DE2052136A1 - Process for the polymerisation of oils finen and catalyst therefor - Google Patents

Description

Mitsui Petrochemical Industries, Ltd., Tokyo, Japan

Process for the polymerization of olefins and catalyst therefor.

The invention relates to an improved method of polymerization or interpolymerization of olefins, which can be used industrially with advantage and also a catalyst which can be used while avoiding the disadvantage of aggregation of the catalyst, and the polymerization with improved specific polymerization activity [polymer yield (g) per millimole of transition metal present in the catalyst is present, per hour of polymerization time per atmosphere of olefin: g / mmol-hour atm.] and productivity [polymer yield (g) per g of transition metal halide used as the solid catalyst component, per hour of the polymerization time per liter of the inert hydrocarbon solvent: f g / g-hour / liter! is carried out. In particular, the invention relates to a process for the polymerization of olefins and with a catalyst that can be used, the process being characterized in that olefins in an inert Hydrocarbon solvent in the presence of a catalyst comprising an organic metal compound and a transition metal halide contains, polymerizes or co-polymerizes as a separate component the solid catalyst component containing the transition metal halide is obtained by

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a transition metal halogen compound, preferably a halogen compound of titanium or vanadium, with a carrier material such as a magnesium halide, preferably magnesium chloride or a manganese halide, preferably the manganese chloride, vigorously mechanically mixed, in such amounts that of the latter preferably at least 0.5 mole based on 1 mole of the former, and more preferably an equimolar amount, and most preferably one molar Excess is present.

The transition metal halogen compound and the organometallic compounds, which are used in the present invention are both per se as catalyst components of Ziegler catalysts, used for the polymerization of olefins are known.

Proposals to use Ziegler catalysts for the polymerization or interpolymerization of olefins by placing them on Inert carrier material! s deposited are known (cf. US Pat. No. 3,166,542 and Belgian Pat. No. 705,220). It it is also known that various conflicting proposals have been made as to the class of those used Carrier materials and the size of the carrier particles. The use of magnesium chloride as a carrier material is also known (see British patent specification 841 822).

It is common to these known procedures that the compound which is used as a catalyst is on a solid support material and is used as such as a catalyst or as a catalyst component, this being done because one has the general knowledge ^ why supports are used, applies, ie you want the menu | edg | _{m of the} catalyst which is present in the polymerization reaction, ie one would like to cause the added catalyst to increase the polymerization conversion of the constituents.

The improvement achieved by such a process enables the polymerization reaction to be carried out with a smaller amount of catalyst than when not using a generator. '' Although this improves the effectiveness of the catalyst, the degree of improvement

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Not necessarily very large and further improvements are worth striving for.

The proposal has also already been made to use a solid-solution To produce a product suitable for use as a catalyst for the polymerization of olefins. This mixed crystallized Product is represented as follows: A partially reduced transition metal halide that was previously formed becomes strong with a metal halide or a metal of either Group II or Group III of the Periodic Table Subjected to crushing treatment, with a crushing

not v / ess than approximately medium having an effective density of / 3 g / mm, such as to cause balls of steel to the mixing crystallization of the partially reduced transition metal halide previously formed with the metal of the group ä tallhalogenid II or III of the periodic table (Japanese Patent Application No. 10516/1963 and U.S. Patent 3,130,003).

In the proposal mentioned above, it is pointed out that the amount of the Group II or Group III metal halide in relation to the partially reduced transition metal xbelogenide is extremely critical in relation to the desired aim of improving the activity of the resulting catalyst. The amount of Group II or III metal halide per mole of partially reduced transition metal halide used is described as being in the range "between 0.5 and 1.0 moles, preferably from 0.1 to 0.5 moles and am most preferably { must be between 0.2 to 0.33 moles.

Will propylene with a catalyst combination of triethylaluminum and a crushed product of titanium trichloride and aluminum chloride polymerized, the catalytic effectiveness (yield of polymer in g / catalyst in g) when aluminum chloride is in the most preferred range of the above, i.e. from 0.2 to 0.33 moles, 135.3 to 137.0, i.e. more than twice as in the case when titanium trichloride is used alone will. However, the amount of aluminum chloride used will be

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increases slightly and if one uses 0.5 mol, the catalytic bo falls Efficiency to 48.9 to 66.3, i.e. approximately one-half "to one-third of the aforementioned catalytic Effectiveness and it approaches the value obtained using titanium trichloride alone. Will the amount used of aluminum chloride is further increased, so that 1 mole of aluminum chloride is used for 1 mole of titanium trichloride, the effectiveness drops strongly to about 1/10 of the value given above and is even worse than when one uses titanium trichloride alone. Experimentally, it has been shown that the catalytic efficiency drops to about a quarter compared to when one Titanium trichloride used alone.

In the above method are the only metal halides of _t Groups II or III which have been described, aluminum chloride as compounds of the group III and beryllium as the compound of group II. Other metal halides of Groups II or III. III are not mentioned. In all examples only aluminum chloride is used. *) and gallium chloride

A finely ground Ziegler catalyst generally tends to agglomerate during the polymerization reaction, with the result that the catalyst material does not take part in the polymerization reaction and therefore additional amounts must be used. In order to avoid the need to use such excessive amounts, the following investigations were carried out. It has now been found that if one combines the aforementioned comminution treatment with the idea of a carrier, a proposal which contradicts the aforementioned idea, a transition metal halide catalyst for use in the polymerization of olefins can be procured which is an excellent one having improved specific Polymerisationeaktivität and not agglomerates further been found that it is possible and carry out the polymerization of olefins with technically effective benefits when using such a catalyst, along with a organometallisohen catalyst compound.

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As previously mentioned, "the proposal of the crushing treatment" treatment as the Group II metal halide mentions only beryllium chloride, a compound which has difficulties "because it cannot be used practically well because it is not only but also its dust is very poisonous, but also because it gives off poisonous fumes and is therefore particularly difficult to handle. No mention is made of other halides of metals of group II. It has now been found that a halide of magnesium of the third period, includes, for example, magnesium chloride, excellent good apezifische polymerization when it is subjected to the crushing treatment with a transition metal, and that it can still be handled easily. the results obtained are very different from those obtained λ with halides of beryllium around the second period and the halides of calcium and zinc of the fourth period, although di they are metals of the same Group II. The halides of metals of the second period, ie beryllium, are highly toxic and the results obtained by using the halides of calcium and zinc are unsatisfactory in terms of the specific polymerization activity. Results are obtained which are slightly improved than when the transition metal halide is used alone. Surprisingly, it has now been found that metals of group II of the third period, which is between the second and the fourth period, ie magnesium, especially magnesium chloride alone, solves the aforementioned two problems at once.

