AU593356B2

AU593356B2 - Process for the preparation of a polyolefin

Info

Publication number: AU593356B2
Application number: AU74180/87A
Authority: AU
Inventors: Gerhard Thum
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1986-06-14
Filing date: 1987-06-12
Publication date: 1990-02-08
Anticipated expiration: 2007-06-12
Also published as: JPS62297304A; EP0249869A3; DE3620060A1; DE3770528D1; ZA874228B; BR8702979A; AU7418087A; IN169604B; EP0249869B1; JP2726044B2; CA1297233C; ES2023144B3; EP0249869A2

Description

r Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPEC IFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: 593356 Complete Specification Lodged: Accepted: Published: Priority: Related Art TNIhis (olrfntt contains the s 1 ~mionf 49 and Is correct foi prn n 9.~ .4 Name of Applicant: HO ECHST AKTIENGESELLSCHAFT Adoressof Applicant-' 45 Bruningstrasse, D-6230 Frankfurt/Main 80, Fdrl Republic of Germany Fdr Actual Inventor: Add,,essifor Service:.

GERHARD THUM EDWD. WATERS SONS, 50 QUEEN STREET, MEBOURNE, AUSTRALIA, 3000.

Complete. Specification for the Invention entitled: PROCESS FOR THE PREPARATIQI N OF A POLYOLE8FIN The following statement is a full description of this invention, lnclivding the best method of performing It known to US

WI,

/9 r HOECHST AKTIENGESELLSCHAFT HOE 36/F 134 Dr.DA/mu Process for the preparation of a polyolef-n The present invention relates to a process for the preparation of a polyolefin by means of a highly active, spherical Ziegler catalyst, by means of which considerable simplifications and advantages in handling and processing the products are achieved.

A large number of catalysts of the Ziegler type for the polymerization of alpha-olefins are already known.

Many of these catalysts are based on magnesium chloride, as the supporting material, this being obtained by reacting an organomagnesium compound R 2 Mg, such as, for example, butylethylmagnesium, with a chlorinated hydrocarbon 15 compound R'-CI, such as, for example, carbon tetrachloride (cf US Patents nos. 4,442,225 and 4,439,539 and German Offenlegungsschrift 3,010,202).

It is not possibl'e, however, in this way to obtain a mag- 20 nesium chloride having a spherical shape.

On the other hand, it is known that globular mwagnesium Schloride is formed wheri an organomagnesium comp-)und R2Mg is reacted with a chlorinated organic compound R'-CI in the presence of an organoaluminum compound, such as triethylaluminum, and an electron donor, sucn as diisoamyl ether (cf European Published Specification 99,284).

r Limitations applying to this are that R' must be a hydro- 30 carbon radical having three or more carbon atoms and the carbon atom adj'acent to the chlorine must be either a seoondary or tertiary carbon atom.

It is also known that catalysts can be prepared by reacting magnesium cloride with alkoxy compounds ef the elements of the I 'to VI main group and/subgroup of the periodic system, followed by treatment with a compoun of titanium, zirconium or vanadium (cf German Offenlegungsschrift 2 3,025,759). In addition to a Low contact catalyst activity 5 kg of polymer/mmoL of Ti), however, the catalyst granules in these catalysts do not have a spherical shape. Furthermore, these catalysts only afford products having a broad distribution of molecular weight which are unsuitable for certain applications, such as, for example, precision injection molding or the blow-molding of special hollow articles.

Finally, it is possible to obtain, in a very involved process of preparation, a catalyst based on magnesium chloride and having spherical granules. This requires a two-stage reduction reaction with alkyl aluminum halides and organometallic compounds of magnesium, zinc or aluminum, followed by pre-polymerization, again in one or two stages (cf European Published Specification 143,002). However, this catalyst can only be employed in the gas phase copolymerization of ethylene with higher alpha-olefins. Disadvantages in the resulting copolymers are, additionally, the 20 high residual content of titanium in the polymer, tne low density and the broad particle size distribution of the polymer.

SIt has now been found that it is possible to prepare in a simple manner a highly active and, at the iime time, spherical catalyst by means of which it is possible to obtain globular polysters of alpha-olefins which are distinguished by a narroq particle size distribution and, at the same time, a large average particle diameter.

