DE2600688A1 - PROCESS AND CATALYST FOR THE MANUFACTURING OF POLYOLEFINS - Google Patents

Description

SHIP ν. FÜNER STREHL SCHÜBEL-HOPF EBBINGHAUS

MUNICH 9O, MARIAHILFPLATZ 2 & 3 POSTAL ADDRESS: D-8 MÜNCHEN 95, POST BOX S5O1 6O

• dipl. chem. dr. otmar dittmann (+1076)

karl ludwig schiff

dipl. chem. dr. alhxander v. funer

dipl. ing. peter strehl

dipl. chem. dr. ursula schübel-hopf

dipl. 1m <3. dieter ebbinghaus

telephone (obo) 48 2o 54

telex 6-23 566 auro d

telesramme auromarcpat Munich

January 9, 1976 NIPPON OIL COMPANY, LTD- DA-Il 969

Priority: January 10, 1975, No. 5014/75, Japan

Process and catalyst for the production of polyolefins

The invention relates to new catalysts for the polymerization of olefins and is particularly concerned with a process for polymerization of olefins in which olefins are polymerized or copolymerized in the presence of a catalyst serving as a component contains a solid which, by pulverizing one or more titanium compounds together, forms a component represent a Ziegler catalyst with a magnesium halide and / or manganese halide and an aromatic hydrocarbon has been obtained, and the one organ oaluminiumverb in manure and / or Contains organozinc compound. This gives polyolefins with high bulk density in high yield and the step for removing of catalyst residues becomes unnecessary.

There are already a catalyst in the specified field that of a magnesium halide and one applied to it

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Transition metal compound, such as a titanium compound (Japanese patent application 12105/64) and a catalyst which is composed of jointly pulverized magnesium halide and titanium tetra- ' Chloride is known (BE-PS 742 112}.

However, when the productivity and handling of the resulting slurry are taken into consideration, it is in the manufacture It is desirable for polyolefins that the bulk density of the polymer formed is as high as possible. In this regard is the method described in the aforementioned published Japanese patent application 12105/64 disadvantageous because the The bulk density of the formed polymer is low and the catalyst does not have a satisfactory polymerization activity. The process according to BE-PS 742 112 is also disadvantageous in that the bulk density of the polymer formed is low, although the catalyst shows high polymerization activity. It is therefore desirable to improve both known methods.

The invention is therefore based on the object explained above Eliminate disadvantages. According to the invention, new polymerization catalysts are to be made available with their help Polymers with high bulk density in high yield in an advantageous Procedure formed v / ground. According to the invention, an advantageous process for polymerization or copolymerization is also intended are provided by olefins in the presence of these polymerization catalysts.

The invention accordingly relates to a method of production of polyolefins by polymerization or copolymerization of olefins with the aid of a catalyst composed of a titanium-containing Pesticide and an organoaluminum compound and / or Organozinc compound exists. This catalyst is characterized by that it contains a reaction product as a titanium-containing solid, which by pulverizing together or Grinding of the following ingredients has been formed:

1) A magnesium halide and / or manganese halide,

2) an aromatic hydrocarbon and

3) one or more tetravalent and / or trivalent titanium

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Links.

The invention also provides an improved catalyst for the polymerization or copolymerization of olefins.

The use of the catalyst according to the invention has the advantage that its polymerization activity is high enough to reduce the partial pressure of the monomer in the polymerization. the Achieved high bulk density of the polymer formed allows an improved production efficiency of the process and the amount the catalyst residue in the polymer formed is so small that the step for in the production of the polyolefin Removal of the catalyst becomes unnecessary. In this way, a simplified work-up of the polymer is achieved and according to the invention therefore, a process for the production of polyolefins is available which, as a whole, is extremely economical

The invention is also advantageous with regard to the particle size of the polymer obtained, since it has a high bulk density the number of fine particles less than 50 microns in size is so small that it becomes easy at the stage of processing of the polymer, as in centrifuging and transporting the powder, to handle the particles of the polymer.

Details of the characteristic features of the invention will be apparent from the description below.

Magnesium chloride, magnesium fluoride, magnesium bromide and magnesium iodide are suitable as magnesium halide which can be used according to the invention and mixtures of these compounds. Magnesium chloride is particularly preferred.

