Chemical compound

This application is a divisional of Ser. No. 08/867,214, now U.S. Pat. No. 6,255,531, which was filed on Jun. 2, 1997.

The present invention relates to a chemical compound which can have an uncharged or ionic structure. In combination with a metallocene, this can form a novel catalyst system which is advantageously used for the polymerization of olefins. Here, the use of aluminoxanes such as methylaluminoxane (MAO) as cocatalyst can be omitted and high catalyst activities can nevertheless be achieved.

The role of cationic complexes in Ziegler-Natta polymerization using metallocenes is generally recognized (M. Bochmann, Nachr. Chem. Lab. Techn. 1993, 41,1220). MAO as hitherto most effective cocatalyst has the disadvantage of being used in a high excess. The preparation of cationic alkyl complexes opens up the route to MAO-free catalysts having comparable activity.

The synthesis of cationic alkyl complexes is achieved by

a) protolysis of metallocene compounds using, for example, weakly acid ammonium salts of the very stable, nonbasic tetra(pentafluorophenyl)borate anion (e.g. [PhMe 2 NH] + [B(C 6 F 5 ) 4 ] − ),

b) abstraction of an alkyl group from metallocene compounds with the aid of strong Lewis acids, where the Lewis acids employed can be either salts of the formula (Ph 3 C + BR 4 − ) or strong, uncharged Lewis acids such as B(C 6 F 5 ) 3 or by

c) oxidation of dialkylmetallocene complexes using, for example, AgBPh 4 or [Cp 2 Fe][BPh 4 ].

The synthesis of “cation-like” metallocene polymerization catalysts is described in J. Am. Chem. Soc. 1991,113, 3623. In this reference, the alkyl abstraction from an alkyl metallocene compound is carried out by means of tris(pentafluorophenyl)borane. EP 427 697 claims this synthetic principle and a corresponding catalyst system comprising a neutral metallocene species (e.g. Cp 2 ZrMe 2 ), a Lewis acid (e.g. B(C 6 F 5 ) 3 ) and aluminum alkyls. A process for preparing salts of the formula LMX + XA − according to the above-described principle is claimed in EP 520 732.

EP 558 158 describes zwitterionic catalyst systems which are prepared from metallocene dialkyl compounds and salts of the formula [R 3 NH] + [BPh 4 ] − . The reaction of such a salt with, for example, Cp 2 *ZrMe 2 leads to the intermediate formation of a methylzirconocene cation by protolysis with elimination of methane. This reacts via C—H-activation to form the zwitterion Cp 2 *Zr + -(m-C 6 H 4 )-BPh 3 − . In this, the Zr atom is covalently bonded to a carbon atom of the phenyl ring and is stabilized via an agostic hydrogen bond.

According to this reaction principle, the protolysis of a dialkylmetallocene species using a perfluorinated [R 3 NH] + [B(C 6 F 5 ) 4 ] − salt in the first step likewise gives a cationic species, but the subsequent reaction (C—H-activation) to give zwitterionic complexes is not possible. Salts of the formula [Cp 2 Zr-R-RH] + [B(C 6 F 5 ) 4 ] − are thus formed. U.S. Pat. No. 5,348,299 claims corresponding systems in which dimethylanilinium salts having perfluorinated tetraphenylborate anions are used.

A disadvantage of the systems described is that the protolysis results in formation of an amine from the ammonium salts and this coordinates to the strongly Lewis-acid cation and is thus not polymerization-active.

EP 426 637 describes a process in which the Lewis-acid CPh 3 + cation is used. B(C 6 F 5 ) 4 − functions as weakly coordinating anion. This offers the advantage that after abstraction of a CH 3 group the resulting CH 3 CPh 3 no longer has coordinated properties. In this way, cationic complexes of sterically unhindered metal centers can also be prepared.

WO 95/14044 describes carboboranes as constituents of catalyst systems.

Diboranes which are bridged by a hydrogen atom and an alkyl group are described in WO 95/24269. These systems have the disadvantage that the H-acid functions present therein do not rule out an interaction with the cationic system.

It is an object of the invention to find a chemical compound which has a low tendency to coordinate and which avoids the disadvantages of the prior art.

The present invention according!y provides a chemical compound and a process for preparing this chemical compound. It further provides a catalyst system comprising at least one metallocene and at least one chemical compound of the invention as cocatalyst. In addition, a process for preparing polyolefins is described.

The chemical compound of the invention corresponds to the formula:

where

R are, independently of one another, identical or different and are each a halogen atom or a C 1 -C 40 -group such as a C 1 -C 40 -alkyl, C 1 -C 40 -haloalkyl, C 6 -C 40 -aryl, C 6 -C 40 -haloaryl, C 7 -C 40 -aralkyl or C 7 -C 40 -haloaralkyl group,

X are, independently of one another, identical or different and are each a C 1 -C 40 -group such as a C 1 -C 40 -alkylene, C 1 -C 40 -halo-alkylene, C 6 -C 40 -arylene, C 6 -C 40 -haloarylene, C 7 -C 40 -arylalkylene or C 7 -C 40 -haloarylalkylene, C 2 -C 40 -alkynylene, C 2 -C 40 -halo-alkynylene, C 2 -C 40 -alkenylene or C 2 -C 40 -haloalkenylene group,

M are, independently of one another, identical or different and are each an element of group 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, f is 0or 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.

When a=0, the formula represents an uncharged chemical compound; when a≧1, the formula represents a negatively charged compound having b cations A c+ as counterions.

If the chemical compound of the formula I has a plurality of groups MR j , these can be identical or different from one another.

The structural unit X connects the elements M to one another by means of covalent bonds. X can have a linear, cyclic or branched carbon skeleton.

R is preferably a C 1 -C 40 -hydrocarbon radical which can be halogenated, preferably perhalogenated, by halogens such as fluorine, chlorine, bromine or iodine, in particular a halogenated, in particular perhalogenated, C 1 -C 30 -alkyl group such as trifluoromethyl, pentachloroethyl, heptafluoroisopropyl or monofluoroisobutyl or a halogenated, in particular perhalogenated, C 6 -C 30 -aryl group such as pentafluorophenyl, heptachloronaphthyl, heptafluoronaphthyl, 1,2,3-trifluorophenyl, 1,3,5-trifluorophenyl, heptafluorotolyl, 3,5-bis(trifluoromethyl)phenyl, 2,4,6-tris(trifluoromethyl)phenyl or 2,2′(octafluoro)biphenyl. X is preferably a C 6 -C 30 -arylene group, a C 2 -C 30 -alkenylene group or a C 2 -C 30 -alkynylene group, each of which can be halogenated, in particular perhalogenated;

Preferably j=1 or 2 when M is an element of group IIa, j=2 or 3 when M is an element of group IIIa, j=3 or 4 when M is an element of group IVa and j=4 or 5 when M is an element of the group Va. M is particularly preferably boron as an 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;

i, g, h and k are very particularly preferably 0;

As A, preference is given to carbenium ions (R 3 C + ) or quaternary ammonium ions having an acid H function (R 3 NH + ). Particular preference is given to quaternary ammonium salts having acid H functions.

If a ≧1 and all M are boron, it is preferred that the number of boron atoms is ≦4, particularly preferably 2.

