CA2072490A1

CA2072490A1 - Catalyst and process for the preparation of high-molecular-weight polyolefins

Info

Publication number: CA2072490A1
Application number: CA002072490A
Authority: CA
Inventors: Walter Kaminsky; Florian Renner
Original assignee: Individual
Current assignee: Hoechst AG
Priority date: 1991-06-28
Filing date: 1992-06-26
Publication date: 1992-12-29
Also published as: GR3031728T3; DE4121368A1; EP0523416A2; ES2138961T3; EP0523416A3; DE59209759D1; ATE185819T1; EP0523416B1; ZA924751B; AU1857692A; AU653029B2; JPH05331230A

Abstract

Abstract of the disclosure:

Catalyst and process for the preparation of high-molecular-weight polyolefins High-molecular-weight polyolefins, in particular those of propylene, which have high tacticity are obtained by polymerization of copolymerization of .alpha.-olefins using a catalyst system comprising an aluminoxane and a supported catalyst component, the latter being prepared from an inorganic support material, preferably SiO2, and a metallocene.

Description

HOECHST AKTIENGESELLSCH~FT HOE 91/F 199 ~ ~.2~ e Description Catalyst and process for the preparation of high-molecular-weight polyolefins :
The pre~ent in~ention reiates primarily to a ~upported cataly~t component which, together with an aluminoxane a~
cocatalyst, is suitable for the preparation of high-molecular-weight polyolefins.

High-molecular-weight polyolefins (such as, for example~
- polypropylene having an M~ of > 500,000) are particularly suita~le for the production of films, sheets or large-cavity articles, such as, for example, tubes or moldings for automobile manufacture.

It i5 known that metallocene ca~alysts are able to polymerize olefins to give polyolefins having a narrow molecular weight distribution (M~/M~ = 2-3) and hiyh stereoregulatory (isotactic and syndiotactic polymers) (EP~A 185,918). Compared with polymers prepared using classical Ziegler catalysts, however, thPy have the disadvantage, with the exception of polyethylene, of a lowered m~ltiny point and an excessively low molecular weight (Angew. Chem. Int. Ed. Engl., 29 (1990) 279; Chem.
I.ett. (1989) 1853).

EP-A 232 595 describes a supported catalys-t component which is obtained by reacting a (inorganic) support material with at least one metallocene and at least one transition-metal compound containing no cyclopentadienyl radical. This catalyst component is employed exclusively for the polymerization or copolymerization of athylene.
It is said to give polyethylene having improved bulk density and at the same time ensure that the amount o~
aluminoxane as cocatalyst is reduced compared with conventional metallocene catalyst components.

f~

- 2 ~
The object of the present invention was thus to find a catalyst sys~em or a polymerization process which make~
it possible to prepare, in particular, pol~propylene or copolymers of propylene of high molecular weight and high melting point, the products additionally h ving high ~; ~tereor~gularity and a narrow molecular weight distribution.

The invention relates to a supported catalyst component obtainable from an inorganic support material and a metallocene.

Suitable inorganic ~upport materials are oxides of the metals of main groups II-IV or sub-group IV of the ; Periodic Table of the Elements and iron oxides, or mixtures thereof. Preference is given to the oxide~ of the metals magnesium, calcium, aluminum, silicon, titanium and iron, and mixtures thereof. Particular preference is given to commercially available silicon - dioxides, especially I~Silica Davison Grade 952".

The oxides to be used according to the invention prefer-ably have a BET surface area (cf. J. Am. Chem. 6OC. 60(1938) 309) of 10-1000 m2/g, preferably 100-500 m2/g, a water content of 10-8-6~ by weight, preferably less than 0.1% by weight, and a particle size of bstween 10 and 200 ~m.

Thermal pretreatment of the inorganic support in a stream of inert gas ox in vacuo at temperatures of 30-1000C for 1-50 hours is advantageous.

This thermal pretreatment is preferably carried out in a fluidized bed under a nitrogen atmosphere at temperatures of 200-800 DC for a tLme matched to thP amount of material, but for at least 2 hours.

It is furthermore expedient, when the pretreatment is complete, to separate the ab~orbed ga3e~ from the support material in a subsequent ~tep by pumping in vacuo at ~ temperatures above 80C (time requirement about `: 5 10 hours).

