DE19632558A1 - Supported organo-metallic compounds useful as co-catalyst in highly active olefin polymerisation catalyst system - Google Patents

Abstract

Supported chemical compounds of formula (I) are new. Ac<+> = a cation; c = 1-10; b \- 0; T = a support; y \- 1; a = 0-10; a <.>y = c <.> b; N = a unit of formula (II); R = substituents, e.g. halogen or groups containing 1-40 carbon (C) atoms; X = 1-40 C groups; M = group IIa, IIIa, IVa and/or Va element(s); d, e, f = 0 or 1; g, h, k, r = 0-10; i = 0-1000; j = 1-6; S = spacers forming a covalent bond between M and T; w, z = 0, 1 or 2. Also claimed are (a) catalyst system containing (I); (b) the preparation of a polyolefin by polymerising olefin(s) in the presence of this catalyst system; and (c) polyolefins prepared in this way.

Description

The present invention relates to a supported chemical compound, which can be neutral or ionic and in combination with one Metallocene can form a catalyst system, which is suitable for polymerization of olefins. Here, the use of aluminoxanes such as Methyl aluminum oxane is not used as a cocatalyst and is still high Catalyst activity can be achieved.

The role of cationic complexes in Ziegler-Natta polymerization Metallocenes are generally recognized (M. Bochmann, Nachr. Chem. Lab. Techn. 1993, 41, 1220).

MAO as the most effective cocatalyst to date has the disadvantage of being very high Excess to be used. The representation of cationic alkyl complexes opens the way to MAO-free catalysts with comparable activity. The synthesis of cationic alkyl complexes is successful

• a) Protolysis of metallocene compounds with weak, for example acidic ammonium salts of the very stable, non-basic Tetra (pentafluorophenyl) borate (e.g. [PhMe₂NH] ⁺ [B (C₆F₅) ₄] ⁻),
• b) by abstraction of an alkyl group from metallocene compounds with With the help of strong Lewis acids, both salts of Form (Ph₃C⁺BR₄⁻) as well as strong, neutral Lewis acids such as B (C₆F₅) ₃ can serve or through
• c) Oxidation of metallocene dialkyl complexes with, for example, AgBPh₄ or [Cp₂Fe] [BPh₄].

The synthesis of "cation-like" metallocene Polymerization catalysts, is in J. Am. Chem. Soc. 1991, 113, 3623 described. In it the alkyl abstraction from one Metallocene dialkyl compound using tris (pentafluorophenyl) borane. This synthesis principle and a corresponding one is described in EP 427,697 Catalyst system consisting of a neutral metallocene species (e.g. Cp₂ZrMe₂), a Lewis acid (e.g. B (C₆F₅) ₃) and aluminum alkyls claimed. A process for the preparation of salts of the general form LMX⁺ XA⁻ according to the principle described above is in EP 520.732 claimed.

EP 558, 1 58 claims zwitterionic catalyst systems which are prepared from metallocene dialkyl compounds and salts of the form [R₃NH] ⁺ [BPh₄] ⁻. The implementation of such a salt with z. B. Cp _* ₂ZrMe₂ provides a zirconocenemethyl cation by protolysis with methane elimination. This reacts via CH activation to the zwitterion Cp _* ₂Zr⁺- (m-C₆H4) -BPh₃⁻.

According to this reaction principle, one is formed after protolysis Metallocene dialkyl species with a perfluorinated [R₃NH] ⁺ [B (C₆F₅) ₄] ⁻ salt in first step also a cationic species, now the subsequent reaction (C-H activation) to zwitterionic complexes is not possible. It thus form salts of the form [Cp₂Zr-R-RH] ⁺ [B (C₆F₅) ₄] so. In US 5,348,299 Corresponding systems are claimed, with dimethylanilinium salts perfluorinated tetraphenylborate anions can be used. The carrier such systems serve a better morphology of the polymer and is in WO 9109882.

The disadvantage of previous carrier methods, as described in WO91 / 09882 are described, is that the ionic catalyst system only is physically bound to the carrier. It can therefore easily pass through  Solvent can be detached from the carrier surface. The then carried out homogeneous polymerization leads to a poorer morphology of the polymer.

The present invention thus relates to a supported chemical compound, as well as a process for producing this supported chemical compound, which is covalently bound to a carrier material. It also affects one Catalyst system containing at least one transition metal compound and at least one supported chemical compound according to the invention as Cocatalyst. In addition, a process for the production of polyolefins in Presence of the supported chemical compound described.

The supported chemical compound consists of a carrier T, y units N. of formula (II) below, which is covalent to the support are bound as well as b units A.

The supported chemical compound has the general formula (I)

wherein
A ^{c + is} a cation,
c is an integer from 1 to 10,
b is an integer 0,
T is a carrier
y is an integer 1,
a is an integer from 0 to 10, where a · y = c · b, and
N is a unit of formula (II)

wherein
R independently of one another are identical or different substituents of M such as a halogen atom or a C₁-C₄₀ carbon-containing group is such as a C₁-C₄₀-alkyl, C₁-C₄₀-halogeno-alkyl, C₆-C₄₀-aryl, C₆-C₄₀ -Halo-aryl, C₇-C₄₀- arylalkyl or C Halogen-C₄₀-halogeno-arylalkyl group,
X, independently of one another, the same or different, are a C₁-C₄₀ carbon-containing group, for. B. a divalent carbon-containing group such as a C₁-C₄₀-alkylene, C₁-C₄₀-halogeno-alkylene, C₆-C₄₀-arylene, C₆-C₄₀-halogeno-arylene, C₇-C₄₀-arylalkylene or C₇-C₄₀ - Halogen-arylalkylene, C₂-C₄₀-alkynylene, C₂-C₄₀-halogeno-alkynylene, C₂-C₄₀-alkenylene or C₂-C₄₀-halogeno-alkenylene group, or a three-membered carbon-containing group such as a C₁-C₄₀- Alkantriyl-, C₁-C₄₀- haloalkanetriyl-, C₆-C₄₀-arentriyl-, C₆-C₄₀-halarenetriyl-, C₇-C₄₀-arenalkanetriyl-, C₇-C₄₀-halarenalkanetriyl-, C₂-C₄₀-alkynetriyl-, C₂-C₄₀-halo -, C₂-C₄₀-alkentriyl or C₂-C₄₀-haloalkentriyl group,
M are, independently of one another, the same or different and represent an element of group IIa, IIIa, IVa or Va of the periodic table of the elements,
d is 0 or 1, e is 0 or 1, f is 0 or 1,
g is an integer from 0 to 10, h is an integer from 0 to 10, k is an integer from 0 to 10, r is an integer from 0 to 10,
i is an integer from 0 to 1000,
j is an integer from 1 to 6,
S are the same or different spacers which connect M covalently to T,
w are the same or different 0, 1 or 2, and z is 1 or 2.

If a = 0, it is a neutral unit N; if a is 1, so it is a negatively charged unit N.

Each of the y units N of the formula (II) is from M via one or more Spacer S covalently bound to the carrier T. Each spacer S can be a or have several covalent bonds to the carrier T. This is in formula (I), (II), (III) and (IV) symbolized by the sign. The clarity for the sake of formula (II), the bond to the support (i.e.) is exemplary only for a spacer S, but the other spacers S can also be used tie to the carrier.

The supported chemical compound of formula (I) has several groups MRS, these can be the same or different. The number the substituent R in a group MRS depends on the valency and the Binding of M. Preferred is z = 1 and all w = 0.

The spacer S preferably has the formula (III)

wherein R ', the same or different, is a C₁-C₄₀ carbon-containing group such as a C₁-C₄₀ alkylene, C₁-C₄₀ halogen alkylene, C₆-C₄₀ arylene, C₆-C₄₀ halogen arylene, C₇- C₄₀-arylalkylene or C₇-C₄₀-halo-arylalkylene, C₂-C₄₀-alkynylene, C₂-C₄₀-haloalkynylene, C₂-C₄₀-alkenylene, C₂-C₄₀-halo-alkenylene, C₁-C₄₀- Aryleneoxy-, C₁-C₄₀-alkylarylenoxy-, a C₁-C₄₀-arylalkyleneoxy group, -NR ′ ′ -, -CO-, -CO₂-, -PR ′ ′ -, -P (O) R ′ ′ -, - Si (R ′ ′) ₂-O-Si (R ′ ′) ₂-, -CO-SiR′′₂-, or -CONR ′ ′ - where R ′ ′ is a C₁-C₄₀ carbon-containing group like a C₁- C₄₀-alkyl, C₁-C₄₀-halogeno-alkyl, C₆-C₄₀-aryl, C₆-C₄₀-halo-aryl-, C₇-C₄₀-arylalkyl- or C₇-C₄₀-halo-arylalkyl-, C₂-C₄₀- Alkynyl, C₂-C₄₀ halogeno-alkynyl, C₂-C₄₀ alkenyl, C₂-C₄₀ halo alkenyl, C₁-C₄₀ aryloxy, C₁-C₄₀ alkylaryloxy or a C₁-C₄₀ arylalkyloxy group, or R is a heteroatom-containing group such as -SO-, -SO₂-, -S-, -O-, -NH₂-, or -PH-,
n is an integer 1,
Q is Si, N, P, S or O,
q is 0 or 1,
B is a substituent of Q and is NH₂, PH₂ or a C₁-C₄₀ carbon-containing group such as a C₁-C₄₀-alkyl, C₁-C₄₀-halogeno-alkyl, C₆-C₄₀-aryl, C₆-C₄₀-halogeno-aryl -, C₇-C₄₀-arylalkyl or C₇-C₄₀-halogeno-arylalkyl-, C₂-C₄₀-alkynyl, C₂-C₄₀-halo-alkynyl, C₂-C₄₀-alkenyl, C₂-C₄₀-halo-alkenyl, C₁-C₄₀ aryloxy, C₁-C₄₀ alkylaryloxy or a C₁-C₄₀ arylalkyloxy group -NR′′₂, -COR ′ ′ -,
-CO₂R ′ ′ -, -PR′′₂, -P (O) R′′₂, -Si (R ′ ′) ₂-O-Si (R ′ ′) ₃-, -CO-SiR′′₃- , -CONR′′₂, -SOR ''; -SO₂R '' -, -SO₂R '', -SR '', -OR '', -NHR '' or -PHR '', where R '' is a C₁-C₄₀- carbon-containing group such as a C₁-C₄₀-alkyl -, C₁-C₄₀-halogeno-alkyl, C₆-C₄₀-aryl, C₆-C₄₀-halogeno-aryl, C₇-C₄₀-arylalkyl- or C₇-C₄₀-halogeno-arylalkyl-, C₂-C₄₀-alkynyl-, C₂-C₄₀-halogeno-alkynyl, C₂-C₄₀-alkenyl, C₂-C₄₀-halogeno-alkenyl, C₁-C₄₀-aryloxy, C₁-C₄₀-alkylaryloxy or a C₁-C₄₀-arylalkyloxy group,
and p is an integer 0.

