DE19632557A1 - 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 chemical compound which is neutral or can be ionic. In combination with a metallocene can these form a new catalyst system, which is advantageous for polymerization is used by olefins. Here, the use of Aluminoxanes such as methylaluminoxane (MAO) are not used as cocatalysts and still high catalyst activities are 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 to be used in high excess. The representation of cationic Alkyl complexes open the way to comparable MAO-free catalysts 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 anion (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 Metallocenalkyl compound using tris (pentafluorophenyl) borane. EP 427 697 describes this synthesis principle and a corresponding one 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 558 158 describes zwitterionic catalyst systems which are prepared from metallocendialkyl compounds and salts of the form [R₃NH] ⁺ [BPh₄] ⁻. The implementation of such a salt with z. B. Cp₂ _* ZrMe₂ provides a zirconocenemethyl cation by protolysis with methane elimination. This reacts via CH activation to the zwitterion Cp₂ _* Zr⁺- (m-C₆H₄) -BPh₃⁻. The Zr atom is covalently bound to a carbon atom of the phenyl ring and is stabilized via an agostic hydrogen bond.

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 disadvantage of the systems described is that after protolysis from the Ammonium salts form an amine, which attaches to the strongly Lewis acidic cation is coordinated and therefore not active in polymerization.

In EP 426 637 a method is described in which the Lewis acidic CPh₃⁺  Cation is used. B (C₆F₅) ₄⁻ acts as the weakly coordinating anion. This has the advantage that after abstraction of a CH₃ group that resulting CH₃CPh₃ no longer has coordinative properties. Consequently can also cationic complexes from sterically unimpeded metal centers being represented.

Diboranes bridged by a hydrogen atom and an alkyl group are described in WO 95/24269. These systems have the disadvantage that the contained H-acidic functions interact with the not exclude cationic system.

The task was a chemical compound with less Finding a tendency to coordinate, which has the disadvantages of the prior art avoids.

The present invention thus relates to a chemical compound and a Process for the preparation of this chemical compound. It also affects one Catalyst system containing at least one metallocene and at least one chemical compound according to the invention as cocatalyst. In addition, a Process for the preparation of polyolefins described.

The chemical compound according to the invention corresponds to the general one Formula:

wherein
R independently of one another, identically or differently, are a halogen atom 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 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 trivalent carbon-containing group such as a C₁-C₄₀-alkanetriyl -, C₁-C₄₀- haloalkanetriyl-, C₆-C₄₀-arentriyl-, C₆-C₄₀-haloarentriyl-, C₇-C₄₀- arenalkanetriyl-, C₇-C₄₀-haloalkenetriyl-, C₂-C₄₀-alkynetriyl-, C₂-C₄₀- haloalkintriyl- , C₂-C₄₀-alkentriyl or C₂-C₄₀-haloalkentriyl group,
M are, independently of one another, the same or different and represent an element of groups IIa, IIIa, IVa or Va of the periodic table of the elements,
a is an integer from 0 to 10, b is an integer from 0 to 10, c is an integer from 0 to 10 and a = b · c,
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,
i is an integer from 0 to 1000,
j is an integer from 1 to 6 and
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.

If a = 0, it is a neutral chemical compound; if a is 1, it is a negatively charged compound with b cations A ^{c +} as counter ion.

If the chemical compound of the formula I has several groups MR _j , these can be the same or different from one another. The number j of the radicals R in a group MRj depends on the binding nature and the valency of M.

The structural unit X connects the elements M by covalent bonds together. X can be a linear, cyclic or branched carbon skeleton exhibit.

R is preferably a C₁-C₄₀ hydrocarbon radical which is substituted with halogens such as fluorine, Chlorine, bromine or iodine halogenated can preferably be halogenated, especially a halogenated, especially 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 is preferably a C₆-C₃₀ arylene group, a C₂-C₃₀ alkenylene group or a C₂-C₃₀ alkynylene group which is halogenated, especially perhalogenated can.

Preferably, j = 1 or 2 if M is a group IIa element, j = 2 or 3 if 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 boron as element of group IIIa.

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 and k are preferably 0 or 1.

As A are carbenium ions (R₃C⁺) or quaternary ammonium ions with a acidic H function (R₃NH⁺) preferred. Quaternaries are particularly preferred  Ammonium salts with acidic H functions.

Examples of the chemical compound according to the invention are:

Instead of the N, N-dimethylanilinium cation [C₆H₅CH₂N (CH₃) ₂H] ⁺ can alternatively, CPh₃⁺ can be used as a cation.

