preferably the same, and are C ₁ -C ₁₀ alkyl or C ₆ -C ₁₈ aryl; or two R ¹⁶ residues together with the atoms bonding them form a cycle; and R ¹⁷ are the same or different, preferably the same, and are C ₆ -C ₁₈ aryl, which may be substituted by alkyl, haloalkyl or fluoro. In particular, R ¹⁶ is ethyl, propyl, butyl or phenyl, and R ¹⁷ is phenyl, pentafluorophenyl, 3,5-bis-trifluoromethylphenyl, mesityl, xylyl or tolyl (European patents NN 277003; 277004 and 426638). An aluminum compound, such as alumoxane and / or aluminum alkyl, is preferably used as a cocatalyst.

причем в формулах (IIIа) и (IIIб) остатки R¹⁸ могут быть одинаковыми или разными и обозначают C₁-C₆-алкильную группу, C₆-C₁₈-арильную группу, бензил или водород; и "p" обозначает целое число 2-50, предпочтительно 10-35.Alumoxane, in particular alumoxane of formula (IIIa) for the linear type and / or formula (IIIb) for the cyclic type, is particularly preferably used as cocatalyst:

moreover, in formulas (IIIa) and (IIIb), the residues R ¹⁸ may be the same or different and represent a C ₁ -C ₆ alkyl group, a C ₆ -C ₁₈ aryl group, benzyl or hydrogen; and “p” is an integer of 2-50, preferably 10-35.

Preferably, the R ¹⁸ moieties are the same and are methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.

If the R ¹⁸ residues are different, then they are preferably methyl and hydrogen, or alternatively methyl and isobutyl, with hydrogen or isobutyl preferably being contained in an amount up to 0.01-40% [residue number R ¹⁸ ].

 Methods for producing alumoxanes are known.

 Regardless of the type of preparation, for all solutions of alumoxane, a common variable is the content of unreacted starting aluminum compound, which is in free form or in the form of an adduct.

 You can pre-activate the metallocene before use in the polymerization reaction using alumoxane formula (IIIa) and / or formula (IIIb). Due to this, the polymerization activity is clearly increased and the morphology of the grain composition is improved. The preactivation of the transition metal compound is carried out in solution. While preferably metallocene is dissolved in a solution of alumoxane in an inert hydrocarbon. An inert hydrocarbon is an aliphatic or aromatic hydrocarbon. Toluene is preferably used.

The concentration of alumoxane in the solution is in the range of about 1 weight. % to the saturation border, preferably 5-30 wt.% based on the total amount of solution. The metallocene can be used in the same concentration, but preferably it is used in an amount of 10 ^-4 to 1 mol per mol of alumoxane. Preactivation lasts from 5 minutes to 60 hours, preferably 5-60 minutes. Work at a temperature of from -78 ^o C to 100 ^o C, preferably at 0 - 70 ^o C.

 Using metallocene, prepolymerization can be carried out. For prepolymerization, the olefin used in the polymerization or one of the olefins used in the polymerization is preferably used.

 To control the morphology of the grain composition, metallocene can also be applied to a carrier. Suitable carriers are, for example, silica gels, aluminas, solid alumoxane or other inorganic carriers, such as magnesium chloride. A suitable carrier is also a powder of a polyolefin in a finely divided form. The preparation of a supported cocatalyst, for example, can be carried out as described in European Patent 578838.

 When using the above cocatalysts, the actual [active] polymerization catalyst consists of a reaction product of a metallocene with one of these compounds. Therefore, this reaction product is first obtained, preferably outside the polymerization reactor, in a separate step, using a suitable solvent.

 To remove the catalytic poisons present in the olefin, it is preferable to purify with an aluminum alkyl, for example trimethylaluminum or triethylaluminum. This purification can be carried out in the polymerization system itself, or the olefin is contacted with an aluminum compound before being added to the polymerization system and then separated again.

The polymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or periodically, in single or multi-stage, at a temperature of from -60 ^o C to 250 ^o C, preferably at 30-100 ^o C, particularly preferably at 50-80 ^o C.

 As a molecular weight regulator and / or to increase activity, hydrogen is added, if necessary. The total pressure in the polymerization system is 0.5-100 bar. It is preferable to carry out the polymerization in a particularly technologically interesting pressure range from 5 to 64 bar.

In this case, the metallocene is used in a concentration calculated on the transition metal, 10 ^-3 - 10 ^-8 , preferably 10 ^-4 - 10 ^-7 mol of the transition metal per dm ^{3 of} solvent, respectively per dm ³ of reactor volume. Alumoxane is used in a concentration of 10 ⁻⁵ to 10 ⁻¹ mol, preferably 10 ⁻⁴ to 10 ⁻² mol, per dm ^{3 of} solvent, respectively, per dm ³ of reactor volume. The other specified cocatalysts are used in approximately equimolar amounts with respect to the metallocene. In principle, however, higher concentrations are also possible.