The metallocene6 to be used according to the invention are preferably ~hose of the formula I

/ ~ / R' Rs M \ (I) \, R2 \ R4 in which Ml is titanium, zirconium, vanadium, niobium or tan-talum, R1 and R2 are identical or diffierent and ars a hydrogen atom, a halogen atom, a Cl-C10-alkyl group, a Cl-C10-i. alkoxy group, a C6-C1O-aryl group~ a C6-C10-aryloxy : 15 group, a C2 C10-alkenyl group, a C,-C40~arylalkyl group, a C7-CI,0-alkylaryl group or a C8~C40~arylalkenyl group, 3 and R4 are identical or diffe:rent and are a mono-: cyclic or polycyclic hydrocarbon radical which can ~o~n a ~andwich s~ructure with the centxal atom M1, R5 is . R6 R6 16 R6 R6 R6 R6 R6 `i - M2-, - M2 _ M2 , - M2-CR82-, - C-, - O - M~ g--RC-, 4 ~ sf~ ~
=AlR6 r ~0~1 =NR5, =CO~ =pR6 or =P(o)R6, whare R6~ R7 and RB are identical or different and are a hydrogen atom, a halogen atom, a Cl C10-alkyl group, a C1-C10-fluoroalkyl group, a C6 C10-fluoroaryl group, a C6-Cl0-aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40 arylalkyl group, a C8-C40-arylalkenyl group or a C7-C4n-alkylaryl gxoup, or R6 and R7 or R6 and RB, in each case toge~her with ~he atoms connecting them, form a ring, and :~ 10 M2 is silicon, germanium or tin.

In the formula I, M1 is a metal from the sroup consi~ting of titanium, zirconium, vanadium, niobium and tantalum, preferably zirconium.

Rl and R2 are identical or different and are a hydrogen atom, a Cl-C10-, preferably Cl-C3 alkyl group, a Cl-C10 , preferably C1-C3-alkoxy group, a C6-C10-, preferably C~-C8-aryl group, a C6-C10, preferably C6-Ca-aryloxy ~roup, a C2-C10-, preferably C2-C4-alkenyl group, a C7 C40-~ prefer-ably C7-C10-arylalkyl group, a C7-C40-, prefarably C7-C12~
alkylaryl group, a CB_C~O-~ preferably C3-Cl2-arylalkenyl group, or a halo~en atsm, prefexably chlorine.

R5 i~ a ~ingle-membered or multimembered bridge which link~ the radical~ R3 and R4 and i~

R6 Rs ~6 F~ 6 5~6 R6 R6 M2 _M2 _M2 - M2-CR82, -C- - O - M2 ~ _C-, ~' R7 R7 R7 R' ~' R7 R7 =AlR6, -O-, -NR6, =CO, =pR6 or =P(o)R6, where R6, R7 and R3 are identical or different and are a hydrogen atom, a halogen atom, pre~erably chlorine, a C1-C10-, preferably a C1-C3-alkyl group, in particular a methyl group, a _ 5 _ 2 ~ 7 ~
C1-C10-fluoroalkyl group, preferably a CF3 group/ a C6 C10-fluoroaryl group, pref~rably a p~ntafluorophenyl group, a C~-C10-, preferably C6-Ca-aryl group, a Cl~C10-, pr~fera~ly C1-C4-alkoxy groupO in particular a metho~y group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-, preferably C7-C10-arylalkyl group, ~ C~-C40-, preferably C8-C12-arylalkenyl group or a C~-C40-, preferably C7-Cl2-alkylaryl group, or R6 and R7 or R~ and R8, in each case together with the atoms connecting them, form a ring.

M2 is ~ilicon, germanium sr tin~ preferably silicon or gPrmanium.

R5 is preferably =CR6R7, =SiR6R7, _o_, =pR6 or =p(o)R6 To prepare syndiotactic polyolefins, metallocenes I are employed in which R3 and R4 are different. In this case, ; 15 R3 and R4 are preferably fluorenyl or cyclopentadienyl, it ;being possible for these parent structures to contain additional substituents as defined for R1. These ~ubsti-tuents, together with the atoms connecting them, may form additional - substituted - rings.