B can connect two spacers S to one another. means an or several covalent bonds to the carrier T.

If q is 0, R ′ binds to the support, if q is 1, Q binds the carrier.

B are substituents of Q that do not bind to the support.

In formula (III), Q is particularly preferably Si and q = 1.  

R in formula (II) is preferably a C₁-C₄₀ hydrocarbon radical with Halogens such as fluorine, chlorine, bromine or iodine preferably halogenate perhalogenated can be, in particular a halogenated, in particular perhalogenated C₁- C₃₀ alkyl group such as trifluoromethyl, pentachloroethyl, heptafluoroisopropyl or Monofluoroisobutyl or a halogenated, especially perhalogenated C₆-C₃₀- Aryl group such as pentafluorophenyl, heptachloronaphthyl, heptafluoronaphthyl, Heptafluorotolyl, 3,5-bis (trifluoromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl or 2,2 ′ (octafluoro) biphenyl.

X in formula (II) is preferably a C₆-C₃₀ arylene group, a C₂-C₃₀- Alkenylene group, a C₂-C₃₀ alkynylene group, a C₆-C₃₀ arentriyl group, a C₂-C₃₀-alkentriyl group or a C₂-C₃₀-alkyne triyl group which halogenates, in particular can be perhalogenated.

Preferably j = 1 or 2 when M is a Group IIa element; j = 2 or 3 when M is a Group IIIa element; j = 3 or 4 if M is an element of group IVa and j = 4 or 5 when M is an element of group Va. M is particularly preferably an element from group IIIa., In particular boron.

i is preferably an integer from 0 to 6, particularly preferably 0 or 1.

a, b and c are preferably 0, 1 or 2.

g, h, k and r are preferably 0 or 1.

As A ^{c +} in formula (I) cations of group Ia, IIa, IIIa of the periodic table of the elements, a carbenium, oxonium or sulfonium cation or a quaternary ammonium compound are preferred, in particular carbenium ions (R₃C⁺) or quaternary ammonium ions with an acidic H function (R₃NH⁺) preferred. Quaternary ammonium salts with acidic H functions are particularly preferred.

The supported chemical represents a particularly preferred embodiment Compound of formula (IV)

wherein
M is an element of group IIIa of the periodic table of the elements,
R independently of one another are identical or different substituents of M such as a halogen atom or a C₁-C₄₀ carbon-containing group are such as a C₁-C₄₀-alkyl, C₁-C₄₀-halogeno-alkyl, C₆-C₄₀-aryl, C₆-C₄₀ - Halogen-aryl, C₇-C₄₀-arylalkyl or C₇-C₄₀-halogeno-arylalkyl group,
j is an integer from 1 to 4,
z is 1 or 2,
T is a carrier
S is a spacer which is covalently linked to T and preferably has the formula (III),
a is 0, 1 or 2,
A can be a cation of group Ia, IIa, IIIa of the Periodic Table of the Elements, a carbenium, oxonium or sulfonium cation or a quaternary ammonium compound,
b is 0, 1 or 2 and
c is 0, 1 or 2.

The carrier T is preferably a porous inorganic or organic Solid. On its surface, the y units N are covalent through one or several spacers S bound. The carrier preferably contains at least one inorganic oxide, such as silicon oxide, aluminum oxide, zeolites, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, ThO₂, Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na₂SO₄, Al₂ (SO₄) ₃, BaSO₄, KNO₃, Mg (NO₃) ₂, Al (NO₃) ₃, Na₂O, K₂O, or Li₂O, in particular silicon oxide and / or aluminum oxide. The carrier can also contain at least one polymer, e.g. B. a homo- or copolymer cross-linked polymer or polymer blends. Examples of polymers are  Polyethylene, polypropylene, polybutene, polystyrene, cross-linked with divinylbenzene Polystyrene, polyvinyl chloride, acrylic-butadiene-styrene copolymer, polyamide, Polymethacrylate, polycarbonate, polyester, polyacetal or polyvinyl alcohol.

The carrier has a specific surface area in the range from 10 to 1000 m² / g, preferably from 150 to 500 m² / g. The average particle size of the carrier is 1 to 500 μm, preferably 5 to 350 μm, particularly preferably 10 to 200 µm.

The carrier is preferably porous with a pore volume of the carrier of 0.5 to 4.0 ml / g, preferably 1.0 to 3.5 ml / g. A porous support has a certain Proportion of voids (pore volume). The shape of the pores is mostly irregular, often spherical. The pores can be small Pore openings must be connected to one another. The pore diameter is preferably about 2 to 50 nm. The particle shape of the porous support is depending on the after-treatment and can be irregular or spherical. The Particle size of the carrier can e.g. B. by cryogenic grinding and / or Sieving can be set arbitrarily.

To produce the supported chemical compound according to the invention can be a carrier starting material T-H with at least one starting compound N-G are implemented. The surface of the base material of the carrier supports this functional groups H, which preferably have the following formula (V):

- (D) _s (E) _t (V),

in which
D is Al, B, C, Si, N, P, O or S,
s is 0 or 1,
E identically or differently, a halogen, a hydroxy, carboxylic acid chloride, carboxamide, aryl halide, benzyl halide, alkyl halide, alkoxy, aryloxy, alkylamine, arylamine, alkylphosphine, arylphosphine, thioether, thio, Cyanate, isocyanate, cycloalkadienyl, sulfonic acid, aldehyde, keto, alkenyl or aryllithium group or a carbon-containing group containing cycloalkadienyl or cycloalkadienyllithium groups and
t is 1, 2, 3, 4 or 5.

The functional groups H of the carrier starting material T-H can by chemical functionalization with reactive compounds or already exist. The carrier starting material T-H can also by heating at temperatures from 50 ° C to 1000 ° C in an inert gas stream or in a vacuum at 0.01 bar to 0.001 bar or by chemical inerting by reaction with aluminum, magnesium, boron or lithium alkylene or through chemical functionalization with reactive compounds.

For example, carrier starting materials made of SiO₂ in the following way be functionalized. A suspension of SiO₂ (pretreated: 4 h; 200 ° C, 0.01 bar) in a suitable solvent, such as pentane, hexane, heptane, Toluene or dichloromethane is included with a functional group Silyl chloride compound reacted, heated at boiling temperature for several hours and then washed with a suitable solvent. The Reaction temperature is preferably at least 50 ° C, especially 50 ° C up to 150 ° C. The reaction time is 1 to 600 minutes, preferably 1 to 2 Hours. Preferably the silyl chloride compound is equimolar Ratio based on the proportion of hydroxyl groups on the surface of the SiO₂ used. The reaction is carried out under inert conditions. Suitable solvents for the washing process are e.g. B. pentane, hexane, Heptane, toluene or dichloromethane optionally mixed with amines intercept HCl. Then in a vacuum at 20 to 200 ° C. and 0.01 to 0.001 bar solvent residues removed.  

In the starting compound N-G, N is as defined in formula (II) and G are Leaving groups such as -OR², Hal, -NR²₂, -H, -CO, -SR²₂, -SO₂ or -PR²₃, wherein R² is defined as R, which upon reaction with the carrier starting material T-H forming one or more covalent bonds between N and T be split off.

Examples of starting compounds N-G are:

The reaction of T-H and N-G can be carried out in a suitable solvent such as Pentane, heptane, toluene, dichloromethane or dichlorobenzene, in which the Carrier starting material T-H is suspended and a solution of Starting compound N-G is added dropwise. Or the base material T- H is reacted with a solution of the compound N-G with stirring so that 50 to 400% of the pore volume of the carrier component can be filled. A washing process can then be carried out as described above and Residual solvents can be in a vacuum at 20 to 200 ° C and 0.01 to 0.001  be removed in cash. The production of the supported chemical compound is at -80 to 200 ° C, preferably at -20 to 100 ° C. and a contact time between 15 minutes and 25 hours, preferred performed between 15 minutes and 5 hours.

