DE2209874A1 - Polyolefins - Google Patents

Description

Code 2386 2>

_n Jt ^F " ^2umstei " ssn- - Dr. E. Assmann

Dr.R.KGenr; js!: O! _S sr - Dk-i.Phya.R. liolzbauer Dr. F. Z ^ -. AL.-zin j.:n.

P ο t e n I ο η w ö I t β 8 Munich 2, Bräuhausstraße 4 / III

STAMICARBON NV, HEERLEN (the Netherlands) polyolefins

The invention relates to a method for polymerizing GC olefins in a liquid distribution agent and / or liquid monomers .in the presence a catalyst obtained by activating the reaction product of a tetravalent titanium compound and / or another transition metal compound, in particular a vanadium compound and an organometallic compound with an organo-aluminum compound.

German Offenlegungsschrift 2,027,302 describes a process for the polymerization of olefins at temperatures above 110 ⁰ C using a catalyst system which is prepared by using as starting material a Ubergangsmetallverbxndung and both an organo-aluminum compound selected as an organo-magnesium compound. It is polymerized at such high temperatures that a solution of the polymer is produced in the distribution medium. The catalyst components are added sequentially or simultaneously a monomergesättigten, 110 ⁰ C, heated to temperatures above the distribution means.

From the American patent specification 3,392,159 it is known that the Order of addition of the catalyst components has a very strong influence can affect the final properties of the catalyst system. this applies in particular to the activity. When adding an organomagnesium compound for a titanium compound, catalysts are obtained whose activity is that of the addition of the titanium compound to the organomagnesium compound

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formed catalyst systems by several orders of magnitude.

The present invention now aims at a process for polymerisation of G-olefins in the presence of catalysts of the Ziegler type, in which excellent yields of polymer are obtained. In particular, so high yields are obtained that the catalyst residues are not from the Polymer need to be removed. Additional benefits are discussed below.

According to the invention, the polymerization takes place in a liquid distribution agent and / or a liquid monomer in the presence of a catalyst, produced by - and this is the feature of the invention - an aluminum halogen compound of the general formula R AlX, in which R is a hydrocarbyl

πι ο ^ m

group having 1-30 carbon atoms and X represent a halogen atom and m represent a Number below 3 is allowed to react with an organomagnesium compound then this reaction mixture with a tetravalent titanium compound and / or another transition metal compound, in particular a vanadium compound brings together, after reduction of the major part of the tetravalent titanium and / or the other transition metal, optionally the catalyst suspension formed washed out and / or heated and finally this catalyst system before and / or during the polymerization with an organo-aluminum compound activated. This organoaluminum compound is generally selected from the group of the trial aluminum alkyls, alkyl aluminum halides and alkyl aluminum hydrides chosen. Instead of alkyl groups, one or more unsaturated hydrocarbons can also be used groups are bound to aluminum.

As an aluminum compound of the general formula R A1X "can Compounds with 1, 2 or 3 halogen atoms in the molecule can be used. The halogen atoms do not necessarily have to be identical to one another. The The bromides or chlorides and especially the chlorides are preferred. The hydrocarbyl radical or radicals represented by R can be saturated or single or be polyunsaturated hydrocarbon radicals, such as alkyl, aryl, cycloalkyl, Aralkyl, alkenyl or alkadienyl. These radicals represented by R can be the same or be different. Alkyl radicals, in particular alkyl radicals with 1-4 carbon atoms and very particularly ethyl or isobutyl groups, are preferred. Man can use aluminum chloride or aluminum bromide per se, but also compounds like e.g. monoethylaluminum dichloride, sesquiSthylaluminumchlorid and Diethylaluminum chloride, but of course also the corresponding

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bonds with other alkyl groups. So are the corresponding isobutyl aluminum compounds very useful. Mixtures of compounds with the above formula can also be used as the starting point, and mixtures of this type can be used, e.g. Include trialkylaluminum compounds, provided that the mean composition corresponds to the above formula. Preferably one cares that the value of m is less than 2.5.