It has been found that halides of manganese of Group VII of the Periodic Table, and in particular manganese chloride, are also more excellent Catalyst with excellent specific Polymerisat ionsaktivi tat can be used.

Furthermore, g-rounds, that magnesium chloride ι-iü / odsr MavÄ _t ;: an rid preferably m at least the equimolar Kar.30 in Bas; : the transition metal halide denaturation and on mei ^ in jevor ^ v ,. f.

molar cnorselus are used * JEb vm.j vol ^r ^ ^; . u.;>: r · > - ': ■ that it would ϋβΥ'-λνΐι. ^ - ς saln * Mag> _i} 3lu.sctiloriä 1: ■. '■ .-, ■ ^iJ V: - a .

: ο -ι 1 1 ί ■ ' ^Λ - - β

BATH ORIGINAL

chloride to be used in amounts above the upper critical Limits were with respect to the amount of metal halides of Group II or Group III in the case of the aforementioned Crushing treatment had started.

It is an object of the present invention to provide a solution to the technical problems involved in the aforementioned | Crushing treatments occur, although they are not described, but which are caused by the beryllium chloride, which was specifically disclosed therein, as well as calcium chloride and zinc chloride, the latter compounds not mentioned, i.e. it is an object of the present invention to

unavoidable

to eliminate the deadly gases and the specific polymerization activity compared with the cases where the transition metal halides are used alone. The solution the aforementioned problems is achieved by using magnesium chloride, a preferred example of the metal halide Group II, the use of which has not been disclosed in the aforementioned prior art proposals, in which a grinding treatment is carried out, and the problem is also similarly caused by the use of manganese halide solved, a process for the polymerization of olefins having excellent specific polymerization activity and without the catalyst agglomerating is created. The invention is also concerned with an improved catalyst for use in the aforementioned procedure.

According to the process of the invention, a transition metal halogen compound is preferably a halogen compound of either titanium or vanadium and magnesium chloride and / or manganese chloride violently mechanically comminuted with one another, whereby a solid catalyst component of a transition metal halide receives «Practically no change in width at half peak height or half-peak width (half-peak breath) of the hand-held diffraction diagram or the X-ray diffraction espkiruaa over crystals with the X-ray diffraction method, itself ν-Λ ·· um & <g?: egg halide or manganese halide independently

. ni '.? 4 Heine violently mechanically crushed. Will this "* ι. ^., Edooh be similar in the presence of a *. ! 109820/2108

BATH ORIGINAL

_ 7 -

Comminuted transition metal halide compounds, it is observed that an increase occurs in the half-peak width of the magnesium halides or manganese halides mentioned above and it is found that The object according to the invention can be achieved if one uses a comminution product of either magnesium halide or manganese halide and the aforementioned transition metal halide compound, at which the increase was observed was used.

What is described below as vigorous mechanical co-crushing means that co-crushing is carried out to the extent that the half-peak width of the diffraction spectrum of magnesium lia ^ ogenide, especially chloride or manganese halide, especially manganese chloride, according to the X-ray diffraction method is greater than λ those of these compounds before they are crushed.

The X-ray diffraction method is carried out under the following conditions using the apparatus described below »A Rotaflex type X-ray diffraction apparatus (with 1 °, 1 °, 0.15 mm gap (manufactured by Rigaku Denki Company, Ltd., Japan)) is used to measure the X-ray diffraction spectrum, this is done in se. 104) level of magnesium chloride and the (003) level of hangan chloride after they have been crushed. The CuK _β rays supplied by a 50 KV 100 mA X-ray generating device are used as X-rays. The co-crushing is carried out in such a way that the aforementioned half-peak width is exceeded. There is no restriction on the extent to which the half-peak width must be exceeded; it only has to exceed the half-peak width of the compounds before their co-comminution. In general, 1.1 times, and preferably 1.2 times, is sufficient.

Although it is believed that the increase in the half-peak width of the diffraction spectra as a result of the decrease in the lily diameter

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ser of the crystals and the simultaneous presence of either a complex or a solid solution between the metal halide compound and the transition metal halide, there is no confirmation of this hypothesis. As the transition metal halide is still found in the dry pestilent after the comminuted product is washed well in an inert hydrocarbon and dried in vacuo at room temperature a complex or a solid solution is believed to be formed. The present invention is of course not based such an assumption is limited.

As mentioned earlier, in the known method in which the aforesaid co-crushing took place, it became twofold Improvement in catalytic efficiency compared to when the transition metal halide was used alone, found when the proportions of aluminum chloride used were 0.2 to 0.33 per mole of transition metal halogen compound. Was the however, the amount of aluminum chloride used was increased to 0.5 mol, no remarkable improvement could be observed, and when the aluminum chloride was used in an equimolar amount, the catalytic efficiency was improved instead of being improved became, worsened,

where the effectiveness was only a quarter of the effectiveness, than using the transition metal halide alone. In the present invention, magnesium chloride and / or manganese blue are used preferably in an amount of at least 0.5 mol and particularly preferably in a molar excess, based on the transition metal allhalogen compound is used. For example, one can use a preferred excess ranging from 2 to 500 moles. A lot is especially recommended in the area above. 5 to 100 moles. It is not necessary to use a particularly large excess, since the use of a larger amount is the Polymerization activity not improved. Appropriately will an excess amount necessary for the co-grinding treatment suitable let chosen.

To improve the polymerization activity of the solid catalyst and also to improve activity reproducibility, becomes the water that is attached to the magnesium or manganese halide

ORIGINAL INSPECTED

is absorbed, preferably removed before the co-grinding treatment. In order to remove the adsorbed water, a customary dryer is generally used and drying is carried out under reduced pressure and / or at 100 to 600 ^° C. Any other method for removing water can also be used. But you also get a catalyst with sufficiently high activity,

when using the commercially available magnesium halides or manganese halides.
Although there is no particular limitation on the particle size of the magnesium or manganese chloride before they are co-crushed, average particle sizes not larger than that of a sieve with a mesh size of 0.833 mm (20 mesh) are preferred.