A cation A ^{c +} can then be introduced. For this purpose, the reaction product of TH and NG can be reacted with a carbon-containing alkali or alkaline earth metal compound such as lithium pentrafluorobenzene or lithium tris (trifluoromethyl) benzene and then reacted with a compound AV, in which A is as defined in formula (I) and V is one Leaving group is defined as G.

The supported chemical compound according to the invention can be used together with a transition metal compound as a catalyst system for olefin polymerization. When the supported chemical compound of the general formula (I) is reacted with a transition metal compound M 1 L _x stabilized by ligand L (here M 1 is a transition metal, L is a ligand and x is an integer from 1 to 6, which depends on the valency of M 1) b neutral compounds AL and b · c catalytically active compounds are formed

as a cocatalyst component.

The transition metal compound M¹L _x contains at least one metal central atom M¹ to which at least one n-ligand, e.g. B. a cyclopentadienyl ligand is bound. Chiral metallocenes are preferred. In addition, substituents such. B. halogen, alkyl, alkoxy or aryl groups to the metal central atom M¹. The metal central atom is preferably an element of III., IV., V. or VI. Subgroup of the Periodic Table of the Elements, in particular from the IV. Subgroup of the Periodic Table of the Elements, such as Ti, Zr or Hf.

Among cyclopentadienyl ligands are unsubstituted cyclopentadienyl radicals and substituted cyclopentadienyl radicals such as methylcyclopentadienyl, indenyl, 2- Methylindenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, benzoindenyl, Fluorenyl, benzofluorenyl, tetrahydrofluorenyl, octahydrofluorenyl residues too understand. The π ligands, e.g. B. Cyclopentadienyl ligands can be bridged or be bridged, with single and multiple bridges - too via ring systems - are possible. The term metallocene also includes Compounds with more than one metallocene fragment, so-called multinuclear Metallocenes. These can be any substitution pattern and Show bridging variants. The individual metallocene fragments of such polynuclear metallocenes can be both of the same kind and from each other to be different. Examples of such multinuclear metallocenes are e.g. B. described in (EP-A-632063, JP-A-04/80214, JP-A-04/85310, EP-A-654476).

Unbridged or bridged metallocenes of the formula are particularly preferred II,

wherein
M¹ is a metal of III., IV., V. or VI. Subgroup of the Periodic Table of the Elements, in particular Zr or Hf,
R¹ are the same or different and a hydrogen atom, SiR³, wherein R³ the same or different is a hydrogen atom or a C₁-C₄₀- carbon-containing group such as C₁-C₂₀-alkyl, C₁-C₁₀-fluoroalkyl, C₁-C₁₀- alkoxy, C₆-C₂₀-aryl Are C₆-C₁₀-fluoroaryl, C₆-C₁₀-aryloxy, C₂-C₁₀-alkenyl, C₇-C₄₀-arylalkyl, C₄₀-C₄₀-alkylaryl or C₈-C₄₀-arylalkenyl, or a C₁-C₃₀ carbon-containing group such as C₁-C₂₅ -Alkyl, e.g. B. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C₂-C₂₅-alkenyl, C₃-C₁₅-alkylalkenyl, C₆-C₂₄-aryl, C₅-C₂₄-heteroaryl such as pyridyl, furyl or quinolyl, C₇-C₃₀- arylalkyl , C₇-C₃₀-alkylaryl, fluorine-containing C₁-C₂₅-alkyl, fluorine-containing C₆- C₂₄-aryl, fluorine-containing C₇-C₃₀-arylalkyl, fluorine-containing C₇-C₃₀-alkylaryl or C₁-C₁₂-alkoxy, or two or more radicals R¹ can be so be connected to one another such that the radicals R¹ and the atoms of the cyclopentadienyl ring connecting them form a C₄-C₂₄ ring system, which in turn can be substituted,
R² are the same or different and a hydrogen atom, SiR³, wherein R³ the same or different is a hydrogen atom or a C₁-C₄₀- carbon-containing group such as C₁-C₂₀-alkyl, C₁-C₁₀-fluoroalkyl, C₁-C₁₀- alkoxy, C₆-C₁₄-aryl Are C₆-C₁₀-fluoroaryl, C₆-C₁₀-aryloxy, C₂-C₁₀-alkenyl, C₇-C₄₀-arylalkyl, C₄₀-C₄₀-alkylaryl or C₈-C₄₀-arylalkenyl, or a C₁-C₃₀ carbon-containing group such as C₁-C₂₅ -Alkyl, e.g. B. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C₂-C₂₅-alkenyl, C₃-C₁₅-alkylalkenyl, C₆-C₂₄-aryl, C₅-C₂₄-heteroaryl, e.g. B. pyridyl, furyl or quinolyl, C₇-C₃₀- arylalkyl, C₇-C₃₀-alkylaryl, fluorine-containing C₁-C₂₅-alkyl, fluorine-containing C₆- C₂₄-aryl, fluorine-containing C₇-C₃₀-arylalkyl, fluorine-containing C₇-C₃₀-alkylaryl or C₁- Is C₁₂-alkoxy, or two or more radicals R¹ can be linked to one another in such a way that the radicals R¹ and the atoms of the cyclopentadienyl ring connecting them form a C₄-C₂, ring system, which in turn can be substituted,
l is 5 for v = 0, and l is 4 for v = 1,
m is 5 for v = 0 and m is 4 for v = 1,
L are the same or different and represent a halogen atom or a hydrocarbon-containing radical having 1-20 carbon atoms, e.g. B. C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₂₀-alkoxy, C₆-C₁₄-aryloxy or C₆-C₄₀-aryl,
x is an integer from 1 to 4, where in the case of M 1 = Ti, Zr or Hf x is preferably 2,
Z denotes a bridging structural element between the two cyclopentadienyl rings, and v is 0 or 1.

Examples of Z are groups M²R⁴R⁵, where M² is carbon, silicon, Is germanium or tin and R⁴ and R⁵, the same or different, is a C₁-C₂₀- Hydrocarbon group such as C₁-C₁₀ alkyl or C₆-C₁₄ aryl mean. Z is preferably CH₂, CH₂CH₂, CH (CH₃) CH₂, CH (C₄H₉) C (CH₃) ₂, C (CH₃) ₂, (CH₃) ₂Si, (CH₃) ₂Ge, (CH₃) ₂Sn, (C₆H₅) ₂Si, (C₆H₅) (CH₃) Si, (C₆H₅) ₂Ge, (C₆H₅) ₂Sn, (CH₂) ₄Si, CH₂Si (CH₃) ₂, o-C₆H₄ or 2,2 ′ - (C₆H₄) ₂. Z can also use one or more radicals R¹ and / or R² is a mono- or polycyclic Form ring system.

Chiral bridged metallocenes of the formula II are preferred, in particular those in which v is 1 and one or both cyclopentadienyl rings so are substituted so that they represent an indenyl ring. The indenyl ring is preferably substituted, especially in 2-, 4-, 2,4,5-, 2,4,6-, 2,4,7- or 2,4,5,6-position, with C₁-C₂₀ carbon-containing groups, such as C₁-C₁₀ alkyl or C₆-C₂₀-aryl, where two or more substituents of Indenyl rings together can form a ring system.  

