AU622026B2

AU622026B2 - Process for the preparation of ethylene (co) polymers

Info

Publication number: AU622026B2
Application number: AU55071/90A
Authority: AU
Inventors: Andreas Heinrich
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1989-05-17
Filing date: 1990-05-17
Publication date: 1992-03-26
Anticipated expiration: 2010-05-17
Also published as: AU5507190A; BR9002291A; CA2016930A1; JPH039903A; EP0398167A3; EP0398167A2

Description

F

622026 Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: S Complete Specification Lodged: Accepted: Published: Priority 4

I

Related Art

E(-

CEI

Tr P II

P

a r Dt at a I Name of Applicant Address of Applicant Actual Inventor Address for Service HOECHST AKTIENGESELLSCHAFT 50 Bruningstrasse, D-6230 Frankfurt/Main 80, Federal Republic of Germany ANDREAS HEINRICH WATERMARK PATENT TRADEMARK ATTORNEYS.

LOCKED BAG NO. 5, HAWTHORN, VICTORIA 3122, AUSTRALIA Complete Specification for the invention entitled: PROCESS FOR THE PREPARATION OF ETHYLENE (CO)POLYMERS The following statement is a full description of this invention, including the best method of performing it known to

I

HOECHST AKTIENGESELLSCHAFT HOE 89/F 147K Dr.DA/PP Description Process for the preparation of ethylene (co)polymers.

The invention relates to a process for the (co)polymerization of ethylene to form coarse particles of polymer having a narrow particle size distribution and a high bulk density by using catalyst particles whose carrier component is a dissolved magnesium alcoholate.

Processes in which the starting materials for Ziegler Natta catalysts are dissolved magnesium alcoholates are known.

0o o 0 0 For instance, a catalyst system is known whose transition 00 00o metal component is produced by the reaction of a dis- Sooo solved magnesium alcoholate with titanium tetrachloride S 0o a o- 15 (cf. EP 262,790). The catalyst component is used together oo 0 with an aluminum compound for the polymerization of olefins, in particular of propylene.

It is also known to prepare the soluble magnesium com- L rpound by reacting magnesium metal, magnesium halide or Mg(OEt), with an alcohol in the presence of a donor (for example carboxylic acids, glycol ethers) and to react this reaction mixture with titanium tetrachloride. This gives a catalyst component which is suitable for the preparation of coarse-particle polyethylene having a high bulk density (cf. EP 114,526). One of the disadvantages s. of this process is the excessive use of titanium tetrachloride (Ti fixed to Ti used is for example 1 500 to 2000).

Furthermore, a process for the preparation of a catalyst component is known in which first a dissolved magnesium dialkoxide, a silicon compound and an electron donor are reacted together and the reaction product is reacted with a titanium compound (cf. EP 156,512). This catalyst 2 component is used together with an organoaluminum compound for the polymerization of propylene.

The reaction of the starting materials gives a crude product which must be purified in several washing operations with organic solvents.

The object is to provide a simple process for catalyst Ipreparation which allows the preparation of catalysts which produce a polymer having a high average and uniform particle diameter and a high bulk density.

S 10 It has now been found that this object is achieved if a i dissolved magnesium alcoholate is reacted with a titanium Scompound and subsequently with an aluminum compound.

I Modification of the preparative method and the use of i electron donors improves the bulk density of the polymer .t'"15 particles.

The present invention accordingly provides a process for the preparation of an ethylene polymer having a uniform coarse particle shape and a high bulk density by the C C polymerization of ethylene or of ethylene with up to .tt 20 by weight, relative to the total amount of monomers, of a 1-olefin of the formula R 9

-CH=CH

2 in which R 9 is a C C straight-chain or branched alkyl radical having 1 to 12 carbon atoms, in suspension, in solution or in the gas phase, at a temperature of 20 to 120 0 C and a pressure of S 25 2 to 60 bar in the presence of a catalyst composed of the S C Ccc reaction product of a magnesium alcoholate with a tetra- Svalent transition metal compound and an organoaluminum compound, which comprises carrying out the polymerization in the presence of a catalyst which is composed of a) the over-all product from the reaction al) of a magnesium alcoholate of the formula I Mg(R)(OR 2

(I)

FI MW- 7^ r' 3 dissolved in an inert solvent, in which formula R 1 and R 2 are either identical and are a radical

-CH

2 CHR6R or -(CH 2 )nOR 8

R

6 being a hydrogen atom or a Ci-C 6 -alkyl radical, R 7 a C 2

-C

6 -alkyl radical, R 8 a Ci-C 4 -alkyl radical and n an integer from 2 to 6, or V R1 and R 2 are different, R 1 has the meaning given above and R 2 is a Ci-C 2 0 -alkyl radical, with i i a2) a tetravalent transition metal compound of the formula II MX (OR 3 4- (II) i in which M is titanium, zirconium or hafnium, R 3 is Sa C 1 -C-alkyl radical and X is a halogen atom and m i

T

C is an integer from zero to 4, c i t S a3) an organoaluminum compound of the formula III C t A IR( OR 5 ')pX 3 (III) in which R 4 and R 5 are identical or different and are C1 a C 1

-C

6 -alkyl radical, X is a halogen atom, q is a ccc C number from zero to 3 and p is a number from zero to 11 in the ratio Mg:Ti:Al of 1 0.05 to 2 0.3 to i c,Q20 4, and b) a trialkylaluminum having 1 to 6 carbon atoms in the alkyl radicals or the reaction product of a trialkylaluminum or dialkylaluminum hydride with isoprene.

The mixed catalyst component a to be used according to the invention is prepared using a magnesium alcoholate of the formula I Mg(OR) (OR)

(I)

In this formula, R 1 and R 2 are identical or different. If 1

I-

i ,:i

I

I i i 1i: :Y f i 3 c

B

C

Ctt ct c ct

(CC

C C9C -4

R

1 and R 2 are identical, they are a radical -CH 2

CHR"R

7 or a radical -(CH 2 )nOR 8 in which R 6 is a hydrogen atom or a

C

1 -C-alkyl radical, preferably a C 1

-C

3 -alkyl radical, R 7 is a C 2

-C

6 -alkyl radical, preferably a C 3

-C

5 -alkyl radical,

R

8 is a C 1

-C

4 -alkyl radical, preferably a Ci-C 2 -alkyl radical and n is an integer from 2 to 6. If R 1 and R 2 are different, R 1 has the meaning given above and R 2 is a C 1

C

20 -alkyl radical, preferably a C 3 -Co 1 -alkyl radical.