-T-he invention therefore relates to a processlor the PF:t-r_ pa.ratiqn of a polyolefin by polymerizing alpha-olefj at a temperature from 50 to 150 0 C and under a p ure of 1 to 40 bar in the presence of a cat t composed of a transition metal component (c onent A) and an organomeu tallic compound (comp t B) in which the component A has been formed bracting an organomagnesium compound with an or aluminum compound, an electron donor, an organic V -2a- A process for the preparation of a polyolefin by polymerization of alpha-olefins at a temperature from 50 to 150"C and under a pressure of 1 to 40 bar in the presence of a catalyst composed of a transition metal component selected Sfrom the group comprising magnesium and aluminum chloride supported titaniums or zirconiums (component A) and an organometallic compound selected from the group comprising aluminum compounds of the formula AlR6p Y 3 in which p is 1, 2 or 3 and R 6 is an alkyl or aryl radical having 1 to atoms and Y is hydrogen, a helogen atom or an alkoxy or aryloxy group each of which has 1 to 20 carbon atoms in a ratio A:B of 1:1 to 1:1000 calculated on titanium or a .zirconium and aluminum in which the component A has been formed by reacting an organomagnesium compound with an 15 organoaluminum compound, an electron donor, an organic chlorine compound and a transition metal compound, which comprises carrying which the component A occuring in the form of a solid compound of spherical particles having an average diameter of 20 to 110 pm, a ratio of the mass average diameter Dm to the number average diameter Dn less than 1.5 and a ratio of largest to smallest diameters from 1.05 to 1.15 has been prepared by c a) reacting an organomagnesium compound of the formula

S

l t R MgR 2 in which R 1 and R 2 are identical or different alkyl 2 radicals having 2 to 12 carbon atoms with an organoaluminum compound of the formula AlR 3

(OR

4 )3 in which R 3 and R 4 are identical or different alkyl radicals having 1 to 8 carbon atoms and n denotes 0, 1, 2 or 3, or with the product from the reaction of aluminum trialkyl or aluminum dialkyl hydrides with diolefins containing 4 to 20 carbon atoms, and a primary, aliphatic chlorinated hydrocarbon iOl an amount of 0.01 to 15 mol of the organoaluminum compound and 0.5 to mol of the chlorinted hydrocarbon, relative to 1 mol of the organomagnesium compound, at a temperature from 30 to 110 0

C,

b) treating the resulting solid with an oxygen-containing compound of aluminum, silicon, phosphorus, or sulfur, nitrogen or a silicon compound having alkyl or aryl radicals containing 1 to 8 carbon atoms as an electron S donor in an amount of 0.1 to 1 mol per gram atom of the magnesium present in the solid, at a temperature from 0 to 100 0 C, and ,NV*4 4 4

I

JI

*^1 3 compries carrying o1utte polymeri7ation in the presnce of a catalyst in which the component A has been prepared by a) reacting an organomagnesium compound of the for ula R MgR in which R and R are identical or diff ent alkyl radicals having 2 to 12 carbon atoms w h an organoaluminum compound of the formula AIR 3(OR R 3n in which R and R are identical or different aLky tradicaLs having 1 to 8 carbon atoms and n denotes 1, 2 or 3, or with the product from the reaction o aluminum trialkyls or aluminum dialkyl hydrides with i olefins containing 4 to carbon atoms, and a prima aliphatic chlorinated hydrocarbon in an amount of'0 .01 to 15 mol of the organoaLuminum compound and 0.5 t 2.5 moL of the chlorinated hydrocarbon, relative to 1 m of the organomagnesium compound, at a temperature fom 30 to 1100C, S. b) treat ng the resulting solid with an electron donor in "an amo nt of 0.1 to 1 mot per gram atom of the magnesium pr ent in the solid, at a temperature from 0 to 1000C, .r 4 c) reacting the supporting material thus obtained with a compound of titanium or zirconium or the formula MeXm

(OR

5 )4-m in which Me is Ti or Zr, R 5 is an alkyl radical having 2 to 10 carbon atoms, X is a halogen atom and m is an integer from 0 to 4, in an amount of 0.1 to 2 mol per gram atom of the magnesium present in the supporting material, and at a temperature from 30 to 1200C.

A solid of spherical shape is initially formed. For this purpose, an organomagnesium compound is reacted with an organoaluminum compound and a primary, aliphatic chlorinated hydrocarbon The organomagnesium compound is a magnesium diatyl of the formula R MgR 2 in which R and R are identical or different alkyl radicals having 2 to 12 carbon atoms.