Isotactic polymers are prepared using metallocenes I in which R3 and R'' are identical or difexent. R3 and R4 ar0 then preferably indenyl, tekrahydroindenyl, cyclopent~-dienyl or fluorenyll it being po6sible for the~e parent structures to carry addikional 6ubstituents as defined for R1. The~e substituents, together the atoms connecting them, may form additional - substituted - rings.

Preferred metallocenes for the preparation of syndio~
tactic polymers are (arylalkylidene)-~9-fluorenyl)~cyclo-pentadienyl)zirconium dichloride, (diarylmethylene)-(9-fluorenyl)(cyclopentadienyl)zirconium dichloride and (dialkylmethylene)(9-fluorenyl)(cyclopentadienyl)-zirconium dichloride.
., 6 ~ J ~
Particular preference is given to (methyl(phenyl)-me~hylene)-(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, (diphenylmethylene)(9-fluorenyl)tcyclo-pentadienyl~zirconium dichloride and (dimethylmethylene)-(9-fluorenyl)(cyclopentadienyl)zixconium dichloride.

Preferred metallocenes for the preparation of isotactic polyolefins are t rac-dimethylsilyl-~is-(1-indenyl)zirconium dichloride, rac-diphenylsilyl-bis-(1-indenyl)~irconium dichloride, rac dimethylsilyl-bis-~tetrahydro-l-indenyl)zirconium : dichloride, rac-diphenylsilyl-bis-(tetrahydro-1-indenyl)zirconium dichloride, rac-ethylene-bis-(tetrahydro-1-inden~l)zirconium dichloride, rac-ethylene-bi~-(1-indenyl)zirconium dichloride, rac~dimethylsilyl-bis-(2 methyl-4,6~diisopropylindenyl)~
zirconium dichloride, rac-dimethylsilyl-bis-(2,4,6-trimethylindenyl)zirconium dichloride and rac-dimethylsilyl-bis-(2-methyl-4,5-benzoindenyl)-zirconium dichloride.

Unbridged metallocenes, such as, for example (cyclo-pentadianyl)2ZrCl2, can also be converted to a ~upported catalyst component by the process according to the invention/ this component being particularly suitable fo.r the preparation of high-molecular-weight akactic poly-olefins or high-molecular-weight polyethylene.

Said metallocenes I are known and process~s f~r ~heir preparation are described in the literature (cf.
J. Organomet. Chem. 288 (1985) 63 67/ EP-A 320 7S2, EP-A 336 127, EP-A 387 690 and EP-A 302 424).

The reaction of the metallocene of the formula (I3 with the pretreated inorganic support ma~rial is carried out ~ ~ Y~ 2 ~

by vigorous stirring under inert gas in a solvent/ which may be aromatic, aliphatic or additionally haloyena~ed, by adding the metallocene to the pretreated support material in the form of a solid or æuspension or metering the latter into a solution of the metallocene to be supportedr in both cases at temperatures of -30C to 120C. Examples of sui~able solven~s are toluene, dichloromethane and hexane, in which the metallocene is reacted in a ratio of from lx10-5 to 5x10-2 mol, preferably from 1 x 10-5 to 1 x 10-3 mol, of M1/g of support. The metallocene concentration in the solvent i~ between 0.1 and Io-6 mol/l, preferably hetween 0.01 and 10-5 mol/l, it also being possible for some of the organometallic compound to be in undissolved form as a suspension.

The reaction duration is between 15 minutes and 48 hours, preferably between 1 hour and 20 hours.

This process is distinguished by a high degree of Lmmobi-lization of the metallocene on the support used.

It is advantageous, in order to remove small, adhering : 20 residual amounts o~ non-immobilized me~allocene, to wash khe catalyst component prepared in this way with a suitable solvent, such as, for example, anhydrous and oxygen-free toluene, under inert conditions, it being possible to uRe an extractor (for example a Soxhlet extractox) in order to a~oid larye amounts of solvents.

