FI112368B - Process for Polymerization of Olefins - Google Patents

Abstract

A process for the preparation of polyolefins by homopolymerisation or copolymerisation of olefins at a temperature of from 100 to 200 DEG C and a pressure of from 0.5 to 100 bar in the presence of a catalyst containing at least one metallocene and at least one cocatalyst, characterised in that the metallocene is a compound of the formula I <IMAGE>

Description

112368

A process for polymerizing olefins

The present invention relates to a process for the preparation of polyolefins at high temperatures.

Methods for the preparation of polyolefins using homogeneous catalyst systems consisting of a metallocene-type transition metal component and a cocatalyst, e.g., aluminoxane-type oligomeric aluminum -A-485 822).

The high pressure high temperature polymerization of ethylene with soluble metallocenes is first described in DE 31 50 270 at pressures greater than 10,000 kPa (100 bar) and later in EP 260 999 at pressures greater than 50,000 kPa (500 bar). In short reaction times, low density polyethylenes are formed within minutes. However, the catalysts hitherto described have been obtained by low pressure polymerization of ethylene at temperatures above 100 ° C with low molecular weight polymers.

EP 303 519 seeks to overcome this defect by the addition of silicon compounds, however, whereby the polymerization activity is greatly reduced.

In EP 416 815, attempts were made to make metallocenes 25 more suitable for higher temperature ranges, in particular '1'! because of "constrained geometry" ligands. Above 100 ° C, however, a wide distribution of polymers or copolymers with a Mw / Mn, in part, well above 3 is obtained.

It is further known that when the partial pressure rises, i. as the concentration of the monomer increases, the molecular weight of the formed polymers increases. However, this method can increase the molecular weight by increasing the monomer pressure to ... (200,000 kPa (2,000 bar)), however, the high polymerization pressure requires higher equipment and financial costs.

112368 2

In addition, it is known, for example from DE-A-3 808 267, that high molecular weights can be achieved using hafnosocenes. The disadvantages are, in comparison with zirconocenes, the lower polymerization activity of hafnocenes 5 and the higher price.

Thus, the object of the invention was to provide a process which operates at temperatures above 100 ° C and avoids the disadvantages of the prior art. Surprisingly, it has been found that this task can be solved by the use of certain metal-10 lossene catalyst systems.

The invention thus relates to a process for the preparation of homopolyolefins by polymerization or copolymerization of at least one olefin at a temperature of 100-150 ° C and a pressure of 50-10000 kPa (0.5-100 bar) in the presence of a catalyst containing at least one metallocene and

at least one cocatalyst characterized in that the metallocene is a compound of formula I

R5

20 I

: / r3 • Vi Rb ^ AR9 Si ^ J: 25 »V, / V o rz / \ r * / i V 30 r7 _ / ^^ r10 r8 R9 t · where M1 is titanium or zirconium, R1 and R2 are the same or different and represents: hydrogen atom, C 1-10 alkyl group, C 1-10 alkoxy group, C 6-10-103636 3 aryl group, C 6-10 aryloxy group, C 2-10 alkyl group, C 7-10 -arylalkyl group, C7-40 alkylaryl group, C6-40 arylalkenyl group or halogen atom, R3 and R4 are the same or different and represent 5 hydrogen atoms, halogen atom, C1-30 alkyl group, C1-10 fluoro group, A C 6-10 fluoroaryl group, a C 6-10 aryl group, a C 1-10 alkoxy group, a C 2-10 alkynyl group, a C 7-10 arylalkyl group, a C 5-10 arylalkenyl group, or a C 7-10 alkyl aryl group, or R 3 and R 4 taken together with the ring atoms to which they are attached form the same or different R 5, R 6, R 7, R 8, R 9 and R 10 and represent a hydrogen atom, a halogen atom, a C 1-30 alkyl group, a C 1-10 alkyl group; f fluoroalkyl group , A C6-10 fluoroaryl group, a C6-10 aryl group, a C1-10 alkoxy group, a C2-10 alkynyl group, a C7-104 arylalkyl group, a C8-40arylalkenyl group or a C7-40alkyl group, or a R6 group, R 7, R 8, R 9 and R 10 each form a ring together with the atoms to which they are attached. Preferably R 5 and / or R 7 are not hydrogen atoms.