Di-n-butylmagnesium, di-n-octylmagnesium, n-butyl-n-octylmagnesium, n-butyl-ethylmagnesium, n-butyl-sec-butylmagnesium or mixtures of these compounds are preferred.

A suitable organoaluminum compound is an aLkyL aluminum or alkoxy aluminum compound of the formula AIR 3 i(OR )3-n in which R 3 and R are identical or different alkyL radicals having 1 to 8 carbon atoms and n denotes Q, 1, 2 or 3. The product from the reaction of aluminum-trialkyls or aluminum dialkyl hydrides having hydrocarbon radicals with diolefins containing 1 to 6 carbon atoms, preferably isoprene, is aLso equally suitable. Aluminum isoprenyl may be mentioned as an example.

Examples of suitable primary, aliphatic chlorinated hydrocarbons are carbon tetrachloride, chloroform, methylene chloride, 1-chloropropane or 1,1,1-trichLoroethane, and it is also possible to employ mixtures. It is preferable Sto use chloroform and 1-chloropropane.

The spherical-haFed solid is prepared by dissolving the 20 organomagnesium compound and the organoaluminum compound in an inert, liquid hydrocarbon under an atmosphere of nitrogen or argon. This solution i combined, while simultaneously stirring at a temperature from 30 to 110 0 C, preferably from 40 to 80 0 C, with a solution of the chlorinated hydrocarbon. The reaction can be carried out by adding the chlorinated hydrocarbon to the solution of the organomagnesium and organoaluminum compound in the liquid hydrocarbon, or vice versa.

It is possible to vary both the reaction time and the degree of dilution of the reactants within wide limits in this reaction. The reaction time is 30 minutes to several hours, preferably 1 hour to 5 hours. The reactants are employed in the form of 0.5-molar to 15-molar solutions.

The mixture contains up to 0.15 mol, preferably up to 0.10 mol, of the organoaluminum compound and up to 2.5 mol, preferabLy up to 2.0 mol, of the chlorinated hydrocarbon, relative to one moo of organomagneslu1 compound.

5 The solid formed is composed essentially of magnesium chloride together with a little aluminum chloride. Before being reacted further, it is preferably washed several times with a liquid hydrocarbon.

The solid is composed of spherical particles having an average diameter of 20 to 110 pm, preferably 60 to 90 pm.

The ratio of the mass average diameter, Dm, to the number average diameter, Dn, is less than 1.5 and is preferably between 1.01 and 1.15. The ratio of greatest to small diameter D/d is within the range from 1.05 to 1.15.

The spherical-shaped solid is then suspended in a liquid hydrocarbon, the concentration not being decisive for further reaction. It is preferable, however, to use a suspension which is as concentrated as possible and at the same time readily stirrable and which contains 0.1 to preferably 0.3 to 0.9, mol of magnesium chloride per Litre 6- Liquid hydrocarbon.

An electron donor is then added to the suspension of the spherical-shaped solid. Suitable electron donors are oxygen-containing compounds of aluminum, silicon, phosphorus or sulfur, nitrogen or silicon compounds having alkyl or aryl radicals containing 1 to 8 carbon atoms, such as, for example, triethylamine or hexamethyldisilane, or aliphatic or aromatic ethers containing identical or different organic radicals.

S 30 It is preferable to use alkoxyaluminum compounds, dialkyl sulfites, aliphatic ethers and alkyl silicates.

The electron donor is added to the spherical-shaped solid in a molar ratio of 0.1 to 1, preferably 0.1 to 0.6, relative to 1 gram atom of magnesium, at a temperature from 0 to 100 0 C, preferably from 30 to 80 0

C.

Depending on the reactivity of the reactants, the reaction time is 0.5 to 5 hours, preferably 1 to 3 hours.

6 The spherical-shaped supporting material obtained in this manner is either washed several times with an inert liquid hydrocarbon at 0 to 100 0 C, preferably at 20 to 60 0

C,

or is immediately reacted, under an atmosphere of nitrogen or argon, with a compound of titanium or zirconium of the formula MeXm(OR 5 )4-m in which Me is Ti or Zr, R 5 is an alkyl radical having 2 to 10 carbon atoms, X is a halogen atom, preferably chlorine, and m is an integer from 0 to 4, but prefe;'ably 2 or 4. It is possible to employ a mixture of several of these compounds.

