RU2510646C2 - Metallocene compound, catalyst composition including it and method of olefin polymerisation, applying it - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention is aimed at metallocene compound, which can ensure process of polymerization with obtaining olefin polymer or copolymer with high polymerization activity and stability, which are preserved for long time, and catalyst composition, which includes it, and method of olefin polymerization, applying it. Metallocene compound is described by the following formula (4HInd)(Cp')MX₂, where 4Hind represents group, that has tetrahydroindenyl core, Cp' represents indenyl group, 4HInd is non-substituted, and Cp' is non-substituted or substituted with one or several substituents, and substituents are identical to each other or different from each other and represent radical, selected from group, consisting of alkyl or aryl group, and M represents transition metal from group IV of periodic table, and X are identical to each other or different from each other and represent halogen atoms.

EFFECT: catalyst composition contains metallocene compound of formula one and activator, which reacts with metallocene compound in such a way that metallocene compound demonstrates catalytic activation.

13 cl, 5 ex

Description

FIELD OF THE INVENTION

This invention relates to a metallocene compound, and, more specifically, to a metallocene compound that can provide polymerization to produce an olefin polymer or copolymer with high polymerization activity, and a catalyst composition including it and an olefin polymerization method using it.

State of the art

Catalysts containing a transition metal have been widely used for the polymerization of olefin. For example, as described in German patents Nos. 2608933 and 3007725, a metallocene compound containing a transition metal from group 4B of the periodic table, such as zirconium, titanium, hafnium, and cyclopentadienyl ligands, in the presence of an activator, can be used as a catalyst for the polymerization of olefin. such as methylaluminoxane. Examples of cyclopentadienyl ligands include substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl and the like. Various metallocene compounds containing cyclopentadienyl ligands were used as a catalyst for olefin polymerization. And, as you know, the chemical structures of metallocene compounds have a significant impact on the suitability of metallocene as catalysts. For example, the size and location of the substituent associated with the cyclopentadienyl ring have a significant effect on the activity, stereospecificity and stability of the catalyst and the physical properties of the polymer obtained using the catalyst, and the like. Examples of a metallocene compound containing zirconium and cyclopentadienyl ligands substituted with a hydrocarbyl group include bis (alkylcyclopentadienyl) zirconium dichloride (where alkyl is methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl and the like) (J. Chem. Soc. Dalton Trans ., 805 (1981)), bis (pentamethylcyclopentadienyl) zirconium dichloride (J. Amer. Chem. Soc., 100, 3078 (1978)), (pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium (J. Amer. Chem. Soc., 106, 6355 (1984)), bis (di-, tri- or tetraalkylcyclopentadienyl) zirconium dichloride (US patent No. 4874880 ) etc. In addition, a non-crosslinked metallocene compound containing substituted indenyl ligands (US Pat. No. 5,780,659), a metallocene compound containing cyclopentadienyl ligands substituted by a monoalkyl substituent (German patent No. 4312270) are known.

It has recently become known that a catalyst system (composition) comprising a metallocene compound, which consists of substituted cyclopentadienyl ligands and zirconium as a transition metal, and methylalumoxane, has excellent olefin polymerization activity (European Patent No. 129368, US Patent Nos. 4874880 and 5324800 , Makromol. Chem. Rapid Commun., 4, 417 (1983) and the like). And, as is also known, catalyst systems consisting of a metallocene compound containing an alkyl group and / or a halogen atom as a ligand and aluminoxane have high activity in the polymerization of α-olefin, and catalyst systems also have high activity in the polymerization of α-olefin consisting of a metallocene compound and an organoboron compound (Macromolecules 1993,26, 3239; J. Am. Chem. Soc. 1991, 113, 3623).

In addition, as is known, catalyst systems comprising a metallocene compound and an aluminoxane or organoboron compound have the highest activity at a polymerization temperature in the range from 60 to 90 ° C. However, despite the high initial activity of the catalyst at high temperature, the catalysts are unstable at high temperature, and their activity decreases over time polymerization. Therefore, the polymerization performance is reduced, the properties of the obtained polymer are deteriorating, and the resulting polymer is unsuitable for use in the manufacture of various plastic products. In the case of a decrease in the polymerization temperature, the molecular weight of the obtained polymer can be increased, but the catalytic activity will decrease, so that sufficient activity during polymerization cannot be obtained.

Disclosure of invention

The inventors of the present invention have obtained a new metallocene compound having high polymerization activity, and an olefin polymerization catalyst system comprising a new metallocene compound, and have also developed a method for producing a polyolefin using a catalyst system.

Therefore, one object of the present invention is to provide a metallocene compound for the polymerization of an olefin whose catalytic activity and stability are excellent even at a high polymerization temperature. The catalytic activity of the metallocene compound is maintained for a long period of time, and when using the metallocene compound, polymers having the preferred properties are stably obtained.

Another objective of the present invention is to provide a metallocene compound for the polymerization of an olefin, which has various properties and can provide polymerization to obtain a polyolefin having excellent polymer morphology.

Another objective of the present invention is to provide a metallocene compound for the polymerization of an olefin, which can easily provide for the regulation of the molecular weight of the obtained polymer in a homogeneous polymerization medium (solution phase) or an inhomogeneous polymerization medium (gas or suspension phase), and including a catalyst composition and using its method of polymerizing an olefin.

To achieve these and other objectives, the present invention provides a metallocene compound for the polymerization of an olefin, described by the following formula 1.

 Formula 1

(4HInd) (Cp ') MX ₂ ,

where 4HInd is a group having a tetrahydroindenyl core, Cp 'is a group having a cyclopentadienyl core, and 4HInd and Cp' may be unsubstituted or substituted with one or more substituents. The substituents may be identical to each other or different from each other and are radicals selected from the group consisting of an alkyl, alkoxy, alkylsilyl, alkylsiloxy, alkylamino or haloalkyl group containing from 1 to 20 carbon atoms, a cycloalkyl group containing from 3 to 20 carbon atoms, an aryl, arylalkyl, arylsilyl, alkylaryl or aryloxy group containing from 6 to 20 carbon atoms, a dialkylamino group containing from 2 to 20 carbon atoms, a halogen atom and an amino group. M is a transition metal from group IV, V or VI of the periodic table. X can be identical to each other or different from each other and represent radicals selected from the group consisting of a halogen atom, an alkyl or alkoxy group containing from 1 to 20 carbon atoms, an alkenyl group containing from 2 to 20 carbon atoms, aryl, alkylaryl, arylalkyl, aryloxy groups containing from 6 to 20 carbon atoms.

The present invention also provides a catalyst composition for olefin polymerization comprising a metallocene compound and an activator or a metallocene compound and activator supported on an organic or inorganic carrier. The present invention also provides a method for polymerizing an olefin, comprising the step of polymerizing at least one olefin in the presence of a polymerization catalyst composition.