The following examples of metallocenes serve to illustrate the present invention, but have no restrictive character:
Bis (cyclopentadienyl) zirconium dimethyl
Bis (indenyl) zirconium dimethyl
Bis (fluorenyl) zirconium dimethyl
(Indenyl) (fluorenyl) zirconium dimethyl
(3-methyl-5-naphthylindenyl) (2,7-di-tert-butylfluorenyl) zirconium dimethyl
(3-methyl-5-naphthylindenyl) (3,4,7-trimethoxyfluorenyl) zirconium dimethyl
(Pentamethylcyclopentadienyl) (tetrahydroindenyl) zirconium dimethyl
(Cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) zirconium dimethyl
(Indenyl) (1-buten-4-ylcyclopentadienyl) zirconium dimethyl
[1,3-bis (trimethylsilyl) cyclopentadienyl] (3,4-benzofluorenyl) zirconium dimethyl
Bis (cyclopentadienyl) titanium dimethyl
Dimethylsilanediylbis (indenyl) zirconiumdimethyl
Dimethylsilanediylbis (tetrahydroindenyl) zirconium dimethyl
Dimethylsilanediyl (cyclopentadienyl) (indenyl) zirconium dimethyl
Dimethylsilanediylbis (2-methylindenyl) zirconium dimethyl
Dimethylsilanediylbis (2-ethylindenyl) zirconium dimethyl
Dimethylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dimethyl
Dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl
Dimethylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthyl-en-7-ylidene) zirconium dimethyl
Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl
Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) zirconium dimethyl
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) zirconium dimethyl
Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) zirconium dimethyl
Dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dimethyl
Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dimethyl
Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) zirconium dimeth-yl
Dimethylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) zirconium dimethyl-l
Dimethylsilanediylbis (2-methyl-4-naphthylindenyl) zirconium dimethyl
Dimethylsilanediylbis (2-ethyl-4-naphthylindenyl) zirconium dimethyl
Methylphenylsilanediylbis (indenyl) zirconiumdimethyl
Methylphenylsilanediyl (cyclopentadienyl) (indenyl) zirconium dimethyl
Methylphenylsilanediylbis (tetrahydroindenyl) zirconium dimethyl
Methylphenylsilanediylbis (2-methylindenyl) zirconium dimethyl
Methylphenylsilanediylbis (2-ethylindenyl) zirconium dimethyl
Methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dimethyl
Methylphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl
Methylphenylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) zirconium dimethyl
Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl
Methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl
Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) zirconium dimethyl
Methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) zirconium dimethyl
Methylphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) zirconium dimethyl
Methylphenylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dimethyl
Methylphenylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dimethyl
Methylphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) zirconium di-methyl
Methylphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) zirconium dimethyl
Methylphenylsilanediylbis (2-methyl-4-naphthylindenyl) zirconium dimethyl-l
Methylphenylsilanediylbis (2-ethyl-4-naphthylindenyl) zirconium dimethyl
Diphenylsilanediylbis (indenyl) zirconiumdimethyl
Diphenylsilanediylbis (2-methylindenyl) zirconium dimethyl
Diphenylsilanediylbis (2-ethylindenyl) zirconium dimethyl
Diphenylsilanediyl (cyclopentadienyl) (indenyl) zirconium dimethyl
Diphenylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dimethyl
Diphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl
Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl
Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) zirconium dimethyl
Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) zirconium dimethyl
Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) zirconium dimethyl
Diphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) zirconium dimethyl
Diphenylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dimethyl
Diphenylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dimethyl
Diphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) zirconium dimeth-yl
Diphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) zirconium dimethyl-l
Diphenylsilanediylbis (2-methyl-4-naphthylindenyl) zirconium dimethyl
Diphenylsilanediylbis (2-ethyl-4-naphthylindenyl) zirconium dimethyl
1-silacyclopentane-1,1-bis (indenyl) zirconium dimethyl
1-silacyclopentane-1,1-bis (2-methylindenyl) zirconium dimethyl
1-silacyclopentane-1,1-bis (2-ethylindenyl) zirconium dimethyl
1-silacyclopentane-1,1-bis (2-methyl-4,5-benzoindenyl) zirconium dimethyl-l
1-silacyclopentane-1,1-bis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl
1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) zirconium dimethyl
1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) zirconium dimethyl
1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-ethyl-4-phenylindenyl) zirconium dimethyl
1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-ethyl-4-naphthylindenyl) zirconium dimethyl
1-silacyclopentane-1- (2-methylindenyl) -1- (4-phenylindenyl) zirconium di-methyl
1-silacyclopentane-1,1-bis (2-methyl-4-phenylindenyl) zirconium dimethyl
1-silacyclopentane-1,1-bis (2-ethyl-4-phenylindenyl) zirconium dimethyl
1-silacyclopentane-1,1-bis (2-methyl-4,6-diisopropylindenyl) zirconium d-imethyl
1-silacyclopentane-1,1-bis (2-ethyl-4,6-diisopropylindenyl) zirconium di-methyl
1-silacyclopentane-1,1-bis (2-methyl-4-naphthylindenyl) zirconium dimeth-yl
1-silacyclopentane-1,1-bis (2-ethyl-4-naphthylindenyl) zirconium dimethyl-l
Bis (cyclopentadienyl) titanium dimethyl
Ethylene-1,2-bis (indenyl) zirconium dimethyl
Ethylene-1,2-bis (tetrahydroindenyl) zirconium dimethyl
Ethylene-1-cyclopentadienyl-2- (1-indenyl) zirconium dimethyl
Ethylene-1-cyclopentadienyl-2- (2-indenyl) zirconium dimethyl
Ethylene-1-cyclopentadienyl-2- (2-methyl-1-indenyl) zirconium dimethyl
Ethylene-1,2-bis (2-methylindenyl) zirconium dimethyl
Ethylene-1,2-bis (2-ethylindenyl) zirconium dimethyl
Ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) zirconium dimethyl
Ethylene-1,2-bis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl
Ethylene-1,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-- ylidene) zirconium dimethyl
Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) zirconium dimethyl
Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) zirconium dimethyl
Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) zirconium dimethyl
Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) zirconium dimethyl
Ethylene-1- (2-methylindenyl) -2- (4-phenylindenyl) zirconium dimethyl
Ethylene-1,2-bis (2-methyl-4-phenylindenyl) zirconium dimethyl
Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) zirconium dimethyl
Ethylene-1,2-bis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl
Ethylene-1,2-bis (2-ethyl-4,6-diisopropylindenyl) zirconium dimethyl
Ethylene-1,2-bis (2-methyl-4-naphthylindenyl) zirconium dimethyl
Ethylene-1,2-bis (2-ethyl-4-naphthylindenyl) zirconium dimethyl
Propylene-2,2-bis (indenyl) zirconium dimethyl
Propylene-2-cyclopentadienyl-2- (1-indenyl) zirconium dimethyl
Propylene-2-cyclopentadienyl-2- (4-phenyl-1-indenyl) zirconium dimethyl
Propylene-2-cyclopentadienyl-2- (9-fluorenyl) zirconium dimethyl
Propylene-2-cyclopentadienyl-2- (2,7-dimethoxy-9-fluorenyl) zirconium dimethyl
Propylene-2-cyclopentadienyl-2- (2,7-di-tert-butyl-9-fluorenyl) zirconium dimethyl
Propylene-2-cyclopentadienyl-2- (2,7-dibromo-9-fluorenyl) zirconium dimethyl
Propylene-2-cyclopentadienyl-2- (2,7-diphenyl-9-fluorenyl) zirconium dimethyl
Propylene-2-cyclopentadienyl-2- (2,7-dimethyl-9-fluorenyl) zirconium dimethyl
Propylene-2- (3-methylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) zirconium dimethyl
Propylene-2- (3-tert-butylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) zirconium dimethyl
Propylene-2- (3-trimethylsilylcyclopentadienyl) -2- (3,6-di-tert-butyl-9-- fluorenyl) zirconium dimethyl
Propylene-2-cyclopentadienyl-2- [2,7-bis (3-buten-1-yl) -9-fluorenyl] zirconium dimethyl
Propylene-2-cyclopentadienyl-2- (3-tert-butyl-9-fluorenyl) zirconium dimethyl
Propylene-2,2-bis (tetrahydroindenyl) zirconium dimethyl
Propylene-2,2-bis (2-methylindenyl) zirconium dimethyl
Propylene-2,2-bis (2-ethylindenyl) zirconium dimethyl
Propylene-2,2-bis (2-methyl-4,5-benzoindenyl) zirconium dimethyl
Propylene-2,2-bis (2-ethyl-4,5-benzoindenyl) zirconium dimethyl
Propylene-2,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-ylidene) zirconium dimethyl
Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) zirconium dimethyl
Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) zirconium dimethyl
Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) zirconium dimethyl
Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) zirconium dimethyl
Propylene-2- (2-methylindenyl) -2- (4-phenylindenyl) zirconium dimethyl
Propylene-2,2-bis (2-methyl-4-phenylindenyl) zirconium dimethyl
Propylene-2,2-bis (2-ethyl-4-phenylindenyl) zirconium dimethyl
Propylene-2,2-bis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl
Propylene-2,2-bis (2-ethyl-4,6-diisopropylindenyl) zirconium dimethyl
Propylene-2,2-bis (2-methyl-4-naphthylindenyl) zirconium dimethyl
Propylene-2,2-bis (2-ethyl-4-naphthylindenyl) zirconium dimethyl
1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl] he-xane
1,6-bis [methylsilylbis (2-methyl-4,5-benzoindenyl) zirconium dimethyl] h-exane
1,6-bis [methylsilylbis (2-ethyl-4-phenylindenyl) zirconium dimethyl] hexane
1,6-bis [methylsilylbis (2-methyl-4-naphthylindenyl) zirconium dimethyl] hexane
1,6-bis [methylsilylbis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl] hexane