Examples of preferred compounds are TiCl 4 FiCl 3 (OEt), TiCl 3 (0-iPr), TiCL 2 (OEt) 2 TiCl 2 (0-iPr) 2 TiC 2 (0-CH 2

CH

6

H

5 )2 TiCI(o-iBu) 3 Ti(OEt) 4 Ti(O-Pr) 4 or Ti(0-iPr) 4 STiCL 4 TiCL 2 (OEt) 2 and Ti(OEt) 4 or a mixture of these compounds are very particularly preferred.

n "o In the reaction described above, the titanium or zircon- 20 ium compound is employed in an amount of 0.1 to 2 mol, Spreferably 0.2 to 1.8 mol, relative to one gram atom of magnesium in the spherical-shaped supporting material.

The reaction temperature is 30 to 120 0 C, preferably to 95 0 C, and the reaction time is 30 minutes to several hours, preferably 1 to 5 hours, depending on the required coating of titanium or zirconium.

The catalyst component A prepared in this manner is finally .i freed from soluble impurities, such as metal compounds or halogen coipounds, by repeated washing with an inert hydrocarbon at ji 'temperature from 0 to 100°C, preferably from to 50 0 C The catalyst component A prepared in accordance with the invention is in the form of spherical particles which have an average diameter of 20 to 110 PUm preferably 60 to pm, and in which the ratio of mass average diameter, -7 Dm, to number average diameter Dn, is Less than preferably 1.01 to 1.2. The ratio D/d is within the range from 1.02 to 1.12.

The component A is employed for the polymerization of alphaolefins in the form of a suspension in an inert hydrocarbon, or, after removing the suspending agent, in the dry state. The polymerization of ethylene or propylene is preferred, or the copoLymerization of ethylene and/or propylene with an alpha-olefin having 4 to 10 carbon atoms and one or more double bonds, such as, for example, 1butene, isobutene, 1-hexene or 1,3-butadiene.

She polymerization can be carried out either continuously 13 or discontinuously in the gas phase or in saturated hydrocarbons having 3 to 15 carbon atoms, such as, for example, propane, butanes, pentanes, hexanes, heptanes, cyclohexanes or mixtures of such compounds.

20 In general, hydrogen is also additionally employed as a 4 e rr molecular weight regulator, and an aluminum compound of ,the formula AIR 6 pY3-p in which p is 1, 2 or 3 and R is an alkyl or aryl radical having 1 to 20 carbon atoms and Y is hydrogen, a halogen atom or an alkoxy or aryloxy group each of which has 1 to 20 carbon atoms, is employed as the component b (co-catalyst).

Examples are halogen-contaiinig organoaluminum compounds, such as dialkyl aluminum halides, alkyaal .minum dihalides or alkylaluminum sesquichLorides, and also aluminum trialkyls or aluminum alkyL hydrides, which can be employed on their own or as a mixture.

It is preferable to use aluminum trialkyls, such as, for exa n)le, aluminum triethyl or aluminum triisobutyl.

The polymerization temperature is 50 to 150 0 C, preferably to 100 0 C, and the pressure is 1 to 40 bar, preferably 3 to 12 bar.

8 The polymers and copolymers prepared in the process according to the invention are distinguished by a compact, uniform, spherical shape, together with a very narrow particle size distribution. The ratio of mass average diameter, Dm, to number average diameter Dn, is less than 1.5, preferably 1.02 to 1.3. The ratio D/d is within the range from 1.05 to 1.2. The diameter of the polymer particle is within the range from 100 to 1800 pm, preferably 600 to 1500 pm. The polymers have a high bulk density and can be processed in an excellent manner.

A further advantage of the catalyst according to the invention is its high contact catalyst activity, so that only very small amounts of the catalyst are required for the polymerization. As a result, it is not necessary either to subject the polymers to an additional after-treatment, such as, for example, involved washing or purifying operations. Nor does any undesirable discoloration of the product occur through residues of catalysts, which can 20 frequently result in the stability to light of the polymers being impai~ed.

0 The residual content of titanium or zirconium in the polyr. mers prepared in accordance with the invention is less 25 than 4 ppm, frequency less than 2 ppm.

Above all, however, considerable simplifications and advantages in handling, crying and processing are achieved by virtue of the spherical shape and the associated very 30 good free flow of the polymers and copolymers.

The invention is illustrated below in greater detail by Ci means of the examples.