Pure mechanical co-crushing exists in the present one Invention also no particular restriction, and devices with which the material can be comminuted so, to the half-peak width of the diffraction spectrum determined by the X-ray diffraction method that exceeds the magnesium or manganese halide before their co-crushing can be used will.

As such, mechanical crushers, processes, etc. can be named for example: vibrating ball mill, a rotary ball mill or a disk-like vibrating mill, Impact mills or a stirring device in which a crushing effect occurs as required. Although There are no restrictions on what material the balls are made of, in the case of ball mills, materials are best which are re-resistant to corrosion caused by halides. A ball diameter is preferred used, which is less than a tenth of the inner diameter of the rotary cylinder used. The bullets will preferably used in such a number that the apparent volume of the space occupied by the balls, one third to nine tenths of the internal volume of the rotary cylinder p matters. On the other hand, ea is preferred that the total volume of the material to be treated in the tire

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fahr corresponds to a tenth of the apparent volume of the room, which is filled by the balls.

The temperature and the duration of the co-grinding are not particularly limited. As long as the co-crushing is achieved to such an extent that the aforementioned half-peak width of the diffraction spectrum, determined by the X-ray diffraction method of magnesium or manganese halide, is above that of the compounds prior to their co-crushing, these can be chosen arbitrarily. In general, temperatures in the range of O ⁰ and 200 ⁰ C and preferably used, and from 0 to 16O ⁰ C is generally sufficient for a time in the order of 1 to 100 hours, but lower or higher temperatures or considerably shorter times or longer times can also be appropriately selected so long as the aforementioned half-peak width conditions are achieved. Although additional heating or cooling is not required, this can be done if desired.

If desired, longer conversion times can also be selected will. The treated solid material obtained by the co-crushing treatment can be used directly as the polymerization catalyst component, but it can also be used after unreacted transition metal halogen compound by washing with, for example, an inert Hydrocarbon solvent used to polymerize olefins has been removed. Such working procedures as the crushing treatment, the washing of the treated solid material, the removal of the solvent and the transport of the catalyst are preferably carried out in an atmosphere of an inert gas.

As the transition metal halide compound which is mixed with the magnesium or manganese halide, all compounds known as transition metal halide compounds of the Ziegler catalysts can be used. Halogen compounds such as titanium or vanadium are particularly preferred. As epic examples

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⁰ AD OHlGiNAL

e Ile those are mentioned that are liquid, such as titanium tetrachloride, Titanium tetrabromide, (Ditanmonoethoxytriehlorid, Vanadiumtetraohlorid and vanadium oxytrichloride, and those that are solid, titanium trichloride, lithium dichloride, vanadium trichloride, .Eitandibutoxydichlorid and titanium oxide dichloride, the compounds being tetravalent State are preferred, and tetravalent lithium compounds are particularly suitable, and! Ditanium tetrachloride is most preferred.

Viarum such a surprising improvement in the specific Polymerisat ionsen: - occurs when magnesium or manganese chloride are used as a C o-comminution bicomponent en is not clear. These compounds are halides of aluminum, when used as i Co-crushing components, very superior. This also applies to the Pail when halides of calcium or zinc are used, which are not known, but which can be referred to together by the expression "Group II metals". It is believed, however, that the halides of calcium, zinc or aluminum with. of the organometallic compound of the other catalyst compound during the polymerization reaction.% . :. ^ act and form soluble products, with the result that egg.utj.on takes place and the complex formed first is dispersed, resulting in the dispersion of the transition metal halogen compound and, as a result, aggregation of the transition metal compound occurs in the known processes with The result is that hardly any improvement in activity can be observed. On the other hand, it is believed that the elution by the reaction as described hereinabove does not occur in the case of the halides of magnesium and manganese, and therefore the aggregation of the transition metal components does not occur in the present invention and, in addition, it is believed that Metal halide acts co-catalytically on the transition metal halide during the polymerization reaction. However, the present invention is not intended to be limited to any such speculation or theories.

As the organometallic catalyst component which together with the transition metal halogen catalyst component which is as here

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organometallic compounds of aluminum or zinc are preferred. For example, compounds of the formulas IUAl, R ₂ AlX, RAlX ₂ , EAl (ORX), R ₂ Al (OR) and R ₅ Al ₃ X _{5 can be} mentioned where R is an alkyl group with 1 to 6 carbon atoms or an aryl group with 6 to 10 carbon atoms and X is halogen or hydrogen, and where R and X, if they occur in plurality, can be the same or different, or compounds of the formula R ' ₂ Zn, where R ^{1 is} an alkyl group having 1 to 6 carbon atoms. Specific examples of these compounds include triethyl aluminum, tripropyl aluminum, dibutyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum hydride, ethyl aluminum, dichloride, aluminum, diboxyl aluminum, diboxylaluminium, diboxylaluminium, diboxylaluminium, diboxylaluminium, ethylzichloride, diboxylaluminumethyl, and dibutylaluminumethyl, dibutylaluminum, diboxylaluminium, ethylzichloride, and dibutylzichloroethoxychloride, dibutylaluminumethylthoxychloride, tripropylaluminum tripropylaluminum, tripropylaluminum, diethylaluminum. taking triethylaluminum md triisobutylaluminum for use are particularly useful in the present invention.

The process according to the invention, in which the polymerization or copolymerization of olefins is carried out in the presence of the catalyst described above, can be carried out according to the same processes as are known for the polymerization of olefins with Ziegler catalysts. If desired, it is also possible to dispense with separating off the catalyst. The reaction can be carried out by adding a catalyst which contains magnesium chloride and / or manganese chloride and which has been co-crushed with a halogen compound of, for example, titanium or vanadium, and an organometallic compound, such as, for example, an organometallic compound of aluminum or zinc, in an inert solvent, for example hexane, heptane or kerosene, where care must be taken that Kätälysatorgätze such as oxygen or water are essentially not present, and then the olefin is introduced into ethylene, for example. A polymer used sation level of usually 20 to 300 °, and preferably 60 to 200 ⁰ C can! And the polymerization reaction can be carried out at a pressure of between kg usual atmospheric pressure to 100 / cm ^2,

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is preferably between 2 to 60 kg / cm. A concentration of the transition metal halogen compound, which contains crushed solid catalyst, from about 0.001 to 3 1 g / ltr. Solvent, is sufficient, and a concentration of the organic metal compound of 0.05 to 10 mmol / ltr. Solvent is satisfactory.

