Title of Invention

NEW HOMOGENEOUS OLEFIN PLOYMERIZATION CATALYST COMPOSITION

Abstract 165/MA8/98 ABSTRACT A process fox preparation of new homogenous olefin polymerization catalyst composition, in particular a composition comprising a metallocene and en aluminoxane or a reaction product. Aluminoxanes having C2-C10 alkyl groups can conveniently be used in homogeneous olefin polymerization catalyst compositions prepared by contacting a) a metallocene containing a cyclopentadienyl ring substituted by a 40, and c) an organic solvent which dissolves said metallocene and said aluminoxane or a reaction product of them, and recovering said homogeneous olefin pol3rmerization catalyst composition.
Full Text

polymerization. Also the storage stability of higher aluminoxanes is much better. The structure of the higher aluminoxanes will not change during storage, which is the case with MAO.
The higher alkyl aluminoxane used according to the invention preferably contains C2-10 alkyl groups, especially branched alkyl groups, e.g. ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, i-butyl, n-pentyl, iso-arayl, sec-amyl, tert-amyl, iso-hexyl, sec-hexyl, or tcrt-hexyl groups. Particularly preferably the higher alkyl aluminoxane contains C3-6 allcyl groups, especially branched aJkyl groups.
The metallocene used accordmg to the invention preferably includes a catalytically active transition metal or lanthanide complexed by one or more, e.g. 1 or 2 homo-or heterocyclic cyclopentadienyl ligands. Where the metallocene contains more than one cyclopentadienyl ligand moiety, then a noniing-substituted cyclopentadienyl ligand moiety may be present. However it is preferred that all the cyclopentadienyl ligand moieties be ring-substituted.
Ring substitution may be for example by pendant gi-oups (e.g. hydrocarbyl or hydrocarbyloxy groups optionally attached via heteroatoms such as O, N, S, P, Si or Ge or via multiply bonded carbon atoms), by fused rings (e.g. such as to produce fused bicyclic or polycyclic structures with 5- and 6 membered homo- or heterocyclic rings, which (other than one five membered ring) may be saturated or unsatui-atcd, e.g. indenyl, tetrahydroindenyl, fluorenyl and octahydi'ofluorenyl groups), by bridging groups attached to the metal or to a second optionally ring-substituted homo- or heterocyclic cyclopentadienyl ring (for example with the linkei moiety providing at least one backbone atom selected from carbon, silicon, oxygen, sulphur, nitrogen and phosphorus, e.g. being an alkylcne or silylene bridge), or by combinations of such substituents, for example witli bridging or pendant gi'oups being attached to rings fused to tlic cyclopentadienyl ligand moiety rather tlian directly to the oyclopentadienyl ring.
The ring substituent(s) on the cyclopentadienyl ring are preferably such as to permit an extension to the n-electron system of the cyclopentadienyl ring, especially preferably such as to further disperse the negative charge on the ring; thus the ring is especially preferably substituted by n-electron withdrawing groups, e.g. polyatomic groups attached via heteroatoms such as 0, S, N or P or via multiple bonded carbons.

The catalyst composition of the invention may comprise the mctallocenc and the higher alkyl aluminoxanc cither unreactcd or more preferably as their reaction product. The metalloccne, aluminoxane or metallocene:aluminoxane reaction product may if desired be on a particulate support, e.g. a porous inorganic or inorganic material (e.g. silica) or alternatively they may be in solution in an organic solvent. If desired, one of the metallocene and tlie aluminoxane may be on a particulate support with the other present as a solid, as a liquid or in solution. If desired the metallocene and aluminoxane may be brouglit into contact only in the olefm polymerization reactor or while being dosed into the reactor.
Viewed from a further aspect the invention provides the use of an aluminoxane containing alkyl groups containing at least two carbon atoms as a co-catalyst with a metallocene pro-catalyst containing a ring-substituted homo- or heterocyclic cyclopentadienyl .sandwich ligand for the polymerization of an olefm.
Viewed from anodicr aspect the invention provides the use of a metalloccne containing a ring-substituted homo- or heterocyclic cyclopentadienyl sandwich ligand as a pro-catalyst vvith an aluminoxane co-catalyst contauiLig at Icasil two carbon atoms for tlie polymerization of an olefm.
Viewed from a still further aspect the invention provides the use as a catalyst for olefin polymerization of the reaction product of an aluminoxane containing alkyl groups containing at least two carbon atoms and a metallocene containing a ring-substituted homo- or heterocyclic cyclopentadienyl sandwich ligand.
Viewed from a yet still further aspect the invention provides a process for the preparation of an olefin polymerization catalyst, said process comprising contacting a metallocene pro-catalyst containing a ring-substituted homo- or heterocyclic cyclopentadienyl sandwich ligand witli an aluminoxane containing alkyl groups containing at least two carbon atoms, preferably in an organic solvent or solvent mixture in which said metalloccne and almninoxane are soluble and optionally in the presence of a porous particulate support, and if desired recovering the reaction product of said metallocene and almninoxane, preferably supported on said particulate support.
Viewed from a yet still further aspect the invention provides a method of olefm polymerization comprising contacting an olefm with a metalloceneialuminoxane catalyst composition, characterized in that as said catalyst composition is used a

metallocene pro-catalyst containing a ring-substituted homo- or heterocyclic cyclopentadienyl sandwich ligand ajid an aJimiinoxane co-catalyst containing alk>'l groups containing at least two carbon atoms or the reaction product thereof.
Thus using the present invention one may replace MAO as the olefin polymerization co-catalyst in homogenous catalyst compositions. Moreover, using the present invention one may produce a homogenous olefin polymerization catalyst composition suitable for use in gas phase, slurry phase or liquid/solution phase polymerizations.
In a preferred embodiment, the process of the invention involves contacting a) a metallocene of the general formula (I):

wherein Cp or each same or different Cp is one of a mono- or polysubstituted, fused or non-fuse3, homo- (" iso-) or heterocyclic cyclopentadienyl ligand, indenyl ligand, tetrahydromdenyl ligand, fluorenyl ligand, or octahydrofluorenyl ligand, Y or each same or different Y is a substituent at tlie cyclopentadienyl ring of said Cp ligand and is one of an -OR, -SR, -NR2, -CiK or R)=, or -PR2 radical, R or each same or different R being one of a substituted or unsubstituted Ci-Cig hydrocarbyl group, a tri-Ci-Cg hydrocarbylsilyl group, a tri-Cj-Cg hydrocarbyloxy silyl group a mixed Ci-Cg hydrocarbyl and Ci-Cg hydrocarbyloxy silyl groups, a tri-Ci-Cg hydrocarbyl germyl group, a tri-Ci-Cg hydrocarbyloxy germyl group or a mixed Ci-Cg hydrocarbyl and Cj-Cg hydrocarbyloxy germyl group; M is a transition metal of Group 4 of the Periodic Table (lUPAC) and bound to the ligand or ligands Cp at least in an ri^ bonding mode; X or each same or different X is bound to M and is one of a hydrogen, a halogen, a substituted or unsubstituted Cj-Cg hydro¬carbyl group, a Ci-Cg hydrocarbylheteroatom (0, S,'N, P) group or a tri-Ci-Cg hydrocarbyl silyl group or two X form together with M a C4-C20 metallocyclic ring structure; Z is a bridge atom or group between two Cp ligands or between one Cp ligand and the transition metal M; q is, when Cp is unbridged, 0-5 for Cp = cyclo¬pentadienyl, 0-3 for Cp = indenyl or tetrahydroindenyl and 0-1 for Cp = fluorenyl or octahydi-ofluorcnyl, or q is, when Cp is bridged, 0-4 for Cp ^ cyclopentadienyl, 0-2 for Cp •- Indenyl or tetrahydroindenyl and 0 for Cp = fluorenyl or octahydro-


and recovering said homogenous olefin poljmierization catalyst composition.
By mono- or polysubstituted is meant that, in addition to said substituent Y, there may optionally be other substituents at the rings at said ligand or ligands Cp.
By fused or non-fused is meant that any ring at said ligands may be fused or non-fused, i.e. have at least two atoms in common, with at least one further ring.
By homo- and heterocyclic is meant that any ring of said ligands may have only carbon ring atoms (homo- or isocyclic) or may have other ring atoms (e.g. 0, N, S. P) than carbon (heterocyclic).
It has thus been realized that a C2-C10 allcyl aluminoxane (i.e. a non-methyl alurainoxane) can successfully be used as the cocatalyst, if a raetallocene having a -OR', -SR', -NR'2, -C(H or R')», or -PR'2 substiftjent at the cyclopcntadienyl ring is used as the procatalyst.