 When the polymerization is carried out in the form of suspension polymerization or solution polymerization, an inert solvent conventional for the Ziegler low pressure method is used. For example, they work in an aliphatic or cycloaliphatic hydrocarbon; as such should be mentioned, for example, propane, butane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane. Then you can use the gasoline fraction, respectively, the fraction of hydrogenated diesel oil. Toluene is also applicable. Preferably polymerized in a liquid monomer.

 If inert solvents are used, the monomers are added in a gaseous or liquid state.

 The duration of the polymerization is any, since for the catalyst system used according to the invention, only a slight decrease in the activity with respect to polymerization is observed over time.

 The polymers obtained by the method according to the invention are suitable for the manufacture of preforms (semi-finished products) and extruded press products, such as films, plates or large hollow products (for example, pipes). With a suitable choice of monomers, rubbers or elastomers can also be obtained.

The method according to the invention is characterized in that the metallocenes described in the technologically especially interesting temperature range of 50-80 ^° C. at high catalyst activities produce polymers with a very high molecular weight, in the case of prochiral monomers with a very high molecular weight and very high stereotacticity. In addition, in the synthesis of metallocene, it is possible to abandon the costly separation of isomers.

 The metallocene according to the invention is particularly characterized in that in the case of stereospecific polymerization of prochiral olefins, for example propylene, polymers with high stereoregularity and high molecular weight are obtained. Particularly in the case of isospecific polymerization of propylene, isotactic polypropylene with long isotactic block lengths and a high melting point is obtained.

 If various types of central atoms are contained in the metallocene according to the invention, polyolefins with a wide, bi- or multimodal molecular weight distribution are obtained.

 Moreover, with the help of the metallocene according to the invention, the formation of deposits in the reactor can be avoided, and for this it is not necessary to use a catalyst supported on a carrier.

 In addition, the metallocene according to the invention is suitable for the production of ethylene-containing copolymers such as rubbers or elastomers with a high proportion of comonomer and very regular incorporation of the comonomer.

 The following examples should explain the invention in more detail.

 All glass devices are heated in vacuum and purged with argon. All operations are carried out with the exclusion of moisture and oxygen in the vessels of Schlenk. The solvents used are each time freshly distilled in an argon atmosphere over the Na / K alloy and stored in Schlenk vessels.

The determination of the Al / CH ₃ ratio in aluminoxane is carried out by decomposing the sample with sulfuric acid and determining the volume of released hydrolysis gas under normal conditions, as well as by complexometric titration of aluminum in the then dissolved sample, according to Schwarzenbach.

The methylaluminoxane soluble in toluene in suspension polymerization examples and in bulk polymerization using metallocene without a carrier is used as a 10 wt.% Solution in toluene and it contains, according to the determination of aluminum content, 36 mg Al / cm ³ . The average degree of oligomerization, according to a decrease in the freezing point in benzene, is: n = 20. For a toluene-soluble methylaluminoxane, the ratio Al: CH ₃ = 1: 1.55 is determined. The following notation is introduced:
KB is the viscosity coefficient in cm ³ / g,
M _w is the weight average molecular weight in g / mol [determined by gel permeation chromatography];
M _w / M _n — molecular weight dispersion;
Mp - melting temperature in ^o C [determined using DSC, at a heating / cooling rate = 20 ^o C per minute];
II - isotactic index [P = mm + 1/2 mr; determined by ¹³ C-NMR spectroscopy];
Engineering 230/5 - melt flow index, measured according to DIN 53735; in dg / min.

The synthesis used in the examples for the polymerization of metallocenes [used educts are commercially available]:
A. 1,6- {Bis [methylsilyl bis (2-methyl-4-phenyl-indenyl) zirconium dichloride]} -hexane (1)
To a solution of 20 g (97 mmol) of 2-methyl-7-phenyl-indene in 200 ml of toluene containing no oxygen and water and 10 ml of anhydrous and oxygen-free THF in an argon atmosphere at room temperature, 36.1 was added dropwise over 30 minutes ml (97 mmol) of a 20% solution of butyl lithium in toluene. After the addition is complete, it is heated for another 2 hours at 80 ^° C. Then, for 30 minutes and at a temperature of 0-5 ^° C., 7.6 g (24.3 mmol) of 1,6-bis (methyldichlorosilyl) hexane are added dropwise in 10 ml of toluene and additionally stirred for 1.5 hours at room temperature. For processing, 100 ml of water are added, the phases are separated and the organic phase is freed from the solvent. After filtration through 200 g of silica gel (hexane / CH ₂ Cl ₂ = 5: 1), 11.7 g (48%) of the ligand system are obtained in the form of a viscous oil.

To a solution of 11.7 g (12 mmol) of ligand in 150 ml of oxygen and water-free diethyl ether, in an argon atmosphere and at room temperature, 22 ml (59 mmol) of a 20% solution of butyl lithium in toluene are added dropwise over 30 minutes. Upon completion of the addition, another 2 hours are refluxed, the solvent is removed in vacuo and the residue is filtered along with hexane through a G3 Schlenk glass filter (frit). The tetralithium salt is dried for several hours in a vacuum of an oil pump at room temperature and then, at -78 ^° C, 5.5 g (24 mmol) of zirconium tetrachloride in 200 ml of oxygen-free and anhydrous CH ₂ Cl ₂ are added to a suspension. The cooling bath was removed and further stirred for 1 hour at room temperature. The reaction mixture was filtered through a G3 Schlenk glass filter, the filtrate was removed from the solvent in vacuo, and the residue was washed many times with hexane. It is then recrystallized from toluene at -30 ^° C. 7.3 g (47%) of compound (1) are obtained as a mixture of isomers in the form of a yellow amorphous solid.