Examples of magnesium alcoholates of this type are magnesium bis-(2-methyl-l-pentyl alcoholate), magnesium bis-(2-methyl-l-hexyl alcoholate), magnesium bis-(2-methyl-l-heptyl alcoholate), magnesium bis-(2-ethyl-l-pentyl alcoholate), magnesium bis-(2-ethyl-l-hexyl alcoholate), 15 magnesium bis-(2-ethyl-l-heptyl alcoholate), magnesium bis-(2-propyl-l-heptyl alcoholate), magnesium bis-(2-methoxy-l-ethoxide), magnesium bis-(3-methoxy-l-propyl alcoholate), magnesium bis-(4-methoxy-l-butyl alcoholate), 20 magnesium bis-(6-methoxy-l-hexyl alcoholate), magnesium bis-(2-ethoxy-l-ethoxide), magnesium bis-(3-ethoxy-l-propyl alcoholate), magnesium bis-(4-ethoxy-l-butyl alcoholate), magnesium bis-(6-ethoxy-l-hexyl alcoholate), 25 magnesium bis(pentyl alcoholate), magnesium bis(hexyl alcoholate).

Suitable magnesium alcoholates also include the reaction i products of magnesium metal, alkylmagnesium compounds or magnesium alcoholates with alcohols R'OH (R 1 as above).

Among these products, preference is given to the reaction product of a magnesium alcoholate with an alcohol R'OH in the presence of 0.02-0.2 mol of triethylaluminum (as viscosity depressant) at 100 to 140"C.

The dissolved magnesium alcoholate is reacted with a tetravalent transition metal compound of the formula II C C Z CC C in which M is titanium, zirconium or hafnium, preferably titanium or zirconium, R 3 is an alkyl radical having 1 to 9, preferably 1 to 4, carbon atoms and X is a halogen atom, preferably chlorine, and m is zero to 4, preferably 2 to 4. The tetravalent transition metal compound of the formula II or an adduct thereof with one of the electron donors to be used according to the invention is soluble in hydrocarbons.

Examples of the said tetravalent compounds are as follows: TiCl 4 TiCl 3 (0C 2

H

5 TiCl 2 (0C 2

H

5 2 TiCl(0C 2

H

5 3 Ti(0C 2

H

5 4 1 TiCl 3 (0C 3

H

7 TiCl 2 (0C 3

H)

2 TiCl (0C 3

H)

3 Ti (0C 3

H)

4 TiCl 3 (MCAH), TiCl 2 (MCAH) 2 TiCl (0C 4 H) 3 1 Ti (0' 4

H

9 4 1 TiCl 3 (0C 6

H

13 TiCl 2 (0OCH 13 2 TiCl (0C 6

H

13 3 Ti (0C 6

H

1 3 4 1 K Ti (OC 9 1 9) 4 TiBr 4 TiBr 3 (OR) r(R T i Br Tir0 3 3 TiI 4 1 TiI 3 0R 3 Ti1 2 (OR 3 )21 TiI(0R 3

Z~

4 ZrBr, Zrn 4 Zr(0C 2

H

5 4 1 Zr(0C 3

H

7 4 Zr(0C 4

H

9 4 ZrCl 2 (0C 3

H

7 2 preference being given to the use of TiCl 4 ZrCl 4 1 Ti(0C 2

H

5 4 1 Ti(0C 3

H

7 4 1 Zr(0C 3

H

7 4 Ti(0C 4

H,)

4 and Zr(0C 4

H,)

4 t C The third reactant for the preparation of the catalyst component a is an organoaluminum, compound of the formula

III

C C AlR~q(0R 5 )pX 3 -q.p I in which R 4 and R 5 are identical or different and are an alkyl radical having 1 to 6, preferably 1 to 4, carbon atoms, X is a halogen atom, preferably chlorine, and q is a number from zero to 3, preferably 1 to 2, and p is a number from zero to 1, and is preferably less than Suitable organoaluminum compounds are: Al (CAH) 3 1 Al (CAH) 2 C1, A1 2 (CAH) 3 C1 3 A' (C 2 HA)C1 2 AlC1 3

I

4 6 Al(C 3

H

7 3 Al(C 3

H

7 2 C1, A1 2

(C

3

H

7 3 Cl 3 Al(C 3

H

7 )Cl 2 Al(C 4

H

9 3 Al(C 4

H,)

2 C1, A1 2

(C

4

H

9 3 Cl 3 Al(C 4

H

9 )Cl 2 and also mono- and di-halides of different composition.

Preference is given to the use from this group of Al(CzH5) 2 C1, Al.(CH1 5 3 Cl 3 and Al(C 2

H

5 )C1 2 M1ImXy be The catalyst component a-a. formed by the following possible methods, in which each reactant may also be used as the major component among similar compounds.

o U *o 5 I 15 Ii I U Sc I i-i i i i i;j ii_: i 1J 120 C CC t' 2 CLCt t t C 25 i) The solution of the transition metal compound is added to a solution of the magnesium alcoholate and the resulting solid is then reacted with an organoaluminum compound of the formula III.

ii) The solution of the magnesium alcoholate is added to a solution of the transition metal compound and the resulting solid is then reacted with an organoaluminum compound of the formula III.

iii) The solution of the magnesium alcoholate is added to a solution of the transition metal compound and the reaction mixture is then combined with a solution of the transition metal compound and the resulting solid is then reacted with an organoaluminum compound of the formula III.

iv) The solution of a magnesium alcoholate and the solution of the transition metal compound are simultaneously added to previously charged solvent and the resulting suspension is reacted with an organoaluminum compound of the formula III.

v) The solution of a magnesium alcoholate, the solution of the transition metal compound and an organoaluminum compound of the formula III are simultaneously reacted together in the previously charged dispersant.

P, ?A 4

T-

4 7 Furthermore, there are preparative methods which operate by a combination of methods i) to Examples of combinations of this type are methods vi) to viii).

vi) The solution of a magnesium alcoholate and the solution of the transition metal compound are simultaneously added to a previously charged solution of a transition metal compound and the resulting suspension is then reacted with the organoaluminum compound of the formula III.

vii) The solution of a magnesium alcoholate, the solution of the transition metal compound and an organoaluminum compound of the formula III are simultaneously added to a previously charged solution of a transition metal compound.

i viii) The solution of a magnesium alcoholate and the solution of a transition metal compound are simula 4 taneously added to a previously charged solvent and the resulting suspension is reacted in succession with the solution of a magnesium alcoholate, the solution of a transition metal compound and an t organoaluminum compound of the formula III.