Manganese chloride is used as the manganese halide which can be used in the present invention most preferred. According to the invention can preferably also use mixtures of magnesium halide and manganese halide.

Preferred aromatic hydrocarbons, which according to the invention

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are set are polycyclic aromatic compounds. Suitable Examples are naphthalene, phenanthrene, triphenylene, chrysene, 3,4-benzophenanthrene, 1,2-benzochrysene, picene, anthracene, Tetraphen, 1,2,3,4-dibenzanthracene, pentaphen., 3,4-benzopentaphen, Tetracene, 1,2-benzotetracene, hexaphene, heptaphene, diphenyl, fluorene, Diphenylene, perylene, corones, bisantons, ovals, pyrene, perinaphthene and the corresponding halogen-substituted and alkyl-substituted ones Links.

Also monocyclic aromatic compounds such as benzene and toluene and xylene, as well as the corresponding halogen-substituted and alkyl-substituted compounds, can be used.

The titanium compounds used for the purposes of the invention below are not particularly limited. Examples of tetravalent titanium compounds include titanium tetrachloride, titanium tetrabromide, Titanium tetraiodide, monoethoxytitanium trichloride, diethoxytitanium dir chloride, triethoxytitanium monochloride, tetraethoxytitanium, monoisopropoxytitanium trichloride, Mention diisopropoxytitanium dichloride and reaction products of silicon tetrachloride and titanium alkoxideri. to Suitable examples of trivalent titanium compounds include titanium trihalides obtained by reduction of titanium tetrahalides with hydrogen, aluminum, titanium or an organometallic compound. Mixtures can of course also be used such compounds are used. Also vanadium compounds such as vanadium tetrachloride, vanadium trichloride, vanadyl trichloride and vanadyl triethoxide are often used in conjunction with the titanium compound to make the catalysts of the present invention more effective close. The molar ratio of the vanadium compound lies in this pail to the titanium compound, expressed as the ratio of vanadium to titanium, in the range of 2: 1 to 0.01: 1.

The manner of co-pulverizing a magnesium halide and / or manganese halide with an aromatic hydrocarbon and a titanium compound according to the invention is not particularly limited. It can be in the simultaneous presence of all these components can be made or it can be made by adding a magnesium halide and / or manganese halide and

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an aromatic hydrocarbon can be pulverized together and then a titanium compound is added, followed by further Pulverizing is carried out. It can also be done by a reaction product of an aromatic hydrocarbon and a titanium compound are pulverized together with a magnesium halide and / or manganese halide. In order to apply liquid titanium compounds such as titanium tetrachloride, a method can be used according to which the product of joint pulverization of a magnesium halide and / or manganese halide and an aromatic hydrocarbon with a liquid titanium compound is brought into contact and thereafter unreacted titanium compound is removed by washing will. Pas method in which the desired amount of titanium compound is applied by co-pulverization, however, is simpler and in the process of catalyst preparation therefore more desirable. Of course, these process steps should be carried out in an inert gas atmosphere and The ingress of moisture should be prevented as far as possible.

The mixing ratio of the magnesium halide and / or manganese halide and the aromatic hydrocarbon is not particularly limited. However, if too large an amount of the aromatic hydrocarbon is used, the polymerization activity tends to be lowered. at On the other hand, if the amount is too small, the addition of the aromatic hydrocarbon can no longer have any effect will. The weight ratio of magnesium halide is therefore preferred and / or manganese halide to the aromatic hydrocarbon in the range of 1: 0.5 to 1: 0.01.

The amount of the titanium compound to be applied becomes the most advantageous adjusted so that the titanium content of the solid formed is in the range from 0.5 to 10 wt .- ^. So well balanced Activity, based on titanium and on the solid is achieved, it is particularly desirable if the titanium content in the Range from 1 to 8 wt.

The preparation used to pulverize the components together

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direction is not subject to any special restriction; however, ball mills, vibration mills, rod mills and beater mills are usually used. The conditions regarding the pulverization method such as the order of mixing, the pulverization time and the pulverization temperature can be easily determined by those skilled in the art depending on the manner in which the pulverization is carried out. In general, the Pulverisationstemperatur is in the range between ⁰ C and 200 ⁰ C, preferably 2O ⁰ C and 100 ⁰ C, and the Pulverisationsdauer is 0.5 to 50 hours, preferably 1 to 30 hours.