¹ H-NMR (100 MHz, CDCl ₃ ): 6.8 - 7.8 (m, 36H, aromatic H and β-H-indene); 2.1 and 2.3 (2m, 12H, CH ₂ -indene); 1.2-2.0 (m, 18H, 4CH ₂ , CH ₂ Si and CH ₃ Si). Mass spectrum: 1306 M ⁺ ; correctly decomposed sample.

B. 1,2- {Bis [methylsilyl bis (2-methyl-4-phenyl-indenyl) zirconium dichloride]} -ethane (2)
To a solution of 20 g (97 mmol) of 2-methyl-7-phenyl-indene in 200 ml of oxygen-free water and toluene and 10 ml of oxygen-free water and THF in an argon atmosphere, 36.1 g are added dropwise at room temperature for 30 minutes (97 mmol) of a 20% solution of butyl lithium in toluene. After the addition is completed, another 2 hours are heated at 80 ^° C. Then, at a temperature of 0-5 ^° C., 6.2 g (24.2 mmol) of 1,2-bis (methyldichlorosilyl) ethane are added dropwise in 10 ml of toluene and further stirred 1.5 hours at room temperature. For processing, 100 ml of water are added, the phases are separated and the solvent is removed from the organic phase. After filtration through 200 g of silica gel (hexane / CH ₂ Cl ₂ = 5: 1), 11.8 g (52%) of the ligand system are obtained in the form of a viscous oil.

To a solution of 10.8 g (11 mmol) of ligand in 150 ml of oxygen and water-free diethyl ether, in the atmosphere of argon and at room temperature, 21.5 ml (57.6 mmol) of a 20% solution of butyl lithium are added dropwise over 30 minutes in toluene. After the addition is complete, it is refluxed for another 2 hours, the solvent is removed in vacuo and the residue filtered with hexane through a G3 Schlenk glass filter (frit). The tetralithium salt is dried for several hours in a vacuum of an oil pump at room temperature and then, at -78 ^° C, 5.4 g (23 mmol) of zirconium tetrachloride in 200 ml of oxygen and water CH ₂ Cl ₂ are added to a suspension. The cooling bath was removed and further stirred at room temperature for 1 hour. The reaction mixture was filtered through a G3 Schlenk glass filter, the filtrate was removed in vacuo from the solvent, and the residue was washed many times with hexane. It is then recrystallized from toluene at -30 ^° C. 5.6 g (39%) of compound (2) are obtained as a mixture of isomers in the form of a yellow amorphous solid.

¹ H-NMR (100 MHz, CDCl ₃ ): 6.9 - 7.8 (m, 36H, aromatic H and β-H-indene); 2.3 and 2.5 (2m, 12H, CH ₃ -indene); 1.2-1.7 (m, 10H, CH ₂ Si and CH ₃ Si). Mass spectrum: 1250 M ⁺ ; correctly decomposed sample.

B. 1,6- {Bis [methylsilyl- (2-methylindenyl) (2-methyl-4-phenyl-indenyl) zirconium dichloride]} - hexane (3)
To a solution of 15 g (73 mmol) of 2-methyl-7-phenyl-indene in 150 ml of toluene and 10 ml of THF at room temperature, 27 ml (73 mmol) of a 20% solution of butyl lithium in toluene are added dropwise. After the addition is complete, it is heated for another 2 hours at 80 ^° C. Then, at 0-5 ^° C., 11.2 g (36 mmol) of 1,6-bis (methyl-dichlorosilyl) -hexane are added dropwise in 10 ml of toluene and additionally stirred for 1.5 hours at room temperature. The solvent was removed in vacuo and the residue was taken up in toluene and then precipitated LiCl was filtered off. A suspension of 2-methyl-indenyl lithium (obtained by reacting 9.5 g (73 mmol) of 2-methylindene in 100 ml of toluene and 20 ml of THF at room temperature with 27 ml (73 mmol) was added dropwise to the filtrate at room temperature for 30 minutes. ) A 20% solution of butyl lithium in toluene and additional stirring for 1 hour at 50 ^o C) and then stirred for another 2 hours at room temperature. The reaction mixture is mixed with 100 ml of water, the phases are separated and the organic phase is washed with 50 ml of water. The solvent was removed in vacuo and the residue was purified by chromatography on 500 g of silica gel (hexane / methylene chloride = 1: 1). 7.3 g (24%) of the asymmetric ligand system of compound (3) are obtained in the form of a very viscous oil.