An electron donor may be used as a fourth reactant in the preparation of the catalyst component a. This electron donor is an aliphatic or alicyclic ether, an aliphatic k 25 ester, an aliphatic aldehyde or an aliphatic carboxylic oo acid. Examples of electron donors (ED) of this type are: a dimethyl ether, diethyl ether, di-n-propyl ether, di-nbutyl ether, di-iso-amyl ether, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate and acetic acid, preference being given to the use of diethyl ether, dibutyl ether and ethyl acetate.

The electron donor is added to at least one of the three other reactants before or during the reaction.

r I e 5'4

F'

;1 8 The magnesium alcoholate is reacted with the tetravalent transition metal compound at a temperature of -50 to 150"C, preferably at -20 to 120"C, in the course of 0.1 to 10 hours, preferably 0.13 to 4 hours. The reaction rlcry be with the organoaluminum compound 4 carried out at a temperature of -50 to 150"C, prferaply at -20 to 130 0

C,

particularly preferably 20 to 120°CA ii. the course of 0.1 to 10 hours, preferably 0.25 to 4 hours.

Suitable inert solvents for the abovementioned reactions are aliphatic and cycloaliphatic hydrocarbons such as butane, pentane, hexane, heptane, cyclohexane and isooctane, and also aromatic hydrocarbons such as benzene and xylene. It is also possible to use gasoline and hydrogenated diesel oil fractions which have been carefully C15 freed from oxygen, sulfur compounds and moisture.

Magnesium alcoholate, tetravalent transition metal compound organoaluminum cpmpound of the formula III and electron donor (ED)A reacted in the ratio Mg:M:Al:ED of 1 0.05 to 2 0.3 to 4 0 to 2, prefer- 20 ably 1 0.08 to 1 0.4 to 3 0 to 1.

r i ;'i ti: ii

I'"

B

i i 8 In j Ir i tt rCI C tr

I

rII C 4 C C

CC

After the re ction, the suspension of the catalyst component aA'- stirred for zero to 48 hours, preferably zero to 16 hours, at 0 to 150"C, preferably 60 to 120°C The suspension of the catalyst component a which has been prepared in this mannerl- used directly for the polymerization without separating off the dispersant and the byproducts.

25 S.r

IE

The catalyst component b used is a trialkylaluminum having 1 to 6 carbon atoms in the alkyl radicals such as for example triethylaluminum, triisobutylaluminum, triisohexylaluminum or the reaction product of a trialkylaluminum or dialkylaluminum hydride with isoprene, which WAL is known as isoprenylaluminum. Preference is given to triethylaluminum and isoprenylaluminum.

_C

S- 8a The polymerization/4 carried out in one or two stages, as is the case with prior art polymerization processes, preferably as a suspension polymerization in an inert dispersant. Suitable dispersants are the same organic solvents as have been described for the preparation of the catalyst component a. However, it is also possible to polymerize in the gas phase.

t C CC i I CC..

i E i CCC: S CC Ir i- 9 mr-- L 2 Z t- 4- T~ L. 1 preferably as a suspension polymerization j-a- nert dispersant. Suitable dispersant the same organic solvents as have escribed for the preparation of the c st component a. However, it is also possible to l~rmr lr i i -r h r h C0 4 C CC Crr CCCi 4 i .e )quc~.tj xi ~t-L-t IO The polymerization temperature is 20 to 120, preferably to 90 0 C; the pressure is in the range from 2 to preferably 4 to 20 bar.

If the reaction is carried out in two stages, the ratio of the amounts of polyolefins formed in each of the stages 1 and 2 is in the range of 30 70 to 70 30, and the polymer formed in stage 1 is continuously transferred to stage 2. The final polymer mixture is withdrawn 15 continuously from stage 2.

The catalyst system used according to the invention is employed in the polymerization of ethylene or ethylene with up to 10% by weight, relative to the total amount of monomers, of a 1-olefin of the formula R 9

-CH=CH

2 in which

R

9 is a straight-chain or branched alkyl radical having 1 to 12, preferably 1 to 10, carbon atoms. Examples are propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4methyl-l-pentene. Preference is given to the use of propylene, 1-butene and 1-hexene. In this polymerization, the comonomers are preferably introduced in the first stage in which a polymer of relatively high molecular weight is produced.

The total polymer from the second stage is separated from the dispersant and dried in a manner known per se.

I i" ;:i 3 Iii i I: CcL e-er c 1 An advantage of the process according to the invention is the very simple preparation of the transition metal component of the catalyst. This is obtained by simple combination of the individual components under the NC relevant reaction conditions.

1w 4? 9 OI/

IT°

1 10 Washing with an inert hydrocarbon is dispensed with.

Therefore no washing liquor is produced which must be split into its component parts again in further process steps and must be worked up with the generation of effluent.

Even after long periods of continuous operation there are no polymer deposits on the vessel walls and in the connecting lines, and the proportion in the product of particles of a size below 100 pm is significantly smaller.

However, the great advantage of the process according to the invention is that the specifically modified magnesium alcoholate allows the preparation of a catalyst which t ,l gives an ethylene polymer having a very large average particle diameter of 200 to 700 pm and a high bulk t 15 density of above 300 g/dm 3 preferably of above 350 g/dm 3 Consequently, the polymer has a lower residual moisture t i e" content resulting in reduced drying costs.

The particle size distribution is to a high degree uniform.

120 Furthermore, it is possible to regulate the molecular weight of the polyolefins using hydrogen in a signifit c cantly more efficient manner than in prior-art processes.

The invention will be explained using the following s a examples.

The meanings of the symbols are as follows: CTAed reduced catalyst-time activity MFI 190/5 melt flow index in accordance with DIN 53 735, measured at 190 0 °C under a load of 5 kg MFI 190/15 measured at 190°C under a MFI 190/21.6 load of 15 and 21.6 kg respectively r 11 MFR 15/5 MFI 190/15 MFI 190/5 ds 0 median partical size determined by screen classification SD bulk density measured in accordance with DIN 53 468 Example 1 A 1 dm 3 stirred vessel was first charged, while excluding air and moisture, with a solution of 0.1 mol of magnesium 1 bis(2-methyl-l-pentyl alcoholate) in 200 cm 3 of a gasoline S 10 fraction 140-170 0 100 cm 3 of a 0.3 molar solution of TiCl in the gasoline fraction were added with stirring and under an atmosphere of argon at a temperature of in the course of 120 min.

i To the resulting suspension were added dropwise with stirring at 80 0 C in the course of 120 min 100 cm 3 of a 0.8 molar solution of ethylaluminum sesquichloride in the S' gasoline fraction. This gave a reddish-brown precipitate.