According to a non-limiting explanation, an electron pair of the hetcroatom (0, S, N, P) or double bond substituents at the cyclopentadienyl ring delocalizc it's negative charge and help to ionise the metallocene, whereby the transition metal M becomes more cationic (electron density deficient). This improves the catalytic interaction between the metallocene and the aluminoxane and enables the use of higher aluminoxanes like those of the above formula (2). A commercially acceptable homogenous catalyst composition is the result.
According to a preferred embodiment of the invention, the cyclopentadienyl ring is substituted by an organic oxy radical, i.e. Y in the above formula (1) is an -OR radicaJ. According to another preferred embodiment of the invention, the group R of the radical -OR, -SR, -NR2. -CR = or -PR2 is a tri-C i-Cg hydrocarbyl silyl group.
According to the process of the present invention said support is contacted with a metallocene of the general formula (1). It is preferred that the metallocene of the general formula (1) as group R of said substiment Y has a tri-C j-Cy hydrocarbyl silyl or a tri-C j-Cg hydrocarbyloxy silyl group which ai"e capable of Tt interaction with said 0, S, N, or P atoms of Y. Most preferred are tri-C j-Cg alkyl silyl groups, wherein at least one of the Ci-Cg alkyls is a branched Cs-Cg aBcyl group such as isopropyl, isobutyl, sec-butyl, tert-butyl, isoamyl, sec-ainyl, tert-amyl, isohexyl, sec-hexyl, or tert-hexyl. Cyclic alkyls and aiyls arc also preferred groups of the silicone atom.
According to one embodiment of the invention there is only one ligand Cp in the metallocene of formula (1), which preferably is bound to the transition metal M by both said T)^ bond and by a bridge Z preferably containing a heteroatom such as an N bridge.
However, said metallocene of the general formula (I) has most preferably two ligands Cp, i.e. m is 2. According to a still more preferred embodiment, the tvv'o Cp iigands are bridged with each other by a bivalent atom or group Z having at least one chain atom which is one of a carbon, silicon, oxygen, sulphur, nitrogen, or phosphorous atom. Most preferably, the metallocene of the general formula (1) has m'=2, whereby Z is an ethylene or a silylenc bridge.
The transition metal M of group 4 of tlie Periodic Table in the general formula (1) is Ti, Zr or Hf, more preferably Zr or Hf, and most preferably Zr. The valency or oxidation niunber of M is 4.

The preferable atom or group X of said mctalloccne of formula (1) is a halogen atom and/or a Cj-Cg hydrocarbyl group. Most preferably, X is chlorine and/'or methyl. The number of X atoms or groups, i.e. "n",.is preferably 1-3, most preferably 2, considering the limitation given above for the case when Z is a bridge between Cp and M.
Particularly preferred metalloccnes of the general formula (I) are compounds of following structural formula (3).

wherein each of the Yi's and Y2's is the same or different and is one of a hydrogen atom, a halogen atom, an acyl group, an acyloxy group, a substituted or unsubstituted CJ-CIQ hydrocarbyl group, an -OR, -SR, -NR, -C(H or R)=, or -PR2 radical, R being one of a C1-C16 hydrocarbyl group or a tri-Ci-Cg-hydroearbylsilyl group, provided that at least one of the Yj's and Y2's is one of said -OR, -SR, -NR, 'C(H or R)^, or -PR2 radicals; Z is a bivalent atom or group having at least one chain atom which is one of a carbon, silicon, oxygen, sulphur, nitrogen or phosphorus atom, preferably 1-4 carbon and/or silicon chain atoms; each R" is tlie same or different and is one of a hydrogen atom, a halogen atom, a Ci-Cio hydrocarbyl group or ring constituent, or a C1 -C10 hydrocarbyloxy group, M is one of Ti, Zr or Hf; and Xi and X2 are die same or different and are one of a halogen atom and a Ci-Cg hydrocarbyl group. The analogous 4,5,6,7-tetrahydroindenyl derivatives are also useful in the invention.

Particularly preferable mctallocenes of the formula (1) are ethylene-bis(2-tcit-butyi-dlmelhyIsiloxyindenyI)zirconium dichlonde, ethylene-bis(2-tert-butyldimethylsil-oxyindetiyOzirconium dimethyl, preferably ethylene-bis(2-tert-butyldimetyl(siloxy-indenyl)2irconium dimethyl, or their corresponding tetrahydroanalogues.
When using chiral metallocenes, they can be used as a racemate for the prepai-ation of highly isotactic a-olefm polymers. The piu-e R or S foiTn of said metallocene can also be used, e.g. for the production of optically active poljotner.
The metallocene of the general formula (1) is usually prepared by a process involving repeated deprotonations/metallizations of the ai-omatic ligands and introduction of the bridge Z atom or atoms as well as tlie central atom by their halogen derivatives. The preparation of the said metallocehe of the general formula (1) can e.g. be carried out according to a J. Organoraetallic Chem. 288 (1958) 63-67 and EP-A-320762, botli herewith incorporated by reference. See also Scares, J. B. P., Hamidec, A. E., Polym. Reaction Eng., 3 (2) (1995) 131-200, herewith incorporated by reference.
The most preferred metallocenes of the general formula (1), wherein tlie substitucnt Y is a tri-C1-C8 hydrocarbylsiloxy group, is preferably prepared as follows:
The catalyst compounds according to the invention can be prepared from 2- or 3-indannnft Tn the following, the preparation of 2-.siloxy indene derivatives is described to exemplify the preparation of 2- and/or 3-siloxy mdenes. 2-uidanone can be reacted in a suitable solvent with a base and a chlorosilane to fonn 2-sil-oxyindene with a yield of over 80%. Suitable solvents are for example dimethyl-formamide (DMF) and tetrahydrofurane (THF). Suitable bases are for example imidazole and triethylamine (TEA). Suitable chlorosilanes are for example tert-butyldimethylchlorosilane, t-hcxyldimcthylchlorosilane and cyclohexyldimethyl-chlorosilane. The reaction takes place according to the following reaction scheme (II):


According to one embodiment of the invention 2-tert-butyldijnricthylsiloxyindcne is reacted first with butyllithium and then with dimethyl dichlorosilane (Me2SiCl2) to fonn dimcthylsilylbis(2-tert-butyldimethylsiloxyindcne). Butyllithium can be re¬placed with methyllithium, sodium hydride or potassium hydride. Likewise di¬methyl dichlorosilane can be replaced with any dialkyl or diarylsilone. Silicon can be replaced with germanium,
Dimethylsilylbis(2-tert-butyldijnethyIsiloxyindene) can be reacted with butyl¬lithium, which gives the corresponding bislithimn salt. This product can be reacted with zirconiimi tetrachloride to yield dunethyIsilylbis(2-tert-butyldimethylsiloxy-mdenyl)zirconium dichloride as a mixture of the racemic and meso diastereomers. Butyllithium may be replaced as described earlier. Zirconiimi tetrachloride can be replaced with titanium tetracliloride or hafiiium tetrachloride to give the corresponding titanium and ha&ium complexes. The reactions take place according to the following reaction schemes (III-IV):



According to another embodiment of the invention 2-tcrt-butyldimethylsiIoxyindene is reacted first with butyllithium and then with dibromoethane to form bis(2-tert-butyldimethylsiloxyindenyl)ethane. This compound can be reacted with two equivalents of butyllithium, which gives the corresponding bislithium salt. This can then be reacted with zirconium tetrachloride to yield ethylenebis(2-tcrt-butyldi-methylsiloxyindenyOztrconiiun dichloride. The raccmic diastereomer, of the latter is formed in great excess and is easily separated from the meso isomer by fractional crystallization. Catalytic hydrogcnation of racemic ethylenebis(2-tert-butyldi-methylsiloxyindenyl)zirconium dichloride yields the corresponding tetrahydroinden-yl complex. The reaction takes place according to tlie following reaction scheme (V):



In th« reactions above butyllithium may be replaced as described earlier. Zirconium tetrachloride can be replaced with titanium tetrachloride or hafnium tetrachloride to give the corresponding titanium and hafhimn complexes.
According to still another embodiment of the mvention 2-t-hexyldimcthylsiloxy-indene is reacted first with butyllithium and then with dibromoethane to fotm bis(2-t-hexyldimethylsiloxyindcnyl)ethane. This compound can be reacted with ^vo equivalents of butyllithium which gives the coircsponding bislithium salt. This can then be reacted with zirconium tetrachloride to yield ethylenebis(2-t-hexyldi-racthylsiloxyindenyl)zirconium dichloride. The racemic diastcreomer of the latter is formed in great excess and is easily separated from the meso isomer by fractional crystallization. The reaction takes place according to the following reaction scheme (VI);