Although the adjustment of the molecular weight of the polymer can be achieved by varying the polymerization temperature and / or the molar ratio of the catalyst components, the method of adding hydrogen to the polymerization system is effective. In the case of slurry polymerization The yield and the apparent density of the polymer can be increased by adding silicone oil or esters to the polymerization system inflicts.

The process according to the invention can be used for the polymerization and copolymerization of olefins, preferably for olefins containing 1 to 6 carbon atoms such as Ethylene, propylene, 1-butene, 1-hexene and 4-methyl-ipentene.

Compared with Ziegler catalysts, which are used without a carrier or with the catalyst containing an organometallic compound and a catalyst component obtained by Oo-Serkleine- i tion in a * ball mill, an excess of a transition metal-hydrogen compound with a halide of a metal of Group III or a halide of a metal from group II other than magnesium was obtained, the catalyst according to the invention shows a surprisingly high specific polymerization activity and a very high productivity. Furthermore, no difficulties arise in the production of the catalyst according to the invention which are caused by the toxicity of the compound, as is the case, for example, with the beryllium chloride of Pail. Since only a very small amount of the transition metal halogen compound must be used with respect to the resulting olefin polymer, the amount of catalyst contained in the polymer is i ^r t,

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very low. It is therefore possible to dispense with removing the catalyst from the polymer after the end of the polymerization. Since magnesium or manganese halides are soluble in water or alcohol, the polymer can, if desired, be mixed with water and alcohol are treated, and by this treatment, the magnesium or the manganese are eluted and become the same In time, the transition metal compound attached to it can be easily removed. The olefin polymers according to the invention Processes obtained are used as starting materials for films and finely drawn yarns, whose quality requirements are very strict and in which no trace of the catalyst metals must be present. The inventive Catalyst is stable at elevated temperatures where it has high polymerization activity, and therefore is this catalyst suitable for polymerization at elevated temperature, thereby further improving productivity and profitability is achieved.

The following examples illustrate the invention without, however, restricting it. Unless otherwise specified, the co-grinding treatment is used for the production of the transition metal catalyst component, which is located on a carrier, carried out under the following "standard conditions".

A rotary ball mill having a stainless steel rotary cylinder (SUS 27) with an inner diameter of 10 cm, an outer diameter of 11 cm and a length in the axial direction of 11 cm was used, and it was operated at room temperature at a rotational speed of 250 rpm operated. 40 balls with a diameter of 1.27 cm and 15 balls with a diameter of 2.22 cm were used. The balls were made of the same material that was used for the rotary cylinder. The mill was sealed with a polychloroprene gasket.

Unless otherwise stated, the polymerization was carried out under the following “standard conditions”.

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- Ip -

The interior of the stainless steel 2 liter autoclave, which was equipped with a two-blade stirrer, was flushed with nitrogen, then 1 liter. Kerosene, Iriisobutylaluminium and the solid catalyst component which was prepared as described above, filled in the stated order, and then purified hydrogen was introduced in an amount of 3.5 kg / cm-g and the temperature was raised to 9O ⁰ C. The stirrer was operated at a speed of 350 rpm and this suspension polymerization was carried out for 2 hours by continuously introducing purified olefin so that the total pressure remained constant at 7 kg / cm-g. After the polymer suspension had been thoroughly washed with hexane, the polymer was ^{dried in vacuo at 80 °} C. for 15 hours.

The specific polymerization activity means the yield Polymer (g) per polymerization time in hours per 1 mmol of Titanium or vanadium halogen compound per 1 atmosphere of the olefin. On the other hand, productivity means the yield of polymer (g) per hour of polymerization time per 1 g of the solid catalyst component per 1 ltr. Solvent.

Example 1 and Comparative Examples 1 to 4

500 g of anhydrous magnesium chloride (manufactured by Yoneyama Chemical Co., Ltd., Japan) particle size corresponding to a sieve with a mesh size of 0.178 mm (60 mesh) was placed in a quartz tube with an inner diameter of 5 cm "and for 7 hours 550 to 600 ⁰ C dried in a nitrogen stream. the half-peak width of Röntgendiffraktionsspektrums determined by the method described above, was 0.10 when the thus-dried anhydrous magnesium chloride was measured before the co-grinding treatment.

47.2 g (0.495 moles) of this dried anhydrous magnesium chloride and 2.90 ml of titanium tetrachloride (liquid) (0.0263 mol) were placed in a ball mill and kept below the above for 50 hours specified standard co-crushing conditions co-crushed. The crude solid catalyst component thus obtained contained fines

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ORIGINAL

Particles with a particle diameter of 1 to 10 microns and showed good flowability. Part of this solid catalyst component was washed with dehydrated and purified hexane, to remove unreacted titanium tetrachloride, then the particles were dried in vacuo at room temperature for 5 hours. It was found by polarograph that the amount of Titanium compound present per g of the resulting solid purified catalyst component was 21 mg, calculated on the titanium atom. The half-peak width of the X-ray diffraction spectrum the solid magnesium halide catalyst component co-crushed in this way, measured with the method described above, was 0.37 °.

In a 3 liter autoclave was filled 1 liter. Hexane, 50 mg of the co-crushed purified solid catalyst component and 3 mmol of triisobutylaluminum, and then polymerization of Ethylene for 1 hour under the standard polymerization conditions described above by. A white powdery polyethylene with an average molecular weight was obtained of 30,000 and a density of 0.972 g / ml in an amount of 240 g. The specific polymerization activity was this experiment 3320 g / mmol, hour, atm. and productivity was fraudulent 4800 g / g.h .ltr.