M1 is titanium or zirconium, preferably zirconium.

R1 and R2 are the same or different and represent,. a hydrogen atom, a C 1-10 alkyl group, preferably a C 1-3 alkyl group, especially; methyl group, C 1-10, preferably C 1-3 alkoxy, C 6-10, preferably C 6 aryl, C 6-10, preferably C 6-8 * * * aryloxy, C 2-10 preferably a C 2-4 alkenyl group; A C7-4O, preferably a C7-10 arylalkyl group, a C7-4O, preferably a C7-12 alkylaryl group, a C8-4O / preferably C6-12V * arylalkenyl group, or a halogen atom, preferably a chlorine atom.

I ': R3 and R4 are the same or different and represent a hydrogen atom, a halogen atom, a C1-30 / preferably C1-4 alkyl group, especially a methyl group, a C1-10 fluoroalkyl group, preferably a CF3 group , A C6-10 fluoroaryl group, preferably a pentafluorophenyl group, C6-10, preferably C6-10e: *: 35 aryl groups, C1-10, preferably C1-4 alkoxy groups, especially *** also a methoxy group, a C2-10, preferably a C2-4 alkenyl group, a 112368 4 C7-40-, preferably a C7-10 arylalkyl group, a C8-40-, preferably a C8-12 arylalkenyl group, or a C7 -40-, preferably a C 7-12 alkylaryl group, or R 3 and R 4 together with the atoms to which they are attached form the same or different R 5, R 6, R 7, R 8, R 9 and R 10 and represent a hydrogen atom, a halogen atom, -, preferably a C 1-4 alkyl group, especially an isopropyl group, an ethyl group or a methyl group, a C 1-10 fluoroalkyl group, preferably a CF 3 group, a C 6-10 alkyl group. fluoraryl group, preferably 10 pentafluorophenyl groups, C 6-10, preferably C 6 -C 8 aryl group, C 1 -C 10, preferably C 1 -C 4 alkoxy group, especially methoxy group, C 2 -C 10 group preferably C 2 -C 4 alkenyl group, A C7-40, preferably a C7-10 arylalkyl group, a C4-40, preferably a C8-12 arylalkenyl group, or a C7-40- preferably C7-12-15 alkylaryl group, or two or more of R5, R6, R7, R8, R9 and R 10 each forms a one or more ring system together with the atoms to which they are attached.

Particularly preferred are compounds of formula I wherein M1 is zirconium, R1 and R2 are chlorine or methyl, especially chlorine, R3 and R4 are the same or *. different and represent a C 1-4 alkyl group, especially me-; or a phenyl group, R is a C 1-4 alkyl group, especially a methyl or ethyl group, R 6 is hydrogen, and R 7, R 8, "V 25 R 9 and R 10 are hydrogen, a C 1-4 alkyl group, especially ·· *; an ethyl or isopropyl group, or a C6-10 aryl group, especially a phenyl or n-yl group, or two or more *. * * of R7, R8, R9 and R10, in particular R7 and R8, form one or more rings, especially single-ring

t »I

; '' · 3 0 system together with the atoms to which they are attached. Preferably at least one of R 7, R 8, R 9 and R 10 is not hydrogen.