The cocatalyst used in the process according ~o the invention for the prepara~ion of high~molecular-weigh~
polyolefins is an aluminoxane of the formula II

~' \AI O - Al - O n \R9 (II) for the linear type and/or of the formula III
"~
_ _ :: Al- O - _ ~III) : n+2 , for the cyclic type, where, in the formulae II and III, the radicals R9 may be identical or different and are a C1-C6-alkyl group, a Cl-C6-fluoroalkyl group, a C6-C18-aryl group, a C6-Cl6-fluoroaryl group or hydrogen, and n is an : integer from 2 to 50. n is preferably an integer ~rom 10 ~ to 35.
.~
The radicals R9 are preferably identical and arP methyl, : isobutyl, phenyl or benzyl, particularly preferably methyl O

: I-f the radical~ R~ are di~ferent, they are preferably methyl and hydrogen or alternatively methyl and isobutyl./
it beiny prefexred for hydrogen or isobutyl to be present t~ the ex~ent o 0.01-40% (number of radical~ R~) .

It i~ al~o possible to replace the aluminoxane by a mixture comprising ~luminoxane and AlR93. The aluminoxane ~ can be prepared by various methods by known processes.
; 20 One of the mPthods is, for example J to react an aluminum hydrocarbon compound and/or a ~ydridoaluminum hydrocarbon compound with water (in ga~, æolid, liquid or bonded form - for example as w~tex of crystallization) in an inert solvent (such as, for example, toluen~). To prepare an .' .

, ., ~

9 ?~ J ~
aluminoxane containing different alkyl groups Rg, two different trialkylaluminum compound (AlR3 ~ AlR'3), corresponding to the desired composition, are reacked with water (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424~.

The precise structure of the aluminoxanes II and III is unknown.

Irrespective of the preparation method, all aluminoxane solutions have in common a varying content of unreacted aluminum starting compound, which is present in free form or as an adduct.

It is possihle to preactivate the supported catalyst component with an aluminoxane of the formula (II) and/or (III) before use in the polymeri~ation reaction. This significantly increases the polymerization activity and improves the particle morphology. In thi~ case, the supported catalyst is praferably added as a solid to a ~olution of an aluminoxane in an inert hydrocarbon.
Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Preference is given to toluene or a C6-C~O--hydrocarbon.

The conc~ntration of the aluminoxane in the solution i5 in the range ~rom abouk 1% by weight to the saturation limit, preferably from 5 to 30% by weight, in aach ca~e based on the total solution. The metallocenes can be employed in the same concentration (values to be under stood without support), but ~re preferably employed in an amount of from 10-4 to 1 mol per mol of aluminoxane. ~ha preactivation time is from 5 minutes to 60 hours, prefer-ably from 5 to 60 minutes. The reaction temperature isfrom -78C to 100C, preierably from 0 to 70C.

A further possible embod.iment of the process according to the invention comprises using a salt-like compound of the ~, - 10 ~ r~ ~ ~; r formula RXNH,,xBR'4 or of the formula R3PHBR'b as cocatalyst in place of or in addition to an aluminoxane. In these formulae, x = 1, 2 or 3, R = alkyl or aryl, identical or different, and R' = aryl, which may also be fluorinated or partially fluorinated. In this case, the catalyst comprises ~he product of the reaction of the supported metallocene with one of said compounds (cf.
,; EP-A 277 004).

The present inYention thus also relates to a process for the preparation of high-molecular-weight polyolefins by : polymerization or copolymerization of an olefin of the :formula R~CH=CHRb, in which Ra and Rb are identical or : different and are a hydrogen atom or an alkyl radical having 1 to 14 carbon atoms, or Ra and Rb, together with :15 the atoms connecting them, can form a ring, at a tempera-ture of from -60 to 200C, at a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst comprising a tr~n~ition-metal component (metallocene) and an aluminoxane, wherein the transition-metal component is the above-described supported metallocene I.

The polymerization or copol~merization is carried out in a known manner in ~olution, in suspension or in the ga~
phase, continuously or batchwise, in one or more ~tap~, ak a temperature of ~rom -60 to 200C, preferably from 20 to 80C. Olefin~ o~ the ~ormula Ra~CH-CH-Rb are poly-: merize~ or copolymerized. In this formula, R~ and Rb are identical or different and are a hydrogen atom or an alkyl radical having from 1 to 14 carbon atoms. However/
30 Ra and Rbl to~ether with the carbon atoms connecting them, may also form a ringc ~xamples of ~uch oleiins are ethylene, propylene, 1-butene, l-h~ene, 4-methyl-pentene, l-octene, norbornene and norbornadiene. In ;. particular, propylene and ethylene are polymerized.