For comparison, the following experiment was carried out. A 100 ml flask was charged with 10 g (0.1049 mol) of the dried anhydrous magnesium chloride from Example 1 and 50 ml (0.454 mol) of titanium tetrachloride. After the titanium tetrachloride had adsorbed onto the anhydrous magnesium chloride, ie while the flask was standing at 130 to 140 ^° C. for two hours, the magnesium chloride particles were washed well with dehydrated and purified hexane, then dried for 5 hours in vacuo at room temperature, the solid catalyst component being produced containing titanium tetrachloride adsorbed on magnesium chloride. The amount of titanium compound taken up was 0.2 mg calculated in terms of titanium atoms per g of the solid catalyst component. Using 50 mg of this solid catalyst component and

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3 mmol of triisobutylaluminum and a polymerization time for Polymerization of ethylene for 2 hours, an experiment was carried out which corresponded to that of Example 1. However, no polymer was formed (Comparative Example 1).

I ¹ The following experiment was carried out for further comparison purposes. 10 g of the dried anhydrous magnesium chloride from Example 1 were placed alone in a ball mill and ground alone under exactly identical conditions as in Example 1. After the crushing treatment, there was essentially no change in the half-peak width as compared with that before the treatment. The polymerization of ethylene was then carried out as in | Example 1 was carried out except that 203 mg of the independently crushed magnesium chloride thus obtained, 27.5 ml of titanium tetrachloride and 3 mmol of triisobutylaluminum were added simultaneously and that the polymerization time was extended to 2 hours. However, a polymer was not formed (Comparative Example 2).

Instead of magnesium chloride, 66.5 g (0.487 mol) of anhydrous zinc chloride (manufactured by Wako Pure Chemical Industries Ltd., Japan), the half-peak width of the X-ray diffraction spectrum of which was 0.17 ° at a plane of 1.1.2, was used at X ) predried to 25O ⁰ C for 4 hours and then 4 were ml (0.035 mol) of titanium tetrachloride were added to a ball mill and crushed co-un- "under identical conditions as in example 1. The crude solid catalyst component thus obtained was washed with hexane. and The amount of titanium compound fixed was 4 »0 mg calculated in terms of litan atoms per g of the purified solid catalyst component, the half-peak width of which was 0.23 , except that 200 mg of the aforementioned co-crushed purified solid Catalyst component and 3 mmoles of triisobutylaluminum were used, and the polymerization time was extended to 2 hours, the attempt to polymerize ethyl en as described in Example 1 , carried out. However, no significant amounts of polymer were obtained (comparative example 3).

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Instead of magnesium chloride, 455 g of anhydrous calcium chloride (manufactured by Wako Pure Chemical Industries), whose half-peak width of the X-ray diffraction spectrum was 0.22 "at a level of 2.1.1, was predried for 3 hours at 300 to 40O ⁰ C in a nitrogen stream and then 453 ml of titanium tetrachloride was placed in a ball mill. Co-pulverization was carried out under the same conditions as in Example 1. The amount of the titanium compound present per g of the solid catalyst component was 7.0 mg in terms of titanium atoms. the half-peak width was 0.30 The polymerization of ethylene was carried out in the same manner as described in Example 1 except that 210 mg of the co-pulverized solid catalyst component and 3 mmol of triisobutylaluminum were used and the polymerization time increased The polymer was hardly formed (Comparative Example 4).

The results obtained in Example 1 and Comparative Examples 1 to 4 are shown in Table I below. The table also shows the results _r obtained in Comparative Example 1, in which the polymerization was carried out under the same conditions as in Example 1, but using a catalyst containing titanium tetrachloride and triisobutylaluminum.

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BATH ORIGINAL

Table I.

General conditions: tfoergaiigsmetallhalogenverbindungen = titanium tetrachloride (A)

Organic metal compound = triisobutylaluminum 3 mmol

Ex. Transition smetallkataly sat orkonrponent " η . (B) / (A) to > - Manufacturing a lot Polymes ; Polyethylene Specific Per I. 98 α - carrier d. Time of conditions v. Ti, risa yield MoleTu- Polynerisa- dukti Oil CTi
K3 (B) Co-grinding the functional (G) large- action- vity I. ning at d. Time weight Yity (g / s _x - CO It (Molver Poly (Hours.) (1000) (g / mmol. Hours l) cn —K ratio) merisa Hrs. O Ex. 1 tion co 13.9 used IO became σ 9.7 " »Ο Cf. 18.8 co-crushing 1.05 1 3320 4800 Ex. 1 MgCl ₂ ZnCl ₉ nert under 240. 30th ο C. Standard OO Cf. CaCl ₉ conditions Ex. 2 C.
no adsorbed 0.01 2 _ without zer track _ downsizing MgCl ₂ was 3.84 2 37 alone un 19.6 110 Cf. ter Stan Ex. 3 dardbedin Cf. crumbled Ex. 4 diminishes Control
verse. 1 as in 0.8 2 - example 1 track - It 1.66 2 - 9.6 2 Il - 0.5 Z

Example 2 and Comparative Examples 5 and 6

32.5 g of the dried anhydrous magnesium chloride from Example 1 and 3.1 g of titanium trichloride H ("H" indicates that this compound obtained by the hydrogen reduction method), manufactured by Stauffer Chemical Company, USA, were placed in a ball mill and kept for 38 hours under standard conditions co-crushed. The content of titanium compound per g of the resulting solid catalyst component was 24.0 mg calculated on the titanium atom. The half-peak width of the X-ray diffraction spectrum this solid magnesium chloride catalyst after the co-grinding treatment was 0.29 °.

200 mg of the solid catalyst component thus crushed and 3 mmol of triisobutylaluminum were used, and the polymerization of ethylene was carried out for 2 hours. The polyethylene thus obtained had an apparent density of 0.20 g / ml and its melt index was 16.0. The specific polymerization activity was 328 g / mmol _f hour. Atm.

For comparison, instead of magnesium chloride, 77.1 g of anhydrous calcium chloride whose half-peak width of the X-ray diffraction spectrum was 0.22 ° at an in-plane of 2.1.1, manufactured by Wako Pure Chemical Industries Ltd., was placed in a nitrogen stream at 300 to 400 for 3 hours ⁰ C predried and 8.4 g of titanium tetrachloride A ("A" indicates that this compound was produced by aluminum reduction), manufactured by Stauffer Chemical Company, USA, were placed in a ball mill and co-ground under identical grinding conditions as in Example 2 . The content of the titanium compound per g of the solid catalyst component was 120 mg calculated in terms of titanium atoms, and the half-peak width was 0.41 °.