The reaction of the polymerization of olefins with the aid of the catalyst according to the invention is carried out in the same way as the customary polymerization of olefins with the aid of a customary Ziegler catalyst. Conditions that include freedom from oxygen and moisture are maintained throughout the reaction. · To polymerization of olefins include temperatures in the range of 20 to 120 C, preferably 50 to 10O ⁰ C and a pressure ranging from atmospheric pressure

ρ p

to 70 kg / cm, preferably 2 to 60 kg / cm. The regulation of the Molecular weight can be adjusted to a certain extent by changing the polymerization conditions, such as the polymerization temperature and the molar ratio of the catalyst; however, it is more effectively done by adding hydrogen to the Polymerization system. With the aid of the catalyst according to the invention, of course, two-stage or multi-stage polymerization reactions under different polymerization conditions, such as different hydrogen concentration and different polymerization temperatures will.

The process according to the invention can be used for the polymerization of all olefins which can be polymerized with the aid of Ziegler catalysts. For example, it is suitable for the homopolymerization of a (K, -olefin, such as ethylene, propylene, and butene-1, and for the copolymerization of ethylene and propylene, ethylene and butene-1, propylene and butene-1, ethylene and hexadiene 0., 4,

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Ethylene and ethylidene norbornene, and similar combinations, can be used.

Organometallic compounds suitable for the purposes of the invention are organometallic compounds of metals of groups I to IV of the Periodic Table of the Elements, which are generally known as constituents of Ziegler catalysts. Organoaluminum and organozinc compounds are particularly preferred. Representative examples are organoaluminum compounds of the general formulas R, A1, RpAlX, RAlX ₂ , R ₂ AlOR, RAl (OR) X and R ₅ Al ₃ X ₅ , in which R is an alkyl or aryl group and can be identical or different, and X stands for halogen, as well as organozinc compounds of the general formula R ₂ Zn, in which R stands for identical or different alkyl radicals, including trietbyl aluminum, triisobutyl aluminum, tri ^ xyl aluminum, trioctyl aluminum, diethyl aluminum sesquichloride, diethyl zinc and mixtures of such compounds. The amount of these organometallic compounds used in the present invention is not particularly limited; however, the compounds can usually be used in a molar ratio of 0.1 to 1000, based on the titanium compounds (transition metal halides).

In the examples below, the invention will be more preferred by way of example Embodiments described without being limited to these.

example 1

(a) Hgrstellung__des_Katal2sators

8.3 g of commercially available anhydrous magnesium chloride and 1.2 g of naphthalene were placed in a stainless steel vessel with a Given a capacity of 400 ml, which contained 25 stainless steel balls with a diameter of 1.27 cm each. That The mixture was then ball milled for 16 hours at room temperature under a nitrogen atmosphere. After that were 1.7 g of titanium tetrachloride were added and the ball milling was carried out for a further 16 hours at room temperature.

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The solid powder obtained contained 40 mg of titanium per gram of the pesticide.

(b) polymerization

A 2 liter stainless steel autoclave equipped with an induction stirrer was purged with nitrogen and charged with 1000 ml of hexane. Into the autoclave, 1 mmol of triethylaluminum and 30 mg of the above solid was added and the temperature was raised with stirring to 90 ⁰ C. The system, which is due to the vapor pressure of hexane at a pressure of 2 kg /

2
cm above an atmosphere was determined by forcing water

2 fabric to a total pressure of 6.6 kg / cm and then with ethylene

brought to a total pressure of 11 kg / cm, followed by polymerization started. Ethylene was continuously introduced

the total pressure was kept at 11 kg / cm, and the polymerization was carried out for 1 hour. When the polymerization was terminated, the polymer slurry was transferred to a beaker from which the hexane was removed under reduced pressure. 160 g of white polyethylene with a melt index of 5 »1 were obtained. The catalyst activity corresponded to 30,300 g polyethylene / g Ti.hC ₂ H, pressure; 1210 g polyethylene / g pesticide, i.e.CpH, pressure. The powdery polymer had a bulk density of 0.31. The percentage of fine particles less than 44 microns in size was very low, 0.9 %.