The catalyst composition of the present invention has a high polymerization activity, which remains constant, in contrast to that of conventional catalysts, the polymerization activity of which decreases over the course of the polymerization time. Therefore, in the commercial polymerization process, the performance of the catalyst composition of the present invention is excellent. In addition, by using various metallocene compounds of the present invention, an olefin polymer or copolymer having different properties can be obtained by a homogeneous phase (solution) or non-uniform phase (gas or suspension) polymerization process. In addition, by using the catalyst composition of the present invention, the molecular weight, molecular weight distribution and composition distribution can be easily controlled with the obtained olefin polymer or copolymer.

The implementation of the invention

A more complete understanding of the invention and the many advantages associated with it will be better achieved by referring to the following detailed description of the invention.

The metallocene compound of the present invention is an olefin polymerization catalyst containing a ligand having a tetrahydroindenyl core (4HInd), a ligand having a cyclopentadienyl core (Cp '), and a transition metal (M) to which the ligands are bonded, and is described by formula 1.

Formula 1

(4HInd) (Cp ') MX ₂

In formula 1, 4HInd is a group having a tetrahydroindenyl core (fragment), for example, a group having 4,5,6,7-tetrahydroindenyl core, and Cp 'is a group having cyclopentadienyl core, preferably a group having cyclopentadienyl core, such like cyclopentadienyl, indenyl, fluorenyl, azulenyl and the like. 4HInd and Cp 'may be unsubstituted or substituted. In detail, 4HInd may be partially substituted with substituents in an amount of from 1 to 11, and Cp 'may be partially substituted with substituents in an amount of one or more, for example, from 1 to 5. The substituents may be identical to each other or different from each other and represent are radicals selected from the group consisting of alkyl, alkoxy, alkylsilyl, alkylsiloxy, alkylamino or haloalkyl group containing from 1 to 20 carbon atoms, cycloalkyl group containing from 3 to 20 carbon atoms, aryl, arylalkyl oh, arylsilyl, alkylaryl or aryloxy group containing from 6 to 20 carbon atoms, a dialkylamino group containing from 2 to 20 carbon atoms, a halogen atom and an amino group. M is a transition metal from group IV, V or VI of the periodic table, preferably one or more transition metals selected from the group consisting of titanium, zirconium and hafnium from group IV. X can be identical to each other or different from each other and represent radicals selected from the group consisting of a halogen atom selected from the group consisting of fluorine, chlorine, bromine, iodine and the like, alkyl or alkoxy radical containing from 1 to 20 carbon atoms, an alkenyl radical containing from 2 to 20 carbon atoms, an aryl, alkylaryl or aryloxy radical containing from 6 to 20 carbon atoms.

The metallocene compound described by formula 1 can be used individually or in the form of mixtures of two or more of their representatives.  Non-limiting examples of a metallocene compound include dichloride (4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (4, 5, 6, 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (4, 5, 6, 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (4, 5, 67-tetrahydroindenyl) (indenyl) hafnium,  diiodide (4, 567-tetrahydroindenyl) (indenyl) titanium,  diiodide (4567-tetrahydroindenyl) (indenyl) zirconium,  diiodide (4, 5, 6, 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (1-methyl-4, 5, 6, 7-tetrahydroindenyl) (indenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (1-methyl-4, 5, 6, 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (1-methyl-4, 5, 6, 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (1-methyl-4, 5, 6, 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (1-methyl-4, 5, 6, 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (1-methyl-4, 5, 6, 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6, 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dichloride (4, 5, 6, 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (4, 5, 6, 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (4, 5, 6, 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (4, 5, 6, 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (4, 5, 6, 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (4, 5, 6, 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dichloride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) hafnium,  dichloride (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) hafnium,  dichloride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dichloride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) hafnium,  dichloride (1-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (1-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (1-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (1-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (1-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (1-propyl-4, 5, b 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (1-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (1-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (1-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (1-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (1-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) hafnium,  difluoride (4, 5, b 7-tetrahydroindenyl) (1-propylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) hafnium,  dichloride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dichloride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (2-propyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) hafnium,  dichloride (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) hafnium,  dichloride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dichloride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) titanium,  dibromide (4, 5, b 7-tetrahydroindenyl) (2-isopropylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) hafnium,  dichloride (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) hafnium,  dichloride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dichloride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahadroindenyl) (2-n-butylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) hafnium,  dichloride (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) hafnium,  dichloride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dichloride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dichloride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  difluoride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  difluoride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dibromide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  dibromide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  dibromide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  diiodide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) titanium,  diiodide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) zirconium,  diiodide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (indenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium, diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dichloride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (2-methyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-methylindenyl) hafnium,  dichloride (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (1-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-ethylindenyl) hafnium,  dichloride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dichloride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (2-ethyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) zirconium dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-ethylindenyl) hafnium,  dichloride (1-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (1-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (1-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (1-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (1-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (1-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (1-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (1-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (1-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (1-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (1-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-propylindenyl) hafnium,  dichloride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dichloride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (2-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (2-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (2-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (2-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (2-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (2-propyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (2-propyl-4, 5, 6 7- tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7- tetrahydroindenyl) (2-propylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7- tetrahydroindenyl) (2-propylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7- tetrahydroindenyl) (2-propylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7- tetrahydroindenyl) (2-propylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7- tetrahydroindenyl) (2-propylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-propylindenyl) hafnium,  dichloride (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (1-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isopropylindenyl) hafnium,  dichloride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dichloride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (2-isopropyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isopropylindenyl) hafnium,  dichloride (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (1-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-n-butylindenyl) hafnium,  dichloride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dichloride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (2-n-butyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7- tetrahydroindenyl) (2-n-butylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-n-butylindenyl) hafnium,  dichloride (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (1-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (1-isobutylindenyl) hafnium,  dichloride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dichloride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dichloride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  difluoride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  difluoride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  difluoride (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dibromide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  dibromide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  dibromide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  diiodide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) titanium,  diiodide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) zirconium,  diiodide (2-isobutyl-4, 5, 6 7-tetrahydroindenyl) (1-methylindenyl) hafnium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) titanium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) zirconium,  dichloride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) hafnium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) titanium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) zirconium,  difluoride (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) hafnium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) titanium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) zirconium,  dibromide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) hafnium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) titanium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) zirconium,  diiodide (1-methyl-4, 5, 6 7-tetrahydroindenyl) (2-isobutylindenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-phenylindenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-phenylindenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-benzylindenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (2-benzylindenyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (cyclopentadienyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) titanium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (methylcyclopentadienyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (ethylcyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (ethylcyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (ethylcyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (ethylcyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (ethylcyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (ethylcyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (ethylcyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (ethylcyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (ethylcyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (ethylcyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (ethylcyclopentadienyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (propylcyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (propylcyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (propylcyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (propylcyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (propylcyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (propylcyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (propylcyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (propylcyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (propylcyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (propylcyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (propylcyclopentadienyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (n-butylcyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (n-butylcyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (n-butylcyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (n-butylcyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (n-butylcyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (n-butylcyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (n-butylcyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (n-butylcyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (n-butylcyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (n-butylcyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (n-butylcyclopentadienyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (isobutylcyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (isobutylcyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (isobutylcyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (isobutylcyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (isobutylcyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (isobutylcyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (isobutylcyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (isobutylcyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (isobutylcyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (isobutylcyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (isobutylcyclopentadienyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-methyl-3-n-butylcyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (1-methyl-3-n-butylcyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-methyl-3-n-butylcyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-methyl-3-n-butylcyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (1-methyl-3-n-butylcyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-methyl-3-n-butylcyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-methyl-3-n-butylcyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (1-methyl-3-n-butylcyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-methyl-3-n-butylcyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-methyl-3-n-butylcyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (1-methyl-3-n-butylcyclopentadienyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (pentamethylcyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (pentamethylcyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (pentamethylcyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (pentamethylcyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahadroindenyl) (pentamethylcyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (pentamethylcyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (pentamethylcyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (pentamethylcyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (pentamethylcyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (pentamethylcyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (pentamethylcyclopentadienyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (tetramethylcyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (tetramethylcyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (tetramethylcyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (tetramethylcyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (tetramethylcyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (tetramethylcyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (tetramethylcyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (tetramethylcyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (tetramethylcyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (tetramethylcyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (tetramethylcyclopentadienyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) hafnium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) zirconium,  dichloride (4, 5, 6 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) hafnium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) titanium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) zirconium,  difluoride (4, 5, 6 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) hafnium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) titanium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) zirconium,  dibromide (4, 5, 6 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) hafnium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) titanium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) zirconium,  diiodide (4, 5, 6 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) hafnium,  mixtures and compounds thereof,  like them.