In the reactions above butyllithium may be replaced as described earlier. Zirconium tetrachloride can be replaced with titanium tetrachloride or hafiiium tetrachloride to give the corresponding titanium and hafnium complexes. Hydrogenation of etliyl-enebis(2-t-hcxyldimethylsiloxyindenyl)z{rcomum dicliloride yields the con-espond-ing tetrahydroindenyl complex.
Illustrative but non-limiting examples of the preferable corapoimds used according to the invention are, among others, racemic and meso dimethylsilylbis(2-tert-butyldimcthylsiIoxyindenyl)2irconium dichloride, racemic and meso diphenylsilyl-bis(2-tert-butyldimethyIsiloxyindenyI)zirconium dichloride, racemic and meso di-methylsilyIbis(2-t-hexyldimethylsiloxyindenyl)zirconium dichloride, racemic and meso diphenylsilylbis(2-t~hexyldimethyIsiloxyuidenyl)2ircomum dichloride, race¬mic afld ttieso toethylsilylbis(2-cyclohexyldtmethylsiloxyindenyl)2irconium di¬chloride, racemic and meso dimethylsilylbis(2-cyclohexyldimethylsiIoxyindenyI)-zirconium dichloride, racemic and meso dimediyIsilylbisC2'2-tert-butyldiphenyI-siloxyindenyl)2irconiwn dichloride, racemic and meso diphenylsilylbis(2-tert-butyldiphenylsiloxyindenyl)zirconium dichloride, racemic and meso dimetliylsilyl-bis(2-tert-butyldimcthylsiloxy-4,5,6,7'tetrahydroindenyl)zircomum dicliloride, race-

mic and meso diphenylsilylbis(2-tert-butyldimethyIsiloxy-4,5,6,7-teti-ahydroinde-nyl)zirconium dichloride, raccmic and meso dimethylsllylbis(2-t-hexyldimethyl-siIaxy-4,5,6,7-tetrahydroindenyl)zirconiura dichloride, racemic and meso diphenyl-silyIbis(2-t'hexyIdimethyIsiIoxy-4,5,6,7-teti'ahydroindenyI)zirconium dichloride, racemic and meso dimethylsiIylbis(2-cyclohexyldimethylsiloxy-4,5,6,7-tetrahydro-indenyI)zirconium dichloride, racemic and meso diphenylsilyIbis(2-cyclohexyldi-methylsiloxy-4,5,6,7-tetrahydroindenyl)2irconimn dichloride, raccmic and meso dimethylsilylbis(2-tert-butyIdiphenylsiloxy-4,5,6,7-tctrahydroindenyl)zirconium di¬chloride, raccmic and meso diphenyIsiIylbisC2-tert-butyIphenyIsiloxy-4,5,6,7-tetra-hydroindenyl)zirconium dichloride, rac-ethylenebis(2-tert-butyhnethylsiloxyindc-nyl)zirconium dichloride, racemic and meso ethylenebis(2-t-hexyldimcdiylsiloxy-indenyl)zirconium dichloride, racemic and meso eihylenebis(2-cyclohexyldimetliyI-siloxyindenyl)zirconium ■ dichloride, racemic and meso ediylcnebis(2-tert-butyl-diphenylsiloxyindenyOzirconium dichloride, rac-ethylenebis(2-tcrt-butyldimetliyl-siloxy-4,5,6,7-tetrahydroindenyl)zirconium dichloride, racemic and meso ethylcne-bis(2-cyclohexyldimcthylsiloxy-4,5,6,7-tetraliydroindcnyl)zirconimn dichloride, racemic and meso ethylenebis(2-tert-butyIdiphenylsiIoxy-4,5,6,7-tetrahydroinde-nyl)2irconium dichloride and rac-ethylenebis(2-t-hexyldimethylsiloxyindenyl)zirco-nimn dichloride. Titanimn or hafniimi can be used instead of zirconium in corresponding complexes.
Particularly preferred bridged 3-(siloxy)indenyl and 3-(siloxy)-4,5,6,7-tetrahydro-indcnyl metallocenes according to the present invention include: rac- and meso-[ethyIenebis(3-(tcrt-butyldimcthylsiloxy)indenyl)]zirconium dichloride; rac- and meso-[dimethylsilylenebis(3-(tert-butyldimediylsiloxy)indcnyl)]zircomum diclilori-de: rac- and meso-(ethylenebis(3-(t-hexyldimethyIsiIoxy)indenyl)]2irconium dichlo¬ride; rac- and meso-[dimethylsilylenebis(3-(t-hexyldimethylsiloxy)indcnyl))zirco-nium dichloride; rac- and meso-[ethylcnebis(3-(tert-butyldimcthylsiloxy)-4,5,6,7-tetrahydroindenyl)]zircomum dichloride; rac- and meso-[dimcthylsilylenebis(3-(tert-butyldimethylsiloxy)-4,5,6,7-tetrahydroindenyl))zirconium dichloride; rac- and meso-[ethylenebis(3-(t-hexyldimethy!siloxy)-4,5,6,7-tetrahydroindenyI)]zirconium dichloride and rac- and mcso-[dimethylsilyIenebis(3-(t-hexyldimcthylsiloxy)-4,5,6,7-tetraliydroindenyl)]zirconiuni dichloride; and the same hafnium compounds such as; rac- and mcso-[cthylenebis(3-(tert-butyldimethyisiIoxy)indenyl)]hafhium dichloride; rac- and raeso-[dlmethylsilylenebis(3-(tert-butyldimethylsiloxy)inde-nyl)]hafiiium dichloride; rac- and meso-[ethylenebis(3-(t-hexyldimethylsiloxy)-indenyl)]hafiiium dichloride; rac- and meso-[dimediylsilylenebis(3-(t-hexyldimet-hylsiloxy)indcnyl)]hafiiium dichloride; rac- and meso-[ethyIenebis(3-(tert-butyl-

dimethylsiloxy)-4,5,6,7-tetrahydroindcnyl)]hafnium dichloride; rac- and meso-[dimethyIsilylenebis(3-(tcrt-butyldimcthyIsiloxy)-4,5,6,7-tetrahydroindenyl)hafniiim dichloride; rac- and meso-(ethylenebis(3-(t-hexyldimethylsiloxy)-4,5,6,7-tetra-hydi-oindcnyl)]hafiiium dichloride and rac- and mcso-(dimethylsilylenebis(3-(t-hexyldimcthylsiloxy)-4,5,6,7-tetrahydroindenyl)]haftiium dichloride; and the like.
When contacting said metallocene of tlie general formula (I) or (3), the metallocene is preferably dissolved in a chlorinated or non-chlorinated C3-C10 hydrocarbon solvent and most preferably in an aromatic hydrocarbon solvent such as toluene.
In the present process for the preparation of a homogenous olefm polymerization catalyst composition, the metallocene according to formula (1) or (3) is contacted with an aluminoxane of the general formulas (2). Formulas (2) are general formulas including not only linear and cyclic compounds, but also aluminoxane compounds of cage and net structures. See e.g. Harlan, et.al.. J. Am Chem. Soc, 117, (1995) p. 6466, the aluminoxane structures of which are enclosed by reference to disclose one embodiment of the invention.
The aluminoxane used in the process of tlie present invention is preferably an aluminoxane (2), wherein said R' is a C3-C10 ^^^ group, more preferably an isopropyl, isobutyl, sec-butyl, tert-butyl, isoamyl, sec-amyl, tert-amyl isohexyl, sec-hexyl or tert-hcxyl group. The most prefeiied aluminoxane of the formula (3) is preferably an aluminoxane in which 2 It is preferable to contact said metallocene of formula (1) or (3) previous to, imme¬diately before, or at the begiiming of the olefm polymerization, with an alumin¬oxane of formula (2) dissolved or immersed in a chlorinated or unchlorinated hydrocarbon solvent such as hexane or toluene. When contacting said metallocene of the formula (I) or (3) with said aluminoxane of tlie fonnula (2), the molar ratio between the aluminoxane aluminium metal and the metallocene transition metal in the catalyst composition is preferably between 20 and 2000, more preferably 50 and

1500 and most preferably between 100 and 1200. The concentration of metallocene in tlie catalyst composition is preferably regulated to between 0.01 and 100 mmol/'l, more preferably to between 0.1 and 50 mmol/1, even more preferably to between 0.5 and 10 mmol/l, most preferably to between 1 and 5 mtnol/l.
When preparing a supported olefin polymerization catalyst composition according to the present invention, the contacting product between the metallocene of the general formula (1) or (3) and the aluminoxanc of the general formula (2) can be subjected to a prepolymerization with at least one olefin such as propylene and/or ethylene. The prepolymerizatc is then recovered as said supported olefin poly¬merization catalyst composition. The process may also include a step of solidification (e.g. by precipitation, evaporation, crystallization) of said catalyst, whereby a homogenous solid is obtained.
In addition to the above described process for the preparation of a homogenous olefin polymerization catalyst composition, tlie present invention also relates to a homogenous olefin polymerization catalyst composition which has been prepared according to said described process. The mvention also relates to a process for polymerizing at least one olefin by polymerizing in the presence of said homo¬genous olefin polymerization catalyst or a catalyst prepared according to the above described process. In the polymerization (homopolymerization or copolymerization) olefin monomers, such as ethylene, propylene, 1-butylene, isobutylene, 4-methyl-l-pcntene, 3-methyl-l-butene, 4>4-dimethyl-l-pentene, vinylcyclohexene, 1-dccene and their comonomers, can be used. Dienes and cyclic olefins can also be homo- or copolymerized. These a-olcfins and other monomers can be used both in the poly¬merization and prepolymerization using the claimed supported olefin poly¬merization catalyst composition.
The polymerization can be a homopolymerization or a copolymerization and it can take place in the gas, slurry or a solution phase. The claimed catalyst composition can also be used in high pressure processes. Said a-olefins can be polymerized together with higher a-olefins in order to modify the properties of the final product. Such higher olefms arc 1-hexene, 1-octene, 1-decene, etc.
In the following, the present invention is illustrated by non-limited examples.