To a solution of 7.1 g (8.4 mmol) of the ligand system of compound (3) in 50 ml of diethyl ether at room temperature and 15 ml (40 mmol) of a 20% solution of butyl lithium in toluene are added dropwise. After the addition is complete, another 2 hours are refluxed, the solvent is removed in vacuo and the residue with hexane is filtered through a G3 Schlenk glass filter (frit). The tetralithium salt is dried for several hours in a vacuum of an oil pump at room temperature and then, at -78 ^° C, 3.7 g (16 mmol) of zirconium tetrachloride in 50 ml of oxygen and water CH ₂ Cl ₂ are added to the suspension. The cooling bath was removed and further stirred for 1 hour at room temperature. The reaction mixture was filtered through a G3 Schlenk glass filter (frit), the residue was further extracted with 200 ml of methylene chloride and the combined filtrates were then removed from the solvent in vacuo. The residue was washed repeatedly with a mixture of hexane and methylene chloride in a ratio of 1: 1 and then dried. 4.2 g (43%) of compound (3) are obtained as a yellow amorphous solid.

¹ H-NMR (100 MHz, CDCl ₃ ): 6.7-8.0 (m, 28H, aromatic H and β-H-indene); 2.1 and 2.3 (2m, 12H, CH ₃ -indene); 1.2-2.0 (m, 18H, 4CH ₂ , CH ₂ Si and CH ₃ Si).

G. 1,2- {Bis [methylsilyl- (indenyl) (2-methyl-4-phenyl-indenyl) zirconium dichloride]} - ethane (4)
To a solution of 15 g (73 mmol) of 2-methyl-7-phenyl-indene in 150 ml of diethyl ether and 8 ml of THF at room temperature, 27 ml (73 mmol) of a 20% solution of butyl lithium in toluene are added dropwise. After the addition is completed, another 2 hours are heated at 80 ^° C. Then, at 0-5 ^° C., 11.2 g (36 mmol) of 1,2-bis (methyldichlorosilyl) ethane are added dropwise in 10 ml of toluene and the mixture is further stirred 1, 5 hours at room temperature. The solvent was removed and the residue was treated with toluene and then precipitated LiCl was filtered off. A suspension of indenyl lithium (obtained by reacting 8.5 g (73 mmol) of indene in 100 toluene and 20 ml of THF at room temperature with 27 ml (73 mmol) of a 20% solution is added dropwise to the filtrate at room temperature for 30 minutes. butyl lithium in toluene and further stirred for 1 hour at 50 ^° C.) and then further stirred for another 2 hours at room temperature. The reaction mixture is mixed with 100 ml of water, the phases are separated and the organic phase is washed with 50 ml of water. The solvent was removed in vacuo and the residue was purified by chromatography on 500 g of silica gel (hexane / methylene chloride = 1: 1). 9.3 g (31%) of the asymmetric ligand system of compound (4) are obtained as a very viscous oil.

To a solution of 9.1 g (11 mmol) of the ligand system of compound (4) in 150 ml of diethyl ether at room temperature, 17 ml (46 mmol) of a 20% solution of butyl lithium in toluene are added dropwise. At the end of the addition, another 2 hours is refluxed. The solvent was removed in vacuo and the residue with hexane was filtered through a G3 Schlenk glass filter (frit). The tetralithium salt is dried for several hours in a vacuum of an oil pump at room temperature and then, at -78 ^° C, 4.9 g (21 mmol) of zirconium tetrachloride in 200 ml of methylene chloride are added to a suspension. The cooling bath was removed and further stirred for 1 hour at room temperature. The reaction mixture was filtered through a G3 Schlenk glass filter (frit), the residue was further extracted with 400 ml of methylene chloride, and the combined filtrates were then removed from the solvent. The residue is washed repeatedly with 10 ml of methylene chloride and then dried. Obtain 4.3 g (34%) of compound (4) as a yellow amorphous solid.

¹ H-NMR (100 MHz, CDCl ₃ ): 6.9 - 7.8 (m, 28H, aromatic H and β-H-indene); 6.3 (m, 2H, α-H-indene); 2.4 (m, 6H, CH ₃ -indene); 1.2-2.0 (m, 18H, 4CH ₂ , CH ₂ Si and CH ₃ Si).

D. 1,6- {Bis [methylsilyl- (2,3,5-trimethyl-cyclopentadienyl) (2-methyl-4-phenyl-indenyl) zirconium dichloride]} - hexane (5)
To a solution of 15 g (73 mmol) of 2-methyl-7-phenyl-indene in 150 ml of toluene and 8 ml of THF at room temperature, 27 ml (73 mmol) of a 20% solution of butyl lithium in toluene are added dropwise. After the addition is complete, it is heated for another 2 hours at 80 ^° C. Then, at 0-5 ^° C., 11.2 g (36 mmol) of 1,6-bis (methyldichlorosilyl) -hexane in 10 ml of toluene are added dropwise and the mixture is further stirred 1 5 hours at room temperature. The solvent was removed and the residue was treated with toluene and then precipitated LiCl was filtered off. A suspension of 1,2,4-trimethylcyclopentadienyl lithium [obtained by reacting 7.9 g (73 mmol) of 1,2,4-trimethylcyclopentadiene in 100 ml of toluene and 20 ml of THF at room temperature from 27 is added dropwise to the filtrate at room temperature for 30 minutes. ml (73 mmol) of a 20% solution of butyl lithium in toluene and further stirred for 1 hour at room temperature] and then stirred for another 2 hours at room temperature. The reaction mixture is mixed with 100 ml of water, the phases are separated and the organic phase is washed with 50 ml of water. The solvent was removed in vacuo and the residue was purified by chromatography on 700 g of silica gel (hexane / ethyl acetate = 5: 1). 13.5 g (47%) of the ligand system of compound (5) are obtained as a very viscous oil.