The melt flow index MFI (190/5) was deterlnined as specified in DIN 53 735 at 190 0 C and at a loading of 5 kp.

The ratio of Dm to Dn was determined as specified in NF X 11-630 dated June 1981: 1 s( N> ->0 9- Dm= CEni (Di) 3DZi n (Di) 3 Dn= CEni Di3/Eni ni number i of samples of identical diameter Di diameter of the i-th sample.

The particle size distribution Dm/Dn of the component A was determined by image analysis using an IBAS 1. The particle size distribution Dm/Dn of the polymer was determined by sieve analysis as specified in DIN 4188.

Example 1 10.5 mmo of alunimum triethyL were added to 200 mL of a solution of di-n-butymagnesium in heptane (corresponding to 105 milligram atoms of Mg), and the mixture was added dropwise, with vigorous stirring and in the course of minutes, at 45 10 0 C to a mixture of 165 mmol of 1chloropropane and 30 ml of petroleum ether. The mixture was stirred for a further 3 hours at 80 0 C and the solid 0444 20 was extracted by washing 5 times with a total of 1200 ml, #of petroleum ether.

This gave a spherica-shap d solid having an everage diameter (d 50 of 60 Pm.

Mg CL AL 1 2.14 0.04 am/Dn 1.13, D/d 1.1 Example 2 8,5 mmo of aluminum triisopropylate were first added to Z00 mL of a solution of butyloctylmagnesium in heptano (corresponding to 185 milligram atoms of Mg), and the mixture was stirred for 40 minutes at 0 0 C. 370 mmol of chloroform were then added dropwise in the course of minutes at 70 5 0 C. the mixture was stirred for tP at 85 oC and the spherical-shaped solid was washer "Li of petrtieoum ether.

Mg CL AL 1 :I 2.2 0.06 d 50 =80 Im ExampLe 3 670 m L of a s o ut ion of bu t yLo ct y Lma gn es iuLM in hep tan e (correspond'ing to 570 miLLigram atoms of Mg), containing 28.5 mmoL of aLuminum triisobutyL, were added dropwise, wihuniform stirring and in the course of three hours, at7_ 5 0 C toamxueo 0 Lof 100/200 petroLeum e er nd70, ml (860 mmoL) of chloroform. The brown suspension was stirred for a further three hours at 75 0

C,

and the solid was washed 5 times with a totaL of 2500 ml of petroLeum ether.

M1g :CL :AL =1 .2.G5 0.03 DM/Dn =1.09 d 50 90 PMr L-ixampLe 4 The procedure was inaLdgous to that of Example 3, but 650 LI mmqLt of carbon tetrachLoride wer-e used instead of chLoro- Mo l AL 1 2.29 0.05 bn/Dn ;-1.14 do 70 m ExampLe 200 rrL of butyloctyLmagnesium in heptane (corresponing, atoms of Mg), containing 7 mmoL of isoprenyLaluminum, were added dropwi-se, at 75 0 C and in the cojirs~e of 60 minutes, to a mixture of 60 ml of petroleum kkA ether and 30 ml (370 mmcdL) of chtloroform. The mixture was then stir,,-.d for 60 mfirv-tes at 80 0 C and for a further 4hours at 90 0 C. The spheriqaL-shaped solid was washed -t ifes with a total of 1500 mL of petraleum ether.

M9 j CIL AL 1 Z,03 :0.01, DM/On =1.03 d= 75 ~t l r Example 6 11 m zL of aluminum triisopropyLate were added at 40 0 C to 300 ml of a suspension of the solid prepared in ExampLe 1 in 100/200 petroLeum ether (corresponding to 80 milligram atoms of Mg), and the mixture was then stirred for two hours at 950C, and the suspension was cooLed to 500C. 120 mmoL of titanium tetrachLoride, dissolved in 20 mL of petroLeum ether, were added dropwise at this temperature in the course of 30 minutes. The mixture was stirred for a further 4 hours at 900C, and the deep violet precipiate was washed with 5 times 200 ml of petroleum ether. The sphericaL-shaped catalyst component A had an average particle diameter (d 50 of 60 pm.

Mg Ti CL Al 1 0.07 2.68 0.02 Dm/Dn 1.1 d 50 80 Im S* *r 2 0i r* *w 0; 0 a: 0* i* 0r 0- 0* 0 *C 0 0 E t Example 7 0 80 mmol of diethyl sulfite were added at 200C to 500 mL of a suspension in petroleum ether of the solid prepared in E ample 2 (corresponding to 200 milligram atoms of Mg), and the mixture was stirred for two hours at 80 0

C.