Comparative examples
Comparative example 1 Prepnration of the complex solution
A complex solution of metalloccnc was prepared by adding 34 mg of rac-ethylene-bis(2-tert-butyldimediylsiloxyindenyI)zirconiumdichloride into 20 ml moistiu-e and oxygen free toluene. The final solution had a concentration of 2.5 fimol/mi (1.7 mg/ml). To form the metallocene/MAO (methyl aluminoxane) complex, 0.25 ml of said tnetallocene compound solution was added into 10 ml of additional toluene containing 0. H ml of 30 w-% MAO. The final Al/Zr-ratio was 500.
Test polymerization
A test polymerization was carried out in a 3-litcr Biichi autoclave in n-pentane nt 10°C. The ethylene partial pressure was 5 bar and the total pressure was 8.4 bar. Into the reactor, 10 ml of previously prepai-ed complex solution was fed. The total amount of metallocenc compound was 0.63 ^ol (0.44 mg) and the Al/Zr-ratio was 500. After 30 min of polymerization the reaction was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 73 g giving a total catalyst activity of 2540 kgPE/ g*Zr*h.
Comparative example 2 Preparation of the complex solution
A complex solution of metallocene was prepared by adding 34 mg of rac-ctliylcne-bis(2-tert-butyldimethylsiloxyindenyl)zircomumdichloride into 20 ml moisture arid oxygen free toluene. The final solution had a concentration of 2.5 |imol/ml (1.7 mg/ml). To form the metallocene/MAO complex, 1.0 ml of metallocene compound solution was added into 10 ml of additional toluene containing 0.17 ml of 30 w-% M \0. The final Al/Zr-ratio was 200.
Test polymerization
A test polymerization was carried out in a 3-liter Biichi autoclave in n-pentane at 10°C. The ethylene partial pressure was 5 bar and the total pressure was 8.4 bar. Into the reactor, 10 ml of previously prepared complex solution was fed. The total amount of metallocene compound was 2.5 \uno\ (1.7 mg) and the Al/Zr-ratio was

200. After 30 min the polymerization reaction was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 120 g giving a total catalyst activity of 1036 kgPE/ g*Zr*li.
Comparative example 3 Preparation of the complex solution
A complex solution of mctallocene was prepared by adding 34 mg of rac-ethylene-bis(2-tert-butyldiniethylsiloxyindenyl)zirconiumdichloride into 10 ml moistm-e and oxygen free toluene. The fmal solution had a concentration of 2,5 |amol/m] (1.7 mg/ml). To form a raetallocene/MAO complex, 0.25 ml of the metalloccne compound solution was added into 10 ml of additional toluene containing 0.02 mi of 30 w-% MAO. The fmal Al/Zr-ratio was 100.
Test polymerization
A test polymerization was canied out in a 3-liter Btichi autoclave in n-pentane at 70°C. The ethylene partial pressure was 5 bar and the total pressure was 8.1 bar. Into the reactor, 10 ml of the previously prepared complex solution was fed. The total amount of metalloccne compound was 0.63 iimol (0.44 mg) and the Al/Zr-ratio was 100. After 30 rain, the polymerization reaction was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 12 g giving a total catalyst activity of 406 kgPE/ g*2r*h.
Comparative example 4 Preparation of the complex solution
A complex solution of metallocene was prepared by adding 20.9 mg of rac-ethylene-bis(indenyl)zirconiumdichloride mto 20 ml moisture and oxygen free toluene. The final solution had a concentration of 2.5 jimol/ml (1.045 mg/ml). To form a raetallocene/MAO complex, 1.0 ml of the metallocene compound solution was added into 10 ml of additional toluene containing 0.43 ml of 30 w-% MAO. The fmal Al/Zr-ratio was 500.
Tilt polymerization
A test polymerization was carried out in a 3-liter Btichi autoclave in n-pentanc at TO^C. The ethylene partial pressure was 5 bar and the total pressui-e was 8.6 bar.

Into the reactor, 2.5 ml of the previously pvepaj-ed complex solution was fed. The total amount of metallocene compound was 0.63 jimol (0.2(5 mg) and the Al/Zr-ratio was 500. After 30 min of polymerization the reaction was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 25 g giving a total catalyst activity of 842 kgPE/ g*Zr*h.
Comparative example 5 Preparation of the complex solution
A complex solution of metallocene was prepared by adding 20.9 mg of rac-ethyiene-bis(indenyl)zirconiumdichloride into 20 ml moisture and oxygen free toluene. The final solution had a concentration of 2.5 )imol/mJ (1.045 mg/ml). To form a metallocene/MAO complex, 1.0 ml of the mctallocene compound solution was added into 10 ml of additional toluene containing 0,17 ml of 30 w-% MAO. The final Al/Zr-ratio was 200.
Test polymerization
A test polymerization was carried out in a 3-liter Btichi autoclave in n-pentane at VO^C. The ethylene partial pressure was 5 bar and the total pressure was 8.6 bar. Into the reactor, 2.5 ml of previously prepared complex solution was fed. The total amount of metallocene compound was 0.63 jimol (0.26 mg) and the Al/Zr-ratio was 200. After 30 min the polymerization reaction was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 27 g giving a total catalyst activity of 910 kgPE/ g*Zr*h,
Comparative example 6 Preparation of the complex solution
A complex solution of metallocene was prepared by adding 20.9 mg of rac-ethylene-bis(indenyl)zirconiumdichloride into 20 ml moisture and oxygen free toluene. The final solution had a concentration of 2.5 ,uraol/ml (1.045 mg/ml). To form the metallocene/MAO complex, 1.0 ml of the metallocene compound solution was added into 10 ml of additional toluene containing 0.09 ml of 30 w-% MAO. The final Al/Zr-ratio was 100.

Test polymerization
A test polymerization was carried out in a 3-litcr Buchi autoclave in n-pcntane at 70°C. The ethylene partial pressure was 5 bar and the total pressure was 8.6 bar. Into the reactor, 2.5 ml of the previously prepared complex solution was fed. The total amount of metallocene compound was 0.63 |imol (0.26 mg) and tlie Al/Zr-ratio was 100. After 30 min, the.polymerization reaction was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 9 g giving a total catalyst activity of 302 kgPE/ g*Zr*h.
Comparative example 7 Preparation of the complex solution
A complex solution of metallocene was prepared by adding 20 mg of rac-ethylene-bis(2-tert-butyldimcthylsiloxyindenyl)2irconiumdichloridc into 11.5 ml moisture and oxygen free toluene. The fmal solution had a concentration of 2.54 nmol/ml (1.74mg/ml).
Test polymerization
A test polymerization was carried out in a 3-liter Btichi autoclave in n-pentanc at 70^*0. The ethylene partial pressure was 5 bar and the total pressure was 8.2 bar. Into the reactor, 1 ml of the previously prepared complex solution was fed together with 1.1 ml of MMAO-4. MMAO-4 is methyl aluminoxane containing 30 % by weightofisobufylgroups. The total amount of metallocene compound was 2.54 jirniol (1.74 mg) and the AVZr-ratio was 1000, After 12 min, the polymerization vessel was full of polymer and the reaction was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 110 g giving a total catalyst activity of 2357 kgPE/ g*2r*h.
Comparative example 8
Preparation of the metallocene solution
A solution of metallocene was prepared by adding 10 mg (l,2)-ethylene-bis-(lnd«nyl)2lroomumdiohloride into 10 ml moisture and oxygen free toluene. The fmal solution had a concentration of 2.75 jimol/ml (1 mg/ml).