The preparation of a chemical compound according to the invention can, for. B. after the following reaction scheme:

Here is
X is a C₁-C₄₀ 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-halogeno-arylalkylene, C₂-C₄₀-alkynylene, C₂-C₄₀-halogeno-alkynylene, C₂-C₄₀-alkenylene or C₂-C₄₀-halogeno-alkenylene group,
Y, independently of one another, the same or different, is a leaving group, preferably a hydrogen or halogen atom,
R independently of one another, identically or differently, represents a halogen atom 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 group,
Bs a base, preferably an organolithium compound or a Grignard compound,
M are the same or different and mean an element of groups IIa, IIIa, IVa or Va of the periodic table of the elements and
A is a cation of group Ia, IIa, IIIa, the periodic table of the elements, a carbenium, oxonium or sulfonium cation or a quaternary ammonium compound.

The chemical compound according to the invention can be used together with metallocenes can be used as a catalyst system. Metallocenes contain at least one Central metal atom to which at least one n ligand, e.g. B. Cyclopentadienyl Ligand is bound. Chiral metallocenes are preferred. In addition, you can further substituents, such as. B. halogen, alkyl, alkoxy or aryl groups the central metal atom must be bound. The metal central atom is preferably a Element of III., IV., V. or VI. Subgroup of the periodic table of the Elements, in particular from subgroup IV of the periodic table Elements such as Ti, Zr or Hf. Cyclopentadienyl ligand are unsubstituted Cyclopentadienyl residues and substituted cyclopentadienyl residues such as Methylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, Tetrahydroindenyl, benzoindenyl, fluorenyl, benzofluorenyl, Understand tetrahydrofluorenyl, octahydrofluorenyl radicals. The n ligands, e.g. B. Cyclopentadienyl ligands can be bridged or unbridged, where Single and multiple bridging - also via ring systems - possible are. The term metallocene also includes compounds with more than a metallocene fragment, so-called multinuclear metallocenes. these can have any substitution pattern and bridging variants. The individual metallocene fragments of such multinuclear metallocenes can be the same as well as be different from each other. Examples of such polynuclear 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 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-C₂₄ ring system, which in turn can be substituted,
n is 5 for q = 0 and n is 4 for q = 1,
m is 5 for q = 0 and m is 4 for q = 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,
k is an integer from 1 to 4, where in the case of M 1 = Ti, Zr or Hf k is preferably 2,
Z denotes a bridging structural element between the two cyclopentadienyl rings, and q 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 q 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-disilabutane] bis (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 also relates to a catalyst containing at least a transition metal compound according to the invention as a cocatalyst and at least one metallocene, and a method for producing a Olefin polymer by polymerizing at least one olefin in the presence of the catalyst according to the invention. The polymerization can be a homo- or a Be 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 is 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 compound according to the invention can be used alone or together with a Metallocene can be applied to carriers. Suitable carrier materials are for example silica gels, aluminum oxides, solid aluminoxane or others inorganic carrier materials such as magnesium chloride. A A suitable carrier material is also polyolefin powder in finely divided form.

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 chemical according to the invention Compound as well as the catalyst system according to the invention aliphatic or aromatic solvents, such as hexane or toluene, ethereal solvents such as terahydrofuran or diethyl ether or halogenated hydrocarbons, such as methylene chloride or halogenated aromatic hydrocarbons such as o Dichlorobenzene.

Before adding the catalyst system, especially the supported one Catalyst system (containing at least one chemical according to the invention Compound, at least one metallocene, carrier material and / or Polyolefin powder in finely divided form) can also be another Aluminum alkyl compound such as trimethyl aluminum, Triethyl aluminum, triisobutyl aluminum, trioctyl aluminum or Isoprenyl aluminum for inerting the polymerization system (For example, to separate existing catalyst poisons in the olefin) in the Reactor are given. This is in a concentration of 100 to 0.01 mmol of Al per kg of reactor content were added to the polymerization system. Prefers Triisobutylaluminium and Triethylaluminium are in a concentration of 10 to 0.1 mmol Al per kg reactor content. This allows the synthesis of a  supported catalyst system the molar Al / M ratio chosen small will.

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.

Example 1: 1,4-bis (dipentafluorophenylborane) -2,3,5,6-tetrafluorobenzene

1.54 g (5 mmol) of dibromotetrafluorobenzene are dissolved in 40 ml of n-hexane and Chilled to -78 ° C. 6.4 ml of n-BuLi (10 mmol) become slow with this solution added dropwise and stirred for 1 hour. Then 1.90 g (5 mmol) Bis (pentafluorophenyl) boryl chloride dissolved in 40 ml of n-hexane and also to the added dropwise above solution. The suspension obtained slowly increases Warmed to room temperature, whereby a white precipitate separates. This is separated off by filtration and the filtrate obtained in vacuo to evaporated to dryness. The yield of the yellow oil thus obtained resulting, 1,4-bis (dipentafluorophenylboryl) -2,3,5,6-tetrafluorobenzene 81%.