1,6-bis [methylsilyl (2-methyl-4-phenylindenyl) (4,5-benzoindenyl) zirconium dimethyl] hexane
1- [Methylsilylbis (tetrahydroindenyl) zirconium dimethyl] -6- [ethylstannyl (cyclopentadienyl) - (fluorenyl) zirconium dimethyl] hexane
1,6-disila-1,1,6,6-tetramethyl-1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl] hexane
1,4-disila-1,4-bis [methylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl] cyclohexane
[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (pentamethylcyclopentadienyl zirconium dimethyl)
[1,4-bis (9-fluorenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienyl zirconium dimethyl)
[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienyl zirconium dimethyl)
[1- (1-indenyl) -6- (2-phenyl-1-indenyl) -1,1,6,6-tetraethyl-1,6-disila-4-oxahexane] bis (tert-butylcyclopentadienylzirconium dimethyl)
[1,10-bis (2,3-dimethyl-1-indenyl) -1,1,10,10-tetramethyl-1,10-digermadecane] bis (2-methyl-4-phenylindenylzirconium dimethyl)
(1-methyl-3-tert-butylcyclopentadienyl) (1-phenyl-4-methoxy-7-chlorofluorenyl) zirconium dimethyl
(4,7-dichloroindenyl) (3,6-dimesitylfluorenyl) zirconium dimethyl
Bis (2,7-di-tert-butyl-9-cyclohexylfluorenyl) zirconium dimethyl
(2,7-dimesitylfluorenyl) [2,7-bis (1-naphthyl) fluorenyl] zirconium dimethyl
Dimethylsilylbis (fluorenyl) zirconium dimethyl
Dibutylstannylbis (2-methylfluorenyl) zirconium dimethyl
1,1,2,2-tetraethyldisilanediyl (2-methylindenyl) (4-phenylfluorenyl) zirconium dimethyl
Propylene-1- (2-indenyl) -2- (9-fluorenyl) zirconium dimethyl
1,1-dimethyl-1-silaethylene bis (fluorenyl) zirconium dimethyl
[4- (Cyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] zirconium dimethyl
[4- (Cyclopentadienyl) -4,7-dimethyl-7-phenyl (5,6-dimethyltetrahydroindenyl)] zirconium dimethyl
[4- (Cyclopentadienyl) -4,7-dimethyl-7- (1-naphthyl) (7-phenyltetrahydroindenyl)] zirconium dimethyl
[4- (Cyclopentadienyl) -4,7-dimethyl-7-butyl (6,6-diethyltetrahydroindenyl)] zirconium dimethyl
[4- (3-tert-Butylcyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] zirconium dimethyl
[4- (1-indenyl) -4,7,7-trimethyl (tetrahydroindenyl)] zirconium dimethyl
Bis (cyclopentadienyl) hafnium dimethyl
Bis (indenyl) vanadium dimethyl
Bis (fluorenyl) scandium dimethyl
(Indenyl) (fluorenyl) niobium dimethyl
(2-methyl-7-naphthylindenyl) (2,6-di-tert-butylfluorenyl) titanium dimethyl-l
(Pentamethylcyclopentadienyl) (tetrahydroindenyl) hafnium bromide methyl
(Cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) hafniumdimethyl
(Indenyl) (2-buten-4-ylcyclopentadienyl) titanium dimethyl
[1,3-bis (trimethylsilyl) cyclopentadienyl] (3,4-benzofluorenyl) niobium dimethyl
Bis (cyclopentadienyl) titanium dimethyl
Dimethylsilanediylbis (indenyl) titanium dimethyl
Dimethylsilanediylbis (tetrahydroindenyl) hafniumdimethyl
Dimethylsilanediyl (cyclopentadienyl) (indenyl) titanium dimethyl
Dimethylsilanediylbis (2-methylindenyl) hafniumdimethyl
Dimethylsilanediylbis (2-ethylindenyl) scandiummethyl
Dimethylsilanediylbis (2-butyl-4,5-benzoindenyl) niobium dimethyl
Dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) titanium dimethyl
Dimethylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthyl-en-7-ylidene) titanium dimethyl
Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) titanium dimethyl
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) hafnium dimethyl
Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) scandium methyl
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) titanium dimethyl
Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) hafniumdimethyl
Dimethylsilanediylbis (2-methyl-4-phenylindenyl) niobium dimethyl
Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) vanadium dimethyl
Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) hafniumdimethyl-
Dimethylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) vanadium dimethyl
Dimethylsilanediylbis (2-methyl-4-naphthylindenyl) hafnium bromide methyl
Dimethylsilanediylbis (2-ethyl-4-naphthylindenyl) titanium dimethyl
Methylphenylsilanediylbis (indenyl) titanium dimethyl
Methylphenylsilanediyl (cyclopentadienyl) (indenyl) hafniumdimethyl
Methylphenylsilanediylbis (tetrahydroindenyl) hafniumdimethyl
Methylphenylsilanediylbis (2-methylindenyl) titanium dimethyl
Methylphenylsilanediylbis (2-ethylindenyl) hafniumdimethyl
Methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) hafniumdimethyl
Methylphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) vanadium dimethyl
Methylphenylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) titanium dimethyl
Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) titanium bromide methyl
Methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) titanium dimethyl
Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) hafniumdimethyl
Methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) hafniumdimethyl
Methylphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) titanium dimethyl-
Methylphenylsilanediylbis (2-methyl-4-phenylindenyl) hafniumdimethyl
Methylphenylsilanediylbis (2-ethyl-4-phenylindenyl) vanadium dimethyl
Methylphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) titanium dimeth-yl
Methylphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) hafnium dimethyl-hyl
Methylphenylsilanediylbis (2-methyl-4-naphthylindenyl) hafniumdimethyl
Methylphenylsilanediylbis (2-ethyl-4-naphthylindenyl) titanium dimethyl
Diphenylsilanediylbis (indenyl) titanium dimethyl
Diphenylsilanediylbis (2-methylindenyl) hafniumdimethyl
Diphenylsilanediylbis (2-ethylindenyl) titanium dimethyl
Diphenylsilanediyl (cyclopentadienyl) (indenyl) hafniumdimethyl
Diphenylsilanediylbis (2-methyl-4,5-benzoindenyl) titanium dimethyl
Diphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) hafniumdimethyl
Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) hafnium dimethyl
Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) titanium dimethyl
Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) hafnium dimethyl
Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) titanium dimethyl
Diphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) titanium dimethyl
Diphenylsilanediylbis (2-methyl-4-phenylindenyl) titanium dimethyl
Diphenylsilanediylbis (2-ethyl-4-phenylindenyl) hafniumdimethyl
Diphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) hafniumdimethyl-
Diphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) hafniumdimethyl
Diphenylsilanediylbis (2-methyl-4-naphthylindenyl) hafniumdimethyl
Diphenylsilanediylbis (2-ethyl-4-naphthylindenyl) titanium dimethyl
1-silacyclopentane-1,1-bis (indenyl) hafniumdimethyl
1-silacyclopentane-1,1-bis (2-methylindenyl) hafniumdimethyl
1-silacyclopentane-1,1-bis (2-ethylindenyl) hafniumdimethyl
1-silacyclopentane-1,1-bis (2-methyl-4,5-benzoindenyl) titanium dimethyl
1-silacyclopentane-1,1-bis (2-ethyl-4,5-benzoindenyl) hafniumdimethyl
1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) scandium methyl
1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) hafniumdimethyl
1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-ethyl-4-phenylindenyl) titanium dimethyl
1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-ethyl-4-naphthylindenyl) hafniumdimethyl
1-silacyclopentane-1- (2-methylindenyl) -1- (4-phenylindenyl) hafnium dimethyl
1-silacyclopentane-1,1-bis (2-methyl-4-phenylindenyl) hafniumdimethyl
1-silacyclopentane-1,1-bis (2-ethyl-4-phenylindenyl) titanium bromide methyl
1-silacyclopentane-1,1-bis (2-methyl-4,6-diisopropylindenyl) titanium dimethyl-hyl
1-silacyclopentane-1,1-bis (2-ethyl-4,6-diisopropylindenyl) titanium dimeth-yl
1-silacyclopentane-1,1-bis (2-methyl-4-naphthylindenyl) scandiummethyl
1-silacyclopentane-1,1-bis (2-ethyl-4-naphthylindenyl) hafniumdimethyl
Bis (cyclopentadienyl) titanium dimethyl
Ethylene-1,2-bis (indenyl) scandium methyl
Ethylene-1,2-bis (tetrahydroindenyl) titanium dimethyl
Ethylene-1-cyclopentadienyl-2- (1-indenyl) hafniumdimethyl
Ethylene-1-cyclopentadienyl-2- (2-indenyl) titanium bromide methyl
Ethylene-1-cyclopentadienyl-2- (2-methyl-1-indenyl) hafniumdimethyl
Ethylene-1,2-bis (2-methylindenyl) hafnium dimethyl
Ethylene-1,2-bis (2-ethylindenyl) hafnium dimethyl
Ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) hafnium dimethyl
Ethylene-1,2-bis (2-ethyl-4,5-benzoindenyl) titanium dimethyl
Ethylene-1,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-- ylidene) titanium dimethyl
Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) titanium dimethyl
Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) tit-andimethyl
Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) scandium methyl
Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) hafnium dimethyl
Ethylene-1- (2-methylindenyl) -2- (4-phenylindenyl) titanium dimethyl
Ethylene-1,2-bis (2-methyl-4-phenylindenyl) hafniumdimethyl
Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) hafniumdimethyl
Ethylene-1,2-bis (2-methyl-4,6-diisopropylindenyl) hafniumdimethyl
Ethylene-1,2-bis (2-ethyl-4,6-diisopropylindenyl) titanium dimethyl
Ethylene-1,2-bis (2-methyl-4-naphthylindenyl) titanium dimethyl
Ethylene-1,2-bis (2-ethyl-4-naphthylindenyl) hafniumdimethyl
Propylene-2,2-bis (indenyl) hafnium dimethyl
Propylene-2-cyclopentadienyl-2- (1-indenyl) titanium dimethyl
Propylene-2-cyclopentadienyl-2- (4-phenyl-1-indenyl) titanium dimethyl
Propylene-2-cyclopentadienyl-2- (9-fluorenyl) hafniumdimethyl
Propylene-2-cyclopentadienyl-2- (2,7-dimethoxy-9-fluorenyl) hafnium dimethyl
Propylene-2-cyclopentadienyl-2- (2,7-di-tert-butyl-9-fluorenyl) hafnium dimethyl
Propylene-2-cyclopentadienyl-2- (2,7-dibromo-9-fluorenyl) titanium dimethyl-
Propylene-2-cyclopentadienyl-2- (2,7-diphenyl-9-fluorenyl) hafnium dimethyl-hyl
Propylene-2-cyclopentadienyl-2- (2,7-dimethyl-9-fluorenyl) titanium dimethyl-l
