DE2125107A1 - Process for the preparation of polymerization catalysts - Google Patents

Description

P TEM ΓΑ Μ Wz »Lt Γ:

DR.-ING. FROM KREISLf-P. DFi.-IfSG. SCHDNWALD 2125107 DiVlNO. ϊϋ. MHYi-R DR. FUFS DI P LC !; LYes. MBK FROM KREISLEP.

DIPL.-CHEM. CAROLA JiELLER Oi: .- 1 N G. KLUPSCH Pi .pl. - -I ^ .: ■; - j

COLOGNE 1, OCICUMANNHAUS

Cologne, May 19, 1971 Ke / Ax / Ha

M ONTSCATi ν ι JLILJLJLiLIi

Foro Buon aparte j51 _._ J-fc-iland (Italy).

Process for the preparation of polymerization catalysts

The invention relates to particularly active new catalysts for the polymerization of olefins, processes zvt. their production and the use of the new catalysts for the polymerization of ethylene and its mixtures with α-olefins and / or biolefins.

The homopolymerization and copolymerization of ethylene has so far been carried out with a wide variety of catalyst types. Best known of these are the catalysts, by reacting a titanium or vanadium compound with an organometallic derivative of metals of group I, II and III of the periodic table. The activity of these catalysts proved However, it turned out to be comparatively small and did not make it possible to avoid the Roini ^ mg; of the polymer of

.15 Catalyst esters after the end of the polymerization.

Titanium borohydrides and their derivatives were also used as catalysts for the polymerization of olefins (s.franzöoino.'if:. *! Patent 1 160 064, J'ranzcsi schec Patent 1 18? 180

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2121107

and British Patent 801,401), titanium salts of oxygenated inorganic acids and titanium alkyl derivatives or titanium cycloalkene derivatives have been proposed (see for example German patent 1 100 022 and USA patents 2 91? 501 and 2 922 803). However, these catalysts generally have a lower activity than the above-mentioned catalysts.

A number of titanium mercaptoalkyl derivatives are also known from the literature known, which are used as catalysts for curing paints based on alkyd resins (U.S. Patent 3,030,395). As far as is known, however, they have never been mixed with hydrides or organometallic compounds Connections of elements of the. Groups I, II and III of the periodic table as catalysts for polymerization used by olefins because they have little and sometimes no catalytic activity.

It has now surprisingly been found that it is possible to catalysts having very high activity to obtain ₅ if they are prepared starting from a titanium compound so that at least one of the valencies of the titanium is saturated by X, wherein X is a carbon atom, S- Atoni or an O atom radical of an oxygen-containing inorganic acid or a radical of the formula BR ₁ , wherein R is a hydrogen atom or an aliphatic radical. The possible remaining valencies of the titanium may be satisfied by other residues, for example by halogen, titanium and alkoxy in cases where X is a carbon atom, _s is halogen and carbon in cases in which an S atom X, and Halogen in cases in which X is an O atom residue of an oxygen-containing inorganic acid or a residue

of the formula BRj, is. i

Typical examples of compounds that contain at least one Ti-C bond include: methyltitanium trichloride, Methyl titanium dichloride, ethyl titanium trichloride, Ethyl titanium dichloride, methyl titanium tribromide, ethyl titanium

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tribromide, cyclopentadienyltitanium tricbloride, cyclopentadienyltitanium tribromide, cyclopentadienyltitanium chlorodibuto ::. yd, cyclopentadienyltitanium bromodibutoxide, iv'ethyltitanium chloride mvl dicyclopentadienyldititnnlie. Preferred of these compounds are methyltitanium trichloride and cyclopentaienyltitanium trichloride. All of these compounds react in the presence of slectron donors to form complexes.

As examples of compounds v / enigstens contain a Tiis binding, include: Dicycloj) entadicnyltitEindisulfhydrat, Dicyclopentadienyltitandinnthyldimercaptan, Dicyclc ^ peiitadienyltitandiathyldiraurcaptan, Dicyclopentadienyltitandipropyldiinercaptan, Dicyclopentadienyltitandiphenyldiiaercaptan, Dicyclopentcdienylv-itandibensyldimercaptan, ricyclopentadienyltitanüi-2-äthylphenyldimercaptan, Thiophenylt.itantrichlorid, Di * - chlortitnn --N, IT-diphenyldithi ocarbarant, Cyclopentadienyltitandime thy ldimercaptan _t CyclopantadienyltitanCdir ^ th.y'i.- · dimercapto) chloride and Cyclopentadienyltitanium decylmercaptodichloride. The best results are obtained with thiophenyltitanium trichloride and Ν, Ν-diphenyldithiocarbonate of titanium dichloride.