Test polymerization
A test polymerization was carried out in a 3-liter BUchi autoclave in isobutane at 7PC. The ethylene partial pressure was 5 bar and the total pressure was 15.8. bar. Into.thc reactor, 1.15 ml of the previously prepared complex solution and 2.64 ml HIBAO (HIBAO *= hexaisobutyl aluminoxane; .10 % in hexane was added. The Al/Zr-ratio was 1055. A metal cylinder was tiglitened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into tlie reactor beforehand. The other half of the isobutane was used to wash the catalyst from the metal cylinder into the reactor when streaming throug the cylinder. The reaction time was 60 minutes. After that the ethylene feed valve was closed and the over pressure was released from the reactor. The yield of polymer was 18 g and the total catalyst activity was 64 kgPE/ g*Zr*h.
Comparative example 9
•Preparation of.the metallocene solution
As in comparative example 8
Test polymerization
A test polymerization was carried out in a 3-liter Biichi autoclave in isobutane at 7rC. The ethylene partial pressure was 5 bar and the total pressure was 15.8 bar. Into the reactor, 1.15 ml of the previously prepared complex solution and 1.32 ml of HIBAO 20 % in hexane was added. The Al/Zr-ratio was 527. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane ^yas fed into the reactor beforehand. The otiier half of isobutane was used to wash the catalyst from the metal cylinder into the reactor when streaming throug the cylinder. The reaction time was 60 minutes. After tliat the ethylene feed valve was closed and the overpressure was released from the reactor. The yield of polymer was I g and the total catalyst activity was 8 kgPE/ g''Zr*h.
Comparative example 10 Preparation of the metallocene solution
As in comparative example 8

Test polymerization
A test polymerization was carried out in a 3-liter BUchi autoclave in isobutane at 7I°C. The ethylene partial pressure was 5 bar and the total pressure was 15.8 bar. Into the reactor, 1.15 ml of the previously prepared complex solution and 0.66 mi HIBAO 20 % in hexane was added. The Al/Zr-ratio was 264. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into the reactor beforehand. The other half of the isobutane was used to wash the catalyst from the raetaJ cylinder into the reactor when streaming throug the cylinder. The reaction time was 60 minutes. After that the ethylene feed valve was closed and the overpressure was released from the reactor. The yield of polymer was 3 g and the total catalyst was activity 24 kgPE/ g*Zr*h.
Comparative example 11
Preparation of the metallocene solution
A solution of metallocene was prepared by adding 10 rag of n-butyldicyclopenta-dienylzirconium dicUoride into 10 ml moisture and oxygen free toluene. The final solution had a conceration 2.47 )umol/ml (1 mg/ml).
Test polymerization
A test polymerization was carried out in a 3-liter Biichi autoclave in isobutane at WC, The ethylene partial pressure was 5 bar and the total pressure was 15.5 bar. Into the reactor, 1.0 ml of the previously prepared complex solution and 2.26 ml of 20 % HIBAO in cyclohexane was fed. The AVZr-ratio was 1006. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into the reactor beforehand. The other half of the isobutane was used to wash the catalyst from the metal cylinder into the reactor when streaming throug tlie cylinder. The reaction time was 60 minutes. After that the ethylene feed valve was closed and the overpressure was released from the reactor. The yield of polymer was 13 g and the total catalyst activity was 106 kgPE/ g*Zr*h.
Comparative example 12 Preparation of the metallocene solution
As in comparative example 11

Test polymerization
A test polymerization was carried out in a 3-liter Biichi autoclave in isobutane at 7 PC. The ethylene partial pressure was 5 bar and the total pressure was 15.6 bar. Into the reactor, 1.0 ml of the previously prepared complex solution and 1.13 ml of 20 % HIBAO in hexane was fed. The Al/Zr-ratio was 503. A metal cylinder was tightened to the reactor. The volume of isobutane was 1,8 liters. Half of the isobutane was fed into the reactor beforehand. The other half of the isobutane was used to wash the catalyst from the metal cylinder into the reactor when streaming throug the cylinder. The reaction time was 60 minutes. After that the ethylene feed valve was closed and the overpressure was released from the reactor. The yield of polymer was 6 g and the total catalyst activity was 53 kgPE/ g*Zr*h,
Comparative example 13 Preparation of the metallocene solution
As in comparative example 11
Test polymerization
A test polymerization was carried out in i 3-liter BUchi autoclave in isobutane at 71'C. The ethylene partial pressure was 5 bar and the total pressure was 15.5 bar. Into the reactor, 1.0 nil of the previously prepared complex solution and 0.57 ml of HIBAO 20 % in cyclohexane was fed. The Al/Zr-ratio was 254. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into the reactor beforehand. The other half of the isobutane was used to wash the catalyst from the metal cylinder into the reactor when streaming throug the cylinder. The reaction time was 60 minutes. AJfter that the ethylene feed valve was closed and the overpressure was released from the reactor. The yield of polymer was 6 g and the total catalyst activity was 53 kgPE/ g*Zr*h.
Comparative example 14
Preparation of the metallocene solution
AM in eompuritdvft dxiuinple 11

Test polymerization
A test polymerization was carried out in a 3-liter BQchi autoclave in isobutane at 7I°C. The ethylene partial pressure was 5 bar and the total pressure was 15.8 bar. Into the reactor, 1.0 ml of the previously prepared complex, solution and 1.3 ml tlBAO (TIBAO =^ tetraisobutyl aluminoxane) 30 % in cyclohexane was fed. The AJ/Zr-ratio was 897. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into the reactor beforehand. The other half of the isobutane was used to wash the catalyst from the metal cylinder into the reactor when streaming throug the cylinder. The reaction time was 60 minutes. After that the ethylene feed valve was closed and the overpressure was released from the reactor. The yield of polymer was 3 g and the total catalyst activity was 25 kgPE/ g*Zr*h.
Comparative example 15 Preparation of the metallocene solution
As in comparative example 11
Test polymerization
A test polymerization was carried out in a 3-liter BGchi autoclave in isobutane at 7PC. The ethylene partial pressure was 5 bar and the total pressure was 15.8 bar. Into the reactor, 1.0 ml of the previously prepared complex solution and 0.5 ml of 30 % TIBAO in cyclohexane was fed. The AJ/Zr-ratio was 345. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into the reactor beforehand. The other half of the isobutane was used to wash the catalyst from the metal cylinder into the reactor when streaming throug the cylinder. The reaction time was 60 minutes. After that the ethylene feed valve was closed and the overpressure was released from the reactor. The yield of polymer was 3 g and the total catalyst activity was 25 kgPE/ g*Zr*h.

Examples
Example 1
Preparation of the complex solution
A. complex solution of metallocene/HIBAO was prepared by adding 20 mg of rac-ethylenc-bis(2-ten-butyldimethylsiloxyindenyl)zircomuradichloride into 11.5 ml moisture and oxygen free toluene. The final solution had a concentration of 2.54 ismol/ml (1.74 mg/ml).
Test polymerization
A test polymerization was carried out in a 3-liter Btichi autoclave in n-pentane at 70^C. The ethylene partial pressure was 5 bar and the total pressure was 8.2 bar. Into the reactor, I ml of the previously prepared complex solution was fed together with 2 ml of.HIBAO. The total amount of mctallocene compound was 2.54 (imol (1.74 mg) and the Al/Zr-ratio was 1000. After 20 min, the polymerization was stopped by.closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 60 g giving a total catalyst activity of 777 kgPE/ g*Zr*h.,
Example 2
Preparation of the complex solution
As in example 1
Test polymerization
A test polymerization was carried out in a 3-liter Biichi autoclave in n-pentane at 70'C. The ethylene partial pressure was 5 bar and the total pressure was 8.2 bar. Into the reactor, 1.0 ml of the previously prepared complex solution was fed together with 1 ml of HIBAO. The total amount of mctallocene compound was 2.54 jiinol (1.74 mg) and the Al/Zr-ratio was 500. After 30 min the polymerization reaction was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 62 g giving a total catalyst activity of 535kgPE/g*Z;r*h.