Examples of the chemical compound of the invention are:

In place of the N,N-dimethylanilinium cation [C 6 H 5 N(CH 3 ) 2 H] + , the cation used can alternatively be CPh 3 + .

The preparation of a chemical compound according to the invention can proceed, for example, according to the following reaction scheme:

In this scheme

X is a C 1 -C 40 -group such as a C 1 -C 40 -alkylene, C 1 -C 40 -haloalkylene, C 6 -C 40 -arylene, C 6 -C 40 -haloarylene, C 7 -C 40 -arylalkylene or C 7 -C 40 -haloarylalkylene, C 2 -C 40 -alkynylene, C 2 -C 40 -haloalkynylene, C 2 -C 40 -alkenylene or C 2 -C 40 -haloalkenylene group,

Y are, independently of one another, identical or different and are each a leaving group, preferably a hydrogen or halogen atom,

R are, independently of one another, identical or different and are each a halogen atom or a C 1 -C 40 -group such as a C 1 -C 40 -alkyl, C 1 -C 40 -haloalkyl, C 6 -C 40 -aryl, C 6 -C 40 -haloaryl, C 7 -C 40 -arylalkyl or C 7 -C 40 -haloarylalkyl group,

Bs is a base, preferably an organolithium compound or a Grignard compound,

M are identical or different and are each an element of group IIa, IIIa, IVa or Va of the Periodic Table of the Elements and

A is a cation of group Ia, IIa or IIIa of the Periodic Table of the Elements, a carbenium, oxonium or sulfonium cation or a quaternary ammonium compound.

The chemical compound of the invention can be used together with metallocenes as a catalyst system. Metallocenes comprise at least one central metal atom to which at least one π-ligand, e.g. cyclopentadienyl ligand, is bonded. Preference is given to chiral metallocenes. In addition, further substituents such as halogen, alkyl, alkoxy or aryl groups can be bonded to the central metal atom. The central metal atom is preferably an element of transition group III, IV, V or VI of the Periodic Table of the Elements, in particular from transition group IV of the Periodic Table of the Elements, for example Ti, Zr or Hf. For the purposes of the present invention, cyclopentadienyl ligands are unsubstituted cyclopentadienyl radicals and substituted cyclopentadienyl radicals such as methyl-cyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, benzoindenyl, fluorenyl, benzofluorenyl, tetrahydro-fluorenyl and octahydrofluorenyl radicals. The π ligands, e.g. cyclo-pentadienyl ligands, can be bridged or unbridged, with single and multiple bridges, even via ring systems, being possible. The term metallocene also includes compounds having more than one metallocene fragment, known as multinuclear metallocenes. These can have any substitution pattern and bridging variants. The individual metallocene fragments of such multinuclear metallocenes can be either of the same type or different from one another. Examples of such multinuclear metallocenes are described, for example, in EP-A-632063, JP-A-04/80214, JP-A-04/85310, EP-A-654476.

Particular preference is given to unbridged or bridged metallocenes of the formula II,

where

M1 is a metal of transition group III, IV, V or VI of the Periodic Table of the Elements, in particular Zr or Hf,

R 1 are identical or different and are each a hydrogen atom, SiR 3 , where R 3 are identical or different and are each a hydrogen atom or a C 1 -C 40 -group such as C 1 -C 20 -alkyl, C 1 -C 10 -fluoroalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 10 -fluoroaryl, C 6 -C 10 -aryloxy, C 2 -C 10 -alkenyl, C 7 -C 40 -arylalkyl, C 7 -C 40 -alkylaryl or C 8 -C 40 -arylalkenyl, or a C 1 -C 30 -group such as C 1 -C 25 -alkyl, e.g. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C 2 -C 25 -alkenyl, C 3 -C 15 -alkylalkenyl, C6-C 24 -aryl, C 5 -C 24 -heteroaryl such as pyridyl, furyl or quinolyl, C 7 -C 30 -arylalkyl, C 7 -C 30 -alkylaryl, fluorine-containing C 1 -C 25 -alkyl, fluorine-containing C 6 -C 24 -aryl, fluorine-containing C 7 -C 30 -arylalkyl, fluorine-containing C 7 -C 30 -alkylaryl or C 1 -C 12 -alkoxy, or two or more radicals R 1 can be connected to one another such that the radicals R 1 and the atoms of the cyclopenta-dienyl ring which connect them form a C 4 -C 24 -ring system, which may in turn be substituted,

R 2 are identical or different and are each a hydrogen atom, SiR 3 , where R 3 are identical or different and are each a hydrogen atom or a C 1 -C 40 -group such as C 1 -C 20 -alkyl, C 1 -C 10 -fluoroalkyl, C 1 -C 10 -alkoxy, C 6 -C 14 -aryl, C 6 -C 10 -fluoroaryl, C 6 -C 10 -aryloxy, C 2 -C 10 -alkenyl, C 7 -C 40 -arylalkyl, C 7 -C 40 -alkylaryl or C 8 -C 40 -arylalkenyl, or a C 1 -C 30 -group such as C 1 -C 25 -alkyl, e.g. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C 2 -C 25 -alkenyl, C 3 -C 15 ,-alkylalkenyl, C 6 -C 24 -aryl, C 5 -C 24 -heteroaryl, e.g. pyridyl, furyl or quinolyl, C 7 -C 30 -arylalkyl, C 7 -C 30 -alkylaryl, fluorine-containing C 1 -C 25 -alkyl, fluorine-containing C 6 -C 24 -aryl, fluorine-containing C 7 -C 30 -arylalkyl, fluorine-containing C 7 -C 30 -alkylaryl or C 1 -C 12 -alkoxy, or two or more radicals R 2 can also be connected to one another such that the radicals R 2 and the atoms of the cyclo-pentadienyl ring which connect them form a C 4 -C 24 -ring system, which may in turn be substituted,

n is 5when q=0, and n is 4 when q=1,

m is5 when q=0, and m is 4when q=1,

L are identical or different and are each a halogen atom or a hydrocarbon radical having 1-20 carbon atoms, e.g. C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 1 -C 20 -alkoxy, C 6 -C 14 -aryloxy or C 6 -C 40 -aryl,

k is an integer from 1 to 4, where if M 1 =Ti, Zr or Hf, k is preferably 2,

Z is a bridge structural element between the two cyclopentadienyl rings, and q is 0 or 1.

Examples of Z are groups M 2 R 4 R 5 , where M 2 is carbon, silicon, germanium or tin and R 4 and R 5 are identical or different and are each a C 1 -C 20 -group such as C 1 -C 10 -alkyl or C 6 -C 14 -aryl. Z is preferably CH 2 , CH 2 CH 2 , CH(CH 3 )CH 2 , CH(C 4 H 9 )C(CH 3 ) 2 , C(CH 3 ) 2 , (CH 3 ) 2 Si, (CH 3 ) 2 Ge, (CH 3 ) 2 Sn, (C 6 H 5 ) 2 Si, (C 6 H 5 )(CH 3 )Si, (C 6 H 5 ) 2 Ge, (C 6 H 5 ) 2 Sn, (CH 2 ) 4 Si, CH 2 Si(CH 3 ) 2 , o-C 6 H 4 or 2,2′-(C 6 H 4 ) 2 . Z together with one or more radicals R 1 and/or R 2 can also form a monocyclic or polycyclic ring system.

