DE1950703A1 - Polymerization catalysts and their use for the polymerization of ethylene and its mixtures with alpha-olefins and diolefins - Google Patents

Description

PATENT LAWYERS DR.-ING. BY KREISLER DR.-ING. BEAUTIFUL FOREST DR.-ING.TH. MEYER DR. FUES DiPL-CHEM. ALEK VON KREISLER DIPL.-CHEM. CAROLA KELLER DR.-ING. KLOPSCH COLOGNE 1, DEICHMANNHAUS

Cologne, September 16, 1969 Ke / Ax

MONTECATINI EDISON SpA ,

Foro Buonaparte, 31 ₃ Milan (Italy).

Polymerization catalysts and their use for the polymerization of ethylene and its mixtures with α-olefins and diolefins

The invention "relates to new polymerization catalysts and their use for the polymerization of ethylene and its Gemisohen with ^ -olefins and / or diolefins _e

The polymerization and copolymerization of ethylene has been "so far with a wide variety of catalyst types carried out. One of the "most tested" known catalysts is the product of the reaction of a compound of a transition metal with a metal organic compound of the metals of group I "to III of the periodic Systems.

It is "known that the activity of such a catalyst is increased significantly when used as a catalyst component instead of connecting the transition detail as such, the reaction product of this compound with a solid inorganic support, the hydroxyl groups contains is used. As can be seen from Dutch patent application 6 714 024, in particular very active catalysts known that by reacting an organometallic compound of a metal

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Group I to III of the periodic table with the product the implementation of a liquid halogenated compound obtained from transition materials with buckets of solid support, which consists of magnesium oxide »which does not contain too high a number of hydroxyl groups. In the The aforementioned Dutch patent application states that the anhydrous state of the carrier is the indispensable prerequisite for the formation of catalysts with good properties

According to an earlier proposal by the applicant, catalysts with interesting properties are also obtained using magnesium hydroxide or products based on magnesium hydroxide as a carrier. Also in the case of these ^catalysts% a completely water-free condition was of the carrier as an indispensable prerequisite for the addition of the carrier for the catalyst.

However, it has been found that using anhydrous magnesium oxide and / or magnesium hydroxide as a carrier, although catalysts are obtained that have a have such a high activity that the polymer can be cleaned of catalyst residues after the end of the polymerization it becomes unnecessary, however, that the use of these carriers also has considerable disadvantages. For example, in the In the case of magnesium oxide, the reaction with the transition metal compound is generally considerable Conversion of the halogenated compound of the transition metal into completely inactive and / or only slightly active Accompanied by-products in the polymerization phase which are difficult to remove from the support itself · These By-products significantly worsen the yield of the catalyst, calculated as the weight of the polymer is formed per unit weight of the transition metal present in the catalyst. To achieve a high It is therefore necessary to adjust the amount of active catalyst component applied and thus the productivity

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To increase the amount of carrier, thereby reducing the amount remaining in the polymer Fremdetoffneng "is increased and the" properties of the polymer are degraded · One of the major components of hydroxide is its poor reactivity of the hydroxide with the compound of the transition metal · The end result in this case is also the need to increase the amount of carrier used

According to the invention, it has now surprisingly been found that it is possible to use polymerization catalysts

10 * "with valuable properties to get under certain Conditions are better than the properties of the anhydrous oxides and / or hydroxides of magnesium obtained catalysts by using in the catalyst production starts from carriers that contain chemically unbound water and one by the formula

have the composition shown, where χ is an overlying number that can reach 100 and more, y is a number between 0 and 1 lying above 0, ^ Hg (OH) _2- Z _{x expresses} the number of hydroxyl groups that can be disregarded the type of bond is present in the carrier, and (HgO) “is the number of molecules of chemically unbound water present in the carrier.

They presence of chemically unbound water in the supports used according to the invention was carried out by Investigation of the adsorption isotherm of the MgO-HgO system at different temperatures as well as by examination the X-ray spectrum of the carrier itself detected. Also by the X-ray examination could be determined that the chemically unbound water present in the starting product after the reaction of the carrier had not been converted to the hydroxide in the product with the transition metal compound.