Using 41 mg of the oo-crushed so obtained solid catalyst component and 3 mmol of triisobutylamine, the polymerization of ethylene was carried out under the same operating conditions as in Example 1, but the yield of poly

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- 21 merisate was low (comparative example 5).

For further comparison purposes, the titanium trichloride H was the Stauffer Chemical Company used in Example 2 placed in a ball mill alone and independently among the same Comminuted conditions as in Example 2. The half-peak width had changed after the crushing compared with that before comminution, essentially unchanged.

The polymerization of ethylene was carried out under the same operating conditions as in Example 2 for 2 hours using 45.8 mg of the independently comminuted litantrichloride and 3 mmol of irisobutylaluminum. The apparent density of the resulting polyethylene was 0.19 g / ml and the specific polymerization activity was 52 g / mmol.hr. .Atm. (Ver _r ... "same example 6).

The results obtained in the foregoing Example 2 and Comparative Examples 5 and 6 are combined in FIG ! Table II. The results of the Control experiment 2, in which the polymerization reaction was carried out under identical conditions as in Example 2, but in which one had used a catalyst, the litan trichloride alone and contained triisobutylaluminum.

109820/2108

Table II Terms and Conditions:

«Ο βο • ο

Organometallic compound polymerization temperature

= Titanium trichloride H (A *)

= Triisobutylaluminum 3 mmol = 90 ⁰ C

• Polymerization time (B) / (A ') after
d. Chop up
ration time
(Molar ratio
nis) Manufacturing conditions
worked = 2 hours Polyethylene Enamel
index Specific
Polymerisa
action acti
vity (g /
mmol, hr.
Atm.) example Transition metal catalyst component 18.4 co-crushed
below standard
conditions Amount of Ti
the at the
Polymerisa
use
was det
(mg) yield
(S) 0.20 328 Ex. 2 carrier
(ΒΓ 12.8 as in example 2 4.80 250 - mm compare -
Ex »5 MgCl ₂ - TiCl ₃ alone
crushed
below standard
conditions 4.91 track 10.4 52 Cf.
Ex. 6 CaCl ₂ - 45.8 328 10.0 18 _N )
O
en Control
vera. 2 . - 54.8 137 -

Examples 3 ″ to 6 and Comparative Examples 7 to 9

Ethylene was made under the same working conditions as in example 1 polymerized except that titanium trichloride was used as the transition metal halogen compound and the molar ratio from magnesium chloride to transition metal halogen compound when performing the co-crushing treatment during 120 Hours was varied. The results obtained are shown in Table III.

The changes in the half-peak widths were as follows:

Example 3 Example 4 Example 5 Example 6

For comparison purposes, tests were carried out in a similar manner (Comparative Examples 7 to 9) in which aluminum chloride was used in place of magnesium chloride. The results are given in Table III.

At the start At the end 0.15 ° 0.35 ° 0.15 ° 0.35 ° 0.15 ° 0.31 ° 0.15 ° 0.30 °

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Table III

General conditions: transition metal halogen compound - titanium trichloride H (A ¹ ) Organic metal compound (Β) / (Α ^ι ) to Ti content per lot = Triisobutyl aluminum 'S mMo • Molecular I. (1000) Polyethylene Producti 5 ■ - ro Co-crushed transition metal catalysts
sat orkonrn onent e d. Time of g d. co-zer- d. Ti large- Specific vity ), 0 carrier Co-shredding diminished. tans, Stress (g) weight Polymerisa (g / g / h / ¹ 4 cn (B) tion (Molver fixed kata d. at te activity activity ltr.) ) ■ CO ratio) lysators d. P0I3 (g / mmole hr. ". I. CD (mg) meri- Atm.) sation example used 74 O became 74 to (mg) 61 CS 0.336 254 13.70 144 30th 775 KJ 0.970, 193 14.65 152 74.6 75 O MgCl ₂ 2.95 110 5.40 398 88 70.8 4-61 KJ Ex. 3 η 18.40 24.0 4.80 411 104 505 103 < O "4 η - 593 ID η 5 η 1.04 161.4 9.36 64 55 ( "6 3.60 73.7 4.13 26th 46.9 232 Tergl.- AlCl ^ 15.2 22.4 4.48 6th 43.0 Ex. 7 η - " 8th η π ₉

- do -

Example 7

500 g of anhydrous manganese chloride manufactured by Wako Pure Chemical Industries, Ltd., were placed in a quartz tube and predried at 4,400 ° in a stream of material for 5 hours. The half-peak width of the X-ray diffraction spectrum on a 003 plane of the anhydrous manganese chloride thus dried was before the co-grinding treatment 0.11 °. 27 g of this dried Anhydrous manganese chloride and 2.83 ml of titanium tetrachloride were placed in a ball mill and under standard co-grinding conditions for 47 hours co-crushed. The resulting crude solid catalyst component was washed with hexane and im Vacuum dried. The amount of the titanium compound fixed per g of the purified solid catalyst thus obtained was 19 mg calculated on titanium atoms. The half-peak width of the X-ray diffraction spectrum the 003 level of the solid catalyst component of manganese chloride after the co-crushing treatment 0.22 °.

Ethylene was added for 2 hours under standard polymerization conditions using 186 mg of the aforementioned co-crushed purified solid catalyst and 3 mmoles of triisobutylaluminum polymerized. The yield of polyethylene was 290 g and its melt index was 5.4. The specific polymerization activity was 560 g / mmol hr atm.

Example 8

17.4 g of the dried anhydrous magnesium chloride of Example 1 and 1.7 g of titanium trichloride AA manufactured by Toho Titanium Company, Japan ("AA" means that the compound previously defined as "A" had been activated by grinding) were placed in a ball mill and co-crushed for 20 hours under standard co-crushing conditions. It was confirmed by the polarography that the content of the titanium compound per g of the resulting solid catalyst was 12.5 mg in terms of titanium atoms. The half-peak width of the X-ray diffraction spectrum of the 104 plane of the crystals of this solid catalyst? ¹ ν ι]% - ~ e ~

BAD ORIGINAL 109820 / 2'Oi

- 26 sium chloride "after the co-grinding treatment was 0.24 °.