Preference is given to chiral bridged metallocenes of the formula II, in particular those in which q is 1 and one or both cyclopentadienyl rings are substituted in such a way that they form an indenyl ring. The indenyl ring is preferably substituted, in particular in the 2; 4; 2,4,5; 2,4,6; 2,4,7 or 2,4,5,6 positions, by C 1 -C 20 -groups such as C 1 -C 10 -alkyl or C 6 -C 20 -aryl, where two or more substituents of the indenyl ring can together also form a ring system.

The following examples of metallocene serve to illustrate the present invention but do not restrict it in any way:

bis(cyclopentadienyl)dimethylzirconium

bis(indenyl)dimethylzirconium

bis(fluorenyl)dimethylzirconium

(indenyl)(fluorenyl)dimethylzirconium

(3-methyl-5-naphthylindenyl)(2,7-di-tert-butylfluorenyl)dimethylzirconium

(3-methyl-5-naphthylindenyl)(3,4,7-trimethoxyfluorenyl)dimethylzirconium

(pentamethylcyclopentadienyl)(tetrahydroindenyl)dimethylzirconium

20 (cyclopentadienyl)(1-octen-8-ylcyclopentadienyl)dimethylzirconium

(indenyl)(1-buten4-ylcyclopentadienyl)dimethylzirconium

[1,3-bis(trimethylsilyl)cyclopentadienyl](3,4-benzofluorenyl)dimethyl-zirconium

bis(cyclopentadienyl)dimethyltitanium

dimethylsilanediylbis(indenyl)dimethylzirconium

dimethylsilanediylbis(tetrahydroindenyl)dimethylzirconium

dimethylsilanediyl(cyclopentadienyl)(indenyl)dimethylzirconium

dimethylsilanediylbis(2-methylindenyl)dimethylzirconium

dimethylsilanediylbis(2-ethylindenyl)dimethylzirconium

dimethylsilanediylbis(2-methyl-4,5-benzoindenyl)dimethylzirconium

dimethylsilanediylbis(2-ethyl-4,5-benzoindenyl)dimethylzirconium

dimethylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylen-7-ylidene)dimethylzirconium

dimethylsilanediyl(2-methyl-4,5-benzoindenyl)(2-methyl4-phenylindenyl)dimethylzirconium

dimethylsilanediyl(2-ethyl-4,5-benzoindenyl)(2-methyl4-phenylindenyl)dimethylzirconium

dimethylsilanediyl(2-methyl-4,5-benzoindenyl)(2-ethyl4-phenylindenyl)dimethylzirconium

dimethylsilanediyl(2-ethyl-4,5-benzoindenyl)(2-ethyl4-naphthylindenyl)dimethylzirconium

dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)dimethylzirconium

dimethylsilanediylbis(2-methyl-4-phenylindenyl)dimethylzirconium

dimethylsilanediylbis(2-ethyl-4-phenylindenyl)dimethylzirconium

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dimethylzirconiurr

dimethylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dimethylzircornium

dimethylsilanediylbis(2-methyl-4-naphthylindenyl)dimethylzirconium

dimethylsilanediylbis(2-ethyl-4-naphthylindenyl)dimethylzirconium

methylphenylsilanediylbis(indenyl)dimethylzirconium

methylphenylsilanediyl(cyclopentadienyl)(indenyl)dimethylzirconium

methylphenylsilanediylbis(tetrahydroindenyl)dimethylzirconium

methylphenylsilanediylbis(2-ethylindenyl)dimethylzirconium

methylphenylsilanediylbis(2-ethylindenyl)dimethylzirconium

methylphenylsilanediylbis(2-ethyl-4,ezindenyl)dimethylzirconium

methylphenylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylen-7-ylidene)diylimethyzirconium

methylphenylsilanediyl(2-methyl, 5-benzoindenyl)(2-methyl-4-phenylindenyl)dimethyzirconium

methylphenylsilanediyl(2-ethyl-4,5-benzoindenyl)(2-methyl-4-phenylindenyl)dimethylzirconium methylphenylsilanediyl(2-methyl-4,5-benzoindenyl)(2-ethyl-4-phenylindenyl)dimethylzirconium

methylphenylsilanediyl(2-ethyl-4,5-benzoindenyl)(2-ethyl-4-naphthylindenyl)dimethylzirconium

methylphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dimethylzirconium

methylphenylsilanediylbis(2-methyl-4-phenylindenyl)dimethylzirconium

methylphenylsiianediylbis(2-ethyl-4-phenylindenyl)dimethylzirconium

methylphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dimethylzirconium

methylphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dimethylzirconium

methylphenylsilanediylbis(2-methyl-4-naphthylindenyl)dimethylzirconium

methylphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dimethylzirconium

diphenylsilanediylbis(indenyl)dimethylzirconium

diphenylsilanediylbis(2-methylindenyl)dimethylzirconium

diphenylsilanediylbis(2-ethylindenyl)dimethylzirconium

diphenylsilanediyl(cyclopentadienyl)(indenyl)dimethylzirconium

diphenylsilanediylbis(2-methyl-4,5-benzoindenyl)dimethylzirconium

diphenylsilanediylbis(2-ethyl-4,5-benzoindenyl)dimethylzirconium

diphenylsilanediyl(2-methyl-4,5-benzoindenyl)(2-methyl4-phenylindenyl)dimethylzirconium

diphenylsilanediyl(2-ethyl-4,5-benzoindenyl)(2-methyl-4-phenylindenyl)dimethylzirconium

diphenylsilanediyl(2-methyl-4,5-benzoindenyl)(2-ethyl-4-phenylindenyl)dimethylzirconium

diphenylsiianediyl(2-ethyl-4,5-benzoindenyl)(2-ethyl-4-naphthylindenyl)dimethylzirconium

diphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dimethylzirconium

diphenylsilanediylbis(2-methyl-4-phenylindenyl)dimethylzirconium

diphenylsilanediylbis(2-ethyl-4-phenylindenyl)dimethylzirconium

diphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dimethylzirconium

diphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dimethylzirconium

diphenylsilanediylbis(2-methyl-4-naphthylindenyl)dimethylzirconium

diphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dimethylzirconium

1-silacyclopentane-1,1-bis(indenyl)dimethylzirconium

1-silacyclopentane-1,1-bis(2-methylindenyl)dimethylzirconium

1-silacyclopentane-1,1-bis(2-ethylindenyl)dimethylzirconium

1-silacyclopentane-1,1-bis(2-methyl-4,5-benzoindenyl)dimethylzirconium

1-silacyclopentane-1,1-bis(2-ethyl-4,5-benzoindenyl)dimethylzirconium

1-silacyclopentane-1-(2-methyl-4,5-benzoindenyl)-1-(2-methyl-4-phenylindenyl)dimethylzirconium

1-silacyclopentane-1-(2-ethyl-4,5-berzoindenyl)-1-(2-methyl4-phenylindenyl)dimethylzirconium

1-silacyclopentane-1-(2-methyl-4,5-benzoindenyl)-1-(2-ethyl-4-phenylindenyl)dimethylzirconium

1-silacyclopentane-1-(2-ethyl-4,5-benzoindenyl)-1-(2-ethyl-4-naphthylindenyl)dimethylzirconium