Comparative example 1

9.5 g of anhydrous magnesium chloride and 1.7 g of titanium tetrachloride were placed in a stainless steel vessel with a capacity of 400 ml, which contained 25 stainless steel balls with a diameter of 1.27 cm each. Grinding in the ball mill was then carried out for 16 hours at room temperature under a nitrogen atmosphere. The solid powder obtained contained 39 mg Titanium per gram of solid.

The polymerization was carried out for 1 hour by the same procedure as in Example 1 except that 30 mg of this Solid were used. 145 g of white poly-

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Ethylene obtained with a melt index of 5 _f 5. The catalyst activity was 28,200 g polyethylene / g Ti.hC ₂ H ₄ pressure; 1100 g polyethylene / g pesticide, i.e.CpH ₄ pressure. The powdery polymer obtained had a low bulk density of 0.14.

Example 2

8.3 g of anhydrous magnesium chloride and 1.2 g of naphthalene were added to the vessel of the ball mill described in Example 1 and the mixture was ball milled for 16 hours under a nitrogen atmosphere. The powder formed was kept in contact with 50 ml of titanium tetrachloride ^{at 150 ° C. for 2 hours.} After the end of the reaction, unreacted titanium tetrachloride was removed by washing with hexane, a pesticide being obtained which contained 19 mg of titanium per gram of the solid.

The polymerization was carried out for 1 hour by the same procedure as in Example 1, except that 30 mg of the above-mentioned pesticide were used. 82 g of white polyethylene with a melt index of 8.1 were obtained. The catalyst activity was 32,600 g polyethylene / g Ti.hG ₂ H ₄ pressure; 620 g polyethylene / g pesticide.hC ₂ H ₄ pressure. The bulk density of the powdery polymer formed was 0.24.

Example 5

8.3 g of anhydrous magnesium chloride, 1.2 g of anthracene and 1.7 g of titanium tetrachloride were placed in the ball mill vessel described in Example 1 given. The mixture was ball milled for 16 hours under a nitrogen atmosphere. The educated solid powder contained 42 mg of titanium per gram of the pesticide.

The polymerization was carried out for 1 hour by the same procedure as in Example 1, except that 30 mg of the above-mentioned pesticide was used, whereby 174 g of white polyethylene having a melt index of 5-3 was obtained. The catalyst activity was 31,500 g polyethylene / g Ti.hC ₂ H ₄ pressure; 1320 g polyethylene / g pesticide.hC ₂ H ₄ pressure. The educated

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powdered polymers had a bulk density of 0.35. Example 4

In the ball mill vessel described in Example 1, 8.3 g anhydrous magnesium chloride, 1.2 g of pyrene and 1.7 g of titanium tetrachloride were added and the mixture was stirred under a nitrogen atmosphere Ball milled for 16 hours. The solid powder formed contained 39 mg of titanium per gram of the solid.

The polymerization was then carried out for 1 hour by the same procedure v / ie in Example 1, using 30 mg of des solid as obtained above were used. 131 g of white polyethylene with a melt index of 4.9 were obtained obtain. The catalyst activity was 25,400 g polyethylene / g Ti.h.CpEL pressure or 990 g polyethylene / g solids.h.CgEL pressure. The powdery polymer formed had a bulk density of 0.30.

Example 5

8.3 g of anhydrous magnesium chloride, 1.2 g of pyrene and 1.7 g of titanium tetrachloride were placed in the ball mill vessel described in Example 1 and the mixture was ball milled under a nitrogen atmosphere for 16 hours. The received solid powder contained 38 mg of titanium per gram of solid.

The polymerization was carried out for 1 hour by the same procedure as in Example 1 except that 30 mg of the solid obtained above was used. 165 g of white polyethylene with a melt index of 9.2 were formed. The catalyst activity was 32,900 g polyethylene / g Ti.h.C2H ₄ pressure or 125O g polyethylene / g solids.hC ₂ EL pressure. The powdery polymer formed had a bulk density of 0.33.

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Example 6

In. the ball mill vessel mentioned in Example 1 was 8.3 g anhydrous magnesium chloride, 0.5 g benzene and 0.9 g titanium tetrachloride and the mixture was ball milled under a nitrogen atmosphere for 16 hours. The educated solid powder contained 23 mg titanium per gram of the solid.