Example 3 (repeated example 2) Preparation of the complex solution
Acomplex solution was prepared in situ by adding 10 mg of rao-ethylene-bisCS'lert-butyldimethylsiloxyindenyl)2irconiumdichloride directly into 6 ml of HIBAO solution. The final solution had a concentration of 2.4 pmoL/ml (1.67 mg/ml) and the Al/Zr-ratio is 500.
Test polymerization
A test polymerization was carried out in a 3-liter Biichi autoclave in n-pentane at 70°C. The ethylene partial pressure was 5 bar and the total pressure was 8.4 bar. Into the reactor, 1.0 ml of the previously prepared complex solution was fed. The total amount of metallocene compound was 2.4 ymol (1.65 mg) and the Al/2r-ratio was 500. After 28 min, the polymerization was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 63 g giving a total catalyst activity of 562 kgPE/ g*Zr*h.
Example 4
Preparation of the metallocene solution
A solution of the metallocene was prepared by adding 24 rag of rac-cthylene-bis(2-tert-butyldiniethylciloxyindonyl)sirooruumdichl6ridc into 12 ml mulsluic and oxygen free toluene. The fmal solution had a concentration of 2.95 iimol/ml (2.0 nig/ml).
Test polymerization
A test polymerization was carried out in a 3-liter Biichi autoclave in isobutane at Tl'C. The ethylene partial pressure was 5 bar and the total pressure was 15.3 bar. Into the reactor, 1.0 ml of the previously prepared complex solution and 1.0 ml of 20 % HIBAO in hexane was added. The Al/Zr-ratio was 373. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into the reactor beforehand. The other half of the isobutane was used to wash the catalyst from the metal cylinder into the reactor when streaming throug the cylinder. The reaction time was 60 minutes. After that the ethylene feed valve was closed and the over pressure was released from the reactor. The yield of polymer was 67 g and the total catalyst activity was 494 kgPE/ g*Zr*h.

Example 5
Preparation of the complex solution
A complex solution was prepared in sihi by adding 10 mg of rac-ethylene-bis(2-tert-butyldimethyIsiloxyindenyl)zircomumdichloride directly into 3 ml of a HIBAO solution. The final solution had a concentration of 2.4 (imol/ml (1.67 mg/ml) and the Al/Zr-ratio was 250.
Test polymerization
A test polymerization was carried out in a 3-liter Btlchi autoclave in n-pcntane at TO^C. The ethylene partial pressure was 5 bar and the total pressure was 8.2 bar. Into the reactor, 2.0 ml of the previously prepared complex solution was fed. The total amount of metalloccne compound was 4.8 jimol (3.3 mg) and Al/Zr-ratio was 250. After 30 min, the polymerization was stopped by closing the ethylene feed and releasing the overpressure jfrom the reactor. The yield of polymer was 40 g and the total catalyst activity was 180 kgPE/ g*2r*h.
Example 6
Preparation of the complex solution
A complex solution was prepared in situ by adding 10 mg of rac-ethylene-bis(2-tert-butyldimethylsiloxyindenyl)zircoiiiumdichloride directly into 3 ml of a HIBAO solution. The final solution had a concentration of 2.4 |imol/ml (1.67 mg/ml) and the Al/Zr-ratio was 250.
Test polymerization
A test polymerization was carried out in a 3-liter Btichi autoclave in n-pentane at 70^. The ethylene partial pressure was 5 bar and the total pressure was 8.2 bar. Into the reactor, 1.0 ml of the previously prepared complex solution was fed. The total amount of metallocenc compound was 2.4 pmol (1.65 mg) and Al/Zr-ratio was 250. After 30 min, tiie polymerization was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 20 g and the total catalyst activity was 175 kgPE/ g*2r*h.

Example 7
Preparation of the metallocene solution
A solution of the metallocene was prepared by adding 15 mg of rac-ethylenc-bis(2-tert-butyldimcthylsiloxyindenyl)2irconiumdichIoride into 10 ml moisture and oxygen free toluene. The final solution had a concentration of 2.35 |imol/ml (1.5 mg/ml).
Test polymerization
A test polymerization was carried out in a 3-liter Biichi autoclave in isobutane at 71'C. The ethylene partial pressure was 5 bar and the total pressure was 15.5 bar. Into the reactor, 1.0 ml of the previously prepared complex solution and 1.0 ml of 20 % HIBAO in hexane was added. The AVZr-ratio was 468. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into the reactor beforehand. The other half of the isobutane was used to wash the catalyst from the metal cylinder into the reactor when streaming throug the cylinder. The reaction time was 60 minutes. After that the ethylene feed valve was closed and the over pressure was released from the reactor. The yield of polymer was 118 g and the total catalyst activity was 1100 kgPE/ g*Zr*h.
Example 8
Preparation of the metallocene solution
As in example 7
Test polymerization
A test polymerization was carried out in a 3-liter Biichi autoclave in isobutane at 7rc. The ethylene partial pressure was 5 bar and the total pressure was 15.2 bar. Into the reactor, 1.0 ml of the previously prepared complex solution and 0.54 ml of 20 % HIBAO in hexane was added. The Al/Zr-ratio was 252. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into the reactor beforehand. The other half of isobutane was used to wash the catalyst from the metal cylinder into the reactor when streaming throug . the cylinder. The reaction tmie was 60 minutes. After that the ethylene feed valve was closed and the over pressure was released from the reactor. The yield of polymer was 88 g and the total catalyst activity was 704 kgPE/ g*Zr*h.

Example 9
Preparation of the complex solution
A complex solution was prepared in situ by adding 5 mg of rac-ethylene-bis(2-tert-butyldimethylsiIoxyindenyl)zirconiumdichloridc directly into 6.0 ml of a TIBAO solution. The final solution had a concentration of 1.2 loinol/ml (0.83 mg/ml) and the Al/Zr-ratio was 1000.
Test polymerization
A test polymerization was canied out in a 3-liter BUchi autoclave in n-pentane at TO^C. The ethylene partial pressure was 5 bar and the total pressure was 8,3 bar. Into the reactor, 1.0 ml of the previously prepared complex solution was fed. The total amount of metallocene compound was 1.2 |iraol (0,83 mg) and the Al/Zr-ratio was 1000. After 40 min, the polymerization reaction was stopped by closing the ethylene feed and releasing the ovcrpress'ure from the reactor. The yield of polymer was 22 g giving a total catalyst activity 296 kgPE/ g*Zr*h.
Example 10
Preparation of the complex solution
As in example 1
Test polymerization
A test polymerization was carried out in a 3-liter Biichi autoclave in n-pentane at TO'C. The ethylene partial pressure was 5 bar and the total pressure was 9.2 bar. Into the reactor, 1 ml of the previously prepared complex solution was fed together with 1 ml of TIBAO. The total amount of metallocene compound was 2.54 pjnol (1.74 mg/ml) and the Al/Zr-ratio was 500, After 60 min, the polymerization was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 25 g giving a total catalyst activity 110 kgPE/ g*Zr*h,

Example 11
Preparation of the complex solution
A complex solution was prepared in situ by adding 20 mg of rac-ethylene-bis(2-tert-butyIdimethyIsiIoxyindenyl)zirconiumdichloride directly into 12.0 mJ of a TIBAO solution. The final solution had a concentration of 2.54 ^imol/mJ (1.74 mg/ml) and the AJ/Zr-ratio was 500.
Test polymerization
A test polymerization was carried out in a 3-liter Btichi autoclave in n-pentane at 70'C. The ethylene partial pressure was 5 bar and the total pressure was 8.1 bar. Into the reactor, 1.0 ml of the previously prepared complex solution was fed. The total amount of raetallocene compound was 2.4 jomol (1.67 rag) and the Al/Zr-ratio was 500. After 30 min, the polymerization was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 12 g giving a total catalyst activity 107 kgPE/ g*Zr*h.
Example 12
Preparation of the complex solution
A complex solution was prepared in situ by adding 10 mg of rac-ethylene-bis(2-tcrt-butyldimethylsiloxyindenyOzirconiumdichloride directly into 3.0 ml of a TIBAO solution. The final solution had a concentration of 4.8 fimol/ml (3.3 mg/ml) and die Al/Zr-ratio was 250.
Test polymerization
A test polymerization was carried out in a 3-liter BQchi autoclave in n-pentane at 70'C. The ethylene partial pressure was 5 bar and the total pressure was 8 bar. Into the reactor, 0.5 ml of the previously prepared complex solution was fed. The total amount of metallocene compound was 2.4 }imol (1.67 mg) and the Al/Zr-ratio was 250. After 60 rain, the polymerization was stopped by closing the ethylene feed and rdleuing the overpressure from the rractor, Thr yiftld nf polymer was 8 g giving a total catalyst activity 36 kgPE/ g*Zr*h.

Example 13
Preparation of the metallocene solution
As in example 7
Test polymerization

m
A test polymerization was carried out in a 3-liter Biichi autoclave in isobutane at lyC The ethylene partial pressure was 5 bar and the total pressure was 15.2 bar. to the reactor, 1.0 ml of the previously prepared complex solution and 1.23 ml of 30 % TIBAO in cyclohexane was added. The Al/Zr-ratio was 892. A metal cylinder was tightened to &e reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into the reactor beforehand. The other half of the isobutane was * used to wash the catalyst from the metal cylinder into the reactor when streaming through the^ylinder. The reaction time was 30 minutes. After that the ethylene feed valve was closed and the over pressure was released from the reactor. The yield of polymdr was 60 g and the total catalyst activity was 560 kgPE/ g*Zr*h,
Example 14
Preparation of the metallocene solution
As in example 7
Test polymerization
A test polymerization was carried out in a 3-litcr BUchi autoclave in isobutane at 71'C. The ethylene partial pressure was 5 bar and the total pressure was 15,2 bar. Into the reactor, 1.0 ml of the previously prepared complex solution and 0.65 ml of 30 % of TIBAO in cyclohexane was added. The Al/Zr-ratio was 500. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into the reactor beforehand. The other half of the isobutane was used to wash the catalyst from the metal cylinder into the reactor when streaming throug the cylinder. The reaction time was 30 minutes. After that the ethylene feed valve was closed and the over pressure was released from the reactor. The yield of polymer was 26 g and the total catalyst activity was 260 kgPE/ g*Zr*h.