To a solution of 13 g (16.5 mmol) of the ligand system of compound (5) in 150 ml of diethyl ether at room temperature, 26 ml (70 mmol) of a 20% solution of butyl lithium in toluene are added dropwise. Upon completion of the addition, another 2 hours are refluxed, the solvent is removed in vacuo and the residue together with hexane is filtered through a G3 Schlenk glass filter (frit). The tetralithium salt is dried for several hours in a vacuum of an oil pump at room temperature and then, at -78 ^° C, 7.5 g (32 mmol) of zirconium tetrachloride in 150 ml of methylene chloride are added to a suspension. The cooling bath was removed and further stirred for 1 hour at room temperature. The reaction mixture was filtered through a G3 Schlenk glass filter (frit), the residue was further extracted with 100 ml of methylene chloride and the combined filtrates were then removed from the solvent in vacuo. The residue was washed repeatedly with hexane and then dried. 6.1 g (36%) of compound (5) are obtained as a yellow amorphous solid.

¹ H-NMR (100 MHz, CDCl ₃ ): 6.9-8.0 (m, 18H, aromatic H and β-H-indene); 6.4 (s, 1H, H-cyclopentadiene); 1.9-2.2 (m, 24H, CH ₃ -indene and cyclopentadiene); 1.2-2.0 (m, 18H, 4CH ₂ , CH ₂ Si and CH ₃ Si).

E. 1,6- {Bis [methylsilyl- (3-isopropyl-cyclopentadienyl) (fluorenyl) zirconium dichloride]} - hexane (6)
To a solution of 10 g (60 mmol) of fluorene in 100 ml of toluene and 10 ml of diethyl ether at room temperature, 22 ml (60 mmol) of a 20% solution of butyl lithium in toluene are added dropwise. After completion of the addition, another 2 hours are heated at 80 ^° C. Then, at 0-5 ^° C., 7.8 g (30 mmol) of 1,6-bis / methyldichlorosilyl / hexane are added dropwise in 10 ml of toluene and the mixture is further stirred 1 hour at room temperature. The solvent was removed and the residue was treated with toluene and then precipitated LiCl was filtered off. A suspension of isopropylcyclopentadienyl lithium (obtained by reacting 6.5 g (60 mmol) of isopropylcyclopentadiene in 100 ml of toluene and 10 ml of diethyl ether at room temperature with 22 ml (60 mmol) of a 20% butyl lithium solution was added dropwise to the filtrate at room temperature for 30 minutes. in toluene and further stirred for 1 hour at room temperature) and then further stirred for another 2 hours at room temperature. The reaction mixture is mixed with 100 ml of water, the phases are separated and the organic phase is washed with 50 ml of water. The solvent was removed in vacuo and the residue was purified by chromatography on 700 g of silica gel (hexane / methylene chloride = 10: 1). 13.3 g (63%) of the ligand system of compound (6) are obtained as a very viscous oil.

To a solution of 13 g (18 mmol) of the ligand system of compound (6) in 150 ml of diethyl ether at room temperature, 30 ml (80 mmol) of a 20% solution of butyl lithium in toluene are added dropwise. After the addition is complete, another 2 hours are refluxed, the solvent is removed in vacuo and the residue is filtered with hexane through a G3 Schlenk glass filter (frit). The tetralithium salt is dried for several hours in a vacuum of an oil pump at room temperature and then 8.15 g (35 mmol) of zirconium tetrachloride in 150 ml of methylene chloride are added to the suspension at -78 ^° C. The cooling bath was removed and further stirred for 1 hour at room temperature. The reaction mixture was filtered through a G3 Schlenk glass filter (frit), the residue was further extracted with a total of 300 ml of methylene chloride, and the combined filtrates were further concentrated in vacuo to approximately 1/3 of its volume. At -20 ^° C., 4.6 g (27%) of compound (6) crystallize from this residue as a yellow amorphous solid.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.1 - 8.2 (m, 16H, arom H); 5.5; 5.7 and 6.3 (3m, 6H, H-cyclopentadiene); 2.9 (m, 2H, isopropyl); 1.0-2.0 (m, 30H, 4CH ₂ , CH ₂ Si and CH ₃ -isopropyl).