Particularly preferred are the following zirconocenes: dimethylsilandiyl bis-1- (2-methyl-4-phenylindenyl) zirconium dichloride, 112368 dimethylsilandiyl bis-1- (2-methyl-4- (1-naphthyl) indene). nyyl) zirconium dichloride, dimethylsilandiyl-bis-1- (2-ethyl-4-phenylindenyl) zirconium dichloride, 5-dimethylsilandiyl-bis-1- (2-ethyl-4- (1-naphthyl) indenyl) zirconium dichloride, dimethylsilandiyl bis-1- (2-methylacenaphthyl) indenyl) zirconium dichloride, dimethylsilane bis-1- (2-methyl-4,5-benzoindenyl) zir-10 conium dichloride, phenylmethylsilandiyl 2- methyl 4-phenylindenyl) zirconium dichloride, phenylmethylsilandiyl bis-1- (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride, phenylmethylsilandiyl bis-1- (2-ethyl-4-phenyl), indenyl) zirconium dichloride, phenylmethylsilandiyl bis-1- (2-ethyl-4-naphthylindenyl) zirconium dichloride, phenylmethylsilandiyl bis-1- (2-methylacenaphthyl-20-denyl) zirconium dichloride, phenylmethylsilandiyl-bis-1- (2-methyl-4,5-benzoyl *,, denyl) zirconium dichloride, I '. dimethylsilandiyl-bis-1- (2-methyl-4,6-diisopropyl-1 ', * indenyl) zirconium dichloride, &gt;' '* - 25-phenylmethylsilandiyl-bis-1- (2-methyl-4,6- diisopropyzylphenylindenyl) zirconium dichloride, * '· · - dimethylsilandiyl bis-1- (2-methyl-4-ethylindenyl) zirconium dichloride and dimethylsilandiyl bis-1- (2- methyl 4-isopropylinden-30-yl) zirconium dichloride.

The above metallocenes can be used in ras form, meso form and ras / meso alloys, preferably in ras form.

• l · 1 In principle, any kind of cocatalyst is suitable; A compound which, due to its Lewis acidity, can convert and stabilize a neutral metallocene into a cation.

6 11236?

In addition, there must be no other reaction between the cocatalyst or its anion and the metallocene cation.

The cocatalyst used in the catalyst used according to the invention is preferably aluminoxane or any other organic aluminum compound. Preferably, aluminoxane is a compound of the linear type of Formula Ha and / or the cyclic type of Formula Hb b-O-K 2 O 2 -O 2 -O / Al-O-Al-O-Al (Ma) g ™. In the formulas, R 20 is a C 1-6 alkyl group, preferably methyl, ethyl, n-butyl or isobutyl, especially methyl or butyl, and p is an integer from 4 to 30, preferably 10 to 25, wherein the groups R 20 may also be different. Particularly preferred are methylaluminoxane and methyl 4-butylaluminoxane in which the ratio methyl: butyl = 100-1: 1: 1 butyl comprises n-butyl, isobutyl-

Mixtures of lin or n-butyl / isobutyl and groups have an arbitrary, preferably statistical distribution.

The structure of aluminoxane may also be three-dimensional (J. Am. Chem. Soc. 1993, 115, 4971-4984).

Aluminum oxane can be prepared by a variety of methods: 1 ·, * · 1, min.

1 »V One possibility comprises a method in which water I t; Add carefully to a dilute solution of aluminum trialkyl or various aluminum trialkyl alloys, whereby a solution of aluminum-35 aluminum trialkyl, preferably aluminum trimethyl, is reacted with small portions of water. This is preferably by cooling and vigorous stirring, for example using a high speed mixer. Insoluble aluminoxanes formed in such a reaction can also be used as cocalizers.

Another possibility is to prepare aluminoxanes on a support, for example, by suspending the strainer under inert conditions in a solution of at least one aluminum alkyl and hydrolyzing this suspension with water.

In another method, the finely divided copper-10 sulfate pentahydrate is slurried in toluene in a glass flask and thereto is added enough aluminum trialkyl in an inert gas at about -20 ° C to give 1 mole of CuSO4.5H2O for every 4 Al atoms. After slow hydrolysis with alkane cleavage, the reaction mixture is allowed to stand at room temperature for 24-48 hours, possibly with cooling to avoid raising the temperature above 30 ° C. The aluminoxane dissolved in toluene is then separated from the copper sulphate by filtration and the toluene is distilled off in vacuo.