The metallocene compound of the present invention is not limited to the above examples, but includes a metallocene compound containing ligands having another substituted or unsubstituted tetrahydroindenyl (4HInd) core. The metallocene compound of the present invention can be obtained by the usual method for producing metallocene compounds. For example, as stated in the following examples, bis (tetrahydroindenyl) zirconium dichloride is reacted with zirconium chloride to produce (tetrahydroindenyl) zirconium trichloride, and the resulting (tetrahydroindenyl) zirconium trichloride is reacted with indenyl lithium to produce (tetrahydroindenyl) indenyl) zirconium.

The olefin polymerization catalyst composition (system) of the present invention comprises a metallocene compound and an activator that reacts with the metallocene compound so that the metallocene compound exhibits catalytic activation. As the activator, an individual activator, such as an alkylaluminoxane, an organoaluminum compound, a bulky aromatic fluoride compound, a modified clay, an inorganic oxide representing a Lewis acid, and the like, can be individually used, or mixtures thereof can be used. As the alkylaluminoxane described by formula 2, commercially available alkylaluminoxanes having a linear cyclic or net structure can be used. Non-limiting examples of alkylaluminoxane include hydrocarbylaluminoxanes described by formulas 3 and 4, which are oligomers having a linear or cyclic structure, such as methylalumoxane, ethylaluminoxane, butylaluminoxane, isobutylaluminoxane, hexylaluminoxane, octylaluminoxane, a mixture of alumina, octalaluminoxane, and the like, de aluminoxane an aromatic hydrocarbon, which is a commercial hydrocarbon solution of alumoxane, and more preferably alumoxane, dissolved at that luole. In the present invention, one alumoxane or mixtures of more than one alumoxane can be used.

Formula 2

In formula 2, R 'represents a hydrocarbyl radical containing from 1 to 10 carbon atoms, and x represents an integer in the range from 1 to 70.

Formula 3

Formula 4

In formulas 3 and 4, R 'independently represents hydrocarbyl radicals, preferably linear or branched alkyl radicals containing from 1 to 10 carbon atoms. Namely, R 'can be identical to each other or different from each other. More preferably, the main fractions of R ′ are methyl groups, x is an integer in the range from 1 to 50, preferably from 10 to 40, y is an integer in the range from 3 to 50, preferably from 10 to 40. Alkylaluminoxane can be obtained by various conventional methods, such as adding the proper amount of water to a trialkylaluminum or by reacting a hydrocarbyl compound containing water or an inorganic hydrated salt and a trialkylaluminum, which usually produce a mixture of linear Nogo aluminoxane and cyclic aluminoxane.

In addition, the catalyst composition of the present invention as an additive to remove impurities may contain an organoaluminum compound of the formula 5.

Formula 5

In the formula 5, R ² , R ³ and R ⁴ independently represent an alkyl or alkoxy group containing from 1 to 10 carbon atoms, or a halide group (fluorine group, chlorine group, bromine group, iodine group and the like), and at least at least one of R ² , R ³ and R ⁴ represents an alkyl group. Non-limiting examples of an organoaluminum compound include trialkylaluminum, such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like; dialkylaluminium alkoxide such as dimethylaluminium methoxide, diethylaluminium methoxide, dibutylaluminium methoxide and the like; dialkylaluminium halide such as dimethylaluminium chloride, diethylaluminium chloride, dibutylaluminium chloride and the like; alkylaluminium dialkoxide such as methylaluminium dimethoxide, ethylaluminium dimethoxide, butylaluminium dimethoxide and the like; an alkylaluminum dihalide such as methylaluminum dichloride, ethylaluminum dichloride, butylaluminum dichloride and the like; and mixtures thereof.

In the catalyst composition of the present invention, a structurally-volumetric compound having an aromatic group substituted with fluorine (a structurally-volumetric aromatic fluorinated compound) as an activator can be described by formula 6.

Formula 6

[C] [D]

In formula 6, C is a cation that is a Lewis base combined with a hydrogen ion, or a metal or non-metal compound having oxidizing ability, a D is a compound comprising an element from groups in the range from group 5 to group 15 of the periodic table and organic matter. Non-limiting examples of a structurally volumetric aromatic fluorinated compound (an ionic compound in the form of a fluorine-substituted boron aromatic compound) include tetrakis (pentafluorophenyl) trimethylammonium borate, tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) borate tripropetramonyltetramonethyltammonium tetrapropyltammonium borate (pentafluorophenyl) anilinium borate, tetrakis (pentafluorophenyl) pyridinium borate, tetrakis (pentafluorophenyl) ferrocenium borate, tetrakis (pentafluorophenyl) silver borate, tris ( entaftorfenil) borane, tri (3,4,5-trifluorophenyl) borane, mixtures thereof and the like.