As molecular weight regulator, hydrogen is added if necessary. The overall pre~sure in the pol~m~rization system is from 0.5 to 100 bar. The polymerization i~
preferably carried out in the industrially particularly interesting pressure range of from 5 to 64 bar.

The metallocenes are used in a concentration, based on the transition metal, of from 10-3 to 10-8, preferably from 10-4 to 10-7, mol of transition metal per dm3 of solvent or per dm3 of reactor volume. The aluminoxane or the aluminoxane/AlR93 mixture is used in a concentration of from 10-5 to 10~1 mol, preferably from 10-4 to 10-2 mol, per dm3 of solvent or per dm3 of reactor volume. In principle, however, high~r concentrations are also possi~le.
;

The process according to the invention for supporting the me~allocenes enables, irrespective of the type, surface area and pretreatment of the support, an incorporation rate of from lx10-6 to lx10-2 mol of M1/g of support, preferably from lx10-5 to lx10-3 mol of M1/g of support.

If polymerization is carried out as a suspension or solution of polymerization, an inert solvent which is - customary for the Ziegler low-pressure process is used.
For example, the polymerization is carried out in an aliphatic or cycloaliphatic h~drocarbGn; examplo~ of these which may mentioned are butane/ penkane, hexane, heptane, decane, isooctane, cyclohexane and methylcyclo-hexane.

It is furthermore possible to use a gasolina or hydro-genated diesel oil fraction. Toluene can also be used.
The polymerization is preferably carried in the liquid monomer.

- If inert solvent6 are used, the monomers are metered in gas or liquiù form.

;
:

- 12 ~ s~
The polymerization can be carried out for as long as desired, since the catalyst system to be used according -' to the invention only exhibits a slight time-dependent drop in polymerization activity.

The supported catalyst cvmponent according to the inven-tion is particularly suitable for the preparation of highly isotactic or highly syndiotactic polypropylene having a narrow molecular weight distribution, and of corresponding copolymers of propylene with ethylene or other C4-C16-~-olefins, i.t still being possible to achieve molecular weights of greater than loB g/mol in said cases, even at high polymerization temperatures.

~he polymerization process according to the invention thus enables for the first time, ~or example, general access to i60tactic or syndiotactic polypropylene having a molecular weight of greater than 500,000 g/mol and having a narrow molecular weight distribution. The material prepared in this way has a melting point of about 160C.

For a large range of various metallocen~s, the ca~aly~t system according to the invention thus generally solves the problem, known in particular for pol~propylene, o the excessively low melting point and enabl2s metal-; locenes which can be prepared in a simple manner to be u~ed ~or s~id purpose.

Example 1 Preparation of the supported catalystcomponents :
The support material used was Silica Davison ~rade 952.
The surface area of the material usedl according to BET
measurements, was 350 m2/g~ and the pore diameter was 15 nm (from the N2 desorption curve). The particle size was in the range from 50 to 100 ~m. Before USe/ the material was ignited at 500C for 3 hours and degassed in - 13 ~ 2 ~ ~9 ~
vacuo at 100C for 16 hours.

60 cm3 of a 10-3 molar ~olution of ethylene(indenyl)-zirconium dichloride in toluene were added to 2.7 g of Silica Davison Grade 952. ~he su~pension was stirred at 55C for 16 hours. Subse~uent Soxhlet extracted for 2 days was intended to ensure that the support was free from homogeneous components. Filtration with suction and ; drying in vacuo to constant weight yave a pale yellow solid.
,~
In order to determine the zirconium content, samples of 300 mg were weighed out, digested for one day at 220C in a mixture of 4 ml of ~03 ( 65% strength), 2 ml of HCl04 (70% strength) and 1 ml of HF (40% strength), andl when the acid had stopped fuming, the mixture was taken up in 10 ml of distilled H2O. ~he measurement was carried out on - a Perkin Elmer ICP-OES spectrometer. For Exa~ple 1, a - zirconium content of 1.9 x 10-~ mol of Zr/g of support was obtained. Further data are given in Table 1.
. , Examples 2-4 The supported cataly~ts of Examples ~-4 were prepared analogously to Example 1I khe reastioll condikions selected being 85C/16 hours (Example 2~, 25~C/~ hours (Example 3) and 55C/~ hours (Example 4). The work-up and characterization were carried out analo~ously to Example 1. The changes in amount of catalyst employQd and Zr content found compared with E~ample 1 are ~hown in Table 1.