The polymerization was carried out for 1 hour by the same procedure as in Example 1, except that 30 mg of the above-mentioned pesticide was used. 141 g of white polyethylene with a melt index of 6.1 were obtained. The catalyst activity was 46,500 g polyethylene / g Ti.hC ₂ H ₄ pressure or 1070 g polyethylene / g solids.hC ₂ IL pressure. The bulk density of the powdery polymer was 0.28.

Example 7

8.3 g of anhydrous magnesium chloride, 1.2 g of naphthalene and 0.9 g of titanium tetrachloride were placed in the ball mill vessel described in Example 1 and 0.8 g of vanadium tetrachloride were added and the mixture was ball milled under a nitrogen atmosphere for 16 hours ground. The solid powder formed contained 21 mg of titanium per gram of the solid.

The polymerization was carried out for 1 hour by the same procedure as in Example 1 except that 30 mg of the solid obtained above was used to give 127 g of white polyethylene having a melt index of 8.1. The catalyst activity was 45 800 g of polyethylene / g Ti.hC ₂ H ₄ -pressure and 960 g of polyethylene / g Feststoff.hC ₂ H, pressure. The bulk density of the powdery polymer was 0.37.

Example 8

In the ball mill jar described in Example 1, 8.3 g of anhydrous manganese chloride, 1.2 g of naphthalene and 1.7 g of titanium tetrachloride were added, and the mixture was allowed to stir for 16 hours

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Ground nitrogen atmosphere in the ball mill. The educated solid powder contained 41 mg of titanium per gram of solid.

The polymerization was carried out for 1 hour by the same procedure as in Example 1 except that 30 mg of the solid obtained above was used. This produced 46 g of white polyethylene with a melt index of 7.3. The catalyst activity was 8550 g polyethylene / g Ti.hC ₂ H ₄ pressure or 350 g polyethylene / g solids.hC ₂ H ₄ pressure. The bulk density of the powdery polymer was 0.32.

Comparative example 2

In the ball mill vessel described in Example 1 was 9.5 g anhydrous manganese chloride and 1.7 g of titanium tetrachloride were added, and the mixture was left under a nitrogen atmosphere for 16 hours ground in the ball mill. The solid powder formed contained 38 mg of titanium per gram of the solid.

The polymerization was carried out for 1 hour by the same procedure as in Example 1, except that 30 mg of the solid formed as above was used. 40 g of white polyethylene with a melt index of 3.3 were formed. The catalyst activity was 7900 g polyethylene / g Ti.hC ₂ H ₄ pressure or 300 g polyethylene / g solids.hC ₂ H ₄ pressure. The bulk density of the powdery polymer was 0.13.

Example 9

In the ball mill jar described in Example 1, 8.3 g of anhydrous magnesium chloride, 1.2 g of anthracene and 1.7 g of titanium trichloride (TACB TiCl, .1 / 3 AlCl ₅ from Toho Titanium Co.) were added and the mixture was stirred under a nitrogen atmosphere Ground in a ball mill for 16 hours. The powdery solid formed contained 35 mg of titanium per gram of the solid.

The polymerization was then carried out for 1 hour in the same manner as in Example 1 except that 30 mg of the above solid formed were used. In this way

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114 grams of white polyethylene with a melt index of 7.2 was formed. The catalyst activity was 24,600 g polyethylene / g Ti.hG ₂ H. pressure or 860 g polyethylene / g solids.hC ₂ H. pressure. The powdery polymer formed had a bulk density of 0.32.

Comparative example 3

In the ball mill vessel described in Example 1, 9.5 g of anhydrous magnesium chloride and 1.7 g of the same titanium trichloride, that was used in Example 9 is given. The mixture was then left under a nitrogen sparger for 16 hours ground in the ball mill. The powdery solid formed contained 37 mg of titanium per gram of the solid.

The polymerization was carried out for 1 hour by the same procedure as in Example 1, with the modification that 30 mg of the solid obtained above were used, 104 g of white polyethylene having a melt index of 5-3 being formed. The catalyst activity was 21,400 g polyethylene / g Ti.hC ₂ H. pressure or 790 g polyethylene / g solids.h.CgH, pressure. The powdery polymer obtained had a bulk density of 0.14.