Further, aluminoxanes are obtained by reacting aluminum trialkyl dissolved in an inert aliphatic or aromatic solvent at -10 to 100 ° C with crystalline aqueous aluminum salts. Preferred; ,. heptane and toluene and aluminum sulphate are used. In this case, the volume ratio of solvent to aluminum alkyl used is 1: 1 to 50: 1, preferably 5: 1, and the reaction time, which can be controlled by monitoring the alkene blocking time, is 1 to 200 hours, preferably 10 to 10 hours. 40 hours.

Crystal water-containing aluminum salts are used; · 30 especially those with a high water content of crystals.

• · *:> i (* Preference is given in particular to aluminum sulphate hydrate before; ·. All of the compounds Al2 (SO4) 3-18H2O and Al2 (SO4) 3.16H2O, which have a particularly high crystal water content, namely 18 and correspondingly 16 mol H 2 O / mol Al 2 (SO 4) 3.

'· 35 The following is an example of the preparation of methylaluminoxane: ... ·

11236P

37.1 g of Al 2 (SO 4) 3 to 8Η 256 (0.056 mol, corresponding to one mole of H 2 O) were suspended in 250 cm 3 of toluene, 50 cm 3 of trimethylaluminum (0.52 mol) was added and the reaction was allowed to react at 20 ° C. After a reaction time of 30 hours, about 1 mole of methane had been evolved. The solid aluminum sulfate was then filtered off from the solution. Evaporation of the toluene gave 19.7 g of methylaluminoxane. The yield was 63% of theory. The average molecular weight determined by cryoscopy in benzene was 1170. (The number of Al (R 21) -O-yk-10 units was calculated to be 20.2. Thus, the average degree of oligomerization was about 20.

In yet another alternative process for the preparation of aluminoxanes, the reactions described are carried out directly in suspension medium or liquid monomers added to the polymerization boiler.

In addition to all the previously described processes for the preparation of aluminoxanes, there are other useful methods. Regardless of the type of preparation process, all aluminoxane solutions contain varying amounts of pi-20 unreacted aluminum trialkyl, Al (R20) 3, either in free form or as an adduct.

Alumoxane is used in the above-described

1 I

. solution or suspension obtained from culture methods.

* »; Further useful organic aluminum compounds are compounds of the following formulas: A1R212H, "A1R213, A1R212Cl, A12R213C13 and AlR21Cl2, wherein R21 is C1-6-al-1 * 1 · ;;; a alkyl group, a C 1-6 fluoroalkyl group, a C 6 -is-aryl group, a C 6-18 -alkyl fluoroyl group, or a hydrogen atom. Examples of R 21 are methyl, ethyl, isopropyl, n-butyl, isobutyl or n-1 *. · '3 0 Oct 1 i.

The catalyst used in accordance with the invention may be prepared by reacting the metallocene with an organic aluminum compound by a variety of processes: • 35 1) The organic aluminum compound is introduced in a suitable solvent such as pentane, hexane, 112368. heptane, toluene or dichloromethane at a temperature of -20 to +120 ° C, preferably 15 to 40 ° C, with vigorous stirring with the metallocene. The molar ratio Al: M3 is then 1: 1 to 10,000: 1, preferably 10: 1 to 5,000: 1, and the reaction time is 5 to 120 minutes, preferably 10 to 30 minutes, with an aluminum concentration greater than 0.01 mol / dm3. , preferably greater than 0.1 mol / dm3, and the reaction is carried out in an inert gas.

2) The insoluble or carrier aluminoxane 10 is reacted with an inert solvent such as toluene in a 1-40% by weight suspension, preferably 5-20% by weight, in an aliphatic inert suspension medium such as n-decane, hexane, heptane or diesel oil. with metallocene dissolved in ethylene, hexane, heptane, diesel oil or dichloro-15 methane in a molar ratio Al: M1 of from about 1: 1 to about 10,000: 1, preferably from 1: 1 to 2,000: 1, at -20 to +120 ° C, preferably 15-40 ° C, for a reaction time of 5-120 minutes, preferably 10-30, with vigorous stirring.