Non-limiting examples of modified clay that can be used as an activator include N, N-dimethylanilinium derivative of montmorillonite, N, N-dimethylanilinium derivative of hectorite, mixtures thereof and the like. And examples of the inorganic oxide, which is a Lewis acid, as an activator include fluorinated silica-alumina and the like.

The olefin polymerization catalyst composition of the present invention can be obtained by mixing the metallocene compound of Formula 1 and alumoxane. Where the amount of aluminum aluminoxanes described by formulas 2, 3, 4 and so on is in the range from 1 to 100,000 moles, preferably from 5 to 5000 moles, based on 1 mol of the metallocene compound described by formula 1. In the case of structurally-volume aromatic the fluorinated compound (formula 6) as an organoboron compound; the molar ratio between the organoboron compound and the metallocene compound ([organoboron compound] / [metallocene compound]) will generally be in the range from 1 to 1000, and preferably from 1 to 100. If the metallocene compound of the present invention is mixed with an clay-modified organoaluminum compound, a Lewis acid inorganic compound, and the like, the ratio between the amounts of components in the mixture may vary according to the purpose of use, the type of catalyst, and the like similarly and appropriately installed in accordance with conventional technology.

The compounds of the catalyst composition can be mixed without imposing specific restrictions. For example, the metallocene compound of the formula 1 and aluminoxane are mixed for a period of 5 minutes to 10 hours, preferably 15 minutes to 4 hours. There are no restrictions on the method of mixing the compounds, but it is desirable that the two compounds be mixed under an inert atmosphere of nitrogen or argon in the absence of a solvent or in the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene, xylene or mixtures thereof. The temperature of the mixing method is in the range from 0 to 150 ° C., preferably from 10 to 90 ° C. A catalyst solution in which the catalyst is uniformly dissolved in a hydrocarbon solvent may be used as such, or the catalyst may be used in a solid powder state after removal of the solvent. The solid powder catalyst can be obtained by carrying out a precipitation reaction for the catalyst solution and providing solidification of the precipitate from the reaction.

The present invention also provides a catalyst composition for the polymerization of an olefin obtained by introducing a catalyst composition containing a metallocene compound of the formula 1 and an activator such as alumoxane of the formula 2 into contact with an organic or inorganic carrier. The catalyst composition and / or activator may exist in the form deposited on the carrier, or in the form of insoluble particles of the carrier, as well as in the form of a homogeneous solution. A method of bringing the catalyst composition of the present invention into contact with a carrier will be explained. First, the catalyst is obtained in a solution state by mixing the metallocene compound described by formula 1 and the aluminoxane compound described by formula 2, and the catalyst is contacted with a porous carrier (for example, a carrier in the form of silicon dioxide, characterized by pore sizes ranging from 50 to 500 D and a pore volume in the range from 0.1 to 5.0 cm / g) to obtain a suspension. After that, the mixture is subjected to treatment with an acoustic wave or an oscillating wave, characterized by a frequency in the range from 1 to 10000 kHz, at a temperature in the range from 0 ° C to 120 ° C for a period of time from 1 to 6 hours for uniform infiltration of the catalyst components into the pores carrier. And after that, the catalyst suspension is dried in vacuum or in a stream of nitrogen to obtain a catalyst in a solid powder state. The acoustic wave or oscillating wave is preferably ultrasonic waves, and more preferably a wave having a frequency in the range from 20 to 500 kHz. After exposure to a catalyst by an acoustic wave or an oscillating wave, the step of depositing the catalyst onto the carrier may also include the step of washing the supported catalyst onto a hydrocarbon selected from the group consisting of pentane, hexane, heptane, isoparaffin, toluene, xylene and mixtures thereof.

As a carrier, without limitation, porous inorganic compounds, inorganic salts and organic compounds characterized by the presence of micropores and a large specific surface area can be used. A form of inorganic carrier, to which no particular restrictions are imposed if it is possible to maintain shape during the process of preparing the catalysts supported on the carrier, may be any shape, such as in the case of powder, particles, flakes, foil, fiber and the like. Regardless of the shape of the inorganic carrier, the maximum length of the inorganic carrier is generally in the range from 5 to 200 μm, preferably from 10 to 100 μm, the preferred specific surface area of the inorganic carrier is in the range from 50 to 1000 m ² / g, and the preferred volume then it is in the range from 0.05 to 5 cm ³ / g. In general, the inorganic carrier must be treated before use to remove water or a hydroxyl group from it. The treatment can be carried out by calcining the carrier at a temperature in the range from 200 ° C to 900 ° C in an inert atmosphere such as air, nitrogen, argon and the like. Non-limiting examples of an inorganic salt carrier or inorganic carrier include silica, alumina, bauxite, zeolite, magnesium chloride (MgO), calcium chloride (CaCl ₂ ), magnesium oxide (MgO), zirconium dioxide (ZrO ₂ ), titanium dioxide (TiO ₂ ), boron trioxide (B ₂ O ₃ ), calcium oxide (CaO), zinc oxide (ZnO), barium oxide (BaO), thorium oxide (ThO ₂ ), and mixtures thereof, such as silicon dioxide-magnesium oxide (SiO ₂ - MgO), silicon dioxide-alumina (SiO ₂ -Al ₂ O ₃ ), silicon dioxide-titanium dioxide (SiO ₂ -TiO ₂ ), silicon dioxide-vanadium pentoxide (SiO ₂ -V ₂ O ₅ ), silicon dioxide-t chromium dioxide (SiO ₂ -CrO ₃ ), silicon dioxide-titanium dioxide-magnesium oxide (SiO ₂ -TiO ₂ -MgO) and the like. A small amount of carbonate, sulfate or nitrate may be added to these compounds. Non-limiting examples of an organic carrier include starch, cyclodextrin, a synthetic polymer, and the like.

Examples of a solvent that is used to contact the catalyst of the present invention with a carrier include an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane and the like, an aromatic hydrocarbon solvent such as benzene, monochlorobenzene , dichlorobenzene, trichlorobenzene, toluene and the like, a halogenated aliphatic hydrocarbon solvent such as dichloromethane, trichloromethane, dichloroethane, trichloroethane and the like, and the like. The solvent or mixtures thereof can be used for the method of applying to a carrier. The ratio between the amounts of metallocene compound and alumoxane in the olefin polymerization catalyst composition contacted with the carrier is not particularly limited, but it is desirable that the amount of aluminum alumoxane described by formula 2 be in the range from 1 to 1000 moles, preferably from 1 to 500 moles, based on 1 mol of the metallocene compound described by formula 1.