A portion of this suspension was diluted with the gasoline I l Ec fraction to a Ti concentration of 0.01 mol/dm 3 A 1.5 dm 3 L 20 steel autoclave filled with 750 cm 3 of the gasoline fra%- Stion was charged at 85 0 C under an atmosphere of N 2 with S 3 cm 3 of a 1 Molar triethylaluminum solution and 20 cm 3 of the suspension. The vessel was then first charged with 3.15 bar of hydrogen followed by 3.85 bar of ethylene.

The total pressure of 7 bar was maintained for 2 h, the consumed ethylene being made up. The polymerization was S terminated by decompressing the gases and the polymer was separated from the dispersant by filtration and drying.

This gave 213 g of polyethylene having an MFI 190/5 of 34.9 g/10 min and an MFR 15/5 of 5.8. This corresponds to a CTAed of 1385 g/mmol of Ti-bar.h. The powder had a bulk density of 340 g/cm 3 and a fines content 100 pm) of 8% by weight. The median partical size ds 0 was 330 pm.

I!

-12- Example 2 9.47 g of TiC14 in 100 cm 3 of the gasoline fraction were metered into 100 mmol of magnesium bis(2-methyl-l-pentyl alcoholate) in 400 cm 3 of the gasoline fraction at 25"C in the course of 2 h. Then, 80 mmol of ethylaluminum sesquichloride in 100 cm 3 of the gasoline fraction were added at 0 C in the course of 2 h. The polymerization was carried out as described in Example 1. This gave 155.3 g of polyethylene corresponding to a CTAred of 1008 g/mmol of Ti-bar-h, the product characteristics being as follows: MFI 190/5 36.6 g/10 min; ds 5 380 pm MFI 190/15: 199.1 g/10 min; bulk density: 310 g/dms MFR 15/5 5.4 fines content: 1% 100 pm 00000 S0o0 Example 3 4 0 0 15 7.7 cm 3 of TiCl 4 in 230 cm 3 of the gasoline fraction were metered into 100 mmol of magnesium bis(2-methyl-1-pentyl alcoholate) in 200 cm 3 of the gasoline fraction at 25"C in the course of 2 h. Then 14.88 g of ethylaluminum sesquichloride in 100 cm 3 of the gasoline fraction were added at :20 80"C in the course of 0.5 h.

The polymerization was carried out as described in Example 1. This gave 83.4 g of polyethylene corresponding to a CTAed of 542 g/mmol of Ti.bar of C 2

H

4 the product o 06o having the following characteristics: MFI 190/5 25.4 g/10 min; dso: 490 pm MFI 190/15: 114.6 g/10 min; bulk density: 350 g/dms MFR 15/5 4.5 fines content: 9% 100 pm Example 4 22.2 g of magnesium bis(2-methyl-l-pentyl alcoholate) in 300 cm 3 of the gasolinefraction were metered into 100 cm 3 of a 0.2 Molar solution of TiC14 in the gasoline fraction f 13 at 80°C in the course of 1 h followed by 3.8 g of TiCl 4 in 100 cm 3 of the gasoline fraction at 80°C in the course of 60 min. Then 80 mmol of ethylaluminum sesquichloride L in 128 cm 3 of the gasoline fraction were added at 80°C in the course of 1 h.

A 150 dm 3 vessel was charged with 100 dm 3 of gas oil, mmol of isoprenylaluminum and 30.4 cm 3 of the dispersion. Then, at a polymerization temperature of 85°C, were ailded in the first hour 7.5 kg of ethylene, then 5 kg of ethylene/h were introduced and sufficient H 2 to give an H 2 content in the gas space of 45% by volume. After 60 min, 350 cm 3 of l-butene were additionally introduced in the course of 1.5 h. After 6.25 h, the polymerization was j: 1 terminated at a pressure of 5.8 bar by decompression. The 15 suspension was filtered and the polyethylene powder was dried under a current of hot nitrogen.

8 t t a S This gave 32.4 kg of polyethylene. This corresponds to a catalyst activity of 21.6 g of PE/mmol of Ti. Thi polyethylene powder had an MFI 190/5 of 21.4 g/10 min Lfnd an MFR 15/5 of 4.9. The density was 0.959 g/cm 3 and the bulk density was 440 g/dm 3 The median partical size d.

0 was 320 with a fines content (100 pm.) of 1%.

Example 300 cm 3 of a 0.33 M solution of magnesium bis(2-methyl-1pentyl alcoholate) in the gasoline fraction were metered into 3.3 cm 3 of TiCl 4 in 100 cm 3 of the gasoline fraction at 80°C in the course of 2 h. Then 80 mmol of ethylaluminum sesquichloride in 100 cm 3 of the gasoline fraction were added at 80°C in the course of 2 h.

The polymerization was carried out as described in Example 1. This gave 196 g of polyethylene corresponding to a KZared of 1273 g/mmol of Ti-bar of C 2

H

4 the product having the following characteristics: _i 14 MFI 190/5 41 g/10 min; ds 0 MFI 190/15: 221.0 g/10 min; bulk density: MFR 15/5: 5.4 fines content: 220 pm 320 g/dma 6% 100 pm Example 6 100 mmol of magnesium bis(2-methyl-l-pentyl alcoholate) in 200 cm 3 of gasoline fraction were metered into 5.7 g of Ti(OEt)Cl 3 in 100 cm 3 of the gasoline fraction at 25°C in the course of 2 h. Then 80 mmol of ethylaluminum sesquichloride in 100 cm 3 of the casoline fraction were added at 80°C in the course of 2 h.

The polymerization was carried out as described in Example 1. This gave 167.8 g of polyethylene corresponding to a CTAeBd of 1090 g/mmol of Ti-bar of C 2

H

4 the product having the following characteristics: o e S0 C t 9s r c t t t C a" c .a t t c a E 10 c I 6~lD MFI 190/5 34.9 g/10 min; ds 0 MFI 190/15: 188.9 g/10 min; bulk density: MFR 15/5 5.4 fines content: 260 pm 300 g/dms 3% 100 pm Example 7 To 30 mmol of TiCl 4 in 100 cm 3 of the gasoline fraction were added 3.9 g of di-n-butyl ether and at 25"C in the course of 2 h were metered in 100 mmol of magnesium bis(2-methyl-lpentyl alcoholate) in 300 cm 3 of the gasoline. fraction. Then 18.1 cm 3 of ethylaluminum sesquichloride in 100 cm 3 of the gasoline fraction were added at 80 0 C in the course of 2 h.