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The presence of chemically unbound water represents represents a completely surprising aspect of the invention, since this water according to the teachings of the prior art should not have been present in the carrier

Particularly suitable for the production of very active Catalysts with valuable properties are carriers the above formula, in which χ has values below 2, preferably below 0.5, and y has values below 0.6 *

The catalysts according to the invention are thus the product of the reaction between

Bl) the product obtained by reacting a ^ liquid halogenated compound of titanium or vanadium with a carrier of the composition MgO. ^ G (OH) ₂ _7 _x . (H ₂ 0) _yt in the x, y, / Eg ( OE) ₂ J _x and (H ₂ O) _{7 have} the meanings already mentioned, and

b) a hydride or an organometallic compound of metals of group I, II and III of the periodic table.

You according to the invention supports used are prepared by known processes by hydration of magnesium oxide and / or magnesium hydroxide or products of partial high-temperature calcination of magnesium hydroxide "It can be produced for example by magnesium oxide immersed in water, it long enough, ζ · Β · 1 can be up to 2 hours in case of heating the suspension to temperatures between 50 and 100 ⁰ C, in water, filtered, this suspension and the solid finally dried at a temperature below 10O ⁰ C and under moderate vacuum. The temperature is preferably kept ^{below 60 ° C. during the hydration.}

In accordance with known findings (see, for example, the publication of

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R.I. Razouk and R.Sh. Mikhail in J.Phys.Ohem. 5 <J, 656-40 (1955)) it was found that the maximum amount of water which can be absorbed by the magnesium oxide essentially corresponds to the amount that is stoichiometrically is necessary for the conversion of the oxide to the hydroxide.

It has also been found that the maximum amount of water retained by the oxide depends largely on the heat treatment the oxide has undergone. In the case of the oxides which are obtained by calcining magnesium hydroxide at temperatures below 600 to 800 ⁰ O, the maximum amount of water corresponds essentially to the amount which is stoehiometrically required for the conversion of the oxide into the hydroxide.

In contrast, binding the oxides which are obtained by decomposition of magnesium carbonate or by Caloinierung the hydroxide at temperatures above 800 to 100O ⁰ O, maximum amounts of water that are less than the amounts stöohiometrischen. In the case of hydroxide, the maximum amount of water is not very high and is always less than the stoohiometric amount.

If only a partial hydration of the magnesia is desired, it is sufficient to mix the oxide with water vapor to expose saturated air or inert gas flow for a time sufficient to absorb the desired amount of water enough. This hydration treatment is very suitably carried out in the fluidized bed.

As already mentioned, any type of oxide can be used for the preparation of the hydrating carriers used in the process according to the invention. Preference is given to oxides, the zwisohen by Caloinierung of magnesium hydroxide at temperatures of 500 and 600 ⁰ C are obtained a surface spezifisohe zwisohen 10 and 100 m / g,

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mean grain size of 10 to 30u and a hydroxyl group content have less than about 0.2 groups per mole of oxide.

It has been found, however, and this constitutes another Aspect of the invention is that even if one of Magnesium oxides goes out, which have a very large specific surface (generally over 100 m / g) and as a result their excessively high reactivity cannot be used as such for the preparation of the catalyst are as they are in an uncontrollable manner with the halogenated Compound of the transition metal react and thereby an excessive formation of undesired by-products cause products can be obtained, 'which lead to the manufacture of very active catalysts with properties that are comparable to the properties of high-quality oxides.

It has also been found that it is possible to

~ to get goals with good activity even if / from Magnesium oxides with a relatively small specific

2 assumes a surface area of usually less than 10 m / g, which as such would not be suitable for the production of very active catalysts.

Finally, magnesium hydroxides or products can also be used the partial calcination of hydroxides containing more than 0.2 hydroxyl groups per mole of oxide can be used. In the case of the hydroxide, the hydration process enables according to the invention, furthermore, the recovery of active catalysts even when starting from hydroxides which as such would result in low activity catalysts.

The reaction between the hydrated carriers used according to the invention and the halogenated compound of titanium or vanadium is preferably carried out

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by daa in an excess of the Xi or V-iT bond suspended oxide is implemented.

However, it is also possible to use the Si or T compound as a solution in an inert diluent. The results obtained in this Pail, in particular the yield of polymer per gram of Ti or V, is not as satisfactory as in the case of the Carrying out the reaction in the absence of solvents. ** The reaction can be carried out at temperatures between 0 and 300 ^° C., but work is preferably carried out between 100 and 250 ^° C. As a result of the effect of the reaction, the transition metal remains chemically bonded to the support and cannot be removed by washing with solvents.