In a 3 liter autoclave was filled 1 liter. Hexane, 200 mg of the co-crushed solid catalyst component and 3 mmol of triisobutylaluminum and thereafter polymerization of ethylene was carried out for 2 hours under standard polymerization conditions. The yield of white powdery polyethylene was g, the average molecular weight was 50,000 and the specific polymerization activity was 790 g / mmol. Hours.' .Atm.

Example 9

37.7 g of the dried anhydrous magnesium chloride from Example 1 and 3.8 g of titanium dichloride, manufactured by Toho Titanium Company, were placed in a ball mill, and during 20 Hours co-shredded under standard Oo shredding conditions. The content of the titanium compound per g of the resulting solid catalyst component was 34.3 mg in terms of titanium atoms. The half-peak width. was after the Oo crushing treatment 0.21 °.

200 mg of the thus co-crushed solid catalyst component of magnesium chloride and 3 mmol of triisobutylaluminum were used and ethylene was polymerized under the standard polymerization conditions. The polyethylene thus obtained had an apparent Diohte of 0.21 g / ml and a melt index of 4.0. The specific polymerization activity was 190 g / mmol.hr. .Atm.

Example 10

44.1 g of the dried anhydrous magnesium chloride from Example 1 and 13.4 moles of titanium dibutoxy dichloride were placed in a ball mill given and for 20 hours under standard Oo crushing conditions co-comminuted, then washed with hexane and dried, the solid catalyst component being obtained. The amount of titanium compound which was fixed per g of the solid catalysis torkomponent β was 18.4 mg, calculated on titanium atoms ,, .Di «, .1 jpeak width was after the co-shredding

109820/2108 _eAD original

action 0.20 °,

Ethylene was added for 2 hours under standard polymerization conditions polymerized, 200 mg of the aforementioned co-comminuted solid catalyst component of magnesium chloride and 3rd millimole irisobutylaluminum used. The emerging Polyethylene had an apparent density of 0.24 g / ml and a melt index of 19.8. The specific polymerization activity was 830 g / mmol, hr. . Atm.

Example 11

52.4 g of the dried anhydrous magnesium chloride from Bei- | Game 1 and 3 ml of vanadium tetrachloride were placed in a ball mill and under standard co-grinding conditions for 26 hours co-crushed, then 'was washed with hexane and dried to obtain a solid catalyst component. The amount of vanadium that is fixed per gram of the solid catalyst was 23 mg in terms of vanadium atoms. The half-peak width after the co-grinding treatment was 0.18 °.

The polymerization of ethylene was carried out under the standard polymerization conditions using 200 mg of the aforementioned co-crushed solid catalyst of magnesium chloride and 3 mmol of triisobutylaluminum. However, the polymerization time used in this Pail was 1 hour. The resulting- % de polyethylene had an apparent density of 0.17 g / ml and a melt index of 150 g / mmol.Std. ..Atm.

Example 12 to 18

50 mg of the same purified solid catalyst component was obtained according to Example 1 and 3 mmoles of the various organic metal compounds given in Table IV were used and the polymerization of ethylene was carried out for 1 hour under standard polymerization conditions, whereby Polyethylene. The results are given in Table IV,

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■ - 28 - Table IY

Ex. Organometallic
binding Polyethylene Specific polymers
sat ionic activity
(g / mmol.hour .Atm;) 12th
13th
14th
15th
16
17th
18th Et ₅ al
Et ₂ AlCl
EtAlCl ₂
(1-Bu) ₂ AlH
Et ₂ Al (OEt)
EtAl (OEt) Cl
Bu ₂ Zn Molecular size
weight
(1000) 2200
1200
300
3200
200
250
3000 45
130
284
29
250
500
34

Et = ethyl radical Bu = butyl radical i-Bu = isobutyl

Example 19

Into an autoclave was charged with 991 mg of the obtained according to Example 2 solid catalyst component, 3 mmol of diethylaluminum chloride and 1000 ml of dehydrated hexane and conducted the polymerization for 3 hours at 65 ⁰ C and a propylene pressure of 7 kg / cm by -g. After the polymerization reaction had ended, the polypropylene formed was washed with a large amount of methanol and then ^{dried in vacuo at 80 °} C. for 20 hours. The yield of polypropylene was 70 g and the specific polymerization activity was 7.1 g ppm / mmol / hour / atm.

Example 20

200 mg of the purified solid catalyst component obtained according to Example 1, 3 mmol of triisobutylaluminum and 1 liter were placed in an autoclave. Purified hexane. After the introduction of hydrogen up to a pressure of 3.5 kg / cm ² -g, a

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containing gaseous ethylene / propylene mixture containing 1.5 MoI Ji propylene, are introduced and the polymerization reaction for 2 hours "at 7O ⁰ C., while the pressure in the autoclave" at 10 kg / cm-g was maintained. The yield of ethylene / propylene copolymer was 224 g, the melt index was 2.4 and the number of methyl groups per 1000 carbon atoms was 4. The specific polymerization activity was 209 g EP / mmol. Hours. . Atm.

Example 21

Example 20 was repeated with the exception that a gaseous one Ethylene / 1-butene mixture instead of the gaseous ethylene / Propylene mixture was used. The yield of ethylene / 1-butene copolymer formed was 255 g and the melt index was 3.0 and the number of ethyl groups per 1,000 carbon atoms was 2. The specific polymerization activity was 236 g / mmol, hr. Atm.