The polymerization was carried out as described in Example 1. This gave 87.6 g of polyethylene corresponding to a CTA,d of 569 g/mmol of Ti.bar of C 2

H

4 the product having the following characteristics: MFI 190/5 26.4 g/10 min; ds 0 MFI 190/15: 131.4 g/10 min; bulk density: MFR 15/5 5.0 fines content: 210 pm 350 g/dm3 7% 100 pm I t Example 8 100 mmol of ethylaluminum sesquichloride in 100 cm 3 of the gasoline fraction were added at 80 0 C in the course of 2 h to a solution of 100 mmol of magnesium bis(2-methyl- 1-pentyl alcoholate) and 20 mmol of Ti(OEt) 4 in 300 cm 3 of the gasoline fraction.

The polymerization was carried out as described in SExample 1. This gave 123 g of polyethylene corresponding to a CTAred of 795 g/mmol of Ti-bar of C 2

H

4 the product having the following characteristics: fE MFI 190/5 13.9 g/10 min; dso: 220 pm c MFI 190/21.6: 133.1 g/10 min; bulk density: 340 g/dms V tC MFR 21.6/5 9.6 fines content: 5% 100 pm C cc C Example 9

C

To 100 mmol of magnesium bis (2-methyl-1-pentyl alcoholate) in 200 cm 3 of the gasoline fraction were added about 6 mmol of di-n-butyl ether and then, in the course of 2 h, 30 mmol of TiCl 4 in 100 cm 3 of the gasoline. fraction were metered in at 25"C. Then 80 mmol of ethylaluminum sesquichloride in 100 cm 3 of the gasoline fraction were addnd at 80 0 C in the course of 2 h.

I The polymerization was carried out as described in C e Example 1. This gave 127 g of polyethylene, corresponding Sto a CTAed of 827 g/mmol of Ti.bar of C 2

H

4 the product having the following characteristics: MFI 190/5 24.5 g/10 min; d 5 s: 510 pm MFI 190/15: 137.5 g/10 min; bulk density: 330 g/dms MFR 15/5 5.6 fines content: 0.3% 100 pm Example To 100 mmol of magnesium bis (2-methyl-1-pentyl alcoholate)

A

.1 16 in 200 cm 3 of the gasaline fraction were added 30 mmol of diethyl ether and then 30 mmol of TiCl 4 in 100 cm 3 of the Jasoline. fraction were metered in at 25"C in the course of iI 2 h. Then 80 mmol of ethylaluminum sesquichloride in 100 cm 3 of the gasoline fraction were added at 80 0 C in the course of 0.5 h.

The polymerization was carried out as described in Example 1. This gave 141 g of polyethylene, corresponding to a CTAred of 918 g/mmol of Ti.bar of C 2 H 4 h, the product having the following characteristics: MFI 190/5 28.2 g/10 min; ds 5 370 pm S.MFI 190/15: 150.4 g/10 min; bulk density: 360 g/dms MFR 15/5 5.2 fines content: 5% 100 pm Example 11 I s15 To 22.2 g of magnesium bis(2-methyl-l-pentyl alcoholate) in 200 cm 3 of the gasoline fraction were metered in at 25 C in the course of 3 h a solution of 30 mmol of di-n-butyl ether and 30 mmol of TiC1 4 in 100 cm 3 of the gasoline fracion. Then 100 cm 3 of a 0.8 M solution of ethylaluminum r' c'20 sesquichloride in 100 cm 3 of the gasoline fraction were added at 80 0 C in the course of 1 h.

The polymerization was carried out as described in Example 1. This gave 94.5 g of polyethylene, correspondj ing to a CTAed of 614 g/mmol of Ti.bar of C 2

H

4 the 125 product having the following characteristics: MFI 190/5 32.6 g/10 min; ds 5 390 pm MFI 190/15: 190.4 g/10 min; bulk density: 350 g/dms MFR 15/5 5.8 fines content: 4% 100 pm Example 12 To the solution of 20 mmol of ZrCl 4 and 372 mmol of di-nbutyl ether in 50 cm 3 of the gasoline fraction were metered cr -17in at 60"C in the course of 1 h 100 mmol of magnesium bis(2-ethyl-l-hexyl alcoholate) in 200 cm 3 of the gasoline fraction followed by metering in at 60°C in the course of min of 20 mmol of TiCl 4 in 100 cm 3 of the gasoline fraction. Then 80 mmol of ethylaluminum sesquichloride in 128 cm 3 of the gasoline fraction were added at 80"C in the course of 1 h.

The polymerization was carried out as described in Example 1. This gave 189.7 g of polyethylene', corresponding to a CTAed of 901 g/mmol of Ti.bar of CzH 4 the I product having the following characteristics: MFI 190/5 4.4 g/10 min; d 50 360 pm S. MFI 190/15: 23.3 g/10 min; bulk density: 360 g/dms i MFR 15/5 5.4 fines content: 0.7% 100 pm S:i '15 Example 13 I 4 t SA 2 dm 3 stirred vessel was charged with 250 mmol of magnesium bis(2-methyl-1-pentyl alcoholate) and 12.68 cm 3 of di-n-butyl ether in 500 cm 3 of the gasoline fraction and 9.25 cm 3 of TiC14 in 250 cm 3 of the gasoline fraction were VC'20 metered in at 20"C in the course of 0.5 h. Then 200 mmol of ethylaluminum sesquichloride in 250 cm 3 of the gasoline C t fraction were added at 80 0 C in the course of 0.5 h. The suspension was then stirred for a further 10 h at i The polymerization was carried out as described in 1 J25 Example 1. This gave 138.3 g of polyethylene, corresponding to a CTAed of 898 g/mmol of Ti.bar of CzH 4 the product having the following characteristics: MFI 190/5 27.0 g/10 min; dso: 440 pm MFI 190/15: 130.6 g/10 min; bulk density: 380 g/dms MFR 15/5 4.8 fines content: 5% 100 pm -18- Example 14 To 100 mmol of magnesium bis (2-methyl-l-pentyl alcoholate) in 200 cm 3 of the gasoline fraction were metered in at in the course of 1 h 30 mmol of TiC1 4 in 100 cm 3 of the gasoline fraction. Then 80 mmol of ethylaluminum sesquichloride and 4 cm 3 of di-n-propyl ether in 100 cm 3 of the gasoline fraction were added at 80 C in the course of h.