As a Bsicprlele of compounds which ο ine TJ-O-Ro. ^ 1 an oxygen-containing rv.q? <: εχ> Λ- see acid included, may be mentioned: Titanyl sulfate, Trd chlortitanoxytriiaethylsilan, ^ CH,) ₇ Gi0 / ^ Ti, trichloro titanium-p-toluene sulfonate, triclilortitanium silicate, titanium nitrate, titanium orthophosphate, titanium hypochlorite, titanium phosphate nitrite, titanium hypochlorite, titanium phosphate Titanium-ilicate, titanium vanadate, an ^ oniuratitai-yl carbonate, titanyl perchlorate and titanyl perphosphate. Preferred of these compounds are Ti-OSO ^, _{TiCl 5} OSi (CH ^) ₅ , ^ CH) GiQ / Ώ PCH ₅ -C ₆ H ₇₄ -SO ₅ -TiCl ₇ .

₇ GiQ /, Ώ.,

ij- lative for the Illa ^ ce in front. VoTbindur'non, which contain -u -.- A r.tens (Jb-) ο Ti-rI ^ -Ilijidun ^ are Ti (TJ ^) ₇ ,

1 0 9 8 A S / 1 "'S 3

BAD ORiGlNiAt

) ₂ and

The catalysts-in accordance with the Erfindtmg thus consist of the product obtained by reaction of a hydride or an organometallic compound of metals of Group I ₁ II and III of the Periodic Byuteiru-, with the product> that is obtained by reacting a Tita: · - 'connection' in which at least one valence of titanium cTvlp - *?.!

a radical X is saturated, where X is a carbon atom

Tlest

S atom or a 0 atom of an oxygen-containing inorganic acid or a radical of the formula BR ₄ , in which R

is a hydrogen atom or an aliphatic radical * with ψ a carrier consisting of an anhydrous magnesium halide, in particular MgClp or UgBi? «, under conditions under which the magnesium halide is deactivated, or by guiding the previously activated Ilngncsurahalogenid with the above-mentioned titanium compound nusa:; .

Under the expression “magnesium halide in activated porosity; V is a halide to be understood, which is characterized is that in its X-ray spectrum, the diffraction line of the highest intensity, which is in the Gpectrum of the normal Halide is present, appears in greatly weakened intensity, and / or that such a halide is a

Has a surface of more than 5 πι '/ g.

In the case of anhydrous magnesium chloride, the ro nt r; r. η diagram of the activated form, characterized in that the diffraction line, which appears at a lattice spacing d of 2.56% and has _{the highest intensity in the spectrum of normal TgOl 9} , is present with a greatly weakened intensity, while a in its place A widened halo appears, which lies in the range of the grid spacing d from 2.56 to 2.95 S.

Likewise, the X-ray diagram of activated l,! GBrp is thereby marked that the Bemgungsliuic at d-2,9.3 -

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γ; _

(the III IlcJntgendiagram of normal Mgßr _{o has} the highest intensity) occurs with a strongly weakened intensity, while a broadened halo appears in the area of the grating - from nt and en d = 2.80 to 3, - ^ 5 jL .

According to a preferred method, the load applied to the carrier Katalysatorkompononte is by co-grinding the titanium compound and the anhydrous LIt. (. Yiesiu, n ~ halcgenids prepared by known methods during such ¹ time and under such Llahlbedingungen that the conversion of the anhydrous magnesium halides in the active form according to the invention is achieved * Preferably dry grinding is carried out in a ball mill. In addition to grinding, the preparation can also be carried out by simply mixing the titanium compound with the previously activated magnesium halide in the solid state. In this case, however, the compounds are preferably used as Suspension used in an inert solvent.