Example 5 .
,! Ethylene(tetrahydroindenyl)zirconium dichloride was used as a further starting compound. In a modification of the examples above, the compound, which is more soluble in toluene, particularly at elevated temperatures, tha~ is ~' , - 14 _ ~ ~ r the unhydrated zirconocene, was added as a ~olid.

4.22 g of Silica Davison Grade 952 and 323 mg (0.75 mmol) of the metallocene were stirred at 70C for 2 hours in 50 ml of toluene. The sample con~ained 8.4 x 10-5 mol of Zr/g of support. Further data are shown in Table 1.

Example 6 The same stoichiometry as in Example 5 was selected, but the batch was increased in size.

14.4 g of Silica Davison Grade 952 were stirred at 70C
for 2 hours with 1.06 g (2.47 mmol) of said metallocene in 175 ml of toluene. The work-up and characterization were carried out analogously to Example 1. In excellent agreement with Example 5, the sample likewi~e contained 8.4 x 10-5 mol of Zr/g of support.

Example 7 315 mg of Silica Davison Grade 952 were stirred at 70C
for 16 hours with 227 mg (0.53 mmol) of ethylenebis~
(tetrahydroindenyl)zirconium dichloride in 10 ml of toluene. The work-up and characterization were carried out analogously to Example 1. The s~mple contained 4.5 x 10-4 mol of Zr/g of support.

- 15 ~ 2~
Table 1 ;

: ~ plA Employed Found ound mol of Zr/~ mol of Zr/g mg of Zr/g ~ of support o support of support L~ 2 . 2 X 10-5 1 . 9 X 10-5 1 . 8 2 2.3 x 10-5 2.1x 10-5 ~.~

; ~ 3 . 8 X 10-5 3 . 3 X 10-5 3 1 4 5.8 x 10-5 5.5 x 10-5 .~ . 1 ..
_ _ . ~
1.7 x 10-4 8.4 x 10-5 7.6 .~ 6 l 7 x lO~ ~ O~ 7.6 - 20 7 1.7 x 10 4.5 x 10 ~0.7 Polymerization examples Example 8 1 dm3 reactor which had been dried by heating in vacuo, had been flushed sever21 tLmes and was held at 50C by means of a thermostat, was filled in a counter stream of argon with 100 ml of toluene, 600 mg of aluminoxane and i 310 mg of the supported metallocene in Example 1. After a prereaction time of one hour with stirring, 2 bar of propene were injected. After a reaction time of 1~ hours~
th~ excess pxeqsure was released~ and the batch was quenched by means of ethanol. In order to remove catalyst residues, the mi~ture was stirred in ethanolic HCl for one day. After subsequent dxying the polypropylene was .

- 16 - G~
separated from the support by extraction with decalin at 140GC. After precipitation of the hot decalin solution in ethanol, filtration with suction and drying in vacuo at 70C, silica-free pol~propylene was obtained as a white material in a yield of 2.1 g.

The viscosity average molecular weight of the ~ample was det~rmined in decalin (135C) for a sample weight of 15 mg in 50 ml. For evaluation, the values K = 1 x 10 4 :.and ~ = 0.8 were used. A viscosity average molecular ;.10 weight M~ of g58 r ~00 was obtained. DSC mea~urement gave a melting point of 160.1C.

Examples 9-11 The polymerizations were carried out analo~ously to .Example 8. The catalyst amounts employed were 587 mg : 15 (Example 9), 460 mg (Example 10) and 340 mg (Example 11).
Further data and the characterization of the products are ~ shvwn in Table 2.

: Example 12 ; In a modification of the examples above, the hetero~
genized form of the hydrogenated zirconocene o~ Example 5 was employed hexe. The polymerization was carried out : analogously to Example 8 using 328 mg of supported catalyst components. Further data and the characteriza-~ion of the product are given in Table 2.