Propylene-2- (3-methylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) hafniumdimethyl
Propylene-2- (3-tert-butylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl-) titanium dimethyl
Propylene-2- (3-trimethylsilylcyclopentadienyl) -2- (3,6-di-tert-butyl-9-- fluorenyl) titanium dimethyl
Propylene-2-cyclopentadienyl-2- [2,7-bis (3-buten-1-yl) -9-fluorenyl] hafniumdimethyl
Propylene-2-cyclopentadienyl-2- (3-tert-butyl-9-fluorenyl) titanium dimethyl-l
Propylene-2,2-bis (tetrahydroindenyl) hafnium dimethyl
Propylene-2,2-bis (2-methylindenyl) hafniumdimethyl
Propylene-2,2-bis (2-ethylindenyl) titanium dimethyl
Propylene-2,2-bis (2-methyl-4,5-benzoindenyl) titanium dimethyl
Propylene-2,2-bis (2-ethyl-4,5-benzoindenyl) hafniumdimethyl
Propylene-2,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylen-7-ylidene) hafniumdimethyl
Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) hafnium dimethyl
Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) ti-tandimethyl
Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) hafnium dimethyl
Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) t-itanedimethyl
Propylene-2- (2-methylindenyl) -2- (4-phenylindenyl) hafniumdimethyl
Propylene-2,2-bis (2-methyl-4-phenylindenyl) titanium dimethyl
Propylene-2,2-bis (2-ethyl-4-phenylindenyl) hafnium dimethyl
Propylene-2,2-bis (2-methyl-4,6-diisopropylindenyl) titanium dimethyl
Propylene-2,2-bis (2-ethyl-4,6-diisopropylindenyl) hafniumdimethyl
Propylene-2,2-bis (2-methyl-4-naphthylindenyl) titanium dimethyl
Propylene-2,2-bis (2-ethyl-4-naphthylindenyl) titanium dimethyl
1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) hafniumdimethyl] hexa-n
1,6-bis [methylsilylbis (2-methyl-4,5-benzoindenyl) titanium dimethyl] hexane
1,6-bis [methylsilylbis (2-ethyl-4-phenylindenyl) hafniumdimethyl] hexane
1,6-bis [methylsilylbis (2-methyl-4-naphthylindenyl) titanium dimethyl] hexa-n
1,6-bis [methylsilylbis (2-methyl-4,6-diisopropylindenyl) hafnium dimeth-yl] hexane
1,6-bis [methylsilyl (2-methyl-4-phenylindenyl) (4,5-benzoindenyl) titanium dimethyl] hexane
1- [Methylsilylbis (tetrahydroindenyl) hafniumdimethyl] -6- [ethylstannyl (cyclopentadienyl) - (fluorenyl) titanium dimethyl] hexane
1,6-disila-1,1,6,6-tetramethyl-1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) hafnium dimethyl] hexane
1,4-disila-1,4-bis [methylsilylbis (2-methyl-4-phenylindenyl) hafniumdimethyl] cyclohexane
[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (pentamethylcyclopentadienylhafniumdimethyl)
[1,4-bis (9-fluorenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienylhafniumdimethyl)
[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutanlbis (cyclopentadienyltitanium dimethyl)
[1- (1-indenyl) -6- (2-phenyl-1-indenyl) -1,1,6,6-tetraethyl-1,6-disila-4-oxahexane] bis (tert-butylcyclopentadienyltitanium dimethyl)
[1,10-bis (2,3-dimethyl-1-indenyl) -1,1,10,10-tetramethyl-1,10-digermadecane] bis (2-methyl-4-phenylindenylhafniumdimethyl)
(1-methyl-3-tert-butylcyclopentadienyl) (1-phenyl-4-methoxy-7-chlorofluorenyl) titanium dimethyl
(4,7-dichloroindenyl) (3,6-dimesitylfluorenyl) titanium dimethyl
Bis (2,7-di-tert-butyl-9-cyclohexylfluorenyl) hafniumdimethyl
(2,7-dimesitylfluorenyl) [2,7-bis (1-naphthyl) fluorenyl] hafniumdimethy-l
Dimethylsilylbis (fluorenyl) titanium dimethyl
Dibutylstannylbis (2-methylfluorenyl) hafniumdimethyl
1,1,2,2-tetraethyldisilanediyl (2-methylindenyl) (4-phenylfluorenyl) tit-andimethyl
Propylene-1- (2-indenyl) -2- (9-fluorenyl) hafniumdimethyl
1,1-dimethyl-1-silaethylenebis (fluorenyl) titanium dimethyl
[4- (Cyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] titanium dimeth-yl
[4- (Cyclopentadienyl) -4,7-dimethyl-7-phenyl (5,6-dimethyltetrahydroindenyl)] hafniumdimethyl
[4- (Cyclopentadienyl) -4,7-dimethyl-7- (1-naphthyl) (7-phenyltetrahydroindenyl)] titanium dimethyl
[4- (Cyclopentadienyl) -4,7-dimethyl-7-butyl (6,6-diethyltetrahydroindenyl)] hafniumdimethyl
[4- (3-tert-Butylcyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] hafniumdimethyl
[4- (1-indenyl) -4,7,7-trimethyl (tetrahydroindenyl)] titanium dimethyl
Bis (cyclopentadienyl) zirconium dichloride
Bis (indenyl) zirconium dichloride
Bis (fluorenyl) zirconium dichloride
(Indenyl) (fluorenyl) zirconium dichloride
Bis (cyclopentadienyl) titanium dichloride
Dimethylsilanediylbis (indenyl) zirconium dichloride
Dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride
Dimethylsilanediylbis (cyclopentadienyl) (indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methylindenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethylindenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4,6-düsopropyhndenyl) zirconium dichloride
Ethylene-1,2-bis (indenyl) zirconium dichloride
Ethylene-1,2-bis (tetrahydroindenyl) zirconium dichloride
Ethylene-1,2-bis (2-methylindenyl) zirconium dichloride
Ethylene-1,2-bis (2-ethylindenyl) zirconium dichloride
Ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) zirconium dichloride
Ethylene-1,2-bis (2-methyl-4-phenylindenyl) zirconium dichloride
Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) zirconium dichloride
Ethylene-1,2-bis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride
Propylene-2,2-bis (indenyl) zirconium dichloride
Propylene-2,2- (cyclopentadienyl) (indenyl) zirconium dichloride
Propylene-2,2- (cyclopentadoenyl) (fluorenyl) zirconium dichloride
Bis (cyclopentadienyl) (η⁴-butadiene) zirconium
Bis (methylcyclopentadienyl) (η⁴-butadiene) zirconium
Bis (n-butyl-cyclopentadienyl) (η⁴-butadiene) zirconium
Bisindenyl (η⁴-butadiene) zirconium
(tert.butylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silane (η⁴-butadiene) zirconium
Bis (2-methylbenzoindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbisindenyl (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methylbenzoindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium
Isopropylidene (cyclopentadienyl) (fluorenyl) (η⁴-butadiene) zirconium
Isopropylidene (cyclopentadienyl) (indenyl) (η⁴-butadiene) zirconium
[4-η5-cyclopentadienyl) -4,7,7-trimethyl- (η5-4,5,6,7-tetrahydroindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbisindenyl (η₄-butadiene) zirconium
Dimethylsilanediylbis (2-methylbenzoindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbisindenyl (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methylbenzoindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbisindenyl (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methylbenzoindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylbenzoindenyl) (2-methyl-4-phenylindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium
Methylphenylmethylene- (fluorenyl) (cyclopentadienyl) (η⁴-butadiene) zirconium
Diphenylmethylene (fluorenyl) (cyclopentadienyl) (η⁴-butadiene) zirconium
Isopropylidene (3-methylcyclopentadienyl) (fluorenyl) (η⁴-butadiene) zirconium
Dimethylsilanediyl- (3-tert-butylcyclopentadienyl) (fluorenyl) (η⁴-butadiene) zirconium
Diphenylsilanediyl- (3 (trimethylsilyl) cyclopentadienyl) (fluorenyl) (η⁴-butadiene) zirconium
Phenylmethylsilanediylbis (2-methyl-indenyl) (η⁴-butadiene) zirconium
Phenylmethylsilanediylbisindenyl (η⁴-butadiene) zirconium
Phenylmethylsilanediylbis (2-methyl-4,5-benzoindenyl) (η⁴-butadiene) zirconium
Phenylmethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-indenyl) (η⁴-butadiene) zirconium
Phenylmethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylin-denyl) (η⁴-butadiene) zirconium
Phenylmethylsilanediyl (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium
Phenylmethylsilanediylbis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium
Phenylmethylsilanediylbis (2-ethyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium
Phenylmethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium
Phenylmethylsilanediylbis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium
Ethylene bis (2-methyl-indenyl) (η⁴-butadiene) zirconium
Ethylene bisindenyl (η⁴-butadiene) zirconium
Ethylene bis (2-methyl-4,5-benzoindenyl) (η⁴-butadiene) zirconium
Ethylene (2-methyl-4,5-benzoindenyl) (2-methyl-indenyl) (η⁴-butadiene) zirconium
Ethylene (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) (η⁴-butadiene) zirconium
Ethylene (2-methylindenyl) (4-phenylindenyl) (η⁴-butadiene) zirconium
Ethylene bis (2-methyl-4,5-benzoindenyl) (η⁴-butadiene) zirconium
Ethylene bis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium
Ethylene bis (2-methyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium
Ethylene bis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium
Ethylene bis (2-ethyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium
Ethylene bis (2-ethyl-4,6-diisopropyl-indenyl) (η⁴-butadiene) zirconium
Ethylene bis (2-ethyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2-ethyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium
Dimethylsilanediylbis (2,3,5-trimethylcyclopentadienyl) (η⁴-butadiene) zirconium
1,6- {bis [methylsilyl-bis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium]} hexane
1,6- {bis [methylsilyl-bis (2-ethyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium]} hexane
1,6- {bis [methylsilyl-bis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium]} hexane
1.6 - {(bis [methylsilylbis (2-methyl-4,5-benzoindenyl) (η⁴-butadiene) zirconium]} hexane
1,6- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-indenyl) (η⁴-butadiene) zirconium]} hexane
1,2- {bis [methylsilyl-bis (2-methyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium]} ethane
1,2- {bis [methylsilyl-bis (2-ethyl-4-phenyl-indenyl) (η⁴-butadiene) zirconium]} ethane
1,2- {bis [methylsilyl-bis (2-methyl-4-naphthyl-indenyl) (η⁴-butadiene) zirconium]} ethane
1,2- {bis [methylsilyl-bis (2-methyl-4,5-benzoindenyl) (η⁴-butadiene) zirconium]} ethane
1,2- {bis [methylsilyl- (2-methyl-4-phenyl-indenyl) (2-methyl-indenyl) (η⁴-butadiene) zirconium]} ethane.