The dark gray suspension was cooled to 500C and washed with 1300 ml of petroleum ether. 230 mmoL of titanium t'trachloride were then added dropwise at this temperature in the course of 30 Minutes. Further reaction at 95 °C Safforded a violet, spherical-shaped catalyst component A, which was washed in suspension with 5 times 200 ml of petroleum ether.

Mg Ti CL AL 1 0.07 2.28 0.02 Dm/Dn 1.1 d 5 g 80 pm E;xample 8 The procedure was anaLogous to that of Example 7, but the

I

Il at +r 12 solid from Example 5 was employed instead of the solid from Example 2.

M Ti CL AL 1 0.11 2.05 0.02 Dm/Dn 1.04 d50 70 pm Example 9 120 mmol of dipropyl sulfite were added at 35 0 C to 500 ml of a petroleum ether suspension of the solid prepared in accordance with Example 3 (corresponding to 200 milligram atoms of Mg), and the mixture was stirred for 90 minutes at 80 0 C. The gray suspension was then washed several times with petroleum ether at 60 0 C. A mixture of 270 mmol of titanium tetrachLoride and 30 mmol of titanium tetraethylate, dissolved in 50 ml of petroleum ether, was added dropwise at this temperature 'P the course of minutes. The mixture was stirred for minutes at 80 0

C

and for 120 minutes at 95 0 C, and the violet precipitate 20 was then washed with 10 times 200 ml of petroleum ether.

Mg Ti CL AL 1 0.2 2.5 0.04 Dm/Dn 1.2 90 pm Example The procedure was analogous to that of Example 6, but the solid from Example 4 was employed instead of the solid from Example 1.

30 Mg Ti ct Al 1 0.13 2.35 0.14 D/Dnl 1.15 O 70 pm Example i The procedure was analogous to that of Example 7, but mmol of diethyl silicate were employed instead of diethyl sulfite.

Mg Ti Cl AI 1 0.0 2.13 0.02 a.

I

Ir t ~t I, t i' 1~ .j F i; S13 xample 12 The procedure was analogous to that of Example 11, but a mixture of 210 mmol of dichlorodiethoxytitanium and 30 mmoL of titanium tetrachloride was employed instead of titanium tetrachloride.

Mg Ti Cl Al 1 0.05 2.33 0.03 Example 13 The procedure was analogous to that of Example 6, but employing the solid from Example 3 and 40 mmol of diisobutyl ether instead of aluminum triisopropylate.

Mg Ti CL AL 1 0.09 2.46 0.01 Example 14 The procedure was analogous to that of Example 6, but employing the solid from Example 3 and a mixture of 120 mmol of titaniu tetraethylate and 30 mmol of titanium tetrachloride instead of titanium tetrachloride.

Mg Ti Cl Al 1 0.19 2.17 0.08 Examples 15 to 34 The polymerization of ethylene was carried out in 1,000 ml of petroleum ether under the conditions mentioned in the table in a 1.5 litr'e steel autoclave in the presence of c, hydrogen as molecular weight regulator and at a temperature of 85 0 C and a pressure of 7 bar. 4 mmol of triethyli" 30 aluminum (TEA) or 3 mmol of tr isobutylaluminum (TIBA) were added as component B. The bulk density of the globular polyethylene was 300 to 450 g/l and its density was 0.910 to 0.985 g/cc. 7he D/d *as within the range from 1.05 to 1.2.

The content of material finer than 300 pm was less than 0.01 The residual rontent of titanium in the polymer was less than or equal to 4 ppm.

uu.