Example 2: bis (dipentafluorophenylboryl) acetylene

1.06 g (5 mmol) of bis (chlorodimethylsilyl) acetylene are dissolved in 40 ml of n-hexane dissolved and cooled to -78 ° C. 1.90 g are slowly added to this solution (5 mmol) bis (pentafluorophenyl) boryl chloride in 40 ml of n-hexane was added dropwise. It is stirred for 1 hour at -78 ° C and then slowly warmed to RT.  

Solvent and the resulting dimethyldichlorosilane are in a high vacuum away. The remaining yellow oil is then fractionally distilled. 2.2 g (61.7% yield) of bis (dipentafluorophenylboryl) acetylene are obtained.

Example 3: [(Dipentafluorophenylboron) ethynyl] trimethylsilane

1.12 g (5 mmol) (iodoethynyl) trimethylsilane are dissolved in 40 ml of tetrahydrofuran dissolved and cooled to -78 ° C. 3.2 ml n-BuLi (5 mmol, 1.6 M in hexane) was slowly added dropwise and the mixture was stirred for 2 hours. Subsequently 1.90 g (5 mmol) of bis (pentafluorophenyl) boryl chloride in 40 ml Dissolved tetrahydrofuran and also added dropwise to the above solution. The suspension obtained is slowly warmed to room temperature, whereby a white precipitate deposits. This is separated off by filtration. The solvent is removed in vacuo from the filtrate obtained. The remaining yellow oil is then fractionally distilled. Fall in the process 1.66 g (75% yield) of [(dipentafluorophenylboron) ethynyl] trimethylsilane.

Example 4: [(Diphenylphosphino) ethynyl] dipentafluorophenylborane

1.05 g (5 mmol) of diphenylethynylphosphine are dissolved in 40 ml of diethyl ether and cooled to -78 ° C. 3.2 ml n-BuLi (5 mmol, 1.6 M slowly added dropwise and stirred for 2 hours. There is a spontaneous red / brown coloring of the solution. Then 1.90 g (5 mmol) Bis (pentafluorophenyl) boryl chloride dissolved in 40 ml of tetrahydrofuran and added to the added dropwise above solution. The suspension obtained slowly increases Warmed to room temperature, whereby a precipitate separates. This will separated by filtration and the filtrate obtained in vacuo to dryness constricted. The yield of the orange oil obtained in this way [(Diphenylphosphino) ethynyl] dipentafluorophenylborane is 57%.  

Example 5: Triphenylcarbenium [(dipentafluorophenylborane) -2,3,5,6- tetrafluorophenyl] tripentafluorophenyl borate

0.62 g of bromopentafluorobenzene (2.5 mmol) are dissolved in 40 ml of n-hexane and 1.6 ml of n-BuLi (2.5 mmol, 1.6 M in hexane) were added at -78 ° C. The Suspension is stirred at -10 ° C for 1 hour. Then 2.1 g (2.5 mmol) 1,4-bis (dipentafluorophenylboryl) -2,3,5,6-tetrafluorobenzene in 40 ml Slowly added n-hexane to the above solution. The suspension obtained is slowly warmed to room temperature, with a precipitate separates. This is separated off by filtration and the filtrate obtained in Vacuum concentrated to dryness. The lithium salt thus obtained is in 40 ml n-pentane and 0.7 g (2.5 mmol) at room temperature Triphenylmethyl chloride added. After 8 hours of stirring, the orange solid filtered. The filtrate is extracted into methylene chloride to remove the resulting LiCl cut off. Precipitation with n-pentane gives an orange solid (yield 56%).

Example 6

10 g SiO₂ (MS 3030, PQ, dried at 600 ° C in a stream of argon) were in 50 ml of toluene suspended and slowly added dropwise with stirring Solution of 100 mg (0.229 mmol) dimethylsilanediylbis (2- methylindenyl) zirconium dimethyl and 128 mg (0.153 mmol) 1,4 bis (dipentafluorophenylborane) -2,3,5,6-tetrafluorobenzene in 3 ml toluene transferred. The mixture was allowed to stir at room temperature for 1 h and then this was removed Solvent in an oil pump vacuum to constant weight. To the 1 g of the supported were introduced into the polymerization system Resuspended catalyst in 30 cm³ Exxsol.