Suitable liquid halogenated compounds of Ti and V are from the group of halides, oxyhalides and Halogen alcoholates for the production of the catalyst, for example titanium tetrachloride, vanadium tetra chloride, VanadyltetraohlorId, TJrtantrichloraoetylaeetonat and

Titanium trichlomonobutylate.

particularly suitable for the preparation of the catalyst, organometallic compounds are Al (C ₂ H ₅₎ ,, Al (O ₂ H _{5) 2} 01, Al (iO ₄ H _{9) 3,} Al (iO ₄ H _{9) 2} Cl, Al ₂ (C ₂ H ₅ ) JCl ₃ , A1 (C ₂ H ₅ ) ₂ H, Al (iC ₄ H ₉ ) ₂ H, Al (O ₂ H ₅ ) ₂ Br, Li-Al (O ₄ H ₉ ) ₄ , ■ "Li-IC ₄ H ₉ , Mg (C ₂ H ₅ ) ₂ .

The molar ratio of the organometallic compound to the Ti or V compound is not critically important. at If the catalysts are used for the polymerization or copolymerization of ethylene, this ratio is preferably between 50 and 1000.

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The polymerization of ethylene or its mixtures with α-olefins and / or diolefins is carried out by known processes, ie in the liquid phase, in the presence or absence of an inert solvent or in the gas phase. The temperature of the polymerization or copolymerization can be between -80 ° and + 2GO ⁰ O, but it is preferable to use normal pressure or increased pressure between 50 and 100 ⁰ C ·

The molecular weight of the polymer can be adjusted by known methods, for example by polymerization in the presence of alky! halides, halides and organometallic compounds of Zn and Cd or of hydrogen, as is known, the activity becomes the usual Ziegler catalysts made from transition stables and organometallic compounds of metals of Group I to III are obtained by the presence of hydrogen and the other chain transfer agents used to adjust the molecular weight decreased.

In the case of the catalysts according to the invention, however, it has been found that it is possible to obtain polymers of low or very low molecular weight without significantly reducing the activity of the catalyst. In practice it is possible to keep the molecular weight of polyethylene within set a region of interest, the values of the measured in tetralin at 135 ⁰ C limiting viscosity (intrinsic viscosity). between 1.5 and 3 dl / g, without the polymer yield of the catalyst falling to values below which it is necessary to clean the polymer of catalyst residues after the polymerization.

The polyethylene obtained in this way is an im essential linear, highly crystalline polymer that

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• ζ

has a density of 0.96 g / om or higher and has processing properties, in particular with regard to injection molding, which are very good and better than the properties of polyethylene with normal Ziegler catalysts is obtained. The ash content of the polymer which has not been cleaned of catalyst residues is generally below 100 ppm and the Cl content below about 30 ppm «

As already mentioned, the hydrated carriers according to the invention surprisingly not only allow

the formation of catalysts with properties that are comparable with the properties in terms of activity and low chlorine content in the polymer, which are typical of catalysts made with anhydrous magnesium oxide and / or magnesium hydroxide as a carrier rather, they offer some significant advantages when used, the most important of which are the following are:

The content of Ti and V, which are bound to the support and are present in the catalytically active state, is im Ratio to oxide decidedly higher. This means that it is possible to use the catalysts according to the invention Polymers with a lower content of foreign substances and therefore to be preserved with more valuable properties. The reactivity of the Ti or V compound with the Hydroxide is higher. This also has the result that a polymer with a much higher purity is obtained.

-In the following examples, the. Percentages on weight unless otherwise stated.

example 1
60 g of magnesium oxide, which has an average particle size of

15 to 20 yu and a specific surface area of 60 m / g. and furthermore a weight loss of less occurring during calcination at 1000 ^{° C. for 24 hours}

than $ 1 Khatib, 4 hours, heated to 100 ⁰ C. After the 009816/1700

Drying, the mass was _{suspended in 340 ml of TiCl 4} , which had been ^{heated to 136 0} O. The suspension was stirred for 1 hour at this temperature. The solid was then filtered off hot, twice with boiling TiOl * and then with n-heptane Washed and finally dried to completely remove unreacted TiOl. 7.2 g of solid by-products were separated from the TiCl., which essentially consisted of TiOCIp , 1 wt .- ^ Cl present.