Polymerization Examples
Example 1
The dried reactor with a capacity of 16 dm ³ is first flushed with nitrogen and then with propylene and 10 dm ^{3 of} liquid propylene are charged. Then 30 cm ^{3 of a} toluene solution of methylaluminoxane are added and the mixture is stirred at 30 ^° C. In parallel, 3.4 mg of metallocene (1) is dissolved in 20 cm ^{3 of a} toluene solution of methylaluminoxane (23 mmol Al) and left to stand for 15 minutes to proceed. The solution is then added to the reactor, heated to a polymerization temperature of 50 ^° C (4 ^° C / min) by adding heat, and the polymerization system is kept at cooling at 50 ^° C for 1 hour. By adding 20 ml of isopropanol, the polymerization is stopped, the excess monomer is degassed and the polymer is dried in vacuo. 0.17 kg of polypropylene is obtained.

The activity of the catalyst is 50 kg of polypropylene / g of metallocene per hour. KB = 1041 cm ³ / g; so pl. = 154 ^o C; extractable heptane, the proportion is 1.3%; M _w / M _n = 6.4.

Example 2
The polymerization of Example 1 is repeated, with the difference that 4.3 mg of metallocene (1) are used and the polymerization temperature is 60 ^° C. 0.45 kg of polypropylene is obtained.

The activity of the catalyst is 105 kg of polypropylene / g of metallocene per hour. KB = 764 cm ³ / g; so pl. = 154 ^o C; extractable with heptane, the proportion is 1.9%; M _w / M _n = 2.9.

Example 3
The polymerization of Example 1 was repeated, with the difference that 4.4 mg of metallocene (1) was used and the polymerization temperature was 70 ^° C. 1.08 kg of polypropylene was obtained. The reactor contains only a very thin layer of sediment on the inner wall and on the mixer.

The activity of the catalyst is 245 kg of polypropylene / g of metallocene per hour. KB = 518 cm ³ / g; so pl. = 153 ^o C; extractable with heptane, the proportion is 2.4%; M _w / M _n = 2.7.

Example 4
The polymerization of Example 1 was repeated, with the difference that 2.7 mg of metallocene were used (2). 0.17 kg of polypropylene is obtained.

The activity of the catalyst is 31 kg of polypropylene / g of metallocene per hour. KB = 845 cm ³ / g; so pl. = 154 ^o C; M _w / M _n = 3.7. extractable with heptane, the proportion is 7.7%.

Example 5
The polymerization of Example 1 is repeated, with the difference that 4.3 mg of metallocene (2) are used and the polymerization temperature is 60 ^° C. 0.71 kg of polypropylene is obtained.

The activity of the catalyst is 74 kg of polypropylene / g of metallocene per hour. KB = 564 cm ³ / g; so pl. = 153 ^o C; M _w / M _n = 3.0; extracted with heptane, the proportion is 4.6%.

Example 6
The polymerization of Example 1 is repeated, with the difference that 3.8 mg of metallocene (2) are used and the polymerization temperature is 70 ^° C. 0.95 kg of polypropylene are obtained. The reactor has only a very thin layer of sediment on the inner wall and on the stirrer.

The activity of the catalyst is 125 kg of polypropylene / g of metallocene per hour. KB = 392 cm ³ / g; so pl. = 153 ^o C; M _w / M _n = 2.6; extractable with heptane, the proportion is 4.1%.

Example 7
The dried 24 dm ³ reactor is purged with propylene and 12 dm ^{3 of} liquid propylene is charged. Then add 30 cm ³ toluene solution of methylaluminoxane (40 mmol Al) and the mixture is stirred for 5 minutes at 30 ^o C.

In parallel, 2.0 mg of compound (3) was dissolved in 15 cm ^{3 of a} toluene solution of methylaluminoxane (20 mmol Al) and left to stand for 5 minutes for the reaction to proceed. The solution is then introduced into the reactor, heated to a polymerization temperature of 70 ^° C. (7 ^° C./min.) By applying heat, and the polymerization system is held at 70 ^° C. for 1 hour by cooling. The polymerization is stopped by the addition of 10 normal DM ^{3 of} gaseous CO ₂ . The excess monomer is degassed, the polymer is dried in vacuo. 0.51 kg of polypropylene is obtained.

The activity of the catalyst is 255 kg of polypropylene / g of metallocene per hour. KB = 365 cm ³ / g; so pl. = 154 ^o C; II = 97.5%; MFI (230/5) = 2.8 dg / min; M _w = 517599 g / mol; M _w / M _n = 2.4.

Example 8
Do as in example 7, however, the polymerization temperature is 50 ^o C. the activity of the catalyst is 134 kg of polypropylene / g metallocene per hour. KB = 517 cm ³ / g; so pl. = 159 ^o C; II = 98.4%; MFI (230/5) = 0.9 dg / min; M _w = 786500; M _w / M _n = 2.4.

Example 9
Act as in example 7, however, the metallocene used is compound (4).

The activity of the catalyst is 402 kg of polypropylene / g of metallocene per hour. KB = 142 cm ³ / g; so pl. = 152 ^o C; II = 96.9%; Engineering (230/5) = 86 dg / min; M _w = 153500 g / mol; M _w / M _n = 2.0.