The present invention provides a method for polymerizing an olefin, comprising the step of polymerizing at least one olefin in the presence of a polymerization catalyst composition that contains a metallocene compound of the formula 1, optionally an activator such as an alumoxane compound of the formula 2, an organic or inorganic carrier, and things like that. The olefin polymerization catalyst composition of the present invention may exist in the form supported on an inorganic carrier (silica, alumina, silica-alumina mixture and the like) or in the form of insoluble carrier particles, as well as in the form of a homogeneous solution. Thus, the olefin polymerization process of the present invention can be implemented by carrying out the polymerization reaction in a solution phase, a suspension phase, a mass phase or a gas phase. The conditions for each polymerization reaction can vary according to the state of the catalyst (homogeneous or heterogeneous phase (phase when applied to a carrier)), the polymerization method (solution polymerization, suspension polymerization, gas-phase polymerization), the properties of the target polymer or the form of the polymer. In the case of polymerization in the solution phase or the suspension phase, the solvent or the olefin itself can be used as the reaction medium. Examples of the solvent include propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, 1,2-dichloroethane, chlorobenzene and the like, and if necessary can be used a mixture of solvents with a specific quantitative ratio.

The olefin used in the polymerization may be one olefin or a mixture of two or more olefins. That is, the olefin polymerization catalyst composition of the present invention can be used for copolymerization of a monomer / comonomer, as well as homopolymerization of the monomer. Examples of olefins preferred for polymerization or copolymerization include α-olefins, cyclic olefins, dienes, trienes, styrenes and the like, α-olefins include an aliphatic olefin containing from 2 to 12, preferably from 2 to 8, carbon atoms, more specifically, ethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1, 4-methylpentene-1, 3-methylpentene-1, heptene-1, octene-1, decen-1, 4, 4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, 3,4-dimethyl-1-hexene and the like, α-olefins can be polymerized to obtain an alternating homopolymer I copolymer, random copolymer or block copolymer. The copolymerization of α-olefins includes the copolymerization of ethylene and α-olefin containing from 3 to 12, preferably from 3 to 8, carbon atoms (e.g. ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene -1, ethylene and octene-1 and the like) and copolymerization of propylene and α-olefin containing from 4 to 12, preferably from 4 to 8, carbon atoms (propylene and butene-1, propylene and 4-methylpentene-1, propylene and 4-methylpentene-1, propylene and hexene-1, propylene and octene-1). In the copolymerization of ethylene or propylene together with another α-olefin, the amount of the other α-olefin can be 90% (mol) or less, based on the amount of the total monomer, and, specifically, in the case of a conventional ethylene copolymer, 40% (mol) or less, preferably 30% (mol) or less, and more preferably 20% (mol) or less, and in the case of a conventional propylene copolymer, from 1 to 90% (mol), preferably from 5 to 90% (mol), and more preferably from 10 up to 70% (mol).

As cyclic olefins, cyclic olefins containing carbon atoms in an amount in the range of from 3 to 24, preferably from 3 to 18, can be used. Examples of cyclic olefins include cyclopentene, cyclobutene, cyclohexene, 3-methylcyclohexene, cyclooctene, tetracyclodecene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,5,6-trimethyl-2-norbornene, ethylene norbornene and things like that. Cyclic olefins can be copolymerized together with α-olefins, and the amount of cyclic olefin is in the range from 1 to 50% (mol), preferably from 2 to 50% (mol), based on the amount of copolymer. Preferred dienes and trienes include a polyene containing from 4 to 26 carbon atoms and comprising two or three double bonds. Specific examples of dienes and trienes include 1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene, 2-methyl-1,3-butadiene and the like. Preferred examples of styrenes include styrene or substituted styrene substituted with an alkyl group, an alkoxy group or a halogenated alkyl group containing from 1 to 10 carbon atoms, a halogen atom, an amino group, a silyl group and the like.

In the polymerization or copolymerization of an α-olefin in accordance with the present invention, the amount of metallocene compound described by Formula 1 is not limited to a certain extent. However, the concentration of the central metal of the metallocene compound described by formula 1 in the polymerization reaction system is preferably in the range from 10 to 10 mol / L, and more preferably from 10 ^-7 to 10 ^-2 mol / L. If the amount of the metallocene compound does not fall within this range, the activity of the catalyst may be insufficient, or an excessively excessive amount of catalyst may be used. In the polymerization or copolymerization of the present invention, the polymerization temperature can also vary over a wide range in accordance with reagents, reaction conditions, and the like. When carrying out solution polymerization, the temperature is generally in the range from 0 to 250 ° C., and more preferably from 10 to 200 ° C. When conducting suspension or gas phase polymerization, the temperature is generally in the range from 0 to 120 ° C, and more preferably from 20 to 100 ° C. The polymerization pressure is generally in the range from atmospheric pressure to 500 kg / cm, and more preferably from atmospheric pressure to 50 kg / cm. The polymerization reaction can be carried out under the reaction conditions of a batch type, semi-continuous type or continuous type. The polymerization can be carried out in two or more stages under different reaction conditions. The molecular weight of the final polymer obtained using the olefin polymerization catalyst of the present invention can be controlled by changing the polymerization temperature or by injecting hydrogen into the reactor. Preferably, the olefin material obtained has a density in the range of 0.91 to 0.94 g / cm ³ .

The olefin polymerization catalyst composition of the present invention can be used not only in the basic polymerization of olefin monomers, but also in the prepolymerization of olefin monomers. In the prepolymerization process, the olefin polymer or copolymer is produced in an amount in the range from 0.05 to 500 g, preferably from 0.1 to 300 g, and more preferably from 0.2 to 100 g, based on 1 g of catalyst. Examples of an olefin that is suitable for use in prepolymerization include α-olefins containing from 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 3-methyl-1-butene, 3-methyl-1-pentene and the like. The olefin more suitable for use in the prepolymerization is the same olefin as that used in the main polymerization.

For a better understanding of the present invention, preferred examples are provided hereinafter. However, the present invention is not limited to the following examples. In the following examples, the olefin polymerization catalyst was prepared according to the Slap method, in which the flow of air and moisture was completely blocked, and purified and dried nitrogen was used as an inert gas. The solvent was dried with sodium metal in an inert atmosphere of nitrogen. The melt index (IR) and the value of the IRVN (melt index at high load) of the polymer were measured in accordance with ASTM D1238, and the density of the polymer was measured in accordance with ASTM D1505.