When it comes to the preparation of the present catalyst systems using organomagnesium compounds are compounds with at least one hydrocarbyl group bonded directly to magnesium through a carbon atom. Preferably there are two similarly linked groups each Magnesium atom present. These two groups do not have to be alike. The hydrocarbyl group is an alkyl, an aryl, a cycloalkyl, an aralkyl, an alkadienyl or an alkenyl group. In general, the number is Carbon atoms in the hydrocarbon radical 1 to 30; but this number is not critical. Examples of magnesium compounds suitable for the present process are diethylmagnesium, dipropylmagnesium, di-isopropylmagnesium, Dibutyl or isobutyl magnesium etc. but also didecyl magnesium and didodecyl magnesium, Dicycloalkylmagnesium with identical or different cycloalkyl groups having 3 to 12 carbon atoms and preferably 5 or 6 carbon atoms. An alkyl and a cycloalkyl group can also be bonded to magnesium. Of the aromatic magnesium compounds, diphenylmagnesium is particularly important called, although other compounds such as ditolyl and dixylyl magnesium as well as magnesium aryls derived from compounds having two or more condensed or non-condensed aromatic rings are applicable. Of the aforementioned dihydrocarbyl magnesium compounds a group may be replaced in whole or in part by another group, for example a halogen atom or an oxyhydrocarbyl group.

A magnesium dialkyl having 1-4 carbon atoms is preferably used in the alkyl group and more particularly dibutyl magnesium.

The preparation of the organomagnesium compound can be carried out in a manner known per se Manner, e.g. starting from the so-called Grignard compounds (see e.g. Organometallic Compounds, Vol. 1 G.E. Coates, M.L.H. Green and K. Wade; Organometallic compounds F. Runge). Such Grignard compounds are generally produced by reacting magnesium with organic halides in ethereal solution. However, this implementation can also be carried out without the presence of

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Athern take place. The presence of ethers in the production of the Grignard compounds is applicable for the preparation of the present process Magnesium compounds less favorable. It turns out that then the activity of the from them resulting catalyst systems is adversely affected. The ethers become complex-bound to magnesium and cannot be completely removed, not even by heating the Grignard compounds in a vacuum. Probably the decrease in activity is caused by ether residues that are still present. Solutions of organomagnesium compounds are therefore of particular advantage used in inert solvents, which according to the method of the Dutch Patent application 69.08526 are made.

A halide, an alkoxide, is preferably used as the titanium compound or mixtures of these compounds, in particular the chloride. Except for the tetravalent ones Titanium compound can contain lesser amounts of trivalent titanium compounds to be present. When using mixtures, there are generally no limits to the components to be incorporated into them. Any halide or alkoxide or any mixed compound which is useful per se can also be used together be used with others. Furthermore, titanium iodide, which is generally not used as such, can probably be found in mostly insignificant amounts among others Titanium compounds find application. In certain cases this has a favorable one Influence on the properties of the resulting polymer.

In addition to or instead of the titanium compound, compounds can optionally also be used other transition metals, e.g. vanadium, molybdenum, zirconium or chromium are used such as VCl., VOC1 ", dialkoxyvanadium dichloride, MOCl, ZrCl

4 ο Ο 4

and chromium acetylacetonate. These compounds become vanadium compounds preferred.

For the catalyst systems used in the process according to the invention is, as already stated, preferably of such solutions from organomagnes ium connections assumed. These are then mixed with an aluminum compound having the above formula. Although many of these aluminum compounds are liquid, it is usually advisable to use these solutions in inert distribution media, so that they are easy to process Reaction product is obtained, which can still be stirred well.

The amounts of aluminum and magnesium compounds are to be dug up in such a way that the molar ratio between X and Mg is at least 0.01: 1. This ratio can be chosen to be noticeably larger. But in general it is

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with a ratio of over 100: 1 there is no further advantage. The advantage has an X / Mg ratio between 0.1 and 10: 1.