Example 15
Preparation of the metallocene solution
A solution of metallocene was prepared by adding 16 mg of rac-ethylene-bisCZ-teit-bulylJiuittliylgiloxyindenyOzirconiiimdichlorid? into 10 ml of moisture and oxygen free toluene. The final solution had a concentration of 2.47 pmol/ml (1.6 mg/ml).
Test polymerization
A test polymerization was carried out in a 3-liter Blichi autoclave in isobutane at 7rC. The ethylene partial pressure was 5 bar and the total pressure was 15.4 bar. Into a metal cylinder, 1.0 ml of the previously prepared complex solution and l.O ml of 20 % HIBAO in hexane was fed. The Al/Zr-ratiu was 500. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters. Half of the isobutane was fed into die reactor beforehand. The other half of the isobutane was used tn wn. Example 16
Preparatluu uf the complex fioiution
As in example I Test polymerlz:atlon
A test polymerization was earned out in a 3-litcr Btichi autoclave in n-pentane at 70°C, The ethylene partial pressure was 5 bar and the total pressure was 8.7 bar. Into the reactor, 1.0 ml of the previously prepared complex solution was fed together with 1.2 ml of EAO (EAO = ethylaluminoxane). The total amount of metallocene compound was 2.54 ^mol (1.74 mg) and the Al/Zr-ratio was 1000. The reaction time was 60 minutes. After 60 min, the polymerization was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 40 g giving a total catalyst activity 174 kgPE/ g*2r*h.

Example 17
Preparation of the complex solution
r
As in example 1
Test polymerization
A test polymerization was carried out in a 3-liter Biichi autoclave in n-pentane at TO^C. The ethylene partial pressure was 5 bar and the total pressure was 9 bar. Into the reactor, 1.0 ml of the previously prepared complex solution was fed together with 0.6 ml of EAO. The total amount of metallocene compound was 2.54 |imol (1.74 mg) and the Al/Zr-ratio was 500. After 60 rain, the polymerization was stopped by closing the ethylene feed and releasing the overpressure from the reactor. The yield of polymer was 35 g giving a total catalyst activity 153 kgPE' g*Zr*h.
Example 18
Preparation of the metallocene solution
A solution of the metallocene was prepared by adding 17 mg of raC'Cthylene-bis(3-tert-butyldiraetbyIsiloxyindcnyl)zirconiumdichloride into 10 ml of moisture and oxygen free toluene. The final solution had a concentration of 2,5 jjmol/ml (1.7 mg/ral).
Test polymerization
A test polymerization was carried out in a 3-liter Btichi autoclave in isobutanc at 71'C. The ethylene partial pressure was 5 bar and the total pressure was 15.5 bar. Into a metal cylinder, 1.0 ml of the previously prepared complex solution and l.O ml of 20 % HIBAO in hexane was fed. The Al/Zr-ratio was 500. A metal cylinder was tightened to the reactor. The volume of isobutanc was 1.8 liters. Half of the isobutanc was fed into the reactor beforehand. The odier half of the isobutane was used to wash the catalyst from the metal cylinder into the reactor when passing the cylinder. The reaction time was 60 minutes. After that the ethylene feed valve was closed and the overpressure was released from the reactor. The yield of polymer was 126 g and the total catalyst activity was 552 kgPE/ g*2r*h.

Example 19
Preparation of the metallocene solution
As in example 18
Test polymerization
A test polymerization was carried out in a 3-liter Btichi autoclave in isobutane at 71*0. The ethylene partial pressure was 5 bar and the total pressure was 15.8 bar. Into a metal cylinder, 1.0 ml of the previously prepared complex solution and 0.5 ml of 20 % HIBAO in hexane was fed. The Al/Zr-ratio was 250. A metal cylinder was tightened to the reactor. The volume of isobutane was 1.8 liters, Half of the isobutane was fed into the reactor beforehand. The other half of the isobutane was used to wash the catalyst from the metal cylinder into the reactor when passing the cylinder. The reaction time was 60 minutes. After that the ethylene feed valve was closed and the overpressure was released from the reactor. The yield of polymer was 90 g and the total catalyst activity was 395 kgPE/ g*Zr*h.

'Table1
Cqnditions in homopolymerization are Pc2 = 5 bar, temperature 70'C in pentane. compound 1 - rac-ethylcne-bis(2-tert-butyIdimethy]siloxyindenyl}zlrconiumdichlO' ride, compound 2 = rac-ethylene.bis(2-tert-butyIdimethylsiioxyindcnyi)zircomum. dimethyl compound 3 » raC'ethyIene-bis(2-tert-butyIdimethyIsiIoxytetrahydroinde» nyl)zirconiumdichloride, compound 4 = rac-ethylene-bis(3-tert-butyIdiinethy]siloxy-indenyI)zirconiumdichloride, REF. Compound 1 = ethyIene-bis(indenyl)zircomuni-dichloride, REF. Compound 2 * n-butylcyclopentadienyl zirconiumdichloride MAO = 30 w-% methylalumoxane in toluene, HIBAO = heksaisobutylalumoxane, TIBAO = tetraisobutylalumoxane, EAO - ethylalumoxane, MMAO = modified metylalumoxane oontaimng 10 Vo isobutyl groups.




•ac-ethylene-bis(2-tert-butylmethylsiloxyindenyl)zirconiundichloride (compound 1)


rac-ethylene-bis(2-tert-butylipcthylsiloxyindcnyI}zirconiumdichloride (compound 4)

REF. compound 1 = ethylene-bis(mdenyl)zirconiumdichIoride

REF. compound 2 = n-butyloyclopentadienylzirconiumdichloride


I
Some conclusions from the examples of this application
I, General behaviour of rac-ethyIene-bis(2-tert-butyldimethylsHoxylndenyl)-zirconiumdlchlorlde/MAO complex
Comparative examples 1, 2, 3 illustrate the genereal behaviour of siloxy substituted cyclopentadienyl compounds when activated by conventional methylaluminoxane with different Al/Zr-ratios.
2. General behaviour of ethylene-bis(lndenyI)zlrconlumdlchIoride/MAO
complex
Comparative examples 4, 5, 6 illustrate the general polymerization behaviour of non-siloxysubstituted cyclopentadienyl compounds when MAO is used with different Al/Zr-ratios.
3. Polymerization with sUgthly modified MAO
Comparative example 7 indicates that addition of isobutyl groups into MAO does not affect the activity of siloxy substituted compound. This experiment should be compared to comparative example 1,'where pure MAO was used. No significant change in catalyst performance can be seen.
4. Polymerization of siloxy substltuated compounds with hexalsobutylalumln-
oxane (= HIBAO)
Examples 1-6 illustrate the general behaviour of new non-MAO based coactivator system with siloxy substituted compounds. AJ/Zr-ratio will clearly affect onto catalyst activity. Example 7 reflects the use of metallocene compounds having methyls at the metal.
5. Effect of precontact of siloxy substituted metallocene and HIBAO
In example 2 metallocene and HIBAO were fed separately into reactor. In example 3, metallocene and HIBAO were mixed before going into the reactor. No clear difference can be seen in activity. Conclusion: metallocene and coactivator can be fed together or separately into the reactor.

6. Effect of concentration
Examples 5 and 6 indicate that concentration of metallocene compound can be varied quite much without affecting the catalyst activity.
7. Polymerization of siloxy substituted compounds with tetraisobutylalumin¬
oxane (= TIBAO)
Examples 9, 10, 11, 12 will discribe the use of tetraisobutylaluminoxane as a coactivator with siloxy substituted metallocene compounds.
8. Polymerization of siloxy substituted compounds with ethylaluminoxane
(* EAO)
Examples 16, 17 discribc the use of ethylaluminoxane as a coactivator with siloxy substituted metallocene compounds.
9. Comparison of siloxy substituted compounds and corresponding non
substituted compound with HIBAO as a coactivator,
Examples 1, 2, 3 and 5 can be compared directly with comparative examples 8, 9,
10. According to these examples it is evident that siloxy substitution gives huge
enhancement in catalyst activity with HIBAO. The activity increase is more than 10
fold.
10. Comparison of methylated siloxy substituted compounds and corresponding non methylated compound with HIBAO and TIBAO as a coactivator.
Example 5 and 8 present the affect of methylation of the siloxy substituted compound. The activity increase is 4 times when HIBAO is used as a coactivator. In examples 9 and 13 coactivator is TIBAO and activity is 2 times higher with methylene substituted compound. By methylation is meant that in stead of chlorines, methyls are attached to the metal of the metallocene.