1-silacyclopentane-1-(2-methylindenyl)-1-(4-phenylindenyl)dimethylzirconium

1-silacyclopentane-1,1-bis(2-metyl-4-phenylindenyl)dimethylzirconium

1-silacyclopentane-1,1-bis(2-ethyl-4-phenylindenyl)dimethylzirconium

1-silacyclopentane-1,1-bis(2-methyl-4,6-diisopropylindenyl)dimethylzirconium

1-silacyclopentane-1,1-bis(2-ethyl-4,6-diisopropylindenyl)dimethylzirconium

1-silacyclopentane-1,1-bis(2-methyl-4-naphthylindenyl)dimethylzirconium

1-silacyclopentane-1,1-bis(2-ethyl-4-naphthylindenyl)dimethylzirconium

bis(cyclopentadienyl)dimethyltitanium

ethylene-1,2-bis(indenyl)dimethylzirconium

ethylene-1,2-bis(tetrahydroindenyl)dimethylzirconium

ethylene-1-cyclopentadienyl-2-(1-indenyl)dimethylzirconium

ethylene-1-cyclopentad ienyl-2-(2-indenyl)dimethylzirconium

ethylene-1-cyclopentadienyl-2-(2-methyl-1-indenyl)dimethylzirconium

ethylene-1,2-bis(2-methylindenyl)dimethylzirconium

ethylene-1,2-bis(2-ethylindenyl)dimethylzirconium

ethylene-1,2-bis(2-methyl-4,5-benzoindenyl)dimethylzirconium

ethylene-1,2-bis(2-ethyl-4,5-benzoindenyl)dimethy izirconium

ethylene-1,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylen-7-ylidene)dimethylzirconium

ethylene-1-(2-methyl-4,5-benzoindenyl)-2-(2-methyl-4-phenylindenyl)dimethylzirconium

ethylene-1-(2-ethyl-4,5-benzoindenyl)-2-(2-methyl-4-phenylindenyl)dimethylzirconium

ethylene-1-(2-methyl-4,5-benzoindenyl)-2-(2-ethyl-4-phenylindenyl)dimethylzirconium

ethylene-1-(2-ethyl-4,5-benzoindenyl)-2-(2-ethyl-4-naphthylindenyl)dimethylzirconium

ethylene-1-(2-methylindenyl)-2-(4-phenylindenyl)dimethylzirconium

ethylene-1,2-bis(2-methyl-4-phenylindenyl)dimethylzirconium

ethylene-1,2-bis(2-ethyl-4-phenylindenyl)dimethylzirconium

ethylene-1,2-bis(2-methyl-4,6-diisopropylindenyl)dimethylzirconium

ethylene-1,2-bis(2-ethyl-4,6-diisopropylindenyl)dimethylzirconiurn

ethylene-1,2bis(2methyl-4naphthylindenyl)dimethylzircoflum

ethylene-1,2-bis(2-ethyl-4-naphthylindenyl)dimethylzirconium

propylene-2,2-bis(indenyl)dimethylzirconium

propylene-2-cyclopentadienyl-2-(1-indenyl)dimethylzirconium

propylene-2-cyclopentadienyl-2-(4-phenyl-1-indenyl)dimethylzirconium

propylene-2-cyclopentadienyl-2-(9-fluorenyl)deimethylzirconuum

propylene-2-cyclopentadienyl-2-(2,7-dimethoxy-9-fluorenyl)dimethylzirconium

propylene-2-cyclopentadienyl-2-(2,7-di-tert-butyl-9-fluorenyl)dimethylzirconium

propylene-2-cyclopentadienyl-2-(2,7-dibromo-9-fluorenyl)dimethylzirconium

propylene-2-cyclopentadienyl-2-(2,7-diphenyl-9-fluorenyl)dimethylzirconium

propylene-2-cyclopentadienyl-2-(2,7-dimethyl-9-fluorenyl)dimethylzirconium

propylene-2-(3-methylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dimethylzirconium

propylene-2-(3-tert-butylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dimethylzirconium

propylene-2-(3-trimethylsilylcyclopentadienyl)-2-(3,6-di-tert-butyl-9-fluorenyl)dimethylzirconium

propylene-2-cyclopentadienyl-2-[2,7-bis(3-buten-1-yl)-9-fluorenyl]dimethylzirconium

propylene-2-cyclopentadienyl-2-(3-tert-butyl-9-fluorenyl)dimethylzirconium

propylene-2,2-bis(tetrahvdroindenyl)dimethylzirconium

propylene-2,2-bis(2-methylindenyl)dimethylzirconium

propylene-2,2-bis(2-ethylindenyl)dimethylzirconium

propylene-2,2-bis(2-methyl-4,5-benzoindenyl)dimethylzirconium

propylene-2,2-bis(2-ethyl-4,5-benzoindenyl)dimethylzirconium

propylene-2,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylen-7-ylidene)dimethylzirconium

propylene-2-(2-methyl-4,5-benzoindenyl)-2-(2-methyl4-pheniylindenyl)dimethylzirconium

propylene-2-(2-ethyl-4,5-benzoindenyl)-2-(2-methyl4-phenylindenyl)dimethylzirconium

propylene-2-(2-methyl-4,5-benzoindenyl)-2-(2-ethyl4-phenylindenyl)dimethylzirconium

propylene-2-(2-ethyl-4,5-benzoindenyl)-2-(2-ethyl4-naphthylindenyl)dimethylzirconium

propylene-2-(2-methylindenyl)-2-(4-phenylindenyl)dimethylzirconium

propylene-2,2-bis(2-methyl-4-phenylindenyl)dimethylzirconium

propylene-2,2-bis(2-ethyl-4-phenylindenyl)dimethylzirconium

propylene-2,2-bis(2-ethyl-4,6-diisopropylindenyl)dimethylzirconium

propylene-2,2-bis(2-methyl-4-naphthylindenyl)dimethylzirconium

propylene-2,2-bis(2-ethyl-4-naphthylindenyl)dimethylzirconium

1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dimethylzirconium]hexane

1,6-bis[methylsilylbis(2-ethyl-4-phenylindenyl)dimethylzirconium]hexane

1,6-bis[methylsilylbis(2-methyl-4-naphthylindenyl)dimethylzirconium]hexane

1,6-bis[methylsilylbis(2-methyl-4,6-diisopropylindenyl)dimethylzirconium]hexane

1,6-bis[methylsilyl(2-methyl-4-phenylindeny)(4,5-benzoindenyl)dimethylzirconium]hexane

1-[methylsilylbis(tetrahydroindenyl)dimethylzirconium]-6-[ethylstannyl(cyclopentadienyl)(fluorenyl)dimethylzirmonium]hexane

1,6-disila-1,1,6,6-tetramethyl-1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)zirkoniumdimethyl]hexane

1,4-disila-1,4-bis[methylsilylbis(2-methyl-4-phenylindenyl)dimethylzirconium]cyclohexane

[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(pentamethylcyclopentadienyldimethylzirconium)

[1,4-bis(9-fluorenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldimethylzirconium)

[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldimethylzirconium)