Polymerization

In parallel, a dry 16 dm3 reactor was first run 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 of Exxsol diluted into the reactor and the batch at 30 ° C 15 Minutes stirred. The catalyst suspension was then in the Given reactor. The reaction mixture was on the Polymerization temperature of 60 ° C heated (4 ° C / min) and that Polymerization system kept at 60 ° C for 1 h by cooling. Was stopped polymerization by exhausting the remaining propylene. The polymer was dried in a vacuum drying cabinet. The result was 1.4 kg of polypropylene Powder. The reactor showed no deposits on the inner wall or stirrer. The Catalyst activity was 144 kg PP / g metallocene × h.

Example 7

To a solution of 100 mg (0.229 mmol) dimethylsilanediylbis (2- methylindenyl) zirconium dimethyl and 143 mg (0.114 mmol) Triphenylcarbenium [(dipentafluorophenylborane) -2,3,5,6-tetrafluorophenyl] triphenylfluorophenylborate in 50 ml of toluene 10 g SiO₂ (MS 3030, PQ, dried at 600 ° C in a stream of argon) added. It was left for 1 h Stir at room temperature and then removed the solvent in the Oil pump vacuum to constant weight. To infiltrate the Polymerization system became 1 g of the supported catalyst in 30 cm³ Exxsol resuspended.

Polymerization

In parallel, a dry 16 dm3 reactor was first run with nitrogen and then rinsed with propylene and with 10 dm³ of liquid propylene filled. Then 0.5 cm³ of a 20% triisobutylaluminum solution in Varsol diluted with 30 cm³ of Exxsol and added to the reactor 30 ° C stirred for 15 minutes. Then the catalyst suspension was in given the reactor. The reaction mixture was on the Polymerization temperature of 60 ° C heated (4 ° C / min) and that Polymerization system kept at 60 ° C for 1 h by cooling. Was stopped  polymerization by exhausting the remaining propylene. The polymer was dried in a vacuum drying cabinet. The result was 1.8 kg of polypropylene Powder. The reactor showed no deposits on the inner wall or stirrer. The Catalyst activity was 186 kg PP / g metallocene × h.

Claims (10)

1. Compound of formula I. wherein
R independently of one another, identically or differently, are 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 groups IIa, IIIa, IVa or Va of the periodic table of the elements,
a is an integer from 0 to 10, b is an integer from 0 to 10, c is an integer from 0 to 10 and a = b · c,
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,
i is an integer from 0 to 1000,
j is an integer from 1 to 6 and
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. 2. A compound of formula I according to claim 1, wherein
R independently of one another, identically or differently, is a C₁-C₄₀-alkyl, C₁-C₄₀-halogeno-alkyl, C₆-C₄₀-aryl, C₆-C₄₀-halogeno-aryl, C₇-C₄₀-arylalkyl or C₇-C₄₀- Halogen arylalkyl group are and
X, independently of one another, the same or different, is 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-alkinylene, C₂- C₄₀-halogeno-alkynylene, C₂-C₄₀-alkenylene or C₂-C₄₀-halogeno-alkenylene group. 3. A compound of formula I according to claim 1 or 2, wherein R is a halogenated C₁-C₃₀ alkyl group or C₆-C₃₀ aryl group, an optionally halogenated C₆-C₃₀ arylene group, C₂-C₃₀ alkenylene group or C₂-C₃₀ alkynylene group, M is an element of group IIIa des Periodic table of the elements, a, b and c are 0, 1 or 2, g, h and k are 0 or 1, j is 3 or 4, i is 0 or 1 and A is a carbenium ion or a quaternary ammonium ion. 4. A process for the preparation of a compound of formula I according to a or more of claims 1 to 3, wherein a compound of formula YXY in Presence of a base with compounds of the formula MRjY and RY implemented is, and the reaction product is reacted with a compound of formula AY where Y is a leaving group and X, M, R, j and A as in claim 1 are defined.   5. A catalyst system containing a) at least one compound of the formula I, according to one or more of claims 1 to 3 and b) at least one Metallocene. 6. Catalyst system according to claim 5, additionally containing a support. 7. Use of a compound of formula I according to one or more of claims 1 to 3 for the production of a catalyst system according to Claim 5 or 6. 8. Process for producing an olefin polymer by polymerization at least one olefin in the presence of a catalyst according to claim 5 or 6. 9. Use of a compound of formula I according to one or more of claims 1 to 3 for the preparation of an olefin polymer. 10. polyolefin, producible by the process according to claim 8.