, Examples 13 and 14 ., .
The polymerizations were carried out analogously to Example 8 using 262 mg of th~ catalyst of Example 5 at 30C in Example 13 and using 323 mg at 70C in ;Example 14. Further data and the characterization of the ~30 products are given in Table 2.

Example lS

The polymerization was carried out analogou51y to Example 8. In order to be able ~o determine the acti~ity more preci~ely, 963 mg of the catalyst of Example 6 and 2.0 g of aluminoxane were employed. After polymerization for 2 hours at 50C and a propene pressure of 2 bar, 8.7 g of product were obtained after work-up. The acti-vity was 2~.2 kg of PP/mol of Z.r-h-bar.
. .
Example 16 In this example, ethene was employed as the monomer. The polymerization was carried out analogously to ~xample 8.
Using 205 mg of the catalyst component of Example 5, 1.7 g of product were obtained in 10 minutes at 50~C and an ethene pressure of 4 bar.

: Table 2 Example Cat. of T( ~C) 1) M~ m.p. (C) No, Example No. ~g/mol) of product __ I
.~ 8 1 50958,~00 160.1 ~ _ I
: 9 2 ~01,09~,000 158.4 ~,~ 10 . l 2 50 1,333,00D 158.4 ~ _ I
11 50 1,171,000 155.2 ~5 12 50 1,217,000 155.6 ~` 13 _ _ 30 1,145,000 153.6 . 14 5 . - -1,352,000 156.4 ~, 1) Polymerization temperature Ex~mple 17 ., i The polymerization was carried out u~ing 582 mg of ; aluminoxane and 986 mg o~ the catalyst co~lponent. o~
Example 6 at 50C, a propene pressure of 2 bar and a polymerization time of eight hours.

Yield: 2.0 g Activity: 773 g of PP/mol of Zr-h-bar Melti.ng point: 155.8C
30 Isotacticity: 90.2 Isotactic block length: 18.4 . M~: 911,000 g/mol - 19 ~ J
Example 18 . , The polymerization was carried out using 566 mg of aluminoxane and 246 mg of the catalyst component of Example 6 at 50C~ a propene pressure of 2 bar and a polymerization time of three hours, after prereaction of the cat~lyst component in 10 ml of toluene at room temperature for one hour.

Yield: 0.37 g Activity: 1000 g of PP/mol of Zr h bar 10 Melting point: 158.2C
Isotacticity: 96.5%
Isotactic block length: 49.5 ~t 921~000 g/mol The isotacticity was determined by means of l3C-NMR
spectroscopy.

Example 19 ;.
Preparation of the supported catalyst component 4.23 g of Silica Davison 952 and 300.6 mg of ethylenebi6-(indenyl)zirconium dichloride were stirred at 70~C for 16 hours in 50 ml of toluene. A slight red coloration of the support material wa observed after a few minutes.
When the reaction time was complete, the superna~ant solution had become virtually colorless. After exkxaction for one day and drying for 12 hours in vacuo at 40C, the supported catalyst SiBi6 was obtained as a reddish soli~.

Zirconium concentration employed: 1.7 x 10-4 mol of ~r~g of silica Zirconium concentration found: 1.6 x 10-4 mol of Zr/g of silica Degree of immobilization: 94%

Polymerization examples Example 20 The polymerization was carried out analogou~ly to .. Example 8 using 431 mg of the catalyst from Ex~mpla 19 and 0.46 g of methyl aluminoxane (MAO) at a propene pressure of 2 bar, a polymerization temperature of 50C
: and a polymerization tLme of 2 hours.

The yield was 1.20 g, this corresponds to an activity of 11.2 kg/mol of [Zr~. l3C-NMR studies gave an isotacticity ;~ 10 of 96O8% ([mm] = 94.6). Compared with polypropylene prepared under otherwise identical conditions using the : corresponding homogenous catalyst systam, the percentage of [mm] triads in the product obtained here was 9% higher (l3C-NMR). Further data on the characterization are given in Table 3.

Example 21 The polymerization was carried out analogously to Example 20 using 237 mg of the catalyst from Example 19 and 0.35 g of MAO at a polymerization temperakure of 754C. DSC measurements of the products gave a melting point of 162.~C. Further da~a and th~ characterization are given in Table 3.