By means of so-called microwave titrations, in which the organo-aluminum compound was titrated with dibutylmagnesxum solutions, it was found that a reaction between the aluminum and the magnesium compound occurs. The course of this reaction is not clear. Apparently there are several Equivalence points, especially in the case of proportions between halogen and magnesium from 1: 1 and 3: 1 and probably also from 2: 1. With halogen / magnesium ratios of about 2: 1, the titration curves show a particularly irregular course and there are considerable deviations from the curves, which can be obtained by extrapolating the titration curves for lower or higher Values of the halogen / magnesium ratios. The method of microwave titrations is from E.H. Adema and J. Schrama in Anal. Chem. 37 (1965) 225 has been described.

In general, the reaction between the aluminum and the magnesxum compound forms a precipitate. The reaction mixture is preferably stirred until the end of the reaction and then mixes this reaction product with the tetravalent titanium compound, in particular with titanium tetrachloride. Liquid titanium compounds, e.g. titanium tetrachloride, can be added as such, but these can also first be diluted with an inert distribution agent. As already explained, one can use either in addition to or instead of the Titanium compounds also use compounds of other transition metals. The molar ratio between magnesium + aluminum and titanium can be within one vary over a wide range. There is no upper limit to this ratio, but in general it is "not advantageous to have an excessively large amount of magnesium + Using aluminum and in economic terms will soon bring this up clear disadvantages with it. The above ratio is therefore generally not be more than 100: 1. The ratio is preferably between 0.1 and 50: 1 and in particular between 0.5 and 5: 1.

The catalyst systems according to the invention can be used both for the polymerization of ethylene than of propylene, butylene, pentylene, hexylene, 4-methylpentylene and other Ck-olefins with at least 3 carbon atoms serve, but it can several olefins can also be copolymerized, they can also be used in the Copolymerization of one or more α-olefins with polyunsaturated Preliminary bindings are used. In the context of the present invention are

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different embodiments of the catalyst production possible. For example, the titanium compound can be mixed with the reaction product of the aluminum and magnesium compound, the titanium compound generally being added dropwise to this reaction product, at ambient temperatures, but also at higher or lower temperatures. The reduction of the titanium compounds can take place at temperatures up to about 100 ⁰ C readily. In this case, however, slightly stereospecific catalysts are obtained which, although they can be used for the polymerization of ethylene, are to be regarded as less suitable for most of the polymerization of olefins with at least 3 carbon atoms. It will be therefore preferable in many cases to use catalysts which are prepared in such a way that the mixing of the aluminum + magnesium compound with the titanium compound at reduced temperature and preferably takes place at temperatures below 0 ⁰ C. On the one hand, this increases the stereospecificity, but on the other hand it is found that catalyst particles with a regular shape are also formed, which in turn means that the resulting polymer also consists of regularly shaped particles. In addition, it is often possible to increase the filling weight, which is particularly desirable in many cases. This embodiment of the catalyst production can therefore also result in advantages in the polymerization of ethylene.

If the titanium compound is mixed with the reaction product of the aluminum and magnesium compound and allowed to react, a catalyst suspension is obtained. The solids fraction can be separated from the distribution agent with the reaction products dissolved therein and then, if required, the solid product separated off can be washed out with fresh distribution agent. Finally, the optionally washed-out suspension of the reduced titanium compounds can also be ^{heated to temperatures above 150 °} C. and preferably above 200 ^° C., which means a further increase in the stereospecificity of the catalyst.