The present invention further relates to a catalyst containing at least one supported chemical compound according to the invention as Cocatalyst and at least one metallocene. In addition, a process for Preparation of an olefin polymer by polymerizing at least one olefin  described in the presence of the catalyst of the invention. The Polymerization can be a homo- or a copolymerization.

Olefins of the formula R ^α -CH = CH-R ^β are preferably polymerized, in which R ^α and R ^{β are} identical or different and are a hydrogen atom, a halogen atom, an alkoxy, hydroxyl, alkylhydroxy, aldehyde, carboxylic acid or carboxylic acid ester group or a saturated or unsaturated hydrocarbon radical having 1 to 20 carbon atoms, in particular 1 to 10 carbon atoms, which can be substituted by an alkoxy, hydroxyl, alkylhydroxy, aldehyde, carboxylic acid or carboxylic acid ester group, or R ^α and R ^β form one or more rings with the atoms connecting them. Examples of such olefins are 1-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, styrene, cyclic olefins such as norbornene, vinylnorbornene, tertacyclododecene, ethylidene norbornene, dienes such as 1, 3-butadiene or 1,4-hexadiene, biscyclopentadiene or methyl methacrylate.

In particular, propylene or ethylene are homopolymerized, ethylene with one or more C₃-C₂₀-1 olefins, especially propylene, and / or one or more C₄-C₂₀-dienes, especially 1,3-butadiene, copolymerized or copolymerized with norbornene and ethylene.

The polymerization is preferred at a temperature of -60 to 300 ° C, particularly preferably 30 to 250 ° C, carried out. The pressure is 0.5 to 2500 bar, preferably 2 to 1500 bar. The polymerization can be continuous or discontinuously, in one or more stages, in solution, in suspension, in the Gas phase or be carried out in a supercritical medium.

The supported system can again be contaminated as a powder or solvent resuspended and as a suspension in an inert suspension medium in the Polymerization system be metered.  

A prepolymerization can be carried out with the aid of the catalyst according to the invention respectively. For prepolymerization, preference is given to (or one of the) in the Polymerization used olefin (s) used.

For the production of olefin polymers with a broad molecular weight distribution catalyst systems are preferably used, the two or more contain various metallocenes.

Cleaning is required to remove catalyst poisons present in the olefin with an aluminum alkyl, for example trimethyl aluminum, triethyl aluminum or triisobutyl 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.

If necessary, hydrogen is added as a molecular weight regulator and / or to increase the activity. The total pressure in the polymerization system is 0.5 to 2500 bar, preferably 2 to 1500 bar. The compound according to the invention is used in a concentration, based on the transition metal, of preferably 10 ^-3 to 10 ^-8 , preferably 10 ^-4 to 10 ^-7 mol of transition metal per dm³ of solvent or per dm³ of reactor volume.

Suitable solvents for the preparation of both the invention supported chemical compound as well as that of the invention Catalyst systems are aliphatic or aromatic solvents, such as for example hexane or toluene, ethereal solvents such as Terahydrofuran or diethyl ether or halogenated hydrocarbons, such as for example methylene chloride or halogenated aromatic Hydrocarbons such as o-dichlorobenzene.  

Before adding the catalyst system (containing at least one supported chemical compound according to the invention, and at least one Metallocene) can also be another alkyl aluminum compound such as for example trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, Trioctylaluminium or Isoprenylaluminium for inerting the Polymerization system (for example to separate existing Catalyst poisons in the olefin) are added to the reactor. This is in one Concentration of 100 to 0.01 mmol Al per kg reactor content Polymerization system added. Triisobutylaluminum and Triethylaluminum in a concentration of 10 to 0.1 mmol Al per kg Reactor contents used. This can help in the synthesis of a supported Catalyst system the molar Al / M ratio can be chosen small.

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

General information: Production and handling of organometallic Connections were made in the absence of air and moisture Argon protection (Schlenk technology). All of the required solvents were pre Use by boiling over suitable desiccants and for several hours followed by absolute distillation under argon. The characterization of the Connections are made using ¹⁹F-NMR spectroscopy.

example 1 Chlorobis (pentafluorophenyl) borane

4.69 g (40 mmol) of trichloroborane are condensed in a two-necked flask with a dry ice cooler at -78 ° C. 19.31 g (40 mmol) of dimethylbis (pentafluorophenyl) stannane are added rapidly. The mixture is stirred at room temperature for 30 minutes and stirred at 100 ° C. for a further 2 hours. A very violent reaction occurs, with dichlorodimethylstannane being deposited on the cooler with increasing reaction time. The remaining dichlorodimethylstannane is sublimed out of the resulting light brown suspension and the remaining bottoms are fractionally distilled over a short column.
¹¹F-NMR (C₆D₆): δ = -129.5 ppm, -145.4 ppm, -161.3 ppm.

Example 2 Bis (pentafluorophenyl) borane

6.9 g (20 mmol) of chlorobis (pentafluorophenyl) borane are cooled to -78 ° C. and 8.9 g (100 mmol) of chlorodimethylsilane are slowly added dropwise. When warmed to room temperature, the borane dissolves and a white precipitate forms. The mixture is stirred for 1 hour, the precipitate is filtered off and washed with 20 ml of pentane.
¹¹F-NMR (C₆D₆): δ = -134.8 ppm, -148.4 ppm, 160.7 ppm.

Example 3 2,3,5,6- (tetrafluorophenyloxymethyl) triethoxysilane

3.32 g (20 mmol) 2,3,5,6-tetrafluorophenol are dissolved in 50 ml toluene and 8 ml n-butyllithium (2.5 M in hexane) are added at 0 ° C. After warming to room temperature, the solution is stirred for a further 2 hours. Then 4.3 g (chloromethyl) triethoxysilane (20 mmol) are added dropwise and the reaction mixture is boiled under reflux for 6 hours. The suspension obtained is filtered and the solvent is stripped off in vacuo. The remaining light yellow liquid is fractionally distilled.
¹¹F-NMR (C₆D₆): δ = -141.04 ppm, -163.34 ppm.

Example 4 [Bis (pentafluorophenyl) -2,3,5,6- (tetrafluorophenyloxymethyl) - triethoxysilane] borane

5.6 g (20 mmol) 2,3,5,6- (tetrafluorophenyloxymethyl) triethoxysilane are dissolved in 50 ml diethyl ether and 8 ml n-butyllithium (2.5 M in hexane) are added at 0 ° C. The solution is stirred for one hour after warming to room temperature. The light yellow solution is then added dropwise to 7.6 g of chlorobis (pentafluorophenyl) borane (20 mmol) in 50 ml of diethyl ether. The suspension obtained is filtered and the solvent is stripped off in vacuo. The remaining white solid is recrystallized from diethyl ether / pentane.
¹¹F-NMR (C₆D₆): δ = -135.8 ppm, -142.04 ppm, -149.9 ppm, -165.34 ppm, 161.8 ppm.

Example 5 2,3,5,6- (tetrafluorophenyloxy) chlorodimethylsilane

3.32 g (20 mmol) 2,3,5,6-tetrafluorophenol are dissolved in 50 ml toluene and 8 ml n-butyllithium (2.5 M in hexane) are added at 0 ° C. After warming to room temperature, the solution is stirred for 2 hours. 2.6 g of dichlorodimethylsilane (20 mmol) are then added dropwise. The suspension obtained is filtered and the solvent is stripped off in vacuo. The remaining colorless liquid is fractionally distilled.
¹¹F-NMR (C₆D₆): δ = -143.01 ppm, -164.52 ppm.