The polymerization was carried out as described in Example 1. This gave 134.7 g of polyethylene, corresponding to a CTAred of 875 g/mmol of Ti-bar of C 2

H

4 the product having the following characteristics: S III MFI 190/5 31.8 g/10 min; dso: 340 pm hI MFI 190/15: 178.0 g/10 min; bulk density: 360 g/dms S. *15 MFR 15/5 5.6 fines content: 5% 100 pm Example To a solution of 0.6 cm 3 of TiC1 4 and 5 mmol of di-n-butyl ether in 50 cm 3 of the gasoline, fraction were metered in at 0o*" 25°C in the course of 1 h 22 g of magnesium bis(2-methyl- 1-pentyl alcoholate) in 200 cm 3 of the gasoline fraction ti\ c followed by metering in 10 g of TiCl 4 in 100 cm 3 of the gasoline fraction in the course of 60 min. Then 18.1 mmol of ethylaluminum sesquichloride in 110 cm 3 of hexane were I *o.o added at 80 0 C in the course of 1 h.

0 The polymerization was carried out as described in Example 1. This gave 151.2 g of polyethylene, corresponding to a CTAud of 982 g/mmol of Ti.bar of C 2

H

4 the product having the following characteristics: MFI 190/5 33.0 g/10 min; dso: 490 pm MFI 190/15: 159.4 g/10 min; bulk density: 310 g/dms MFR 15/5 4.8 fines content: 2% 100 pm -I 19- Example 16 To 100 cm 3 of the gasoline fraction were simultaneously metered in at 25 0 C in the course of 1 h 195 cm 3 of a 0.52 M solution of magnesium bis(2-methyl-l-pentyl alcoholate) in the gasoline fraction and 3 cm 3 of TiC14 in 100 cm 3 of the gasoline fraction. Then 20 g of ethylaluminum sesquichloride in 100 cm 3 of the gasoline. fraction were added at in the course of 0.5 h.

The polymerization was carried out as described in Example 1. This gave 210.4 g of polyethylene, corresponding to a CTAed of 1366 g/mmol of Ti-bar of C 2

H

4 the product having the following characteristics: MFI 190/5 37.4 g/10 min; dso 0 390 pm MFI 190/15: 180.0g/10 min bulk density: 300 g/dm3 C i S* .15 MFR 15/5 4.8 fines content: 2% 100 pm Example 17 To 100 cm of the gasoline. fraction were simultaneously metered in at -25°C in the course of 2 h 100 mmol of magnesium bis(2-methyl-l-pentyl alcoholate) in 200 cm 3 of the gasoline fraction, 30 mmol of TiC14 in 100 cm 3 of the gasoline fraction and 80 mmol of ethylaluminum sesquichloride in 100 cm 3 of the gasoline fraction. The resulting suspension was then heated to 100°C in the course of 105 min and stirred at this temperature for 10 min.

The polymerization was carried out as described in Example 1. This gave 127.4 g of polyethylene, corresponding to a CTAed of 1655 g/mmol of Ti.bar of C 2

H

4 the product having the following characteristics: MFI 190/5 16.2 g/10 min; dso: 270 pm MFI 190/15: 87.6 g/10 min; bulk density: 280 g/dms MFR 15/5 5.4 fines content: 0.2% 100 pm Example 18 To 100 cm 3 of the gasoline fraction were simultaneously metered in at 80"C in the course of 2 h 100 mmol of magnesium bis(2-methyl-l-pentyl alcoholate) in 200 cm 3 of 5 the gasoline fraction, 30 mmol of TiC1 4 in 100 cm 3 of the gasoline fraction and 80 mmol of ethylaluminum sesquichloride and 28 mmol of di-iso-amyl ether in 100 cm 3 of the naphtha fraction.

The polymerization was carried out as described in Example 1. This gave 183.2 g of polyethylene, corresponding to a CTArod of 1190 g/mmol of Ti.bar of CzH 4 the i product having the following characteristics: I MFI 190/5 24.8 g/10 min; dso: 250 pm I MFI 190/15: 123.2 g/10 min; bulk density: 350 g/dms MFR 15/5 5.0 fines content: 4% 100 pm I Example 19 To 100 cm 3 of the gasoline fraction were simultaneously t" metered in at 20"C in the course of 2 h 100 mm:ol of magnesium bis(2-methyl-l-pentyl alcoholate) in 200 cm 3 of the gasoline fraction, 30 mmol of TiC14 in 100 cm 3 of the gasoline fraction and 80 mmol of ethylaluminum sesquichloride and 30 mmol of di-n-butyl ether in 100 cm 3 of the gasoline fraction.

i; The polymerization was carried out as described in Example 1 using 5 mmol of isoprenylaluminum. This gave 207.6 g of polyethylene, corresponding to a catalyst activity of 10,380 g/mmol of Ti-bar of C 2

H

4 the product having the following characteristics: MFI 190/5 8.8 g/10 min; do 0 350 pm MFI 190/15: 42.5 g/10 min; bulk density: 320 g/dma MFR 15/5 5.0 fines content: 0.2% 100 pm 21- Example To 100 cm 3 of the gasoline fraction were simultaneously metered in at 20 C in the course of 2 h 10C mmol of magnesium bis(2-methyl-1-pentyl alcoholate) and 10 mmol of triethylaluminum in 200 cm 3 of the gasoline fraction, mmol of TiC1 4 in 100 cm 3 of the gasoline fraction and mmol of ethylaluminum sesquichloride in 100 cm 3 of the gasoline fraction. The suspension was then kept at a temperature of 105 0 C (under reflux) for 2 h.

The polymerization was carried out as described in Example 1 using 5 mmol of isoprenylaluminum and 0.01 mmol of catalyst. This gave 130.3 g of polyethylene, corresi ponding to a CTAzed of 1692 g/mmol of Ti.bar of C 2

H

4 the product having the following characteristics: t 4 1 '15 MFI 190/5 9.0 g/10 min; dso: 410 pm .t MFI 190/15: 44.8 g/10 min; bulk density: 320 g/dms MFR 15/5 5.0 fines content: 0.5% 100 pm Example 21 A 2 dm 3 stirred vessel was charged with 100 mmol of magnesium bis(2-methyl-l-pentyl alcoholate) and 5 cm 3 of din-butyl ether in 200 cm 3 of the gasoline fraction, and mmol of TiC1, in 100 cm 3 of the gasoline fraction were metered in at 25 0 C in the course of 0.5 h. Then 80 mmol of ethylaluminum sesquichloride in 100 cm 3 of the gasoline S .45 fraction were added at 80 0 C in the course of 0.5 h.