Example 10

In the ball mill vessel described in Example 1 were 5.0 g of anhydrous magnesium chloride, 3.3 g of manganese chloride, and 1.2 g of naphthalene and 1.7 g of titanium tetrachloride were added, and the mixture was ball milled for 16 hours under a nitrogen atmosphere. The solid powder formed contained 40 mg of titanium per gram of the solid.

The polymerization was carried out for 1 hour by the same procedure carried out as in Example 1, with the modification that 30 mg of the solid obtained above were used, wherein 133 g of white polyethylene with a melt index of 4> 8 were obtained. The catalyst activity was 25,200 g polyethylene / g Ti.

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hC ₂ H pressure or 1010 g polyethylene / g solid _{. hC 2} H pressure. The powdery polymer had a bulk density of 0.32.

Example 11

Using 30 rag of the solid obtained in Example 1 and by the method described in Example 1. "procedure hexane, triethylaluminum and the solid were combined and the temperature was raised to 90 ⁰ C. The system was then by the introduction of hydrogen under pressure at a Brought a total pressure of 5.6 kg / cm above atmospheric pressure and then an Ethyleii-Propylen-Misehgas, which contained 2 mol $ propylene,

so that the pressure in the autoclave was kept at 10 kg / cm above atmospheric pressure while the polymerization was carried out for 1 hour. 162 g of a white polymer having a melt index of 2.1 and containing 5.8 methyl groups per 1000 carbon atoms was formed. The catalyst activity was 34,500 g polymer / g.Ti.hC ₂ H, pressure or 1380 g polymer / g. Solid, h. C ₀ H. pressure. The bulk density of the powdery polymer was 0.30.

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Claims (9)

Claims ¹ Ci. A process for the production of polyolefins by the polymerization or copolymerization of olefins using a catalyst which consists of a titanium-containing solid and an organoaluminum compound and / or an organozinc compound, characterized in that a catalyst is used which contains a reaction product as the titanium-containing solid, formed by pulverizing together (1) a magnesium halide and / or manganese halide, (2) an aromatic hydrocarbon and (3) one or more tetravalent and / or trivalent titanium compounds. 2. The method according to claim 1, characterized that a catalyst is used whose titanium-containing . Component using a polycyclic aromatic compound - bond or their halogen or alkyl substitution products as aromatic hydrocarbon has been formed. 3. The method according to claim 1 or 2, characterized in that a catalyst is used whose titanium containing component using a monocyclic aromatic compound or its halogen or alkyl substitution products has been formed as an aromatic hydrocarbon. 4. The method according to any one of claims 1 to 3, characterized in that a catalyst verv / ends in 609829/0 787 which the mixing ratio of magnesium halide and / or Manganese halide to aromatic hydrocarbon, in terms of weight ratio, is in the range of 1: 0.5 to 1: 0.01. 5. The method according to any one of claims 1 "to 4, characterized in that a catalyst is used in which is the amount of titanium compound applied to the solid, expressed as the titanium content of the solid catalyst formed, in the range from 0.5 to 10% by weight, preferably 1 to 8 Wt .- ^, lies. 6. The method according to any one of claims 1 to 5, characterized in that a catalyst is used which the organoaluminum compound and / or organozinc compound in in an amount of 0.1 to 1000 moles per mole of the titanium compound. 7. The method according to any one of claims 1 to 6, characterized in that the polymerization or copolymerization of the olefins at a temperature in the range from 20 to 120 ⁰ C, preferably 50 to 10O ⁰ C, under a pressure in the range of ρ ρ Atmospheric pressure up to 70 kg / cm, preferably 2 to 60 kg / cm, is carried out. 8. The method according to any one of claims 1 to 7, characterized in that the polymerization or copolymerization of the olefins is carried out in the presence of hydrogen. 60 98 29/0787 - ■ 17 - 9. Catalyst for carrying out the process according to one of the Claims 1 to 8, consisting of a titanium-containing solid and an organoaluminum compound and / or an organozinc compound, characterized in that the titanium-containing solid is a reaction product which by joint pulverization of (1) a magnesium halide and / or a manganese halide, (2) an aromatic hydrocarbon and (3) one or more tetravalent and / or trivalent titanium compounds is obtained. 609829/0787