The catalyst prepared according to 2) is directly added as a suspension to the polymerization or separated by filtration or decantation and washed with an inert suspension medium such as toluene, n-decane, hexane, heptane, diesel or dichloromethane. The catalyst may be dried in vacuo and added as a powder, or may be suspended in a solvent-containing suspension, in an inert suspension medium such as toluene, hexane, heptane or diesel oil, and added to the polymerization system. The products having a boiling range of 100 ° C to 200 ° C, preferably a boiling range of 140 ° C to 170 ° C, may be used as diesel oil.

* * ·

The catalyst may also be added in the form of a support. The coupling of the carrier may be carried out according to 2) 35 by reacting a square cocatalyst 10 1 to 2368 (e.g. aluminoxane) with a metallocene without carrier, 3) reacting a metallocene with carboxy (e.g. aluminoxane) 5, 4, reacting the metallocene with cocoa e.g., aluminoxane) reaction mixture with the carrier material, or 5) reacting the carrier metallocene and carrier 10 ton cocatalyst (e.g. aluminoxane) with each other in the presence of the carrier material. Inorganic oxides, preferably silica gels, or polymeric materials may be used as carriers.

The catalyst prepared according to 1), 2), 3), 4) or 5) may also be used as a prepolymer.

Preferably, one of the polymerizable olefins is used for prepolymerization.

The monomers used are straight or branched chain olefins or diolefins having from 2 to 18 carbon atoms.

Examples of these are ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-butene, 3-methyl-1- pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, styrene, cyclopentyl; Te, cyclohexene, norbornene, 1,3-butadiene, 1,4-'* Y 25 pentadiene, 1,4- or 1,5-hexadiene, 1,7-octadiene.

Preferably, ethylene is polymerized or copolymerized; ethylene or propylene with 3 to 18 carbon atoms containing olefin. Particularly preferred is the copolymerization of ethylene with an olefin containing from 3 to 18 carbon atoms. Examples; ', · * 30 of this are copolymers of ethylene / propylene, ethylene / 1-butene, ethyl: * * ethylene / 1-hexene and ethylene / 1-octene, and: * * ethylene / propylene / 1-butene terpolymers.

The polymerization is carried out batchwise or continuously, in one or more steps, whereby only a slight reduction in the time-dependent polymerization activity can therefore be used.

ιχ 112368

The polymerization temperature is 100 to 300 ° C, preferably 100 to 200 ° C. The comonomer represents from 0 to 30 mol%, preferably from 0 to 20 mol%, of the total amount of monomers.

Hydrogen may be used to control the molecular weight, with a partial pressure of 5 to 5,000 kPa (0.05 to 50 bar), preferably 10 to 2500 kPa (0.1 to 25 bar), especially 20 to 1000 kPa ( 0.2-10 bar). In addition, the polymerization temperature can be varied. Polymers of wide distribution can be obtained by a multi-step process or by using mixtures of several metallocenes. In addition, in the process of the invention, the target molecular weight of the polymer is influenced by the type of metallocene of formula I used and the ratio Aluminum / M1 (M1 = central atom of metallocene).

The total pressure of the polymerization system is from 50 to 10,000 kPa (0.5 to 100 bar). Preferably, the polymerization is carried out in a technically interesting pressure range of 100 to 6400 kPa (1 to 64 bar).

The polymerization temperature is from 100 to 200 ° C, preferably from 20 to 120 ° C.

Depending on the melting point and solubility of the resulting polymer, the polymerization may be carried out in solution or suspension, and in the monomer or monomer mixture or gas phase, preferably in solution.

During the polymerization, another aluminum alkyl compound, for example trimethyl-, t- * laluminium, triethylaluminum, triisobutylaluminum, or isoprenylaluminum, may be added before the catalyst is added to liberate the polymerization system. V 30 0.001 mmol Al per kg reactor content In addition, these compounds may also be used as an adjunct to molecular weight control.