A 150 dm 3 vessel was charged with 100 dm 3 of diesel oil, mmol of triethylamine and 58 cm 3 of the dispersion.

Then, at a polymerization temperature of 85"C, 7.5 kg of ethylene/h were introduced and sufficient H 2 to give an H 2 content in the gas space of 40% by volume. After 90 min, 800 cm 3 of 1-butene were additionally introduced in the course of 60 min. After 5.1 h, the polymerization was terminated at a pressure of 4.3 bar by decompression. The 22suspension was filtered and the polyethylene powder was V dried by passing hot nitrogen over it.

This gave 36.8 kg of polyethylene. This corresponds to a catalyst-time activity of 2420 g of PE/mmol of Ti.h. The polyethylene powder had an MFI 190/5 of 29.4 g/10 min and San MFR 15/5 of 4.8. The density was 0.955 g/cm 3 and the bulk density was 410 g/dm. The median partical size ds was 430 pm with a fines content 100 pm) of 4%.

Example 22 A 4 dm 3 stirred vessel was charged with 111.2 g of magnet, sium bis(2-methyl-l-pentyl alcoholate) and 150 mmol of din-butyl ether in 1000 cm 3 of the gasoline fraction and then 16.5 cm 3 of TiC14 in 500 cm 3 of the gasoline fraction were Smetered in at 25°C in the course of 0.5 h. Then 400 mmol :r >15 of ethylaluminum sesquichloride in 500 cm 3 of the gasoline I t fraction were added at 80°C in the course of 0.5 h. The batch was then stirred for a further 45 min at 80 0

C.

A 150 dm 3 vessel was charged with 100 dm 3 of diesel oil, mmol of triethylaluminum and 39 cm 3 of the dispersion.

Then, at a polymerization temperature of 85"C, 7.5 kg of ethylene/h were introduced and sufficient H2 to give an H 2 content in the gas space of 38% by volume. After 60 min, 625 cm 3 of 1-butene were additionally introduced in the Icourse of 1.5 h. After 4.25 h, the polymerization was terminated at a pressure of 5.4 bar by decompression. The suspension was filtered and the polyethylene powder was dried by passing hot nitrogen over it.

This gave 30 kg of polyethylene. This corresponds to a catalyst-time activity of 15.2 kg of PE/mmol of Ti. The polyethylene powder had an MFI 190/5 of 19.5 g/10 min and an MFR 15/5 of 5.2. The density was 0.957 g/cm 3 and the bulk density was 420 g/dm 3 The median partical size ds was 500 pm with a fines content 100 pm) of 3%.

23 Example 23 To 80 cm 3 of a 0.1 molar solution of TiC1 4 in the gasoline fraction were metered in at 80 0 C in the course of 1 h 23 g of magnesium bis(2-ethyl-1-hexyl alcoholate) and mmol of ethyl acetate in 200 cm 3 of the gasoline fraction followed by metering in 5 g of TiC1 4 in 100 cm 3 of the gasoline fraction at 60°C in the course of 60 min. Then mmol of ethylaluminum sesquichloride in 128 cm 3 of the naphtha fraction were added at 80°C in the course of 1 h.

10 t t tt s c t 0 5

CII

r tcC CCC t t

C

1 5 The polymerization was carried out as described in Example 1, at, however, an H 2 pressure of 2.3 bar abs..

This gave 142.1 g of polyethylene, corresponding to a CTAed of 756 g/mmol of Ti.bar of C 2

H

4 the product having the following characteristics: MFI 190/5 4.7 g/10 min; dso 0 410 pm MFI 190/15: 26.8 g/10 min; bulk density: 320 g/dms MFR 15/5 5.7 fines content: 2% 100 pm

CICC

CCC'

Example 24 To a solution of 20 mmol of Zr(iso-OC 3

H

7 4 in 70 cm 3 of the gasoline fraction were metered in at 0°C in the course of min 22.2 g of magnesium bis(2-methyl-l-pentyl alcoholate) in 200 cm 3 of the gasoline fraction followed by metering in 3 cm 3 of TiC1 4 in 100 cm 3 of heptane at in the course of 60 min. Then 20 cm 3 of ethylaluminum sesquichloride in 100 cm 3 of the gasoline fraction were added at 80*C in the course of 2 h.

The polymerization was carried out as described in Example 1, with, however, an H 2 pressure of 3.75 bar abs..

This gave 74.7 g of polyethylene, corresponding to a CTAd of 574 g/mmol of Ti.bar of C 2

H

4 the product having the following characteristics: i~ rCIC- i..

c 2 24 I- t I r C I C i C MFI 190/5 44.1 g/10 min; ds 5 340 pm MFI 190/15 13.8 g/10 min; bulk density350 g/dm s fines content: 1% 100 pm Example 100 mmol of magnesium (2-methyl-l-pentyl alcoholate) in 300 cm 3 of the gasoline fraction (solution 40 mmol of TiC1 4 in 133 cm 3 of the gasoline fraction (solution B) and mmol of Al 2 Et 3 Cl 3 in 100 cm 3 of the gasoline fraction (solution C) were reacted as follows.

200 cm 3 of the gasiLnie fraction were initially charged and, at 20"C in the course of 40 min, 100 cm 3 of solution A and 33 cm 3 of solution B were simultaneously added. The resulting suspension was simultaneously reacted in the course of 2 h with 200 cm 3 of solution A, 100 cm 3 of solution B and 100 cm 3 of solution C. The suspension was then stirred for 3 h at 110°C.

The polymerization was carried out as in Example 1, with, however, an Hz pressure of 2 bar abs. and using 5 mmol of isoprenylaluminum as activator. This gave 189 g of poly- 20 ethylene, corresponding to a CTAed of 1890 g/mmol-h-bar, the product having the following characteristics: 4 'I-k t i i i ?4 'i t tC t C i c MFI 190/5 1.4 g/10 min; ds 0 MFR 15/5: 4.7 bulk density: MFR 21.6/5: 9.0 fines content: 450 pm 0.35 g/dms 0.1% 100 pm Example 26 To a solution of 0.1 mol of magnesium bis(2-methyl-lpentyl alcoholate) in 250 cm 3 of the gasoline fraction 140-170 0 C) were metered in at a temperature of in the course of 50 min 110 cm 3 of a 0.3 molar solution of TiC14 in the gasoline fraction.

i 25 Then 128 cm 3 of a 0.625 molar solution of ethylaluminum sesquichloride in the gasoline fraction were metered in at in the course of 60 min. The batch was then stirred for a further 12 h at 110 0 C. The polymerization was carried out as described in Example 1.