In addition to grinding, the anhydrous en I'agnesiunhalogenide in the active form can also be produced by other processes. For example, the production starting from IiMgX (v / orin R is a hydrocarbon residue and X is a halogen atom) by disproportionation in confessed V.'is or by treatment with halogenated compounds, e.g. gaseous anhydrous hydrogen chloride,

? .y take place,

According to a further process, the preparation is carried out by decomposing compounds of anhydrous gastric halogenides. rrdt Lov / is-Iiasen or acids of the EIRR; irkun ^ vo ^r -Heat under reduced pressure. For example, J.'- gCl ^ can be produced in the activated form by this process, starting from MgGIp solutions in ethanol.

The!.! Engender titanium compounds that the coating applied to the support for the production Katalynutorkomponente

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^ß AD ORlGiNAL

can be used, know in einnni very v.'oiton Beroicl whose lower limit is, for example, less than 0.01 Wt .- / S, based on the support, and its upper size j can be over 30 wt .- / a. Particularly good results with regard to the titanium connection and the carrier "■■; · - Extra yield of polymer is obtained if Γ.i .: Lienge of the titanium connection e. on the carrier 1 am 10 Gev, '-' < • amounts to.

The following hydrides and organometallic compounds are particularly suitable for the production of decicatalv ':' ators: Al (G ₂ II ^) ₅ , Al (O ₂ Hc) ₂ Ol, AlCiO ₄ H ₀ ) ₇ ,

i ^ l ₅₁ Al (G ₂ H) ₂ H, ^, Li (IC ₄ H ₉ ).

₄ H ₉

Bas molar ratio between the organometallic compounds: - manure and the titanium compound is not critically important in the polymerization, of ethylene this is -2. ^ Ratio between? 0 and 1000.

The catalysts according to the invention are used for polymerization and copolymerization of olefins Method used, i.e. in the liquid phase, in the presence or absence of an inert solvent ;: or in the gas phase.

The polymerization or «. Copolymerization can at Ter.ipei-aturen between -80 ° and 200 ⁰ C are performed. It is preferred to work between 50 and 100 ^° C. at normal pressure or elevated pressure.

The molecular weight is adjusted in such a way that, for example, in the presence of alkyl halides niden4 organometallic zinc or cadmium compounds or is carried out in the presence of hydrogen.

It is well known that the activity of normal Ziegler catalysts, from compounds of the transition metals ur-c. from organometallic compounds of the metals of the group

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I, II νιιά III of the periodic system are obtained by the presence of hydrogen and other chain carriers, which are used for the kin 3 te llung the molecular weight in the polymerizate ons system, significantly worsened »in the catalysts according to the LY However, it has been found - this represents a further aspect of the invention - that or is possible because .; Adjusting the molecular weight of the polymer itself to low or very low values without the activity of the catalyst falling significantly. For example, it is possible in the polymerization of Jlthylen, C-I ro! Olekulargewicht of polyethylene V / erte set lying in a range of practical interest and on intrinsic viscosity (Intrinsic Viscosity) of between about 1.5 and 3 dl / g (measured in tetralin at 135 ° C.), without the polymer acid yield with the particularly active catalysts falling to values below which it would be necessary to clean the polymer of catalyst stress clay after the end of the polymerization.

The polyethylene obtained with the new catalysts is an essentially linear and highly crystalline ε polymer, that has a density of 0.96 g / cm - "* or above and excellent processing properties ori. has that in general are better than the processing properties of polyethylene, that with the normal Sie gler-IIataly satoren will be produced. That contains unpurified polymer generally less than 10 parts of the titanium compound per iiillion parts.

Example. 1

In a centrifugal mill with PorsellangefΓ-.ß and spheres were 10 g of anhydrous KgClp and 0.4-5 g CjJItjTiClj milled for 2 hours under nitrogen. This here The milled product obtained contained 1.0? 6 Ti and had a surface area of 9 m / g.

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1000 ml of n ~ heptane and 2 g of Al (IO ^ Hq) ₇ were placed in a 1800 ml stainless steel autoclave. given. The mixture was heated to 75 ° G and 0.12 g of the catalyst component described above was added. Then the pressure was increased with hydrogen

• 2 2

3 kg / cm and then further increased with ethylene to 13 kg / cm.