•> ·

An advantage of the method according to the invention is, * · 'I' that it is capable of producing polymers with a narrow distribution and relatively high molecular weight at temperatures above 100 ° C.

12 1123ή'Ρ

In addition, this process has proved to have a high polymerization result at temperatures above 100 ° C and it is possible to carry out e.g. homogeneous solvent polymerization which, compared to polymerization using conventional titanium catalysts, produces more homogeneous products in ethylene copolymers. The catalysts of the invention are thus preferably suitable for the preparation of LLDPE.

In addition, bridges containing metallocene catalysts 10 can statistically incorporate a copolymer into a copolymer to effectively control the density of the copolymer, thereby reducing the use of the expensive comonomer. The resulting products, when fractionated, were not shown to contain comonomers enriched in the lower molar 15 molar fractions, but the side chains were uniformly distributed throughout the molecular weight of the copolymer. As a result, even at lower densities, a decrease in the constituents to be extracted is observed.

The following examples are intended to further illustrate 20 inventions.

Herein denote:, 'VZ = viscosity number cm3 / g ,; Mw = molecular weight average] f gelatin obtained: Mn = molecular weight average value ^ · {mearomation chromatograms »V 25 J [graph **] Mw / Mn = polydispersity (numbers in g / mol) * ;;; MFI 190/5 Melt Flow Index at 190 ° C and with a load of 5 kg * * '·' * (according to DIN Standard 53 735) SD = bulk density of polymer powder in g / dm3 • 30 Melting points, crystallization points, half-lives Detections, melting and crystallization enthalpies, and glass temperatures: ·, (Tg) were determined by DSC measurements (10 ° C / min heating / - · · t cooling rate).

"* Examples' ·" · 35 All glass containers were heated under vacuum and rinsed with argon. All operations were performed in a Schlenk container protected against moisture and oxygen. The solvents used were distilled before use in an argon atmosphere of Na / K alloy. above and stored in Schlenk containers under inert gas.

Synthesis of the racocimethylsilandiyl bis-1- (2-methyl-4-phenylindenyl) zirconium dichloride of metallocene is carried out according to EP-A-576 970. Synthesis of the racocimethylsilandiyl bis-1- (2-methylacenaphthylindenyl) zirconium dichloride of metallocene is performed according to EP-A-549 900. The synthesis of metallocene ras-dimethylsilandiyl-bis-1- (2-methyl-4,5-benzoindenyl) zirconium dichloride is carried out according to EP-A-549 900.

Methylaluminoxane is obtained as a 10% toluene-15% solution from Witco GmbH and contains 36 mg Al / ml as determined by aluminum determination. The average degree of oligomerization, according to the freezing point reduction, is n = 20 in the Bentene.

Example 1 2 0 A dry 1.5 dm3 mixing reactor is purged with nitrogen to remove oxygen and 0.9 dm3 of inert diesel oil (b.p. 140-170 ° C) is added. The reactor is rinsed with ethylene and heated to 120 ° C. Parallel to this «t ·; (*) 0.3 mg of ras-dimethylsilandiyl-bis-1,11 - (2-methyl-4-phenyl-2H-2'-phenylindenyl) zirconium dichloride in 10 ml of methylaluminoxanone are dissolved in toluene. (12 mmol Ai) and pre-reactor can be started for 15 minutes. Polymerization is initiated by dosing the catalyst solution and raising the ethylene pressure to 400 kPa (4 bar). After one hour of polymerization, the reactor pressure is reduced to normal, reactor pressure cool and slurry I k: the suspension is drained. After filtration and drying for 12 hours · [then 23 g of polyethylenethylene is obtained in a vacuum drying cabinet, corresponding to a reduced contact time yield »· (KZAred) 12 kg / ( mmolZr * h * bar), bulk density 0.205 35 kg / dm3 and VZ 170 cm 3 / g Molecular weight distribution Mw / Mn = 2.4: (by GPC, gel permeation chromatography).