A suspension of 0.533 g of this solid product in 11 n-heptane was placed under nitrogen in a 1.8 1-Autokläven of stainless steel, fitted with a stirrer and heated to 85 ⁰ C. A solution of 2.0 g of aluminum triisobutyl in n-heptane was added to this suspension. Immediately thereafter, ethylene up to a pressure of 10 atmospheres and hydrogen up to a pressure of 4 atmospheres were introduced into the autoclave. The total pressure was maintained by continuously pushing in ethylene throughout the experiment. After 2 hours the polymerization was terminated and the polymer was filtered off and dried. In this way 326 g of powdery white polyethylene were obtained.

Example 2

In a tube furnace 77 g of commercially available Mg (OH) were kept for 17 hours at 100 ⁰ C ₂ (hydrated heavy calcined magnesia of CoErba) under flowing nitrogen. The hydroxide dried at 100 ^° C. and ^{heated to 1000 °} C. for 24 hours had a weight loss of $ 30.8.

After drying, the hydroxide was boiling in 330 ml TiCl. suspended and stirred in it for 1 hour. The solid Product of the reaction was filtered off hot, then twice

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with boiling TiCl. and then washed with n-heptane and finally dried · From the TiCl. became 9 »5 g of by-products were separated off. Contained in the carrier obtained 0.08 ^ Xi and 2 ^ Cl. A lot of 0.83 g of this The carrier was used for the polymerization of ethylene, which was carried out under the conditions mentioned in Example 1 became · After 4 hours, 14-8 g became powdery obtained white polyethylene.

Example 5

A portion of said magnesium oxide in Example 1 was befeuohtet by saturated with water vapor nitrogen for 1 hour at 25 ⁰ C, was passed over it. In this way, a product was obtained which had a weight loss of 4 _t 2 6 when it was ^{kept at 1000 °} C. for 24 hours. Immediately after wetting, 60 g of the hydrated oxide in 340 ml of TiCl ,, which was heated to 136 ⁰ C, suspended. The reaction conditions and the measures for separating off the solid product were the same as described in Example 1. The solid separated from the reaction mixture contained 0.64 $ Ti and 15.656 Cl.

In the excess of TiCl used in the reaction. there were 4.9 g of solid byproducts.

An amount equal to 0.29 g of the catalyst component so prepared was used for the polymerization of ethylene in the manner described in Example 1 · After a polymerization time of 2 hours were 286 g obtained white powdery polyethylene.

Example 4

A second part of the magnesium oxide mentioned in Example 1 was kept in boiling water for 1 hour, after which the suspension was filtered. The moist solid which was separated off was dried by keeping it at 80 ^° C. and 100 mm Hg for 1 hour. A part

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of the dried solid showed a weight loss of 3O 4596f when it was caloiniert 24 hours at 100O ⁰ G. A quantity of 30 g of the hydrated oxide obtained in this way was reacted directly with TL (SIa in the manner described in Example 1). The solid obtained in this way contained 0.23% by weight of Ti and 6.6% by weight. $ 01.

The amount of by-products formed during the reaction was increased after the boiling point of the TiGl _{4 rose.}

averages · This increase was 1 ^{0 O, while it was 3 0} O in the test described in Example 1.

An amount of 0.3066 g of the catalyst component was added . for the polymerization, of ethylene under the conditions mentioned in Example 1 used. After 2 hours 180 g of polyethylene were obtained.

Example 5

A third portion mentioned in Example 1 Magnesia was kept for 1 hour in water of 50 ⁰ C * Subsequently, the excess of water was removed by passing the suspension was held for 30 minutes at 90 ⁰ C and 4OO mm Hg "On a sample of this oxide the weight loss is determined which occurred when the sample was ^{calcined at 1000 °} C. for 24 hours. That weight loss was $ 31.25.

A quantity of 70 g of the hydrated oxide obtained in the manner described above was treated with TiCl. implemented. The rise in the boiling point of TiCl. between the beginning and the. End of the test was 1 ⁰ C. After filtration and evaporation of TiCl. no significant amounts of by-products were found.