The olefin polymerization is carried out so that in a reactor, in which there is already a distributing agent which is introduced into the catalyst prepared in advance. In general, such amounts of catalyst will be used added that the amount of titanium is 0.001 to 10 mmol per liter and preferably 0.01 to 1 mmol per liter. This catalyst system can then be activated by adding an organo-aluminum compound, after which gas-

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shaped or liquid monomer is introduced. It can also be done by initiating a monomer mixture that also contains polyunsaturated monomers are applicable, copolymers are produced. You can also add activating organo-aluminum compounds during polymerisation. This addition can be carried out either continuously or discontinuously. It is even possible to omit activation prior to the polymerization and only activate during the polymerization or vice versa. It can also activation takes place both before and during the polymerization. the Polymerization takes place below the melting point of the polymer, see above that a suspension of the polymer is obtained.

As a distribution agent, both for the preparation of the catalyst as any liquid which can be used to carry out the polymerization is inert with regard to the catalyst system, e.g. one or more saturated aliphatic hydrocarbons such as butane, pentane, hexane, heptane, pentamethylheptane or petroleum fractions; aromatic hydrocarbons e.g. benzene or Toluene or halogenated aliphatic or aromatic hydrocarbons, e.g. tetrachlorethylene. The polymerization can also take place in liquid monomers or in a monomer that is above the critical temperature strongly together is pressed.

The suspension obtained during the polymerization can be worked up in a manner known per se, the catalyst first being deactivated and the catalyst residues are then extracted with appropriate solvents will. However, the catalysts of the invention are so in many cases active that the amount of catalyst in the polymer, namely the titanium content already is so low that there is no need to wash out the catalyst residues.

The polymerization can take place under atmospheric pressure, but also under

increased pressure up to about 2000 kg / cm and can be carried out discontinuously, semi-continuously or continuously, optionally in one or more stages. Polymerization under pressure can reduce the yields m polymer can be further increased, resulting in the production of a polymer with very low catalyst residues. Preferably under Polymerized pressures from 1 to 100 kg / cm.

Modifications known per se can be made in the present process apply .. So e.g. the molecular weight with hydrogen or other for this customary modifiers are regulated.

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The polymerization can also be carried out in several, either, parallel or Carry out stages connected in series with possibly different catalyst compositions, temperatures, residence times, pressures, hydrogen concentrations, etc. In this way, products with such a broad molecular weight distribution can be produced that they have a high flow index by adding in at one stage such conditions, e.g. with regard to pressure, temperature and hydrogen concentration, selects that a polymer with high molecular weight is formed, while in another stage these conditions are selected in such a way that that a product with a lower molecular weight is obtained.

The invention is explained in more detail by the following examples, without to limit oneself to this.

Example I.

8.2 ml of diethylaluminum chloride (pure) and 70 ml of pentamethylheptane (PMH) are mixed with one another in a three-necked flask equipped with a stirrer, reflux condenser and dropping funnel. The mixture is kept under pure nitrogen. Then are added at 20 ⁰ C 47 ml of a 0.35 m Dibutylmagnesiumlösung in pentamethylheptane.

This mixture then is cooled to -60 ⁰ C, followed slowly 19.1 ml TiCl are added dropwise in 20 ml of PMH. ₄ The reaction mixture turns brown. The reaction mixture is allowed to stand with stirring overnight and the temperature is allowed to rise to ambient temperature. This is followed by heating to 210 ^° C. for 15 minutes. The color changes from brown to purple. Titanium concentration: 0.96 mol / liter.

b. Pol} rmerisation_von

1.8 liters of gasoline are introduced one after the other into a 3 liter reactor and such an amount of the suspension prepared according to Example la that the The concentration of the titanium compounds is 1.67 mmol Ti / liter. Afterward Diethylaluminum chloride is added until the concentration is 3.33 mmol / liter is.

The temperature is set to 65 ^° C., after which propylene is fed to the reactor until the partial pressure of the propylene is 3 ata. After a polymerization time of one hour, a yield of 54 g of polypropylene (93% insoluble in the distribution agent) is obtained.