[1-(1-indenyl)-6-(2-phenyl-1-indenyl)-1,1,6,6-tetraethyl-1,6-disila-4-oxahexane]bis(tert-butylcyclopentadienyldimethylzirconium)

[1,10-bis(2,3-dimethyl-1-indenyl)-1,1,10,10-tetramethyl-1,10-digermadecane]bis(2-methyl-4-phenylindenyldimethylzirconium)

(1-methyl-3-tert-butylcyclopentadienyl)(1-phenyl-4-methoxy-7-chlorofluorenyl)dimethylzirconium

(4,7-dichloroindenyl)(3,6-dimesitylfluorenyl)dimethylzirconium bis(2,7-di-tert-butyl-9-cyclohexylfluorenyl)dimethylzirconium

(2,7-dimesitylfluorenyl)[2,7-bis(1-naphthyl)fluorenyl]dimethylzirconium

dimethylsilylbis(fluorenyl)dimethylzirconium

dibutylstannylbis(2-methylfluorenyl)dimethylzirconium

1,1,2,2-tetraethyldisilanediyl(2-methylindenyl)(4-phenylfluorenyl)dimethylzirconium

propylene-1-(2-indenyl)-2-(9-fluorenyl)dimethylzirconium

1,1-dimethyl-1-silaethylenebis(fluorenyl)dimethylzirconium

[4-(cyclopentadienyl)-4 7,7-trimethyl(tetrahydroindenyl)]dimethylzirconium

[4-(cyclopentadiertyl)-4,7-dimethyl-7-phenyl(5,6-dimethyltetrahydroindenyl)]dimethylzirconium

[4-(cyclopentadienyl)-4,7-dimethyl-7-(1-naphthyl)(7-phenyltetrahydroindenyl)]dimethylzirconium

[4-(cyclopentadienyl)-4,7-dimethyl-7-butyl(6,6-diethyltetrahydroindenyl)]dimethylzirconium

[4-(3-tert-butylcyclopentadienyl)-7,7-trimethyl(tetrahydroindenyl)]dimethylzirconium

[4-(1-indenyl)-4,7,7-trimethyl(tetrahydroindenyl)]dimethylzirconium

bis(cyclopentadienyl)dimethylhafnium

bis(indenyl)dimethylvanadium

bis(fluorenyl)dimethylscandium

(indenyl)(fluorenyl)dimethylniobium

(2-methyl-7-naphthylindenyl)(2,6-di-tert-butylfluorenyl)diimethyltitanium

(pentamethylcyclopentadienyl)(tetrahydroindenyl)rrmthylhafnium bromide

(cyclopentadienyl)(1-octen-8-ylcyclopentadienyl)dimethylhafnium

(indenyl)(2-buten-4-ylcyclopentadienyl)dimethyltitanium

[1,3-bis(trimethylsilyl)cyclopentadienyl](3,4-benzofluorenyl)dimethy3niobium

bis(cyclopentadienyl)dimethyltitanium

dimethylsilanediylbis(indenyl)dimethyltitanium

dimethylsilanediylbis(tetrahydroindenyl)dimethylhafnium

dimethylsilanediyl(cyclopentadienyl)(indenyl)dimethyltitanium

dimethylsilanediylbis(2-methylindenyl)dimethylhafnium

dimethylsilanediylbis(2-ethylindenyl)metylscandium

dimethylsilanediylbis(2-butyl-4,5-benzoindenyl)dimethylniobium dimethylsilanediylbis(2-ethyl-4,5-benzoindenyl)dimethyltitanium dimethylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylen-7-ylidene)dimethyltitanium

dimethylsilanediyl(2-methyl-4,5-benzoindenyl)(2-methyl-4-phenylindenyl)dimethyltitanium

dimethylsilanediyl(2-ethyl-4,5-benzoindenyl)(2-methyl-4-phenylindenyl)dimethylhafnium

dimethylsilanediyl(2-methyl-4,5-benzoindenyl)(2-ethyl-4-phenylindenyl)methylscandium

dimethylsilanediyl(2-ethyl-4,5-benzoindenyl)(2-ethyl-4-naphthylindenyl)dimethyltitanium

dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)dimethylhafnium

dimethylsilanediylbis(2-methyl-4-phenylindenyl)dimethylniobium

dimethylsilanediylbis(2-ethyl-4-phenylindenyl)dimethylvanadium

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dimethylhafnium

dimethylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dimethylvanadium

dimethylsilanediylbis(2-methyl-4-naphthylindenyl)methylhafnium bromide

dimethylsilanediylbis(2-ethyl-4-naphthylindenyl)dimethyltitanium

methylphenylsilanediylbis(indenyl)dimethyltitanium

methylphenylsilanediyl(cyclopentadienyl)(indenyl)dimethylhafnium

methylphenylsilanediylbis(tetrahydroindenyl)dimethylhafnium

methylphenylsilanediylbis(2-methylindenyl)dimethyltitanium

methylphenylsilanediylbis(2-ethylindenyl)dimethylhafnium

methylphenylsilanediylbis(2-methyl-4,5-benzoindenyl)dimethylhafnium

methylphenylsilanediylbis(2-ethyl-4,5-benzoindenyl)dimethylvanadium

methylphenylsilanediylbis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylen-7-ylidene)dimethyltitanium

methylphenylsilanediyl(2-methyl-4,5-benzoindenyl)(2-methyl-4-phenylindenyl)methyltitanium bromide

methylphenylsilanediyl(2-ethyl-4,5-benzoindenyl)(2-methyl-4-phenylindenyl)dimethyltitanium

methylphenylsilanediyl(2-methyl-4,5-benzoindenyl)(2-ethyl-4-phenylindenyl)dimethylhafnium

methylphenylsilanediyl(2-ethyl-4,5-benzoindenyl)(2-ethyl-4-naphthylindenyl)dimethylhafnium

methylphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dimethyltitanium

methylphenylsilanediylbis(2-methyl-4-phenylindenyl)dimethylhafnium

methylphenylsilanediylbis(2-ethyl-4-phenylindenyl)dimethylvanadium

methylphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dimethyltitanium

methylphenylsilanediylbis(2-ethyl-4,6-diisopropylindenyl)dimethylhafnium

methylphenylsilanediylbis(2-methyl-4-naphthylindenyl)dimethylhafnium

methylphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dimethyltitanium

diphenylsilanediylbis(indenyl)dimethyltitanium

diphenylsilanediylbis(2-methylindenyl)dimethylhafnium

diphenylsilanediylbis(2-ethylindenyl)dimethyltitanium

diphenylsilanediyl(cyclopentadienyl)(indenyl)dimethylhafnium

diphenylsilanediylbis(2-methyl-4,5-benzoindenyl)dimethyltitanium

diphenylsilanediylbis(2-ethyl-4,5-benzoindenyl)dimethylhafnium

diphenylsilanediyl(2-methyl-4,5-benzoindenyl)(2-methyl-4-phenylindenyl)dimethylhafnium

diphenylsilanediyl(2-ethyl-4,5-benzoindenyl)(2-methyl-4-phenylindenyl)dimethyltitanium

diphenylsilanediyl(2-methyl-4,5-benzoindenyl)(2-ethyl-4-phenylindenyl)dimethylhafnium

diphenylsilanediyl(2-ethyl-4,5-benzoindenyl)(2-ethyl-4-naphthylindenyl)dimethyltitanium