The temperature rose to 85 ° 0 ". The pressure was through constant supply of ethylene kept constant. After 4 hours, 221 g of polyethylene with an apparent Density of 0.292 g / cnr taken from the autoclave. the Polymer yield was 174-000 g / g Ti.

ψ Example 2

Under the conditions described in Example 1, 10 g of anhydrous LigClp with 1.00 g of CE ₅ TiCl _7. ^ ₂ ¹ V ⁰ S ^{G <?} The Ti content of the milled product was 0.75% by weight. The product had a surface area of 9 in'Ve.

Using 0.1481 g of the ground product: '; were polymerized under the conditions mentioned in Example 1, but under a partial pressure of Ethylene of 6 atm. and a Yiasser-stoffialdrui; ^ of 7 atm »351 g of polyethylene obtained, the one apparent Density of 0.4-50 g / cm ^ and one in TetrahydroiiRphtluvlin had a limit of 0.8 dl / g measured at 135 G ». ™ The polymer yield was 3 "6,000 g / g Ti.

Example 3

In a vibrating mill with a porcelain vessel and porcelain balls, 10 g of anhydrous l.'gOlp and 0.55% o, ^ Ii _r iy.O.Uil _v . Milled under nitrogen for 2 hours. The product removed from the mill contained 1.9 Gev /.-? J Ti and had o ^; ..jxj

Surface of 9 m / g.

1000 ml of n-heptane and 2 g of AlCi-C ^ II ^) were placed under nitrogen in a 1800 ml stainless steel autoclave. The mixture was ^{heated to 75 0} G, whereupon 0.1811 g of the above-described I.

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were set. The pressure was then only off with V / a r; c to 3 atm. and then with ethylene to 13 atm. elevated. the As a result, the temperature rose to 85 ° C. The pressure was kept constant by feeding in ethylene.

After 4 hours, the autoclave became 390 g of polyethylene discharged, which has an intrinsic viscosity of 2.0 dl / g (ger.c.c ^ sen in tetralin at 135 ° C) and an apparent density '.

• z

0.405 κ / cnr. The polymer yield was 113 * 000 g / 6 Ti.

Example 4

Under the conditions mentioned in Example 3, 10 g of anhydrous MgCl _{0 were} ground with 2 g of N _i N ~ diphenylthiocarbams of titanium dichloride. The latter compound was prepared by refluxing TiCl4, diphenylanine and CSo as a solution in n-heptane, filtering off the solid product and drying it under reduced pressure. The ground product had a titanium

Content of 1.80 wt -.% And a surface area of 9 m "/ g.

Using 0.0659 g of the milled product, polymerization among those mentioned in Example 3 was carried out Conditions, but at a hydrogen pressure of 7 atm. and an i'ithylenpartialdruck of 6 Ate., 316 g of a polyethylene obtained which has an intrinsic viscosity of 1.0 dl / g (measured in tetralin at 135 ° C) and an apparent density of 0.446 g / cm ^. The polymer yield was 266,000 g / g Ti.

Example %

In a glass mill that is 100 mm long 50 mm in diameter and 550 g with steel balls a diameter of 9 »5 now contained 0.485 g

and 11.635 S anhydrous WgCIp for 16 hours

_{33 2}

ground at 20 ° C under nitrogen. The milled product obtained contained 0.79% Ti and had a surface area of 20 m * "/ g. In a 3 l autoclave" made of stainless Steel fitted with an anchor stirrer,

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were 0.018 \\ rtier.ec /; e πι ?: h learn Oornlsohcr.

and 150 ml of n-meptane together with 2 ril Al (IC ^ II ₀ ) ₇ und; ;.

Nitrogen was introduced and heated at ^ O ⁰ C.

This mixture was then 10 atm. J.tl> ylene and 5 at < , hydrogen pressed on. The Gesanitdruci: was kept constant during the whole experiment by constant liachdx-üc>;. en of ethylene. After 8 SbundRn v.-urüo the loV.ymerisation terminated. The polymer! Sationspz'oduk-υ v. * Ui ^v l; -filtered and the polyi.-ore obtained in this way drynefc.

Here, 120 g of a granular polyethylene were obtained. which had an apparent density of 0.41 g / cirr 'and a limit viscosity / JjJl of 2.14 dl / g. The Pol / üUix-aur / beuto was 845,000 g / g Ti.