The catalyst component separated from the reaction mixture contained 0.225 wt% Ti and 5.6 wt% Cl. A lot

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of 0.401 g of this product was used for the polymerization of ethylene in the manner described in Example 1. After 2 hours, 194 g of polyethylene were obtained.

Example 6

300 g of magnesium oxide, which had a specific surface area of 125 m ² / g and an average particle size of 20 to 25 M, were immersed in water for 1 hour. After the water had been removed in the usual manner, the weight loss was determined on a sample of the product, which occurred after calcination at 1000 ° C. for 24 hours. This weight loss was 31 »4 #. A 60 g quantity of the hydrated oxide was reacted with TiOl * in the manner described in the examples above. The increase in the boiling point between-the beginning and the end der'Reaktion was 1 ⁰ O.

The solid obtained contained $ 0.33 Ti and $ 10.5 Cl. An amount of 0.340 g of this product was used for the Polymerization of ethylene in the manner described in Example 1 used. 198 g were obtained from the autoclave Taken from polyethylene

Example 7

42 g of the magnesium oxide mentioned in Example 6, but not treated with water, were treated with TiCl * under the in Example 6 reacted conditions mentioned · The reaction was violent and proceeded with strong formation of gaseous products. The solid product that is based on the above examples described manner from the reaction mixture was separated and washed, contained 5.3? 6 Ti and 35,596 Cl.

With 0.13 g of this product required for the polymerization of ethylene. the manner described in Example 1 was used, no significant polymer formation was possible -be achieved.

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Example 8

300 g of magnesium oxide, which had a particle size of less than 0.1 u and a specific surface area between 10 and 11 'm / g ", was kept in water for 1 hour. After the excess water had been separated off in the usual way, a sample of the Product found that the weight loss after calcination for 24 hours at 1000 ⁰ C was 32.1 #.

An amount of 65 g of the hydrated product was added to! ΓΙΟΙ. reacted in the usual way. The increase in the boiling point between the beginning and the end of the reaction was 0.5 ^° C. The obtained F 0.7% by weight of Ti and 12.75% by weight of Cl.

tion was 0.5 ⁰ C. The solid obtained contained

An amount of 0.18 g of this solid was used for the Polymerization of ethylene used under usual conditions. After 2 hours, 218.8 g of polyethylene were obtained.

Example 9

60 g of the magnesium oxide mentioned in Example 8 and not treated with water were reacted with TiOT in the manner described in Example 8. Between the beginning and the end of the reaction an increase in the boiling point of 2 ^° O was found. The solid obtained contained 0.1% by weight of Ti and 12.1% by weight of Cl.

Ethylene was polymerized using 0.75 g of the product under the conditions given in the examples above. After 2 hours, 119 g of polyethylene were obtained. ^v

Example 10 .

30 "200 g of magnesium oxide, which has an average particle size of

2 20 to 25 Ά and a specific surface area of 80 m / g

was kept in water for 1 hour. To iin & far 0098 16/1700

.— 15 -

of the excess water in the usual We4.se was on a sample of the product a weight loss of 31.6? 6 found after 24 hours of oiling at 1000 ° C

80 g of the hydrated oxide were in a mixture of 50% by weight of technical grade heptane and 50% by weight of TiCl. suspended. The Seaktionstemperatur throughout the experiment was 116 ⁰ C, the test time: 1 hour · The reaction * "tionsgenisch was then filtered and the solid thus obtained zunäohst with a mixture of 50 wt .- ^ heptane and TiCl., And then with heptane to washed to completely remove the TiCl. 0.38 $ Ti and 5 ^ 01 were found in the washed solid.

Ethylene was added with 0.6 g of this catalyst component polymerized under the conditions described in the preceding examples. After 2 hours, 19O g Polyethylene obtained.

Example 11

100 g of magnesium oxide, which had a particle size of 15 to 20 u and a specific surface area of 60 m / g and ätündiger 24 after calcination at 1000 ⁰ C showed a weight loss of 3.1 #, were incubated at 50 ⁰ G with wasserdampfgesättigtem so Stiokstoff treated for a long time until an amount of water of 4% by weight had been introduced. The oxide had after hydration and 24 hours of heating at 1QOO ⁰ C a weight loss of 7.1 #.