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Example II

a ^ J Manufacture of the catalyst

In a corresponding manner as in example Ia are mixed together at 20 ⁰ C 13.7 ml Monoäthylaluminiumdichlorid with 20 ml of pentamethylheptane (PMH), whereupon this mixture, 100 ml of 0.33 M dibutylmagnesium are added. The mixture is cooled to -5 ⁰ C, followed by 11 ml TiCl- in 21 ml PMH are added dropwise. The mixture is allowed to stand overnight and the temperature to rise to ambient temperature. A brown suspension of a titanium compound is formed. Titanium concentration 0.6 mol / liter.

b. Polymerization of Ethylene

In a 3 1 reactor of the series after 1.8 liters of petrol and 3.6 mmol (2 mmol / L) of tri-isobutyl aluminum are introduced, and heated to 85 ⁰ C.

First, the gasoline is saturated with ethylene and then such an amount of the suspension prepared according to Example Ha is added that the titanium concentration is 0.3 mmol / L. Then ethylene and such an amount of hydrogen are added continuously that a hydrogen concentration of 40% calculated on the total amount of ethylene and hydrogen is maintained in the reactor. The polymerization is carried out under a total pressure of 3 atmospheres. After one hour of polymerization, the yield is 795 g of polyethylene per mmol of titanium per hour and per at ethylene pressure. By way of comparison, the polymerization is carried out using a catalyst prepared according to Example Ha, this is but instead of 13.7 ml Monoäthylaluminiumdichlorid an equivalent amount, that is, 17.4 ml of triethylaluminum used and the mixture cooled to -5 ⁰ C instead of to -60 ⁰ C. The yield is only 87 g. A catalyst is also chosen for comparison, notwithstanding the constituents Monoäthylaluminiumdichlorid, dibutyl magnesium and titanium tetrachloride are simultaneously introduced slowly into a cooled to -5 ⁰ C reactor at the of the method described in Example Ha manufacturing method is followed but for the rest the same production method. A yield of 360 g of polyethylene is now obtained, which, like the aforementioned yield of 87 g per millimole of titanium per hour and per atm of ethylene pressure, is calculated.

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Example III

a. Production_of_CatalYsator

A TiCl -containing suspension is produced in a manner corresponding to that in Example Ha, which is then heated ^{to 210 ° C. for 10 minutes.} The color changes from brown to purple. The suspension is washed out twice with PHM. Titanium concentration 0.6 mol / liter.

Ik polymerization of Butjlen-1

400 ml of cyclohexane are placed in a glass reactor, what amount is then saturated with butylene-1. There will be one in turn 0.4 mmol of TiClg-containing amount of the suspension prepared according to Example IHa and 2 mmoles of dietary aluminum chloride added. After an hour it will the polymerization is ended and the polybutylene thus obtained is isolated from the solution. 4 g of polybutylene-1 are formed, i.e. a yield of 10 g of polybutylene-1 per mmol Ti per hour and per at butylene pressure. The isotactic polymer content (determined by extraction with ether) is 98%.

Example IV

a _; Manufacture of the catalyst

26.4 ml of a 2 M solution of monoethylaluminum dichloride (MEAC) in gasoline are introduced under pure nitrogen into a flask equipped with a stirrer and dropping funnel. At 40 ⁰ C was slowly added 44 ml of a 0.3 m solution of dibutylmagnesium (DBM) in gasoline, with stirring, are added, thereby forming a finely dispersed precipitate. After the addition of dibutyl magnesium has ended, the mixture is ^{stirred at 40 °} C. for a further 20 minutes. Then 2.5 ml of a 4 M TiCl. Solution in gasoline are added dropwise and finally it is diluted to 100 ml with gasoline. The temperature is kept at 40 ⁰ C and after completion of the TiCl. additive will be 45 min. Stirred at 40 ⁰ C. The suspension thus formed contains 528 mmol / liter MEAC, 132 mmol / liter DBM, 100 mmol / liter TiCl. or reaction products of these substances.

b. Polymerization of Ethylene

The polymerization takes place in the manner described in Example Hb, but now using the catalyst prepared according to Example IVa

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systems. Here, too, Ks are added in such quantities that the titanium concentration 0.3 mmol / liter. After one hour of polymerization a yield of 1900 g of polyethylene per mmol of titanium per at ethylene pressure and reached per hour.