Example 6 [Bis (pentafluorophenyl) -2,3,5,6- (tetrafluorophenyloxy) chloro dimethylsilane] borane

2.6 g (10 mmol) 2,3,5,6- (tetrafluorophenyloxy) chlorodimethylsilane are dissolved in 50 ml diethyl ether and 4 ml n-butyllithium (2.5 M in hexane) are added at 0 ° C. The solution is stirred for one hour after warming to room temperature. The light yellow solution is then added dropwise to 3.8 g of chlorobis (pentafluorophenyl) borane (10 mmol) in 50 ml of diethyl ether. The suspension obtained is filtered and the solvent is stripped off in vacuo. The remaining white solid is recrystallized from diethyl ether / pentane.
¹¹F-NMR (C₆D₆): δ = -136.3 ppm, -142.76 ppm, -150.12 ppm, -165.78 ppm, 162.98 ppm.

Example 7 Chlorobis (pentafluorophenyl) borane supported on silica (Cocatalyst A)

5g SiO₂ (MS 3030, PQ, dried at 200 ° C in a stream of argon) are in 50 ml of pentane stirred and at room temperature with 3.8 g (10 mmol) Chlorobis (pentafluorophenyl) borane added. The solvent is decanted off and washed the carrier material again with pentane. Then will the remaining solvent is removed in vacuo and the carrier in vacuo dried.

Example 8 Carrying of [bis (pentafluorophenyl) -2,3,5,6- (tetrafluorophenyloxymethyl) triethoxysilane] borane Silica (cocatalyst B)

5g SiO₂ (MS 3030, PQ, dried at 200 ° C in a stream of argon) in 50 ml pentane stirred and at room temperature with 6.9 g (10 mmol) [Bis (pentafluorophenyl) -2,3,5,6- (tetrafluorophenyloxymethyl) triethoxy-silane] - borane added. The suspension is stirred for 1 hour at room temperature Decanted solvent and the carrier material again with pentane washed. Then the remaining solvent in a vacuum removed and the carrier dried in vacuo.

Example 9 Carrying 2,3,5,6- (tetrafluorophenyloxy) chlorodimethylsilane on silica (cocatalyst C)

5g SiO₂ (MS 3030, PQ, dried at 200 ° C in a stream of argon) in 50 ml pentane stirred and at room temperature with 6.0 g (10 mmol) 2,3,5,6- (Tetrafluorophenyloxy) chlorodimethylsilane added. The suspension becomes 1 Stirred for one hour at room temperature, decanted the solvent and the Backing material washed again with pentane. Then that will  remaining solvents removed in vacuo and the carrier in vacuo dried.

Example 10 Support of bis (pentafluorophenyl) borane on silica (Cocatalyst D)

10 g SiO₂ (MS 3030, PQ, dried at 200 ° C in a stream of argon) were in 40 ml of toluene suspended and at room temperature with 4.76 g of vinyl triethoxysilane transferred. This mixture was allowed to reflux for 18 hours, then filtered and washed three times with 40 ml of methanol. Residues of solvent were in Oil pump vacuum removed.

6.0 g of bis (pentafluorophenyl) borane were dissolved in 40 ml of toluene and added in portions with the modified SiO₂. The obtained one was stirred Suspension for 3 h at room temperature, then filtered off and washed three times little toluene. A free-flowing solid was obtained.

Example 11 Modification of a carrier with trichloroborane

5g SiO₂ (MS 3030, PQ, dried at 200 ° C in a stream of argon) are at -40 ° C to 1.17 g of trichloroborane. The suspension is left on Come to room temperature and stir for another 30 minutes. Then the 30 ml of pentane are added to the suspension and the mixture is stirred for 10 minutes. The solvent is decanted off and the support material is washed again with pentane. The remaining solvent is then removed in vacuo and the Carrier dried in vacuo.

Example 12 Representation of a supported cocatalyst E

5 g of the modified carrier described in Example 11 in 50 ml of pentane are at -40 ° C with 1.75g (10 mmol) of pentafluorophenyllithium in 20 ml Diethyl ether added. The suspension obtained is at 1 hour  Room temperature stirred. Then 2.8 g (10 mmol) Triphenylmethyl chloride added and stirred for a further six hours. The Solvent is decanted off and the carrier material again with pentane washed. Then the remaining solvent in a vacuum removed and the carrier dried in vacuo. To excess Lithium chloride will remove the remaining residue with 50 ml Tetrahydrofuran extracted and then filtered. The residue is × 10 ml of pentane and then washed in an oil pump vacuum dried.

Example 13 Representation of the catalyst system A

A solution of 10 mg (0.023 mmol) dimethylsilanediylbis (2- methylindenyl) zirconium dimethyl in 40 ml of toluene was added in portions with 10 g Cocatalyst A from Example 7 added. The mixture was left at room temperature for 1 hour stir and then remove the solvent in an oil pump vacuum up to Constant weight. For the introduction into the polymerization system 10 g of catalyst system A resuspended in 50 ml Exxsol.

Polymerization

In parallel, a dry 16 dm³ reactor was initially filled with nitrogen and then rinsed with propylene and filled with 10 dm³ of liquid propylene. Then 0.5 cc of a 20% triisobutylaluminum solution in Varsol was added 30 cm³ Exxsol diluted into the reactor and the batch at 30 ° C 15 Minutes stirred.

The catalyst suspension was then added to the reactor. The Reaction mixture was brought to the polymerization temperature of 60 ° C heated (4 ° C / min) and the polymerization system by cooling for 1 h Kept at 60 ° C. The polymerization was stopped by exhausting the remaining propylene. The polymer was dried in a vacuum drying cabinet.  

The result is 1.4 kg of polypropylene powder. The reactor showed no deposits Inner wall or stirrer. The catalyst activity was 140 kg PP / g metallocene × h.

Example 14 Representation of the catalyst system B

A solution of 10 mg (0.023 mmol) dimethylsilanediylbis (2- methylindenyl) zirconium dimethyl in 40 ml of toluene was added in portions with 10 g the cocatalyst B from Example 8 was added. The mixture was left at room temperature for 1 hour stir and then remove the solvent in an oil pump vacuum up to Constant weight. For the introduction into the polymerization system 10 g of catalyst system B resuspended in 50 ml Exxsol.

Polymerization

In parallel, a dry 16 dm³ reactor was initially filled with nitrogen and then rinsed with propylene and filled with 10 dm³ of liquid propylene. Then 0.5 cc of a 20% triisobutylaluminum solution in Varsol was added 30 cm³ Exxsol diluted into the reactor and the batch at 30 ° C 15 Minutes stirred.

The catalyst suspension was then added to the reactor. The Reaction mixture was brought to the polymerization temperature of 60 ° C heated (4 ° C / min) and the polymerization system by cooling for 1 h Kept at 60 ° C.

The polymerization was stopped by venting the remaining propylene. The polymer was dried in a vacuum drying cabinet.

The result is 1.1 kg of polypropylene powder. The reactor showed no deposits Inner wall or stirrer. The catalyst activity was 110 kg PP / g metallocene × h.

Claims (5)

1. Supported chemical compound of formula (I) wherein
A ^{c + is} a cation,
c is an integer from 1 to 10,
b is an integer 0,
T is a carrier
y is an integer 1,
a is an integer from 0 to 10, where a · y = c · b, and
N is a unit of formula (II) wherein
R independently of one another are identical or different substituents of M such as a halogen atom or a C₁-C₄₀ carbon-containing group,
X are independently the same or different and are a C₁-C₄₀ carbon-containing group,
M are, independently of one another, the same or different and represent an element of group IIa, IIIa, IVa or Va of the periodic table of the elements,
d is 0 or 1, e is 0 or 1, f is 0 or 1,
g is an integer from 0 to 10, h is an integer from 0 to 10, k is an integer from 0 to 10, r is an integer from 0 to 10,
i is an integer from 0 to 1000,
j is an integer from 1 to 6,
S are the same or different spacers which connect M covalently to T,
w are the same or different 0, 1 or 2 and z is 1 or 2. 2. A supported chemical compound according to claim 1, which has the formula (IV) wherein
M is an element of group IIIa of the periodic table of the elements,
R independently of one another are identical or different substituents of M such as a halogen atom or a C₁-C₄₀ carbon-containing group,
j is an integer from 1 to 4,
z is 1 or 2,
T is a carrier
S is a spacer which is covalently linked to T,
a is 0, 1 or 2,
A is a cation of group Ia, IIa, IIIa of the Periodic Table of the Elements, a carbenium, oxonium or sulfonium cation or a quaternary ammonium compound,
b is 0, 1 or 2 and
c is 0, 1 or 2. 3. A catalyst system containing a) at least one supported chemical compound according to claim 1 or 2 and b) at least one transition metal compound M¹L _k , wherein M¹ is a transition metal, L is a π ligand and k is an integer from 1 to 6. 4. Process for the preparation of a polyolefin by polymerization of a or more olefins in the presence of the catalyst system according to Claim 3. 5. Polyolefin can be produced by the process according to claim 4.