This gave 131 g of polyethylene having an MFI 190/5 of S22.5 g/10 min and an MFR 15/5 of 4.7. This corresponds to a CTAred of 850 g/mmol of Ti-bar-h. The powder had a bulk V density of 300 g/dm 3 and a fines content 100 pm) of 0.7% by weight. The median partical size ds 0 was 550 pm.

Example 27 t i To 50 mmol of magnesium bis(2-methyl-l-pentyl alcoholate) S" in 100 cm 3 of the gasoline fraction were metered in at in the course of 1 h 15 mmol of TiC14 in 50 cm 3 of the gasoline fraction. Then 60 mmol of ethylaluminum sesquichloride in 50 cm 3 of the gasoline fraction were added at 0 C in the course of 2 h.

SThe polymerization was carried out as described in Example 1 using 3 mmol of triisobutylaluminum.

This gave 190.4 g of polyethylene, corresponding to a CTAred of 1236 g/mmol of Ti-bar.h., the product having the following characteristics: MFI 190/5 25.5 g/10 min; ds 5 275 pm MFI 190/15: 127.0 g/10 min; bulk density; 360 g/dms MFR 15/5 5.0 fines content: 4% 100 pm Example 28 A 4 dm 3 stirred vessel was charged with a suspension of 500 mmol of magnesium ethanolate in 900 cm 3 of the gasoline fraction. To this suspension was added 1 mol of 2-ethylhexanol. Then 50 mmol of triethylaluminum were metered in at 130"C in the course of 16 hours. During this period,

A

-26 the displaced ethanol was distilled off.

To the solution of the magnesium bis(2-ethyl-l-hexyl alcoholate) were metered in at 25 0 C in the course of 2 h 150 mmol of TiC1 4 in 500 cm 3 of the gasoline fraction. Then 500 mmol of ethylaluminum sesquichloride in 500 cm 3 of the gasoline fraction were added at 80 0 C in the course of 2 h.

The polymerization was carried out as described in Example 1.

i This gave 107.2 g of polyethylene, corresponding to a CTA.d of 696 g/mmol of Ti-bar-h, the product having the i c following characteristics: sC t lMFI 190/5 36.5 g/10 min; dso: 575 pm CcC t S, MFI 190/15: 199.4 g/10 min; bulk density: 290 g/dm3 MFR 15/5 5.5 fines content: 0.3% 100 pm Example 29 A 2 dm 3 stirred vessel was charged with a suspension of 250 mmol of magnesium ethanolate in 300 cm 3 of the gasoline fraction. To this suspension were added 500 mmol of 2ethylhexanol. Then 55 mmol of triethylaluminum were metered in at 130 0 C in the course of 16 hours. During this period, the displaced ethanol was distilled off.

"H Then 500 cm 3 of the gasoline fraction were added.

i To the solution of the magnesium bis(2-ethyl-l-hexyl alcoholate) were metered in at 20*C in the course of 4 h 75 mmol of TiC14 in 500 cm 3 of the gasoline fraction. Then 200 mmol of ethylaluminum sesquichloride in 500 cm 3 of the gasoline fraction were added at 20"C in the course of 2 h.

Then the batch was stirred for a further 8 h at The polymerization was carried out as described in Example 1.

it -27- This gave 145.2 g of polyethylene, corresponding to a CTAed Of 943 g/mmol of Ti-bar-h, the product having the following characteristics: SM.FI 190/5 :21.8 g/10 min; d 50 270 pm MFI 190/15: 111.4 g/10 min; bulk density: 350 g/dms MFR 15/5: 5.1 ;fines content: 3% 100 Mm t t it 4 i4 4

Claims

1. A process for the preparation of an ethylene polymer having a uniform coarse particle shape and a high bulk density by the polymerization of ethylene or of ethylene with up to 10% by weight, relative to the total amount of monomers, of a 1-olefin of the formula R 9 -CH=CH 2 in which R 9 is a straight-chain or branched alkyl rudical having 1 to 12 carbon atoms, in suspension, in solution or in the gas phase, at a temperature of 20 to 120°C and a pressure of 2 to bar in the pro one ofa catalyst composd reaction product of a magnesi aleotate with a r e tetravalent tr n metal compound and an organo- nd, which comprises carrying out the polymerization in the presence of a catalyst which is composed of a) the over-all product from the reaction al) of a magnesium alcoholate of the formula I Mg(OR (OR) (I) dissolved in an inert solvent, in which formula R 1 and R 2 are either identical and are a radical -CH 2 CHRR 7 or -(CH,)OR 8 R 6 being a hydrogen atom or a Cl-C-alkyl radical, R' a C 2 -C-alkyl radical, R 8 a Ci-C 4 -alkyl radical and n an integer from 2 to 6, or R 1 and R 2 are different, R 1 has the Smeaning given above and R 2 is a Ci-C 20 -alkyl radical, with a2) a tetravalent transition metal compound of the formula II MX,(OR 3 4 (II) ,o(uble I Ayclroca.rbos. 7x 29 in which M is titanium, zirconium or hafnium, R 3 is a C,-Cg-alkyl radical and X is a halogen atom and m is an integer from zero to 4, a3) an organoaluminum compound of the formula III AIR( OR 5 )p,Xq-p (III) in which R 4 and R 5 are identical or different and are a Cz-C 6 -alkyl radical, X is a halogen atom, q is a number from zero to 3 and p is a number from Szero to 1, in the ratio Mg:Ti:Al of 1 0.05 to o 2 0.3 to 4, and 0404 cae b) a trialkylaluminum having 1 to 6 carbon atoms in B the alkyl radicals or the reaction product of a So°° trialkylaluminum or dialkylaluminum hydride with isoprene.

2. The process as claimed in claim 1, wherein the pre- o0 o paration of the component a is carried out using an electron donor component a4 which may be an aliphatic or alicyclic ether, an aliphatic ester, an aliphatic Saldehyde or an aliphatic carboxylic acid.

3. The process as claimed in claim 1, wherein the mag- 0'o nesium alcoholate of the formula I, the tetravalent O transition metal compound of the formula II, the organoaluminum compound of the formula III and the electron donor are used in the ratio Mg:M:Al:ED of 1 0.05 to 2 0.3 to 4 0 to 2. DATED this 15th day of May 1990. HOECHST AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS "THE ATRIUM" 290 BURWOOD ROAD HAWTHORN. VIC. 3122.