diphenylsilanediyl(2-methylindenyl)(4-phenylindenyl)dimethyltitanium

diphenylsilanediylbis(2-methyl-4-phenylindenyl)dimethyltitanium

diphenylsilanediylbis(2-ethyl-4-phenylindenyl)dimethylhafnium

diphenylsilanediylbis(2-methyl-4,6-diisopropylindenyl)dimethylhafnium

diphenylsilanediylbis(2-methyl-4-naphthylindenyl)dimethylhafnium

diphenylsilanediylbis(2-ethyl-4-naphthylindenyl)dimethyltitanium

1-silacyclopentane-1,1-bis(indenyl)dimethylhafnium

1-silacyclopentane-1,1-bis(2-methylindenyl)dimethylhafnium

1-silacyclopentane-1,1-bis(2-ethylindenyl)dimethylhafnium

1-silacyclopentane-1,1-bis(2-methyl-4,5-benzoindenyl)dimethyltitanium

1-silacyclopentane-1,1-bis(2-ethyl-4,5-benzoindenyl)dimethylhafnium

1-silacyclopentane-1-(2-methyl-4,5-benzoindenyl)-1-(2-methyl-4-phenylindenyl)methylscandium

1-silacyclopentane-1-(2-ethyl-4,5-benzoindenyl)-1-(2-methyl-4-phenylindenyl)dimethylhafnium

1-silacyclopentane-1-(2-methyl-4,5-benzoindenyl)-1-(2-ethyl-4-phenylindenyl)dimethyltitanium

1-silacyclopentane-1-(2-ethyl-4,5-benzoindenyl)-1-(2-ethyl-4-naphthylindenyl)dimethylhafnium

1-silacyclopentane-1-(2-methylindenyl)-1-(4-phenylindenyl)dimethylhafnium

1-silacyclopentane-1,1-bis(2-methyl-4-phenylindenyl)dimethylhafnium

1-silacyclopentane-1,1-bis(2-ethyl-4-phenylindenyl)methyltitanium bromide

1-silacyclopentane-1,1-bis(2-methyl-4,6-diisopropylindenyl)dimethyltitanium

1-silacyclopentane-1,1-bis(2-ethyl-4,6-diisopropylindenyl)dimethyltitanium

1-silacyclopentane-1,1-bis(2-methyl-4-naphthylindenyl)methylscandium

1-silacyclopentane-1,1-bis(2-ethyl-4-naphthylindeiiyl)dimethylhafnium

bis(cyclopentadienyl)dimethyltitanium

ethylene-1,2-bis(indenyl)methylscandium

ethylene-1,2-bis(tetrahydroindenyl)dimethyltitanium

ethylene-1-cyclopentadienyl-2-(1-indeny)dimethylhafnium

ethylene-1-cyclopentadienyl-2-(2-indenyl)methyltitanium bromide

ethylene-1-cyclopentadienyl-2-(2-methyl-1-indenyl)dimethylhafnium

ethylene-1,2-bis(2-methylindenyl)dimethylhafnium

ethylene-1,2-bis(2-ethylindenyl)dimethylhafnium

ethylene-1,2-bis(2-methyl-4,5-benzoindenyl)dimethylhafnium

ethylene-1,2-bis(2-ethyl-4,5-benzoindenyl)dimethyltitanium

ethylene-1,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylen-7-ylidene)dimethyltitanium

ethylene-1-(2-methyl-4,5-benzoindenyl)-2-(2-methyl-4-phenylindenyl)dimethyltitanium

ethylene-1-(2-ethyl-4,5-benzoindenyl)-2-(2-methyl-4-phenylindenyl)dimethyltitanium

ethylene-1-(2-methyl-4,5-benzoindenyl)-2-(2-ethyl-4-phenylindenyl)methylscandium

ethylene-1-(2-ethyl-4,5-benzoindenyl)-2-(2-ethyl-4-naphthylindenyl)dimethylhafnium

ethylene-1-(2-methylindenyl)-2-(4-phenylindenyl)dimethyltitanium

ethylene-1,2-bis(2-methyl-4-phenylindenyl)dimethylhafnium

ethylene-1,2-bis(2-ethyl-4-phenylindenyl)dimethylhafnium

ethylene-1,2-bis(2-methyl-4,6-diisopropylindenyl)dimethylhafnium

ethylene-1,2-bis(2-ethyl-4,6-diisopropylindenyl)dimethyltitanium

ethylene-1,2-bis(2-methyl-4-naphthylindenyl)dimethyltitanium

ethylene-1,2-bis(2-ethyl-4-naphthylindenyl)dimethylhafnium

propylene-2,2-bis(indenyl)dimethylhafnium

propylene-2-cyclopentadienyl-2-(1-indenyl)dimethyltitanium

propylene-2-cyclopentadienyl-2-(4-phenyl-1-indenyl)dimethyltitanium

propylene-2-cyclopentadienyl-2-(9-fluorenyl)dimethylhafnium

propylene-2-cyclopentadienyl-2-(2,7-dimethoxy-9-fluorenyl)dimethylhafnium

propylene-2-cyclopentadienyl-2-(2,7-di-tert-butyl-9-fluorenyl)dimethylhafnium

propylene-2-cyclopentadienyl-2-(2,7-dibromo-9-fluorenyl)dimethyltitanium

propylene-2-cyclopentadienyl-2-(2,7-diphenyl-9-fluorenyl)dimethylhafnium

propylene-2-cyclopentadienyl-2-(2,7-dimethyl-9-fluorenyl)dimethyltitanium

propylene-2-(3-methylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dimethylhafnium

propylene-2-(3-tert-butylcyclopentadienyl)-2-(2,7-dibutyl-9-fluorenyl)dimethyltitanium

propylene-2-(3-trimethylsilylcyclopentadienyl)-2-(3,6-di-tert-butyl-9-fluorenyl)dimethyltitanium

propylene-2-cyclopentadienyl-2-[2,7-bis(3-buten-1-yl)-9-fluorenyl]dimethylhafnium

propylene-2-cyclopentadienyl-2-(3-tert-butyl-9-fluorenyl)dimethyltitanium

propylene-2,2-bis(tetrahydroindenyl)dimethylhafnium

propylene-2,2-bis(2-methylindenyl)dimethylhafnium

propylene-2,2-bis(2-ethylindenyl)dimethyltitanium

propylene-2,2-bis(2-methyl-4,5-benzoindenyl)dimethyltitanium

propylene-2,2-bis(2-ethyl-4,5-benzoindenyl)dimethylhafnium

propylene-2,2-bis(4,5-dihydro-8-methyl-7H-cyclopent[e]acenaphthylen-7-ylidene)dimethylhafnium

propylene-2-(2-methyl-4,5-benzoindenyl)-2-(2-methyl-4-phenylindenyl)dimethylhafnium

propylene-2-(2-ethyl-4,5-benzoindenyl)-2-(2-methyl-4-phenylindenyl)dimethyltitanium

propylene-2-(2 methyl-4,5-benzoindenyl)-2-(2-ethyl-4-phenylindenyl)dimethylhafnium

propylene-2-(2-ethyl-4,5-benzoindenyl)-2-(2-ethyl-4-naphthylindenyl)dimethyltitanium