A 10 g quantity of the hydrated oxide was added with TiCl. implemented in the usual way. The solid obtained in this way contained 0.63 wt. 5fa Ti and 17 »1 wt. 96 Cl. Ethylene was polymerized under the usual conditions with 0.43 g of this solid. After a reaction time 180 g of polyethylene were obtained in 2 hours.

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- ΊΟ "*

Example 12

60 g of magnesium oxide, which has a particle size between 5 and

2 20 u, a specific surface area of 5 m / g and a weight loss of 31.5% after 24 hours of heating to 100O ⁰ G were treated in a fluidized bed with a steam-saturated air stream for 50 minutes at 40 ⁰ O. After this treatment had a sample of the hydrated product after 24 hours of heating at 1000 ⁰ C a weight loss of 36.5 $ · 50 g of hydrated product thus obtained were suspended in 330 ml TiCl α, which was heated to 136 ⁰ C. The reaction conditions and the conditions of separation of the solid substance ^v after the reaction were the same as in the preceding examples. The increase in the boiling point between the beginning and the end of reaction was 3 ⁰ C. The solid product contained 0.25 wt .- # Ti and 7.6 wt -4> ei · ■. '■ \ -.'"■. ■■. ■■■■■. ■■■ -,

Ethylene was added with 0.54 g of this product under the conditions described in the previous examples polymerized. After 2 hours, 302 g of polyethylene were obtained.

k Example 13

With 0.43 g of the catalyst component obtained according to Example 11, ethylene was polymerized under the conditions mentioned in Example 11, but no hydrogen was introduced into the autoclave. After a polymerization time of 2 hours wurden236 g of polymer obtained had a measured in tetralin at 135 ⁰ C intrinsic viscosity of 8.6 dl / g. The intrinsic viscosity of the polymer obtained according to Example 11, on the other hand, was 2.6 dl / g.

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Claims (8)

Patent to a ρ r ü ο h e 1) Catalysts suitable for the polymerization of olefins, consisting of the product of the reaction between a) the solid product that is obtained during implementation a liquid halogenating compound of Ti or V with a solid support, the ohemisch Contains unbound water and has a composition that is determined by the Forme1 MgO. ^ G (OH) ₂ _7 _x . (H ₂ 0) _{y is} expressed in which χ is a number above 0 that can reach 100 and more, y is a number above 0 between 0 and 1, ^ Sg (OH) _2- T _{x is} the number of Expresses hydroxyl groups that are present in the carrier regardless of the type of bond, and (H ₂ O) is the number of molecules of chemically unbound water present in the carrier, b) a hydride of an organometallic "compound of metals of group I, II and III of the periodic table. 2) Catalysts according to claim 1, characterized in that in the formula mentioned in claim 1 of the carrier χ less than 2, preferably less than 0.5, and y is less than 0.6 3) Catalysts according to claim 1 and 2, characterized in that the support has been prepared by hydration of magnesium oxide, which is obtained by calcination of magnesium hydroxide with a specific surface area between 10 and 100 m / g, an average particle size between 10 and 3Ou and a hydroxyl -, group content below 0.2 / mol has been obtained _e 009816/17 00 • I * * 4) Catalysts according to claim 3 »characterized in that that the hydration of the magnesium oxide through pass over a humidified air or inert gas flow over the oxide was carried out at temperatures below 60 ° C " is. 5) catalysts according to claim 1 to 4, characterized in that that the reaction between the liquid halogenated compound of Ti and V, preferably between one Halide, oxyhalide or halogenated alcoholate of Ti or V and the support has been carried out in the absence of inert solvents. 6) catalysts according to claim 1 to 5, characterized v indicates that by converting the solid product, that by reacting the liquid halogenated Ti or V compound with the solid support of the formula Composition expressed in claim 1 obtained has been, with an aluminum trialkyl compound or with an aluminum dialkyl monohalide. 7) Process for the polymerization of ethylene or its Mixtures with an α-olefin and / or a diolefin, characterized in that catalysts according to claim 1 to 6 can be used. 8. The method according to claim 7, characterized in that the polymerization of ethylene is carried out at temperatures between -80 ° and 200 ⁰ C in the presence or absence of an inert liquid and the polymer obtained in this way is used as such without purification of catalyst residues. 009816 / 17Ü0