Examples 22 and 23 The polymerizations were carried out analogously to Example 21, using 319 mg and 279 mg of the catalyst from Example 19 and 0.36 g and 0.37 g of MAO. Furthar data and the characterization are given in Table 3.

- 21 ~ 2 ~
Table 3 ¦ Example Yield Activity in M~, m.p. ( 0C~ [mm]
¦ No. in gkg/mol of ~x103] of Product in %

5 L [zr~ ~PP~

. 20 1.2011.2 518 15~.2 94.6 .` 21 0.51 7.0 675 162.1 1 0 n ~ ~
22 0~80 9~4 63;~ 3 _ _ 23 0 . 62 7 . û 758 162 . 1 :.
,:, . . , . ~

`:~

Claims

1. A supported catalyst component for olefin polymeri-zation, obtainable from an inorganic support mate-rial and a metallocene.

2. A catalyst component as claimed in claim 1, Wherein the inorganic support material is an oxide of a metal from main group II-IV or sub-group IV of the Periodic Table of the Elements, or iron oxide or a mixture thereof.

3. A catalyst component as claimed in claim 1 or 2, wherein the inorganic support material is silicon dioxide.

4. A catalyst component as claimed in one or more of claims 1-3, wherein the mettallocene is a compound of the formula I

(I) in which M1 is titanium, zirconium, vanadium, niobium or tantalum, R1 and R2 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-alkoky group, a C8-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group or a C8-C40-arylalkenyl group, R3 and R4 are identical or different and are a monocyclic or polycyclic hydrocarbon radical which can form a sandwich structure with the central atom M1, R5 is =AlR6, -O-, =NR6, =CO, =PR6 or =P(O)R6, where R6, R7 and R8 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C6-C10-fluoroaryl group, a C6-C10 aryl group, a C1-C10-alkoxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C8-C40-arylalkenyl group or a C7-C40-alkylaryl group, or R6 and R7 or R6 and R8, in each case together with the atoms connecting them, form a ring, and M2 is silicon, germanium or tin.

5. A catalyst component as claimed in one or more of claims 1-4, wherein the metallocene is (aryl-alkylidene)-(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, (diarylmethylene)(9-fluorenyl)(cyclo-pentadienyl)zirconium dichloride or (dialkyl-methylene)(9-fluorenyl)(cyclopentadienyl)zirconium dichloride.

6. A catalyst component as claimed in one or more of claims 1-5, wherein the metallocene is (methyl-(phenyl)methylene)-(9-fluorenyl)(cyclopentadienyl)-zirconium dichloride, (diphenylmethylene)-(9-fluorenyl)(cyclopentadienyl)zirconium dichloride or (dimethylmethylene (9-fluorenyl)(cyclopenta-dienyl)zirconium dichloride.

7. A catalyst component as claimed in one or more of claims 1-6, wherein the metallocene is rac-dimethylsilyl-bis-(1-indenyl)zirconium dichloride, rac-diphenylsilyl-bis-(1-indenyl)zirconium dichloride, rac-dimethylsilyl-bis-(tetrahydro-1-indenyl)-zirconium dichloride, rac diphenylsilyl-bis-ttetrahydro-1-lndenyl)-zirconium dichloride, rac-ethylene-bis-(tetrahydro-1-indenyl) zirconium dichloride or rac ethylene-bis-(1-indenyl)zirconium dichloride.

8. A process for the preparation of a supported cata-lyst component as claimed in one or more of claims 1-7, which comprises reacting the inorganic support material in a solvent with the metallocene.

9. The process as claimed in claim 8, wherein the solvent is toluene.

10. A process for the preparation of a high-molecular-weight polyolefin by polymerization or copolymeriza-tion of an olefin of the formula RaCH=CHRb, in which Ra and Rb are identical or different and are a hydrogen atom or an alkyl radical having 1 to 14 carbon atoms, or Ra and Rb, together with the atoms connecting them, can form a ring, at a tem-perature of from -60 to 200°C, at a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst comprising a transition-metal component (metallocene) and an aluminoxane, wherein the transition-metal component is a supported catalyst component as claimed in one or more of claims 1-7.

11. The process as claimed in claim 10, wherein propy-lene is polymerized or copolymerized.

12. Polypropylene obtainable by the process as claimed in claim 10 or 11.