Example V

The catalyst is prepared according to Example IV a, however now only 1/5 of the amount of TiCl is added, so that the amount of titanium in the Catalyst suspension is 20 mmol / liter.

b. P2ly. ^me rization of_Xthy_l

en

The polymerization is carried out in the manner described in Example Hb, but now in the presence of the catalyst system prepared according to Example Va carried out. Such an amount of this catalyst is added that the titanium concentration is 0.06 mmol Ti / liter. After one hour of polymerization the yield amounts to 11,300 g of polyethylene per mmol of titanium each at ethylene pressure and per hour.

Example VI

a._H ^e £ position_ of the catalytic converter

The catalyst is prepared according to Example IVa, except that monoisobutylaluminum dichloride (MIBAC) is used as the aluminum compound and the amount of di-butylmagnesium is doubled. In this way, a suspension is formed which contains 528 mmol / liter MIBAC, 264 mmol / liter DBM and 100 mmol / L TiCl ₄ or reaction products of these substances.

The polymerization takes place in two ways. One polymerizes ■ Corresponding to Example Hb with the catalyst prepared according to Example VIa. As a comparative experiment of the second method, polymerisation is carried out in the presence of a similar catalyst, which, however, is not activated with tri-isobutylaluminum has been.

With the activated catalyst, 1680 g are formed after one hour Polyethylene per millimole of titanium per at ethylene pressure per hour. With the non-activated

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Catalyst, this yield is only 343 g of a polyethylene with low Filling weight.

Example VII

a. Manufacture of the catalyst

According to the process described in Example IVa is prepared, a catalyst suspension at 25 ⁰ C which 528 mmol / liter MIBAC, 132 mmol / l DBM and 100 mmol / L of TiCl. or reaction products of these substances.

b. Poly_merization_of_ethy_lene

Using the catalyst suspension prepared according to Example VIIa ethylene is polymerized according to the method described in Example Hb. The yield is 2000 g of polyethylene per mmol of titanium each at ethylene pressure per h.

Example VIII

a. Manufacture of the catalyst

For comparison, the method mentioned in Example IVa is used a catalyst suspension prepared, which 528 mmol / L MEAC and 100 mmol / L TiCl. or contains their reaction products.

b. Manufacture of polyethylene

According to the method described in Example Hb, in the presence of the catalyst prepared according to Villa Example polymerized ethylene. The yield is only 190 g of polyethylene per mmol of titanium per at ethylene pressure per hour.

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Claims (26)