14

11236F

Example 2

Example 1 was repeated using 0.5 mg of dimethylsilandiyl bis-1- (2-methylacenaphthylindenyl) zirconium dichloride in the preparation of a catalyst solution. 16 g of polyethylene was obtained, corresponding to a KZAred of 4.7 kg / (mmolZr * h * bar). It had a bulk density of 0.190 kg / dm3 and a VZ of 211 cm 3 / g. Molecular weight distribution M 1 / Mn = 2.5 (by GPC).

Example 3 Example 1 was repeated using 0.4 mg of rac-dimethylsilandiyl-bis-1- (2-methyl-4,5-benzoindenyl) zirconium dichloride to prepare the catalyst solution. 19 g of polyethylene was obtained, corresponding to a KZAred of 6.9 kg / (mmolZr * h * bar). It had a bulk density of 0.210 kg / dm3 and a VZ of 211 cm 3 / g. Molecular weight distribution M 1 / Mn = 2.4 (by GPC).

Example 4

Example 1 was repeated at 140 ° C and ethylene pressure 700 kPa (7 bar). The cooled reaction mixture 20 gave polyethylene having a KZAred of 2.0 kg / - (mmolZr * h * bar) and a VZ of 167 cm3 / g. Molecular weight distribution M „/ Mn = *. 2.3 (by GPC).

: Example 5 * * ♦; * [Dry 16 dm3 mixing reactor is purged with nitrogen to remove oxygen * t "V 25 and added to 8 dm3 of inert" Ί diesel (bp 140-170 ° C) and 300 ml of 1-hexene. Then * ··· 'heated to 120 ° C and pressurized with ethylene to 800 V * kPa (8 bar), in parallel with 4 mg of ras-dimethylsilyl-bis-1,1 '- (2-methyl-4-phenylindenyl) zircon *' 10 ml of sodium dichloride in 10 ml of methylaluminoxane are dissolved in toluene (12 mmol of Al) and preactivated for 15 minutes.

Polymerization is initiated by dispensing the catalyst solution through a barrier and keeping the total pressure constant with the addition of ethylene. After a 1/2 hour polymerization time, the reaction is quenched by the addition of methanol, the pressure is allowed to drop and the reactor is cooled to 20 ° C and the suspension is drained. The suspension is filtered and dried for 12 hours in a vacuum oven to give 408 g of polymer corresponding to a KZArea value of 16 kg / (mmolZr * h * bar). Its VZ is 180 cm3 / g. The MFI 190/5 is 4.26 g / 10 min at a density of 0.934 g / cm 3 at -5.

Comparative Example 1

Example 1 was repeated using 0.4 mg of bis (n-butylcyclopentadienyl) zirconium dichloride to prepare the catalyst solution. After evaporation of the entire suspension medium, 4 g of polyethylene wax was obtained, corresponding to a KZAred value of 0.98 kg / (mmolZr * h * bar). Its VZ was 40 cm3 / g.

Comparative Example 2

Comparative Example 1 was repeated using 0.4 mg of 15 bis-indenylzirconium dichloride. 3 g of polyethylene wax was obtained, corresponding to a KZAred value of 0.74 kg / (mmolZr * h * bar).

Its VZ was 46 cm 3 / g.

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Claims (6)