Example 22

In a 2 liter autoclave, tested up to a pressure of 100 kg / cm −g, which was equipped with a horizontal magnetic stirrer, 1 liter was filled. Kerosene, flushed with nitrogen and then filled 20 ml of dehydrated, purified 1-hexene (purity $ 99), 1 mmol / ltr. Triäthy! Aluminum and 100 mg / ltr. the solid catalyst component prepared according to Example 1 was added. The copolymerization reaction was then carried out for 1 hour at 140 ⁰ O, after a hydrogen pressure of 1 kg / cm -g had been applied to it at the beginning and while one was then continuously

borrowed ethylene in such a way that the total pressure was kept at 40 kg / cm-g, and the stirrer was operated at a speed of 250 rpm. The autoclave was let down and cooled to room temperature, the resulting copolymer was washed well with hexane and dried in vacuo at 80 ^{° C. for 16 hours.} A copolymer of good color and a melt index of 3.0, a density of 0.942 g / ml in an amount of 123 g was obtained. IR analysis showed that the amount

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of methyl groups, "calculated on butyl groups, was 3.5 per 1000 carbon atoms. The specific polymerization activity "was 76 g / niMol. hr. Atm.

Examples 23 Ms 28

47.2 g of the dried anhydrous magnesium chloride des Example 1 and 2.90 ml of titanium tetrachloride were crushed under standard co-grinding oil conditions ground in a ball mill and after a co-grinding time of 6, 15 and 20 hours approximately 1 g each of the solid crude catalyst component taken. The portions thus withdrawn were designated as a, "b and c.

Each of parts a, b and c of the solid crude catalyst component were washed with hexane and dried to obtain the purified solid catalyst components a ¹ , b ^f and c ¹ .

The dried catalyst components a, a ¹ , b, b ¹ , c and c ^f were each used in amounts of 200 mg with 3 mmol of triisobutylaluminium, and the polymerization of ethylene was carried out for 2 hours under standard polymerization conditions to produce polyethylene, and obtained the results shown in Table Y.

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Eabelle V

E.g. Above / rangrsi metal catalyst component Pulp
ning s-
Time
(Hours.) Si content
per g of fe
ster k
catalyst
(mg) Shark
peak-
broad) Polyethylene -Specific
Polymerisa
activity activi
activity
(g / mmol, hrs.
.Atm.) 23
24
25th
26th
27
28 Festivals
Kataly
sator
compo
nent 6th
6th
15th
15th
20th
20th 24
2.5
24 '
11
24
15th 0.14 °
0.14 °
0.23 °
0.24 °
0.27 °
0.28 ° yield
(G) 190
740
310
700
340
830 a
a ¹
b
b ^!
C.
C ¹ 126
51
204
210
227
343

Example 29

The polymerization of ethylene was carried out for 1 hour as described in Example 1, using an ethylene pressure of 3.5 kg / cm -g used and no hydrogen was added. The resulting polyethylene had an average molecular weight of 500,000 and the specific polymerization activity was 6200 g / mmol. Hours. . Atm.

109820/2108

Claims (16)

Patent claims 1. A process for the polymerization of olefins, characterized in that that the polymerization or copolymerization of olefins in an inert hydrocarbon solvent in the presence a catalyst which has an organic metal compound as a catalyst component and an organic metal compound as a solid catalyst component contains a superior metal halogen compound and which contains a transition metal halogen compound through vigorous mechanical oil comminution and a carrier, the carrier being selected from the group consisting of magnesium halides and contains manganese halides. 2. The method according to claim 1, characterized in that the amount of the carrier is at least 0.5 moles for each mole of the transition metal halogen compound amounts to. 3. The method according to claim 1, characterized in that the Amount of the carrier is at least 1 mole per mole of the transition metal halogen compound. 4. The method according to claim 1, characterized in that the amount of carrier used exceeds 1 mole, but not higher is than 500 moles per mole of the transition metal halogen compound. ™ 5. The method according to claim 1 to 4, characterized in that the carrier before being subjected to the oil-crushing treatment is dried to remove adsorbed water. ■ 6. Method according to claim 1 to 5, characterized in that the transition metal halogen compound containing the solid catalyst component and obtained by the crushing treatment Oo _r is washed with an inert Kohlenwasseretofflösungemittel. 7. The method according to claim 1 to 6, characterized in that the transition metal halogen compound is a halogen compound 108820/210 is a metal selected from the group of titanium and vanadium. 8. The method according to claim 7, characterized in that the transition metal halogen compound is a compound which is selected is from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium monoethoxy trichloride, titanium dibutoxy dichloride, titanium oxide dichloride, Contains vanadium tetrachloride, vanadium oxytrichloride, titanium trichloride, titanium dichloride and vanadium trichloride. 9. The method according to claim 1. to 7, characterized in that the organic metal compound catalyst component is an organic ( Niche metal compound of a metal is selected from the group which contains aluminum and zinc. 10. The method according to claim 9, characterized in that the organic metal catalyst component is selected from the group _{comprising the compounds with the formulas R * A1, R 2} AlX, RAlX ₂ , R ₂ Al (OR) RAl (OR) X, R ₅ AlX ₁₅ and R'pZn contains, where R is an alkyl group with 1 to 6 carbon atoms, an ary! Group with 6 to 10 carbon atoms, X is hydrogen, halogen, and R 'is an alkyl group with 1 to 6 carbon atoms, where, if R or X appear in plural, they can be the same or different. 11. The method according to claim 1 to 10, characterized in that the solid catalyst component which contains the transition metal halogen compound is used in an amount which is in the range of 0.001 and 1 g per liter. inert hydrocarbon solvent and that the organic metal compound which is used as the catalyst component is used in an amount which is between 0.05 and 10 mmol per liter. of the solvent. 12. The method according to claim 1 to 10, characterized in that the polymerization or copolymerization reaction at a temperature of 20 to 300 ⁰ C and a pressure in the range from normal atmospheric pressure to 100 kg / om ^{2 is} carried out. 109820/2108 from 13. The method according to claim 1 "to 10, characterized in that the olefin is a G ₁ - to Cg olefin. 14. The method according to claim 1 "to 10, characterized in that that the olefin is selected from ethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene. 15. Catalyst for the polymerization or copolymerization of olefins, characterized in that it is an organometallic compound a metal selected from the group of aluminum and zinc and a transition metal halogen compound together with a solid catalyst component, the latter component being subjected to strong mechanical co-comminution a halogen compound of a transition metal selected from the group comprising titanium and vanadium and a carrier, selected from the group including magnesium halides and manganese halides. 16. The method according to claim 1, characterized in that the carrier is selected from the group consisting of magnesium chloride and Contains manganese chloride. 109820 / 21Q8