PATENT CLAIMS Ί. Process for polymerizing one or more 0, olefins, optionally with one or more polyunsaturated hydrocarbons in a liquid distribution agent and / or liquid monomers and in the presence of a catalyst, obtained by adding an organoaluminum compound before and / or during the polymerization Reaction product of a tetravalent titanium compound and / or another transition metal compound, in particular a vanadium compound and an organometallic compound, characterized in that the polymerization is carried out in the presence of a catalyst which is prepared by using an aluminum halogen compound of the general formula R AlX, in which the m ο — in Symbols R are identical or different and each have a hydrocarbyl group 1-30 carbon atoms and each X represents a halogen atom and m represents one Whole number or a fraction below 3 is allowed to react with an organomagnesium compound, and then this reaction mixture with a tetravalent one Titanium compound and / or another transition metal compound, in particular a vanadium compound, after reduction at least of the greater part of the tetravalent titanium and / or the other transition metal, if necessary, the catalyst suspension formed washes out and / or heated and finally this reaction product, before and / or after it has been brought into the polymerization zone, with the organoaluminum compound activated. 2. The method according to claim 1, characterized in that a molar ratio between aluminum + magnesium and titanium or the transition metal of less than 100: 1 is used in the catalyst production. 3. Process according to claims 1-2, characterized in that a ratio between aluminum + magnesium and titanium or the transition metal of 0.1-10: 1 is selected in the catalyst production. 4. The method according to claims 1-3, characterized in that a molar ratio between aluminum + magnesium and titanium or the transition metal of 0.5-5: 1 is used in the catalyst production. 5. The method according to claims 1-4, characterized in that such amounts of aluminum and magnesium compounds are used in the catalyst production that the molar ratio between halogen and magnesium is a maximum of 0.01-100: 1. 20 9841/1012 6 »Process according to claims 1-5, characterized in that such amounts of aluminum compound and magnesium compound are used in the catalyst production that the molar ratio between halogen and magnesium is between 0.2: 1 and 10: 1. 7. The method according to claims 1-6, characterized in that an aluminum compound of the formula given in claim 1 in which X is chlorine or bromine is used in the preparation of the catalyst. 8. The method according to claim 7, characterized in that the catalyst used is an aluminum compound of the formula given in claim 1 in which X is chlorine. 9. The method according to claims 1-8, characterized in that an aluminum compound of the formula mentioned in claim 1 is used in which each R is selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, alkenyl and alkadienyl . 10. The method according to claim 9, characterized in that one uses an aluminum compound of the formula given in claim 1, in which R represents an alkyl radical having 1-4 carbon atoms. 11. The method according to claim 10, characterized in that an aluminum compound of the formula given in claim 1, in which R was selected from the group consisting of ethyl and isobutyl, is used in the preparation of the catalyst. 12. The method according to claims 1 b / e 11, characterized in that a dihydrocarbyl magnesium compound is used in the preparation of the catalyst. 13. The method according to claim 12, characterized in that a dihydrocarbyl magnesium is used in the preparation of the catalyst, in which the hydrocarbyl group is an alkyl, aryl, cycloalkyl, aralkyl, alkadienyl or alkenyl group. 14. The method according to claims 12-13, characterized in that a dihydrocarbyl magnesium compound is used in the preparation of the catalyst, the hydrocarbyl group of which contains 1-30 carbon atoms. 15. The method according to claims 12 b / e 14, characterized in that a dialkyl magnesium compound with 1-4 carbon atoms per alkyl group is used in the preparation of the catalyst. 16. The method according to claim 15, characterized in that dibutyl magnesium is used in the catalyst production. 209841/1012 17. The method according to claims 15-16, characterized in that the
Catalyst preparation using a solution of a magnesium dialkyl compound in an inert solvent. 18. The method according to claims 1 b / e 17, characterized in that at
a titanium tetrahalide is used in the preparation of the catalyst. 19. The method according to claim 18, characterized in that titanium tetrachloride is used in the catalyst production. 20. The method according to claims 1 b / e 19, characterized in that. During the catalyst production, the reaction mixture of the aluminum + magnesium ^{compound at temperatures below 100 0} C with the titanium compound or the
Transition metal compound is mixed. 21. The method according to claim 20, characterized in that the reaction mixture of the aluminum + magnesium compound in the catalyst production
Temperatures below 0 ⁰ C is mixed with the titanium compound or the transition metal compound. 22. The method according to claims 1 b / e 20, characterized in that in the ■ catalyst production, the catalyst suspension to temperatures above 150 ⁰ C is heated. 23. The method according to claim 22, characterized in that the catalyst suspension is at a temperature above 200 ⁰ C during the catalyst production
is heated. 24. The method according to claims 1 b / e 23, characterized in that the catalyst before and / or during the polymerization with trialkylaluminum
activated. 25. The method according to claims 1 b / e 24, characterized in that the polymerization is carried out under a pressure of 1 to 100 kg / cm. 26. Polymer prepared according to one or more of the above claims. 209841/1012