Example 6

In the mill described in Example 5 vrarden 5 »^ 7 75 g of anhydrous MgCl ₂ and O ₅ IQSO TiOSO g ^ 64 SUmaon at 150 to 160 ⁰ C milled. Under Vei'v / enduny of 0.2519 Z of this mixture 115 S a "polyethylene obtained by polymerization of üthr / Leii in the manner described in Example 2, which had an intrinsic viscosity of 5.5 dl / g. The polymer yield was 83-800 g / g Ti ^

Example 7
In the mill described in Example 5, 0.4570 g, SiO / ^ Ti and 7.5251 g of anhydrous KßOlg were 62 hours.

ground at 20 ^{0 O.} Using 0.062 g of this mixture, 385 g of polyethylene, which had an apparent density of 0.49 g / cm and an intrinsic viscosity of 2.08 dl / g, were obtained by polymerizing ethylene on the V / iron described in Example 5 . The yield of polyra was 91,000 g / g Ti.

Example 8

In a vibrating mill with a porcelain vessel and a Forzellankugelxi 20 g of anhydrous MgClg and 1.4 g of trichlorotitanium p-toluenesulfonate were added 2 hours at the seaming temperature unl-ri- ' Ground nitrogen. In a 1800 ml autoclave from not

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rusting steel, which was provided with anchors 3? Uhrcr, 0.1052 (-j this mixture and 1000 11I n-IIeptane kusuwkou with 2 £ AlCi-U ₇₁ H ₁ -P _{7 were} introduced and heated to 85 ° C the autoclave was 10 atm. ethylene and 3 atm. hydrogen.

The polymerization was terminated after 4 hours. That Polymerization product was filtered off and dried.

This 67 6 of a polyethylene were obtained, the one apparent density of 0.379 g / ern- and a gronaviskossity.r of 3 »Ί dl / g. The polymer yield was 90,600 g / g Ti.

Example <)

On the in Beisjjiel 8 be Gehrieb sr. ο wisely 10 g I.! ßCl ₂ and 1 g Si (OTiGl ₇ ) ^ were ground. In a 1800 ml stainless steel autoclave with anchor stirrer, 0.1631 c of the Genicchec obtained in this way and 10000 ml of n-heptane susaio-aen with 2 g of Al (XG ₇ H ₀ ) _y were introduced under nitrogen and heated to 85 g. The mixture was 9 atm. Ethylene and 4 atm. Y <ater st off pushed. The total pressure was kept constant during the test by continually repressing ethylene. Wax V ¹ hour the polymerization was terminated and the polymer formed was filtered off and dried. This gave 225 β polyethylene which had an apparent density of 0.326 g / cm ^ ν-ηβ an intrinsic viscosity of 2.7 dl / g. The polymer heals θ was 5 ± .000 g / g Ti.

gedepjel. 10

In a glass mill which had a length of 100 mm and a diameter of 50 mm and contained 550 g of steel balls with a diameter of 9 »5 mm, 3.529 g of anhydrous WgCl ₂ and 0.035 g of Ti (BH ₄ ) ₃ 15 Milled for hours under nitrogen at PO ⁰ C. Dnc hri ei'Irri erh ^ lUina product (; rJ, hU-OV 0,1,1 ; i 'il uv.ä hr - \\.? I a · M-oj-riäolr of 1 <j t: / " . J>

1 0 9 8 4 G ■ /: 7 C 3

BAD LOCATION

- Λ "? -

In a 3 liter stainless steel, cu., ^Vrar s equipped with an anchor stirrer 0.0561 g of the diverting mixture and 1500 ml of n-IIopto.a were put together . rü. Al (i ~ C ^ H _Q ) _{7 introduced} under nitrogen and heated to 8G ⁰ C «Aii.f dir ·" «es Gemincih viirdeii 10 Atia. Ethylene xwcl 5 atm gcr.cnten experiment by continuously Nachdrucko - constant of ethylene into the autoclave li'ach · 3 hours the polymerization was terminated · Las polymer was filtered off and dried this vmrclen 93 6 Polyäthyle-i obtain the _v in a TeTx EJI. lin intrinsic viscosity of 2, determined at 135 ° G. The polymer yield was 3'-5 ° CQO g / g

Similar results can also be obtained when Mcx- .a ViGl (PH ₁ ) _o and TiBr (BH ^) _{0 have been used} as catalyst components.