Example 1

A. Preparation of (tetrahydroindenyl) (indenyl) zirconium dichloride

1.065 g (2.66 mmol) of bis (tetrahydroindenyl) zirconium dichloride, 0.66 g (2.83 mmol) of zirconium chloride and 100 ml of toluene were added to a 500 ml round-bottom flask containing nitrogen atmosphere, and the reaction was carried out for 18 hours with stirring at 90 ° C. Upon completion of the reaction, the filtrate was collected by filtering the reaction product. 0.66 g (5.406 mmol) of indenyl lithium was added to a 500 ml flask, and then the filtrate was added and the reaction was carried out at 90 ° C for 18 hours with stirring in a mixed solution. The solvent was removed by suction under vacuum. And after extraction and filtration using 100 ml of dichloromethane, the solvent was removed again. 50 ml of hexane was added to the reaction product to obtain a suspension, and the suspension was filtered and washed using 500 ml of hexane and dried in vacuo to obtain 1.52 g (yield: 72%) of (tetrahydroindenyl) (indenyl) zirconium dichloride. The results of the analysis by the 1 H NMR method (500 MHz, CDCl ₃ ) for the obtained (tetrahydroindenyl) (indenyl) zirconium dichloride were 1.54-1.50 (m, 2, C9H11), 1.79-1.70 (m, 2, C9H11), 2.44-2.38 (m, 2, C9H11), 2.74-2.68 (m, 2, C9H11), 5.32-5.31 (m, 2, C9H11), 6.05-6.34 (m, 1, С9Н11), 6.50-6.46 (m, 2, С9Н7), 6.86-6.85 (m, 1, С9Н7), 7.24-7 22 (m, 2, C9H7), 7.66-7.64 (m, 2, C9H7).

B. Preparation of a catalyst composition

In a 500 ml nitrogen-containing flask, 92 mg of (tetrahydroindenyl) (indenyl) zirconium dichloride and 20 ml of methylaluminoxane (MAO, Albemarle company, 10% solution in toluene) were stirred and the reaction was carried out for 30 minutes to obtain a catalyst solution. To the resulting catalyst solution was added 4 g of silicon dioxide, calcined at 220 ° C, and was exposed to an ultrasonic wave for 1 hour, and the supernatant was discarded. The remaining solids were washed with hexane (1 time) and dried in vacuo to provide the supported catalyst as a free-flowing solid powder.

C. Copolymerization of ethylene / hexene-1

A stainless steel 1 liter autoclave reactor having a jacket for supplying cooling water in order to control the polymerization temperature was purged with isobutane (once) and ethylene (five times) at approximately 110 ° C to remove impurities, and then cooled to 67 ° C. 400 ml of isobutane and 1.0 mol of triisobutylaluminum were added to the washed reactor and stirring was carried out at 75 ° C. To the reactor was also added 100 ml of isobutane and 40 mg of the catalyst supported on a carrier and then added ethylene and 40 ml 1-hexene until a partial ethylene pressure of 130 lb / ⁱⁿ² (g.) (896 kPa (g). ) The polymerization was carried out for 4 hours at 75 ° C while maintaining the total pressure in the reactor was 290 lbs / ⁱⁿ² (g.) (2000 kPa (g.)). During the polymerization ethylene partial pressure was maintained at 130 lb / ⁱⁿ² (g.) (896 kPa (g.)) And continuously with a proportion of 10% (wt.) Was added 1-hexene to add additional ethylene, flow rate of which is measured by mass flow meter . Upon completion of the polymerization, unreacted 1-hexene and isobutane were discharged and 395 g of free flowing polymer was obtained from the reactor. During the 4 hours of the polymerization reaction, the polymerization rate was kept constant. The catalytic activity during polymerization was 2240 g of polymer / g-catalyst-hour, and the IR value (melt index) of the obtained polymer was 1.16 g / 10 min, and the density of the obtained polymer was 0.9277 g / cm.

Example 2

A. Preparation of (tetrahydroindenyl) (2-methylindenyl) zirconium dichloride

3.184 g (8 mmol) of bis (tetrahydroindenyl) zirconium dichloride, 1.873 g (8.4 mmol) of zirconium chloride and 150 ml of toluene were added to a 500 ml round-bottom flask containing nitrogen atmosphere, and the reaction was carried out at 90 ° C for 24 hours with stirring . Upon completion of the reaction, the filtrate was collected by filtering the reaction product. 2.176 g (16 mmol) of 2-methylindenyl lithium was added to a 500 ml flask, and then the filtrate was added and the reaction was carried out at 90 ° C with stirring in a mixed solution for 24 hours. The solvent was removed by suction under vacuum. And after extraction and filtration using 100 ml of dichloromethane, the solvent was removed again. 50 ml of hexane was added to the reaction product to obtain a suspension, and the suspension was filtered and washed using 500 ml of hexane and dried in vacuo to obtain 3.45 g (yield: 52%) of (tetrahydroindenyl) (2-methylindenyl) zirconium dichloride. The results of the analysis by the method of 1 H NMR (500 MHz, CDCl ₃ ) for the obtained dichloride (tetrahydroindenyl) (2-methylindenyl) zirconium were 1.49-1.42 (m, 2, C9H11), 1.75-1.68 ( m, 2, С9Н11), 2.28 (s, 3, С10Н9), 2.37-2.33 (m, 2, С9Н11), 2.69-2.64 (m, 2, С9Н11), 5, 09-5.08 (m, 2, С10Н11), 5.80-5.79 (m, 1, С10Н11), 6.236 (s, 2. С10Н9), 7.13-7.10 (m, 2, С10Н9 ), 7.55-7.53 (m, 2, С10Н9).

B. Preparation of a catalyst composition

In a 500 ml nitrogen-containing flask, 95 mg of (tetrahydroindenyl) (2-methylindenyl) zirconium dichloride and 20 ml of methylaluminoxane (MAO, Albemarle company, 10% solution in toluene) were mixed and the reaction was carried out for 30 minutes to obtain a catalyst solution . To the resulting catalyst solution was added 4 g of silicon dioxide, calcined at 220 ° C, and was exposed to an ultrasonic wave for 1 hour, and the supernatant was discarded. The remaining solids were washed with hexane (1 time) and dried in vacuo to provide the supported catalyst as a free-flowing solid powder.

C. Copolymerization of ethylene / hexene-1

The polymerization was carried out for 4 hours in accordance with the polymerization method of Example 1, except for using 61 mg of the catalyst obtained in the above step, and 317 g of polymer was obtained. The catalytic activity during polymerization was 1650 g of polymer / g · catalyst · hour, and the IR value (melt index) of the obtained polymer was 0.64 g / 10 min, and the density of the obtained polymer was 0.9287 g / cm ³ .