-14- Exanple CataLyst Ti H 2 Time YieLd MFI (190/5) D I d 2m no. corponent [umol [bar] [g of PE/ [g/10 mins.] D n [m] A accord- mmoL of to Ti] exanple 6 0.005 2.5 2 21900 2.95 1.09 910 16 7 0.002 1.4 2 75800 0.05 1.04 1500 17 7 0.03 5.6 5 23100 220 1.18 800 18 8 0.05 3.85 1 19200 70 1.17 980 19 8 0.005 2.5 3 64600 2.3 1.02 1190 8 0.03 5.8 2 12100 230 1.03 790 9 0.003 2.5 38200 0.98 1.09 1150 22 10 0.9n,4 2.5 5 49200 1.15 1.2 750 23 10 0.01 3.85 2 22400 16 1.2 810 24 11 0.05 3.85 2 18400 17 1.18 880 11 0.005 3.85 5 39500 19 1.12 920 v 26 11 0.005 1.4 5 6880) 0.18 1.08 1400 S 20 27 12 0.003 1.4 2 30660 0.12 1.1 1220 28 12 0.025 3.85 2 20100 20 1.13 1100 29 12 0.01 3.85 5 33900 22 1.09 980 12 0.001 5.25 5 16300 170 1.18 770 31 13 0.005 2.5 2 23900 1.9 1.08 1030 2 5 32 13 0.005 3.85 5 39200 14 1.1 940 33 14 0.01 1.4 2 17800 0.05 1.3 680 34 14 0.01 5.8 3 11500 198 1.3 710 1 2• iI

I

15 Example litres of liquid propylene, 20 mL of triethylaluminum, 5.3 ml of methyl p-methylbenzoate and the catalyst component A (0.001 mmol of Ti) from Example 7 were initially placed in a 15 litre steel autoclave. After injecting hydrogen to a pressure of 0.5 bar, polymerization was carried out at 70 C for 1 hour. 800 g of polypropylene having an average diameter (d 50 of 550 pm were obtained.

The bulk density was 380 g/L.

4* 4* f,.

t t ft s

Claims

1. A process for the preparation of a polyolefin by polymerization of alpha-olefins at a temperature from 50 to 150*C and under a pressure of 1 to 40 bar in the presence of a catalyst composed of a transition metal component selected from the group comprising magnesium and aluminum chloride supported titaniums or zirconiums (component A) and an organometallic compound selected from the group comprising aluminum compounds of the formula AIR 6 pYp in which p is 1, 616 p2 or 3 and R is an alkyl or aryl radical having 1 to ti atoms and Y is hydrogen, a halogen atom or an alkoxy or aryloxy group each of which has 1 to 20 carbon atoms in a Sratio A:B of 1:1 to 1:1000 calculated on titanium or zirconium and aluminum in which the component A has been formed by reacting an organomagnesium compound with an organoaluminum compound, an electron donor, an organic chlorine compound and a transition metal compound, which comprises carrying which the component A occuring in the form of a solid compound of spherical particles having an average diameter of 20 to 110 pm, a ratio of the mass 1.05 to 1.15 has been prepared by .c a) reacting an organomagnesium compound of the formula R1MgR 2 in which R1 and R2 are identical or different alkyl radicals having 2 to 12 carbon atoms with an organoaluminum Scompound of the formula AIR (OR in which R and R are Sidentical or different alkyl radicals having 1 to 8 carbon Satoms and n denotes 0, 1, 2 or 3, or with the product from h the reaction of aluminum trialkyl or aluminum dialkyl Shydrides with diolefins containing 4 to 20 carbon atoms, and a primary, aliphatic chlorinated hydrocarbon in an amount of 0.01 to 15 mol of the organoaluminum compound and 0.5 to 1 -17- mol of the chlorinated hydrocarbon, relative to 1 mol of the organomagnesium compound, at a temperature from 30 to 110*C,b) treating the resulting solid with an oxygen-containing compound of aluminum, silicon, phosphorus, or sulfur, nitrogen or a silicon compound having alkyl or aryl radicals containing 1 to 8 carbon atoms as an electron donor in an amount of 0.1 to 1 mol per gram atom of the magnsium present in the solid, at a temperature from 0 to 1000C, and c) reacting the supporting material thus obtained with a compound of titanium or zirconium or the formula MEX (ORS 4 in which Me is Ti or Zr, R is an alkyl radical having 2 to 10 carbon atoms, X is a halogen atoms and m is an integer from 0 to 4, in an amount of 0.1 to 2 mol per gram atom of the magnesium present in the supporting material, and at a temperature from 30 to 120 0 C.

2. The process as claimed in claim 1, wherein alkoxyaluminum compounds, dialkyl sulfites, aliphatic ethers or alkyl silicates are employed as the electron donor.

3. The process as claimed in claim 1, wherein a titanium compound has been used. Ir«rt 0 t DATED this 24th day of November, 1989. ft HOECHST AKTIENGESELLSCHAFT WATERMARK PATENT ATTORNEYS 2ND FLOOR 290 BURWOOD ROAD HAWTHORN VIC. 3122.