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Claims (1)

Claims 1.) Process for the preparation of polymerization catalysts, characterized in that a hydride or an organometallic compound of metals of groups I, II and III of the Periodic Table is reacted with the product which is obtained by bringing together a titanium compound in which at least one valence of titanium is saturated by a radical X, where X is a C atom, an S atom, an O atom radical of an oxygen-containing inorganic acid or a radical of the formula BRh and R is a hydrogen atom or an aliphatic radical, with a of an anhydrous magnesium halide in a form activated before or during the formation of the catalyst, whereby magnesium halide in activated form is to be understood as a halide, in the X-ray spectrum of which a broadened halo with strongly attenuated intensity appears at the point of the diffraction line of highest intensity that occurs with normal halide and / or its surface me hr is more than 3 tn / g. 2.) The method according to claim 1, characterized in that a titanium compound is used in which at least one The valence of titanium is saturated by a carbon atom and the other valences by halogen and / or titanium and / or alkoxy are. 3.) Process according to claim 1 and 2, characterized in that one al
used. that the titanium compound C ₅ H ₅ TiCl, or CH, TiCl 4.) The method according to claim 1, characterized in that a titanium compound is used in which at least one valence of titanium are saturated by an S atom and the other valences by halogen and / or a C atom. 109849/1763 : j. 21 * 510 * - 14 - 5.) Process according to Claim 1 and 4, characterized in that the titanium compound used is thiophenyl titanium trium chloride or the Ν, Ν-diphenyldithiocarbamate of titanium dichloride is used. 6.) Process according to claim 1, characterized in that one uses a titanium compound in which at least one valence of titanium by the O-atom-containing inorganic acid Hest an oxygen and at least one other valency being saturated by halogen. Fe 7.) Process according to claim 1 and 6, characterized in that the titanium compound TiOSO · ^, / (CH ₃ ) - S 107 ^ Ti, (CH ₃ USiOTiCl ₃ , Si (OTiCl ₃ ) ^ or P-CH ₃ C ₆ H ^ SO ₃ TiCl ₃ used. 8.) Process according to claim 1, characterized in that a titanium compound of the general formula Ti (BR ₁ ^) X is used, in which R is a hydrogen atom or an aliphatic radical, X is a halogen atom, η is an integer between 1 and the valence des titanium and m is an integer between 0 and the valence of titanium minus 1. 9.) Process according to claim 1 and b, characterized in that the titanium compound used is Ti (BH ^) ₃ , TiCl (BH ^) ₂ or TiBr (BH). 10.) Process according to claim 1 to 9> characterized in that the magnesium halide used is MgCl ₂ or MgBr ₃ . 11.) The method according to claim 1 to 10, characterized in that the titanium compound with the magnesium halide under the Mg halide activating conditions ground together. 109849/1763 nt - 15 - 12.) The method according to claim 1 to 10, characterized in that the titanium compound with the preactivated by milling Bringing magnesium halide into contact. 15.) Method according to claim 1 to 10, characterized in / that the titanium compound with one of Grignard compounds of the general formula RMgX, in which R is a hydrocarbon rest and X means halogen, obtained by disproportionation or by reaction with halogen compounds Bringing magnesium halide into contact. 14.) The method according to claim 1 to 10, characterized in that (that the titanium compound with a thermal Decomposition of addition compound of Mg halide with Lewis bases or acids under reduced pressure Bringing magnesium halide into contact. 15.) Process according to claim 1 to 14, characterized in that the titanium compound is used in amounts between 0.01 and 30% by weight , preferably between 1 and 10% by weight, based on the magnesium halide. l6.) Method according to claim 1 to 15 »characterized in that that an aluminum alkyl compound, preferably an aluminum trialkyl, is used as the organometallic compound. 17.) Use of catalysts according to claim 1 to l6 for the polymerization of ethylene or its mixtures with α-olefins and / or diolefins, preferably in the temperature range between -80 ° and +200 ⁰ C and optionally in the presence of inert liquids and molecular weight regulators. 109849/1783