Example 3

A. Preparation of (tetrahydroindenyl) (1-n-butylindenyl) zirconium dichloride

3.184 g (8.0 mmol) of bis (tetrahydroindenyl) zirconium dichloride, 1.873 g (8.4 mmol) of zirconium chloride and 150 ml of toluene were added to a 500 ml round-bottom flask containing nitrogen atmosphere, and the reaction was carried out for 90 hours with stirring at 90 ° C. Upon completion of the reaction, the filtrate was collected by filtering the reaction product. 2.85 g (16 mmol) of 1-n-butylindenyl lithium was added to a 500 ml flask, and then the filtrate was added and the reaction was carried out at 90 ° C for 24 hours with stirring in a mixed solution. The solvent was removed by suction under vacuum. And after extraction and filtration using 100 ml of dichloromethane, the solvent was removed again. 50 ml of hexane was added to the reaction product to obtain a suspension, and the suspension was filtered and washed using 500 ml of hexane and dried in vacuo to obtain 3.13 g (yield: 43%) of (tetrahydroindenyl) (1-n-butylindenyl) zirconium dichloride. The results of the analysis by the method of 1 H NMR (500 MHz, CDCl ₃ ) for the obtained dichloride (tetrahydroindenyl) (1-n-butylindenyl) zirconium were 0.89-0.91 (m, 3, C11H12), 1.466-1.493 (reagent, m), 1.68-1.72 (reagent, m), 2.325 (m, 1, С9Н11), 2.415 (m, 1, С9Н11), 2.584 (m, 1, С9Н11), 2.703 (m, 1, С9Н11 ), 2.97-2.98 (m, 2, С11Н12), 4.931 (m, 2, С9Н11), 5.50 (m, 1, С9Н11), 6.0 (m, 1, С11Н12), 6.328 ( m, 1, C11H12), 6.592 (m, 1, C11H12), 7.15-7.19 (m, 2, C11H12), 7.53-7.56 (m, 2, C11H12).

B. Preparation of a catalyst composition

In a 500 ml nitrogen-containing flask, 236 mg of (tetrahydroindenyl) (1-n-butylindenyl) zirconium dichloride and 50 ml of methylaluminoxane (MAO, Albemarle company, 10% solution in toluene) were mixed and the reaction was carried out for 30 minutes to obtain catalyst solution. To the resulting catalyst solution was added 10 g of silicon dioxide, calcined at 220 ° C, and was exposed to an ultrasonic wave for 1 hour, and the supernatant was discarded. The remaining solids were washed with hexane (1 time) and dried in vacuo to provide the supported catalyst as a free-flowing solid powder.

C. Copolymerization of ethylene / hexene-1

The polymerization was carried out for 3 hours in accordance with the polymerization method of Example 1, except for using 61 mg of the catalyst obtained in the above step, and 213 g of polymer was obtained. Within 3 hours of the polymerization reaction, the polymerization rate was kept constant. The catalytic activity during polymerization was 1170 g of polymer / g · catalyst · hour, and the IR value (melt index) of the obtained polymer was 0.22 g / 10 min, and the density of the obtained polymer was 0.9305 g / cm ³ .

Example 4

A. Preparation of (tetrahydroindenyl) (1-ethylindenyl) zirconium dichloride

3.184 g (8.0 mmol) of bis (tetrahydroindenyl) zirconium dichloride, 1.873 g (8.4 mmol) of zirconium chloride and 150 ml of toluene were added to a 500 ml round-bottom flask containing nitrogen atmosphere, and the reaction was carried out for 90 hours with stirring at 90 ° C. Upon completion of the reaction, the filtrate was collected by filtering the reaction product. 2.4 g (16 mmol) of 1-ethylinenyl lithium was added to a 500 ml flask, and then the filtrate was added and the reaction was carried out at 90 ° C for 24 hours with stirring in a mixed solution. The solvent was removed by suction under vacuum. And after extraction and filtration using 100 ml of dichloromethane, the solvent was removed again. 50 ml of hexane was added to the reaction product to obtain a suspension, and the suspension was filtered and washed using 500 ml of hexane and dried in vacuo to obtain 3.58 g (yield: 53%) of (tetrahydroindenyl) (1-ethylindenyl) zirconium dichloride. The results of the analysis by the method of 1 H NMR (500 MHz, COCl ₃ ) for the obtained dichloride (tetrahydroindenyl) (1-ethylindenyl) zirconium were 1,248-1,255 (m, 3, C11H12), 1,466-1,493 (reagent, m), 1.68 -1.72 (reagent, m), 2.325 (m, 1, С9Н11), 2.415 (m, 1, С9Н11), 2.584 (m, 1, С9Н11), 2.703 (m, 1, С9Н11), 2.97- 2.98 (m, 2, С11Н12), 4.931 (m, 2, С9Н11), 5.50 (m, 1, С9Н11), 6.0 (m, 1, С11Н12), 6.328 (m, 1, С11Н12) 6.592 (m, 1, C11H12), 7.15-7.19 (m, 2, C11H12), 7.53-7.56 (m, 2, C11H12).

B. Preparation of a catalyst composition

In a 500 ml nitrogen atmosphere flask, 130 mg of (tetrahydroindenyl) (1-ethylindenyl) zirconium dichloride and 25 ml of methylaluminoxane (MAO, Albemarle company, 10% solution in toluene) were mixed and the reaction was carried out for 30 minutes to obtain a catalyst solution . To the resulting catalyst solution was added 5 g of silicon dioxide, calcined at 220 ° C, and was exposed to an ultrasonic wave for 1 hour, and the supernatant was discarded. The remaining solids were washed with hexane (1 time) and dried in vacuo to provide the supported catalyst as a free-flowing solid powder.

C. Copolymerization of ethylene / hexene-1

The polymerization was carried out for 4 hours in accordance with the polymerization method of Example 1, except for using 59 mg of the catalyst obtained in the above step, and 190 g of polymer was obtained. Within 4 hours of the polymerization reaction, the polymerization rate was slightly reduced. The catalytic activity during polymerization was 790 g of polymer / g · catalyst · h, and the IR value (melt index) of the obtained polymer was 0.18 g / 10 min, and the density of the obtained polymer was 0.9309 g / cm ³ .

Example 5

A. Preparation of (tetrahydroindenyl) (2-phenylindenyl) zirconium dichloride

1.0 g (2.5 mmol) of bis (tetrahydroindenyl) zirconium dichloride, 0.61 g (2.75 mmol) of zirconium chloride and 150 ml of toluene were added to a nitrogen atmosphere round-bottomed flask with a volume of 500 ml over 24 hours with stirring carried out the reaction at 90 ° C. Upon completion of the reaction, the filtrate was collected by filtering the reaction product. 0.991 g (5.0 mmol) of 2-phenylindenyl lithium was added to a 500 ml flask, and then the filtrate was added and the reaction was carried out at 90 ° C for 24 hours with stirring in a mixed solution. The solvent was removed by suction under vacuum. And after extraction and filtration using 100 ml of dichloromethane, the solvent was removed again. 50 ml of hexane was added to the reaction product to obtain a suspension, and the suspension was filtered and washed using 500 ml of hexane and dried in vacuo to obtain 0.9 g (yield: 39%) of (tetrahydroindenyl) (2-phenylindenyl) zirconium dichloride. The results of 1H NMR analysis (500 MHz, CDCl ₃ ) for the obtained (tetrahydroindenyl) (2-phenylindenyl) zirconium dichloride were 1.47-1.49 (m, 2, C9H11), 1.68-1.70 (m. 2, С9Н11), 2.41-2.49 (m, 2, С9Н11), 2.68-2.72 (m, 2, С9Н11), 5.29-5.31 (d, 2, С9Н11), 5.80-5.84 (m, 1, С9Н11), 7.20-7.25 (m, 2, С15Н11), 7.30-7.33 (m, 1, С15Н11), 7.4-7 42 (m, 2, C15H9), 7.58-7.61 (m, 2, C15H9), 7.67-7.70 (m, 2, C15H9).