Example 10
Do as in example 9, however, the polymerization temperature is 50 ^o C. the activity of the catalyst is 176 kg of polypropylene / g of metallocene per hour. KB = 237 cm ³ / g; so pl. = 155 ^o C; II = 97.9%; Engineering (230/5) = 20 dg / min; M _w = 301500; M _w / M _n = 2.7.

Example 11
The procedure is as in Example 7, however, the metallocene used is compound (4) and the polymerization temperature is 50 ^° C. The catalyst activity is 101 kg of polypropylene / g metallocene per hour. KB = 476 cm ³ / g; so pl. = 157 ^o C; AI = 98%; MFI (230/5) = 1.8 dg / min; M _w = 698500; M _w / M _n = 5.8.

Example 12
The dried reactor with a capacity of 24 dm ^{3 was} purged with propylene and loaded with 12 norms. dm ³ hydrogen and 12 dm ³ liquid propylene. Then add 30 cm ³ toluene solution of methylaluminoxane (respectively 40 mmol of Al). In parallel, 2.5 mg of compound (3) was dissolved in 15 cm ^{3 of a} toluene solution of methylaluminoxane (20 mmol Al) and preactivated by incubation for 15 minutes. The solution was then added to the reactor and, with the addition of 60 g of ethylene, polymerization was carried out at 60 ^° C. for 2 hours. The metallocene activity is 205 kg of polypropylene / g metallocene per hour. The ethylene content in the copolymer is 5.4 wt.%.

KB = 339 cm ³ / g; M _w = 384000 g / mol; M _w / M _n = 2.0; so pl. = 136 ^o C; according to NMR spectroscopy, ethylene is predominantly incorporated separately (statistical copolymer).

Example 13
The dried reactor of 150 dm ³ was purged with nitrogen and at 20 ^o C was charged with 80 dm ³ dearomatised gasoline fraction boiling range 100-120 ^o C. Then the gas space was purged, in the absence of nitrogen, by 5-fold 2 propylene pressurization and depressurization of Bar . After adding 50 L of liquid propylene, add 75 cm ^{3 of a} toluene solution of methylaluminoxane (respectively 100 mmol Al) and the contents of the reactor are heated to 50 ^o C. By adding hydrogen, the hydrogen content in the gas space of the reactor is set to 2.0% and then it is maintained constant by additional introducing propylene during the entire copolymerization process (line check by gas chromatography). 16.0 mg of compound (3) was dissolved in 37.5 ml of a methylaluminoxane toluene solution (respectively 50 mmol of Al) and added to the reactor after 15 minutes.

By cooling in the reactor for 11 hours, the polymerization temperature is maintained at 50 ^° C. After removal of hydrogen and propylene up to the pressure of propylene in the reactor, 1.0 bar, after addition of 2.5 kg of ethylene, polymerization is carried out at 50 ^° C. for the next 5 hours. the addition of gaseous CO ₂ to a pressure of 2 bar, the polymerization is stopped and the resulting polymer is separated on the filter (suction) under pressure from a suspension medium. Drying of the product is carried out 24 hours at 80 ^o C under a pressure of 200 mbar. Get 17.5 kg of block copolymer powder, which corresponds to the activity of metallocene 1093 kg of polypropylene / g metallocene per hour.

KB = 209 cm ³ / g; M _w = 217500 g / mol; M _w / M _n = 2.3; so pl. = 156 ^o C; Engineering (230/5) = 12 dg / min. The block copolymer contains 12.2 wt.% Ethylene. Fractionation gives a content of 28.4 wt.% Ethylene / propylene rubber. The glass transition temperature of rubber is -52 ^o C.

Example 14
Example 7 is repeated, however, 2.5 holes are added to the reactor additionally before propylene is added. m ^{3 of} hydrogen. The metallocene activity is 589 kg of polypropylene / g metallocene per hour. KB = 139 cm ³ / g; M _w = 149500 g / mol; M _w / M _n = 1.9; so pl. = 158 ^o C.

Example 15
The dried 16 dm ³ reactor is first purged with nitrogen and then purged with propylene and 10 dm ^{3 of} liquid propylene are charged. Then add 30 cm ³ toluene solution of methylaluminoxane and the mixture is stirred at 30 ^o C. In parallel, 3.0 mg of compound (5) is dissolved in 20 cm ^{3 of} toluene solution of methylaluminoxane (23 mmol Al) and left to stand for 15 minutes to proceed the reaction . The solution is then introduced into the reactor, heated to a polymerization temperature of 50 ^° C (4 ^° C / min) by heat, and the polymerization system is cooled for 1 hour at 50 ^° C. By adding 20 ml of isopropanol, the polymerization is stopped, the excess monomer is degassed and the polymer is dried in vacuo. Get 0.56 kg of polypropylene. There are essentially no deposits on the inner wall and on the reactor stirrer.

The activity of the catalyst is 189 kg of polypropylene / g of metallocene per hour. KB = 449 cm ³ / g; so pl. = 158 ^o C; M _w = 529500 g / mol; M _w / M _n = 2.2.