16 1 1236- '·' A process for the preparation of polyolefins by homopolymerization or copolymerization of at least one olefin at a temperature of 100-150 ° C under a pressure of 50-10,000 kPa (0.5-100 bar) in the presence of a catalyst comprising at least one metallocene and at least one cocatalyst, characterized by that the metallocene is a compound of the formula I 10 R 5 R 75 >> \ r 5 15 R '^ AR9 si ^ R'> '/ V o Rj / \ R5 / p 6 20 K: R * R * *> S 25 wherein M 1 is titanium or zirconium, R 1 and R 2 are the same or different and represent a "hydrogen", C 1-10 alkyl group, C 1-10 alkoxy group, C 6 an aryl group, a C6-10 aryloxy group, a C2-10 alkenyl group, a C7-40 arylalkyl group, a C7-40 alkylaryl group, a C8-40 alkyl, arylalkenyl group, or a halogen atom, and R4 are the same or different and represent; ·, a hydrogen atom, a halogen atom, a C 1-30 alkyl group, a C 1-10 fluoroalkyl group, a C 6-10 fluoroaryl group, a C 6-10 aryl group, a C 1-10 alkoxy group, A C2-10 alkynyl group, a C7-40 aryl - "" - 35 alkyl group, a C8-40 arylalkenyl group, or a C7-40 alkyl aryl group, or R3 and R4 together with the atoms to which they are attached form related, R 5, R 6, R 7, R 8, R 9 and R 10 are the same or different and represent a hydrogen atom, a halogen atom, a C 1-30 alkyl-5 group, a C 1-10 fluoroalkyl group, C 6-10 -fluoroaryl group, C6-10 aryl group, C1-10 alkoxy group, C2-10 alkynyl group, C7-40 arylalkyl group, C8-40 arylalkenyl group or C7-40 alkylalkyl group, or two or more R7 groups, or , R8, R9 and R10 each form a ring together with the 10 atoms to which they are attached. Process according to claim 1, characterized in that the metallocene is a compound of the formula I in which M 1 is zirconium, R 1 and R 2 represent chlorine or methyl, R 3 and R 4 are the same or different and represent a C 1-4 alkyl group or a phenyl group. , R 5 is C 1-4 alkyl, R 6 is hydrogen, and R 7, R 8, R 9 and R 10 are hydrogen, C 1-4 alkyl or C 6-10 aryl, or two or more of R, R, R and R form a ring ring theme together with the atoms to which they are attached. 3. A process according to claim 1, characterized in that the metal; losene is: dimethylsilandiyl-bis-1- (2-methyl-4-phenylindenyl) ·, ·,, l) zirconium dichloride, * · · N, dimethylsilandiyl-bis-1- (2-methyl-4- ( 1-naphthyl) indenyl) zirconium dichloride, dimethylsilandiyl bis-1- (2-ethyl-4-phenylindenyl) -1'-zirconium dichloride, dimethylsilandiyl bis-1- ( 2-ethyl-4- (1-naphthyl) indenyl) zirconium dichloride, dimethylsilandiyl bis-1- (2-methylacenaphthyl) indenyl ** zirconium dichloride, dimethylsilane bis - 1- (2-methyl-4,5-benzoindenyl) zirconium dichloride, 35 phenylmethylsilandiyl bis-1- (2-methyl-4-phenylindenyl) zirconium dichloride, 18 112368 phenylmethylsilandiyl bis-1- (2- methyl 4- (1-naphthyl) indenyl) zirconium dichloride, phenylmethylsilandiyl bis-1- (2-ethyl-4-phenylindenyl) zirconium dichloride, 5-phenylmethylsilandiyl bis-1- (2-ethyl-4- naphthyl-in-denyl) zirconium dichloride, phenyl methylsilandiyl bis-1- (2-methylacenaphthylindenyl) zirconium dichloride, phenylmethylsilandiyl bis-1- (2-methyl-4,5-benzoyl-10 denyl) zirconium dichloride, dimethylsilandiyl bis-1- (2-methyl-4, 6-diisopropylindenyl) zirconium dichloride, phenylmethylsilandiyl bis-1- (2-methyl-4,6-diisopropylindenyl) zirconium dichloride, dimethylsilandiyl bis-1- (2-methyl-4- ethyl indenyl) zirconium dichloride or dimethylsilandiyl bis-1- (2-methyl-4-isopropylindenyl) zirconium dichloride. Process according to one or more of Claims 1 to 3, characterized in that aluminoxane is used as the cocatalyst. • V. Process according to one or more of Claims 1 to 4, characterized in that it polymerizes; or olefins or diolefins having from 2 to 18 carbon atoms. * t * Process according to one or more of Claims 1 to 5, characterized in that the catalyst used is supported and / or prepolymerized. »* 19 112? e. ρ