propylene-2-(2-methylindenyl)-2-(4-phenylindenyl)dimethylhafnium

propylene-2,2-bis(2-methyl-4-phenylindenyl)dimethyltitanium

propylene-2,2-bis(2-ethyl-4-phenylindenyl)dimethylhafnium

propylene-2,2-bis(2-methyl-4,6-diisopropylindenyl)dimethyltitanium

propylene-2,2-bis(2-ethyl-4,6-diisopropylindenyl)dimethylhafnium

propylene-2,2-bis(2-methyl-4-naphthylindenyl)dimethyltitanium

propylene-2,2-bis(2-ethyl-4-naphthylindenyl)dimethyltitanium

1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dimethylhiafnium]hexane

1,6-bis[methylsilylbis(2-methyl-4,5-benzoindenyl)dimethyltitanium]hexane

1,6-bis[methylsilylbis(2-ethyl-4-phenylindenyl)dimethylhafnium]hexane

1,6-bis[methylsilylbis(2-methyl-4-napthylindenyl)dimethyltitatium]hexane

1,6-bis[methylsilylbis(2-methyl-4,6-diisopropylindenyl)dimethylhafnium]-hexane

1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dimethylhafnium]hexane

1,6-bis[methylsilyl(2-methyl-4-phenylindenyl)(4,5-benzoindenyl)dimethyltitanium]hexane

1-[methylsilylbis(tetrahydroindenyl)dimethylhafnium]-6-[ethylstannyl(cyclopentadienyl)-(fluorenyl)dimethyltitanium]hexane

1,6-disila-1,1,6,6-tetramethyl-1,6-bis[methylsilylbis(2-methyl-4-phenylindenyl)dimethylhafnium]hexane

1,4-disila-1,4-bis[methylsilylbis(2-methyl-4-phenylindenyl)dimethylhafnium]cyclohexane

[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(pentamethylcyclopentadienyldimethylhafnium)

[1,4-bis(9-fluorenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldimethylhafnium)

[1,4-bis(1-indenyl)-1,1,4,4-tetramethyl-1,4-disilabutane]bis(cyclopentadienyldimethyltitanium)

[1-(1-indenyl)-6-(2-phenyl-1-indenyl)-1,1,6,6-tetraethyl-1,6-disila4-oxahexane]bis(tert-butylcyclopentadienyldirnethyltitanium)

[1,10-bis(2,3-dimethyl-1-indenyl)-1,1,10,10-tetramethyl-1,10-digermadecane]bis(2-methyl-4-phenylindenyldimethylhafnium)

(1-methyl-3-tert-butylcyclopentadienyl)(1-phenyl-4-methoxy-7-chlorofluorenyl)dimethyltitanium

(4,7-dichloroindenyl)(3,6-dimesitylfluorenyl)dimethyltitanium

bis(2,7-di-tert-butyl-9-cyclohexylfluorenyl)dimethylhafnium

(2,7-dimesitylfluorenyl)[2,7-bis(1-naphthyl)fluorenyl]dimethylhafnium

dimethylsilylbis(fluorenyl)dimethyltitanium

dibutylstannylbis(2-methylfluorenyl)dimethylhafnium

1,1,2,2-tetraethyldisilanediyl(2-methylindenyl)(4-phenylfluorenyl)dimethyltitanium

propylene-1-(2-indenyl)-2-(9-fluorenyl)dimethylhafnium

1,1-dimethyl-1-silaethylenebis(fluorenyl)dimethyltitanium

[4-(cyclopentadienyl)4,7,7-trimethyl(tetrahydroindenyl)]dimethyltitanium

[4-(cyclopentadienyl)4,7-dimethyl-7-phenyl(5,6-dimethyltetrahydroindenyl)]dimethylhafnium

[4-(cyclopentadienyl)4,7-dimethyl-7-(1-naphthyl)(7-phenyltetrahydroindenyl)]dimethyltitanium

[4-(cyclopentadienyl)4,7-dimethyl-7-butyl(6,6-diethyltetrahydroindenyl)]dimethylhafnium

[4-(3-tert-butylcyclopentadienyl)-4,7,7-trimethyl(tetrahydroindenyl)]dimethylhafnium

[4-(1-indenyl)4,7,7-trimethyl(tetrahydroindenyl)]dimethyltitanium

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-diisopropylindenyl)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-(cyclopentadienyl)(fluorenyl)zirconium dichloride

bis(cyclopentadienyl)(η 4 -butadiene)zirconium

bis(methylcyclopentadienyl)(η 4 -butadiene)zirconium

bis(n-butyl-cyclopentadienyl)(η 4 -butadiene)zirconium

bisindenyl(η 4 -butadiene)zirconium

(tert-butylamido)dimethyl(tetramethyl-η5-cyclopentadienyl)silane(η 4 -butadiene)zirconium

bis(2-methylbenzoindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-indenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbisindenyl(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methylbenzoindenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(2-methylbenzoindenyl)(2-methyl-indenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(2-methylbenzoindenyl)(2-methyl-4-phenylindenyl)(η 4 -butadierie)zirconium

dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-4-phenyl-indenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-4,6-diisopropyl-indenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-4-naphthyl-indenyl)(η 4 -butadiene)zirconium

isopropylidene(cyclopentadienyl)(fluorenyl)(η 4 -butadiene)zirconium

isopropylidene(cyclopentadienyl)(indenyl)(η 4 -butadiene)zirconium

[4-η5-cyclopentadienyl)-4,7,7-trimethyl-(η5-4,5,6,7-tetrahydroindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-indenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbisindenyl(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methylbenzoindenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(2-methylbenzoindenyl)(2-methyl-indenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(2-methylbenzoindenyl)(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbisindenyl(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methylbenzoindenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(2-methylbenzoindenyl)(2-methylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(2-methylbenzoindenyl)(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(2-methylindenyll(4-phenylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-4-naphthylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbisindenyl(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methylbenzoindenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(2-methylbenzoindenyl)(2-methylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(2-methylbindenyl)(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-methyl-4-naphthylindenyl)(η 4 -butadiene)zirconium

methylphenylmethylene(fluorenyl)(cyclopentadienyl)(η 4 -butadiene)zirconium

diphenylmethylene(fluorenyl)(cyclopentadienyl)(η 4 -butadiene)zirconium

isopropylidene(3-methylcyclopentadienyl)(fluorenyl)(η 4 -butadiene)zirconium

dimethylsilanediyl(3-tert-butylcyclopentadienyl)(fluorenyl)(η 4 -butadiene)zirconium

diphenylsilanediyl(3-(trimethylsilyl)cyclopentadienyl)(fluorenyl)(η 4 -butadiene)zirconium

phenylmethylsilanediylbis(2-methylindenyl)(η 4 -butadiene)zirconium

phenylmethylsilanediylbisindenyl(η 4 -butadiene)zirconium

phenylmethylsilanediylbis(2-methyl-4,5-benzoindenyl)(η 4 -butadiene)zirconium

phenylmethylsilanediyl(2-methyl-4,5-benzoindenyl)(2-methyl-indenyl)(η 4 -butadiene)zirconium

phenylmethylsilanediyl(2-methyl-4,5-benzoindenyl)(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium

phenylmethylsilanediyl(2-methylindenyl)(4-phenylindenyl)(η 4 -butadiene)zirconium

phenylmethylsilanediylbis(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium

phenylmethylsilanediylbis(2-ethyl-4-phenylindenyl)(η 4 -butadiene)zirconium

phenylmethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)(η 4 -butadiene)zirconium

phenylmethylsilanediylbis(2-methyl-4-naphthylindenyl)(η 4 -butadiene)zirconium

ethylenebis(2-methylindenyl)(η 4 -butadiene)zirconium

ethylenebisindenyl(η 4 -butadiene)zirconium

ethylenebis(2-methyl-4,5-benzoindenyl)(η 4 -butadiene)zirconium

ethylene(2-methyl-4,5-benzoindenyl)(2-methylindenyl)(η 4 -butadiene)zirconium

ethylene(2-methyl-4,5-benzoindenyl)(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium

ethylene(2-methylindenyl)(4-phenylindenyl)(η 4 -butadiene)zirconium

ethylenebis(2-methyl-4,5-benzoindenyl)(η 4 -butadiene)zirconium

ethylenebis(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium

ethylenebis(2-methyl-4,6-diisopropylindenyl)(η 4 -butadiene)zirconium

ethylenebis(2-methyl-4-naphthylindenyl)(η 4 -butadiene)zirconium

ethylenebis(2-ethyl-4-phenylindenyl)(η 4 -butadiene)zirconium

ethylenebis(2-ethyl-4,6-diisopropylindenyl)(η 4 -butadiene)zirconium

ethylenebis(2-ethyl-4-naphthylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2-ethyl-4-phenylindenyl)(η 4 -butadiene)zirconium

dimethylsilanediylbis(2,3,5-trimethylcyclopentadienyl)(η 4 -butadiene)zirconium

1,6-{bis[methylsilylbis(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium]}hexane

1,6-{bis[methylsilylbis(2-ethyl-4-phenylindenyl)(η 4 -butadiene)zirconium]}hexane

1,6-{bis[methylsilylbis(2-methyl-4-naphthylindenyl)(η 4 -butadiene)zirconium]}hexane

1,6-{bis[methylsilylbis(2-methyl-4,5-benzoindenyl)(η 4 -butadiene)zirconium]}hexane

1,6-{bis[methylsilyl(2-methyl-4-phenyl-indenyl)(2-methylindenyl)(η 4 -butadiene)zirconium]}hexane

1,2-{bis[methylsilylbis(2-methyl-4-phenylindenyl)(η 4 -butadiene)zirconium]}ethane

1,2-{bis[methylsilylbis(2-ethyl-4-phenylindenyl)(η 4 -butadiene)zirconium]}ethane

1,2-{bis[methylsilylbis(2-methyl-4-naphthylindenyl)(η 4 -butadiene)zirconium]}ethane

1,2-{bis[methylsilylbis(2-methyl-4,5-benzoindenyl)(η 4 -butadiene)zirconium]}ethane

1,2-{bis[methylsilyl(2-methyl-4-phenylindenyl)(2-methylindenyl)(η 4 -butadiene)zirconium]}ethane.

The present invention also provides a catalyst comprising at least one transition metal compound according to the invention as cocatalyst and at least one metallocene, and also a process for preparing an olefin polymer by polymerization of at least one olefin in the presence of this catalyst according to the invention. The polymerization can be a homopolymerization or a copolymerization.

Preference is given to polymerizing olefins of the formula R α —CH═CH—R β , where R α and R β are identical or different and are each a hydrogen atom, a halogen atom, an alkoxy, hydroxy, alkylhydroxy, aldehyde, carboxylic acid or carboxylic ester group or a saturated or unsaturated hydrocarbon radical having from 1 to 20 carbon atoms, in particular from 1 to 10 carbon atoms, which may be substituted by an alkoxy, hydroxy, alkylhydroxy, aldehyde, carboxylic acid or carboxylic ester group, or R α and R β together with the atoms connecting them form one or more rings. 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, tetracyclododecene, ethylidenenorbornene, dienes such as 1,3-butadiene or 1,4-hexadiene, biscyclopentadiene or methyl methacrylate.

Particular preference is given to homopolymerizing propylene or ethylene, copolymerizing ethylene with one or more C 3 -C 20 -1-olefins, in particular propylene, and/or one or more C 4 -C 20 -dienes, in particular 1,3-butadiene, or copolymerizing norbornene and ethylene.

The polymerization is preferably carried out at a temperature of from −60 to 300° C., particularly preferably from 30 to 250° C. The pressure is from 0.5 to 2500 bar, preferably from 2 to 1500 bar. The polymerization can be carried out continuously or batchwise, in one or more stages, in solution, in suspension, in the gas phase or in a supercritical medium.

The compound of the invention can be applied to supports either alone or together with a metallocene. Suitable support materials are, for example, silica gels, aluminum oxides, solid aluminoxane or other inorganic support materials such as magnesium chloride. Another suitable support material is polyolefin powder in finely divided form.

The supported system can be resuspended as powder or while still moist with solvent and be metered as suspension in an inert suspension medium into the polymerization system.

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

To prepare olefin polymers having a broad molecular weight distribution, preference is given to using catalyst systems comprising two or more different metallocenes.

To remove catalyst poisons present in the olefin, purification using an aluminum alkyl, for example trimethylaluminum, tricthylaluminum or triisobutylaluminum is advantageous. This purification can be carried out either in the polymerization system itself or the olefin is brought into contact with the Al compound and subsequently separated off again before addition to the polymerization system.

As molecular weight regulator and/or to increase the activity, hydrogen is added if required. The total pressure in the polymerization system is from 0.5 to 2500 bar, preferably from 2 to 1500 bar.

The compound of the invention is employed in a concentration, based on the transition metal, of preferably from 10 −3 to 10 −8 mol, preferably from 10 −4 to 10 −7 mol, of transition metal per dm 3 of solvent or per dm 3 of reactor volume.

Suitable solvents for preparing both the chemical compound of the invention and the catalyst system of the invention are aliphatic or aromatic solvents such as hexane or toluene, ether solvents such as tetrahydrofuran or diethyl ether or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocbons such as o-dichlorobenzene.

Before addition of the catalyst system, in particular the supported catalyst system (comprising at least one chemical compound according to the invention, at least one metallocene, support material and/or a polyolefin powder in finely divided form), another aluminum alkyl compound such as trimethylaluminum. triethylaluminum, triisobutylaluminum, trioctylaluminum or isoprenylaluminum can be additionally introduced into the reactor to make the polymerization system inert (for example for removing catalyst poisons present in the olefin). This is added to the polymerization system in a concentration of from 100 to 0.01 mmol of Al per kg of reactor contents. Preference is given to triisobutylaluminum and triethylaluminum in a concentration of from 10 to 0.1 mmol of Al per kg of reactor contents. This enables a low molar Al/M ratio to be selected in the synthesis of a supported catalyst system.

The following examples serve to illustrate the invention.

General procedures: Preparation and handling of organometallic compounds were carried out with exclusion of air and moisture under argon (Schlenk technique). All solvents required were made absolute before use by boiling for a number of hours over suitable desiccants and subsequent distillation under argon.