B. Preparation of a catalyst composition

In a 500 ml nitrogen-containing flask, 124 mg of (tetrahydroindenyl) (2-phenylindenyl) zirconium dichloride and 25 ml of methylaluminoxane (MAO, Albemarle company, 10% solution in toluene) were mixed and the reaction was carried out for 30 minutes to obtain a catalyst solution . To the resulting catalyst solution was added 5 g of silicon dioxide, calcined at 220 ° C, and was exposed to an ultrasonic wave for 1 hour, and the supernatant was discarded. The remaining solids were washed with hexane (1 time) and dried in vacuo to provide the supported catalyst as a free-flowing solid powder.

C. Copolymerization of ethylene / hexene-1

The polymerization was carried out for 3 hours in accordance with the polymerization method of Example 1, except for using 60 mg of the catalyst obtained in the above step, and 70 g of polymer was obtained. Within 3 hours of the polymerization reaction, the polymerization rate was kept constant. The catalytic activity during polymerization was 400 g of polymer / g · catalyst · h, and the IR value (melt index) of the obtained polymer was 0.11 g / 10 min, and the density of the obtained polymer was 0.9257 g / cm ³ .

Comparative example

A. Preparation of the catalyst composition

In a 500 ml nitrogen-containing flask, 84 mg of bis (tetrahydroindenyl) zirconium chloride and 20 ml of methylaluminoxane (MAO, Albemarle company, 10% solution in toluene) were mixed and stirred for 30 minutes to obtain a catalyst solution. To the resulting catalyst solution was added 4 g of silicon dioxide, calcined at 220 ° C, and was exposed to an ultrasonic wave for 1 hour, and the supernatant was discarded. The remaining solids were washed with hexane (1 time) and dried in vacuo to provide the supported catalyst as a free-flowing solid powder.

B. Copolymerization of ethylene / hexene-1

The polymerization was carried out for 1 hour in accordance with the polymerization method of Example 1, except for using 105 mg of the catalyst obtained in the above step, and 123 g of polymer was obtained. Within 1 hour of polymerization, the polymerization rate decreased rapidly, while the initial catalytic activity was high. The catalytic activity during polymerization was 1170 g of polymer / g · catalyst · h, and the IR value (melt index) of the obtained polymer was 0.11 g / 10 min, and the density of the obtained polymer was 0.9226 g / cm ³ .

Claims (13)

1. The metallocene compound of the formula 1
Formula 1

in formula 1, 4HInd is a group having a tetrahydroindenyl core, Cp 'is an indenyl group, 4HInd is unsubstituted, and Cp' is unsubstituted or substituted by one or more substituents, and the substituents are identical to each other or different from each other and are radicals selected from the group consisting of an alkyl or aryl group, and M is a transition metal from group IV of the periodic table, and X are identical to each other or different from each other, etc. dstavlyayut halogen atoms. 2. The metallocene compound according to claim 1, where 4HInd is a group having a 4,5,6,7-tetrahydroindenyl core. 3. The metallocene compound according to claim 1, where M is a transition metal selected from the group consisting of titanium, zirconium and hafnium, and X represents a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine. 4. The composition of the metallocene catalyst for the polymerization of olefins, containing:
metallocene compound of formula 1
Formula 1

where in formula 1 4HInd represents a group having a tetrahydroindenyl core, Cp 'represents an indenyl group, 4HInd is unsubstituted, and Cp' is unsubstituted or substituted by one or more substituents, and the substituents are identical to each other or different from each other and represent radicals selected from the group consisting of an alkyl or aryl group, and M is a transition metal from group IV of the periodic table, and X are identical to each other or different from each other represent halogen atoms; and
an activator that reacts with the metallocene compound so that the metallocene compound exhibits catalytic activation. 5. The metallocene catalyst composition according to claim 4, wherein the activator is selected from the group consisting of alkylaluminoxane, an organoaluminum compound, a structurally volumetric aromatic fluorinated compound, a modified clay, and an inorganic oxide representing a Lewis acid. 6. The metallocene catalyst composition according to claim 5, where the activator is a hydrocarbylaluminoxane of formula 3 or 4, which is an oligomer having a linear or cyclic structure,
Formula 3

Formula 4

where in formulas 3 and 4, R 'independently represents a linear or branched alkyl radicals containing from 1 to 10 carbon atoms, x represents an integer in the range from 1 to 50, and y represents an integer in the range from 3 to 50. 7. The composition of the metallocene catalyst according to claim 6, where the amount of aluminum aluminoxane is in the range from 1 to 100,000 moles per 1 mol of the metallocene compound of formula 1. 8. The composition of the metallocene catalyst according to claim 5, where the structurally volumetric aromatic fluorinated compound is selected from the group consisting of tetrakis (pentafluorophenyl) trimethylammonium borate, tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tripropyl ammonium borate, tripropyl ammonium borate, tripropyl ammonium borate , tetrakis (pentafluorophenyl) borate of anilinium, tetrakis (pentafluorophenyl) borate of pyridinium, tetrakis (pentafluorophenyl) borate of ferrocenium, tetrakis (pentafluorophenyl) borate of silver, tris (pentafluorophenyl) borane, ri (3,4,5-trifluorophenyl) borane, and mixtures thereof, and the modified clay is selected from the group consisting of N, N-dimetilanilinievogo montmorillonite derivative, N, N-dimetilanilinievogo derivative hectorite and mixtures thereof. 9. The composition of the metallocene catalyst according to claim 4, which further includes an organic or inorganic carrier on which the metallocene compound and activator are applied. 10. A method of polymerizing an olefin, comprising the step of polymerizing at least one olefin in the presence of a metallocene compound of formula 1
Formula 1

where in formula 1 4HInd represents a group having a tetrahydroindenyl core, Cp 'represents an indenyl group, 4HInd is unsubstituted, and Cp' are unsubstituted or substituted by one or more substituents, and the substituents are identical to each other or different from each other and represent radicals selected from the group consisting of an alkyl or aryl group, and M is a transition metal from group IV of the periodic table, and X are identical to each other or different from each other and represent halogen atoms. 11. The method of polymerization of an olefin according to claim 10, where the olefin are aliphatic α-olefins containing from 2 to 12 carbon atoms. 12. The method of polymerization of an olefin according to claim 10, where the polymerization reaction is carried out in solution, in suspension, in bulk or in the gas phase. 13. The method of polymerization of an olefin according to claim 10, where the olefin has a density in the range from 0.91 to 0.94 g / cm ³ .