Example 16
The polymerization of Example 1 is repeated, with the difference that 5.6 mg of compound (6) is used and the polymerization temperature is 70 ^° C. 0.17 kg of rubbery polypropylene is obtained. There are essentially no deposits on the inner wall and on the reactor stirrer.

The activity of the catalyst is 30 kg of polypropylene / g of metallocene per hour. KB = 80 cm ³ / g; isotactic Pentaden ( ¹³ C-NMR) = 58% mmmm.

Claims (9)

1. Multicore metallocene compounds of the formula I

where M ¹ denotes a metal of group IVb of the Periodic system of elements;
X represents a halogen atom;
L and L 'are the same or different and denote a π ligand selected from the group consisting of substituted cyclopentadienyl, optionally substituted indenyl and unsubstituted fluorenyl;
k is 2;
B stands for

wherein R ¹ is a divalent hydrocarbon-containing bridging group, the residues of R ² are the same and are a hydrocarbon-containing residue, which is a C ₁ -C ₄ alkyl group;
M ² is silicon. 2. Multicore metallocene compounds according to claim 1, corresponding to the formula II

where M ¹ denotes a metal of group IVb of the Periodic system of elements;
X represents a halogen atom;
residues R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, a C ₁ - C ₁₀ alkyl group, a C ₆ - C ₂₀ aryl group or two adjacent residues R ⁷ and R ⁸ together with binding their atoms form an aromatic cyclic system;
R ⁹ - R ¹⁴ are the same or different and represent a hydrogen atom, a C ₁ - C ₁₀ alkyl group, a C ₆ - C ₂₀ aryl group or two adjacent residues R ⁹ and R ¹⁰ together with the atoms bonding them form an aromatic ring system;
k is 2;
B stands for

wherein R ¹ is a divalent linear C ₁ -C ₆ -alkyl group, in particular 1,2-ethylene or 1,6-hexylene, the residues of R ² are the same and represent a C ₁ -C ₄ -alkyl group;
M ² is silicon. 3. The multicore metallocene compound according to claim 2 of formula II, wherein M ¹ is zirconium or hafnium.  4. Multicore metallocene compounds according to claims 1 to 3, used for the polymerization of olefins. 5. A method for producing a multicore metallocene compound of the formula I according to claim 1, characterized in that the compounds LH and L'H are deprotonated with a base and reacted with reagent A-2

to obtain a compound of formula A-3 or one of its isomers

which is then deprotonated with 4 equivalents of base and reacted with 2 equivalents of metal tetrahalide to give compound A-4

6. A catalytic system for producing a polyolefin containing a multicore metallocene compound and cocatalyst alumoxane, characterized in that it contains a compound of formula I as a multicore metallocene compound

where M ¹ denotes a halogen atom;
L and L 'are the same or different and denote

a ligand selected from the group consisting of substituted cyclopentadienyl, optionally substituted indenyl and unsubstituted fluorenyl;
k is 2;
B stands for

wherein R ¹ is a divalent hydrocarbon-containing bridging group, the residues of R ² are the same and is a hydrocarbon-containing residue, which is a C ₁ -C ₄ -alkyl group;
M ² is silicon. 7. The catalytic system according to claim 6, characterized in that as a multicore metallocene compound, it contains a compound of formula II

where M ¹ denotes a metal of group IVb of the Periodic system of elements;
X represents a halogen atom;
R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, a C ₁ - C ₁₀ alkyl group, a C ₆ - C ₂₀ aryl group or two adjacent residues R ⁷ and R ⁸ together with their binding atoms form an aromatic cyclic system;
R ⁹ - R ¹⁴ are the same or different and represent a hydrogen atom, a C ₁ - C ₁₀ alkyl group, a C ₆ - C ₂₀ aryl group or two adjacent residues R ⁹ and R ¹⁰ together with the atoms bonding them form an aromatic ring system;
k is 2;
B stands for

wherein R ¹ is a divalent linear C ₁ –C ₆ alkyl group, in particular 1,2-ethylene or 1,6-hexylene, and the residues of R ² are the same and represent a C ₁ –C ₄ alkyl group;
M ² is silicon. 8. The catalytic system according to p. 7, characterized in that as a multicore metallocene compound it contains a compound of formula II, in which M ¹ denotes zirconium or hafnium. 9. A method of producing a polyolefin by polymerizing at least one olefin in the presence of a catalytic system containing a multicore metallocene compound and cocatalyst-alumoxane, characterized in that the process is carried out in the presence of a catalytic system containing as a multicore metallocene compound a compound of formula I

where M ¹ denotes a metal of group IVb of the Periodic system of elements;
X represents a halogen atom;
L and L 'are the same or different and denote

a ligand selected from the group consisting of substituted cyclopentadienyl, optionally substituted indenyl and unsubstituted fluorenyl;
k is 2;
B stands for
π
wherein R ¹ is a divalent hydrocarbon-containing bridging group, the residues of R ² are the same and is a hydrocarbon-containing residue, which is a C ₁ -C ₄ -alkyl group;
M ² is silicon.  10. A polymer molded product, characterized in that it is made of at least one polyolefin obtained by the method according to claim 9.