11. Position ofslloxy substituent
Examples 5 and 18 describe the affect of position of substituent. By changing the place of substituent from the 2 position to the 3 position the activity increased 2,5 times.


We Claims:
1. A process for preparation of iww homogenous oletln polyniMizition caUiyst compontioi^ wherein iTy contacting a metallocene pn>-cataIyBt containing a liAg-substituted homo- or heterocyclic cyclopentadien:^ saodwich iigand with an duminoxane containing aik^ groups coHaining at least two caibon atoms, and if desired recovering the reaction product of said metafiocene and aiumiaoxan^
a) the said metallocene comprising of (he general formula (1):
(CpYq^MXaZa (1)
wherein Cp or rach same or different Cp is one of a mono- or polysii>£titutedL fkised or non-fbsed, homo- (» iso-) or heterocyclic cycrlopentadien^ Iigand, indcoyl ligud, tetrab^droinden^ ligan^ fluotenyl Ugmd, or octabjrdtofluoreiiyl figand, Y or each same or differei^ Y is a sobetituent at the cyclopentadiraylrii^ of said C^ figand and is one of an -0R» -SR» -NR3,-0(H or R)«. or-FR% radical, R or each same or diffaent R. being one of a substituted or unsubstituted Ci-Ci« faydrocarb^ group, a tri Ci-Q faydrocaiirylsflyl grotq;). a tii CfCs hythrocaibyloxy si^ groiq), a mixed Ci-Cg bydrocarb^ and Q-Cs faydrooob^oxy geimyt group or a nuxied Ci -Cs tiydrocatt)^ and d -Cs l^drocarty^oxy getmyt gfOi|>; M is a transition metal of groiq> 4 (^ the periodic table (lUPAC) and bound to die Ugand or Hgands Cp is atieast an tf bonding modec X or each same or different Xis bound to M and s one of a faycbogen, a hdogen, a substituted and loisubstituted CfQ hycbocaibyl group, a Ci-Q hydrocaibylheteroatom (0,S.N,I>} or a tri- Cj-Cs hydrocaibyl silyl group or two X from together wtdi M a Ci-CsometaSocyclic ring structure Z is a bridge atom «r groip between two Cjp ligands or between one Cp Ugand and the transition metal m q is, when Qp is unbriciged, 0-5 for Cp - cydcpentacfienly. 0-3 £>r C!p'«indenyl or tetrafaychoindeoyl and 0-1 tat Cp == fluarei^rl or octabydrofluorenyl, or q is, when Q> is biidged, 0-A fx Cp " cyciopeotadieayl, 0*2 fro Q> = indenyl or tetrafayckdndeayl and 0 fi>r Q> =" fluorenyl or octafaydrofluoreoyi; m is 1 or 2; m.q >l;oi80orl,andnis 4-m-o esEcept vdien there is a bridge Zbetween two Q) ligands, in which case n is 4-m. and
b) the said aluminoxane of one of the following fomnilas (2):


Wbemu each R' is the same or c) An organic solvent vfhlch dissolves said metallocene and said ahiniinoxane or a reaction product of tiieni»
and recovering said homogenous olefin polymerization catalyst conq>oratioa
2. Tlieprocess accordiog to claims 1, wherein Y in &ruiula (1) is a-ORradic^


4. The process according to claim 3, wherein R is a tri- CrQ hydrocattryl sil^l group
enable of Ji interaction with sud O, S, N, or P atoms of Y, preferably a tri- Q -C^ aO^l sfiyl
group, wherein at least one of fte Q- alkyls is a branched Cs-Cs aikyl such as isopropyl
isobutyi sec-butyt, teit-butyi, isoaniyl, sec-amyi, or tert-amyl.
5. Hie process according to any of claims 1-4, wherein In said metaflocene if the general
foraiula (1), m is 2, zad, prefersbly, the two Cp hgrndo are brit^ed with each bivalent atom or group Z having at least one chain atom which is one of a caibon, silicon,
oxygen, sulphur, nitrogen or phoEphorus atom, most preferably wherein m is 2 and Z is
ethylene or silylene.
6. Tlie procesas according to any of claims 1-5, wherein said metafloceue of die general
formula (1),M is Zr.
7. Itie process according to any of claims 1 -6, whereui said metaBocene of die general
formula (1), X is a halogen atom and/or a Cj'Cs hydrocaibyl group, pre&rably cUorine
and/'or methyl, mostpre&rably mediyL
8. The process according to any of claims 1-7, ^o-dn by contacth^g said metaBocoie
a)of ttie general formula (I) wldch has die following sbuctural formula (S)


wherein each of the Yi's and Y3 's is the same or di£[erent and is one of a kj^drogen atoia a halogen atom, an acyl group, dcyloxy ffoap, a substituted or unsubstituted Ci-Qo hydrocarbyl group, an - OR, -SR, -NR2, -C(H or R) =, or -PRz. radical, R beii« one of a Ci-Ciyloxy ffovp, M is one of Ti. Zr, or Hf; and Xi and Xi W9 the same or different and is one of a hydrogen atom and a Ct-C 9. The process according to any of claims 1-8,. wherein said metaQoceoe of die formula (1) or 0) is ethylene (Z'tert-butyldunedysiloxy-indenyl) zirconium dichloride^ ethylene-bis(2-tert-tratyIdunetlys3oxy-indenyl)- zirconmm dmelhyl, or a tetrdiydroanalogue ffaereoi; preferaUy etfayieo0>bts(Z-ter(4>utyldimfitlysiloxyindea^)- zirooaium dimetliyl, at a tetra!iy 10. The process according to aoy of claims 1-9, wheron said metaHocene of &e fimnuU
(1) or (3) is disaobed in a chlorinated or un chlorinated CU-Cto faydrocaibon solvent such as
hexane or toluene
11. Ite process accordmg to ai^ of claims I-IO, wherein the formulas (2), said R' is a
C3-C10 aikyl group, preferably an isopropyl an isobutyl, sec-butyl, tert-butyl, isoaniyl, or tert-
am;^ group, ani independently, 2 12. The process acconfing to any of daim 11, wherein the aluminoxane of the formulas
(2) is hexa (isobutylaluminoxane)or tetra (isobutylahuninoxane), preferably hexa
(isobutylaluminoxane).
13. The process according to any of claims 1-12, wherein tfie aluminoxane of the
formulas (2) is dissolved or immersed in a chlorinated or uncUorinated C4-C10 faydrocaibon
solvent such as hexane or toluoieL

14. The process according to any of claims 1-13, vrherdn the molar rMioAl/M between
the aiuminoxane aluminium and the metalloceae transition metal is between 20 to 2000»
preferably between 530 and 1500, most preferably between 100 and 1200.
15. Ihe process according to any of clams 1-14. wherein the coiKenbration of tiiie catalyst
composition is regulated to between 0.01 and 100 mmol/l preferabfy between 0.1 and 50
mmol/l, more preferABly between 0.5 and 10 mmoi/I, most preferablybetween 1 and 5
mmol/l.
16. A method of olefin polymerization con^rising contactii^ an oleOn with a
metaHocene alunmioxne catalyst composition, wherein the said composition is frqmed by •
process as defined in any one of claim 1 -15.


Documents:

165-mas-1998 abstract duplicate.pdf

165-mas-1998 abstract.pdf

165-mas-1998 claims duplicate.pdf

165-mas-1998 claims.pdf

165-mas-1998 correspondence-others.pdf

165-mas-1998 correspondence-po.pdf

165-mas-1998 description (complete) duplicate.pdf

165-mas-1998 description (complete).pdf

165-mas-1998 form-19.pdf

165-mas-1998 form-2.pdf

165-mas-1998 form-26.pdf

165-mas-1998 form-4.pdf

165-mas-1998 form-5.pdf

165-mas-1998 form-62.pdf

165-mas-1998 petition.pdf


Patent Number 198246
Indian Patent Application Number 165/MAS/1998
PG Journal Number 08/2007
Publication Date 23-Feb-2007
Grant Date 20-Jan-2006
Date of Filing 27-Jan-1998
Name of Patentee BOREALIS A/S
Applicant Address LYNGBY HOVEDGADE 96, DK-2800 LYNGBY,
Inventors:
# Inventor's Name Inventor's Address
1 BOREALIS A/S LYNGBY HOVEDGADE 96, DK-2800 LYNGBY,
PCT International Classification Number C08F004/58
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 970349 1997-01-28 Finland