DE3215655A1 - Process and catalyst for the preparation of polyolefins - Google Patents

Abstract

Polyolefins of high bulk density and narrow molecular weight distribution are obtained by polymerisation of olefins in the presence of a catalyst comprising a combination of a solid catalyst component and an organometallic compound. The solid catalyst component is a substance formed by reacting I) a reaction product obtained by reacting 1) a magnesium halide or manganese halide, 2) a compound of the formula Al(OR)nX3-n in which R is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom and n is a number corresponding to the relationship 0 < n </= 3, and 3) a titanium compound and/or a vanadium compound, and II) a compound of the formula Si(OR')mX4-m in which R' is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom and m is a number corresponding to 0 </= m </= 4. c

Description

Process and catalyst for the

position of polyolefins The invention relates to a method for Production of polyolefins using a new polymerization catalyst.

A catalyst was already known in this technical field to use that of a magnesium halide and one applied to it Transition metal compound, such as a titanium compound, existed (described in Japanese Patent Publication No. 12105/1964).

Also known was a catalyst which is obtained by joint Pulverization of a magnesium halide and titanium tetrachloride (BE-PS 742 112).

In the manufacture of polyolefins, however, it is desirable that the catalyst activity is as high as possible. With that in mind, that is methods described in the aforementioned Japanese Patent Publication 12105/1964 still unsatisfactory in terms of polymerization activity, while the process described in BE-PS 742 112 is a slightly improved one Provides polymerization activity, but still needs further improvements.

According to DE-PS 21 37 872, the amount to be used is also Magnesium halide is substantially reduced by putting the magnesium halide together is subjected to copulverization with titanium tetrachloride and aluminum oxide. the Activity per solid, which are regarded as a measure of productivity can, but is not much improved, so that a catalyst with higher activity is desirable.

In addition, it is with regard to the manufacture of polyolefins desired on the production efficiency and handling of the polymer slurry, that the bulk density of the polymer formed is as high as possible. In view thereafter, using the method described in Japanese Patent Publication 12105/1964 Process formed a polymer with a low bulk density and not a satisfactory one Polymerization activity achieved, while in the case of that described in BE-PS 742 112 Process the polymerization activity is high, the bulk density of the formed Polymer is low. For this reason, further improvements are desirable.

The invention is based on the object explained above To eliminate disadvantages of the known methods.

According to the invention, a new polymerization catalyst and a Process for the homo- or copolymerization of olefins with the aid of this polymerization catalyst are made available, with the help of which a polymer with high bulk density with high polymerization vity and obtained in high yield a continuous polymerization process is carried out extremely easily can be.

Other aspects and advantages of the invention are evident from the following Description visible.

The invention relates to a catalyst for the polymerization of Olefins, which are composed of a combination of a solid catalyst component and a Organometallic compound consists, as well as a process for the polymerization of olefins in the presence of this catalyst. The catalyst is characterized in that the solid catalyst component is a substance that is produced by reaction (I) a reaction product formed by reacting (1) at least one compound from the group of the magnesium halides and / or manganese halides, (2) a compound of the general formula Ål (OR) nX3 ~ n, in which R is a hydrocarbon radical with 1 to 24 carbon atoms, X is a halogen atom and n is a number corresponding to the relationship O <n = 3 and (3) at least one compound from the group of titanium compounds and / or vanadium compounds, and (II) a compound of the general formula Si (OR ') mX4 m 'in which R' is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom and m is a number corresponding to the relationship O <the relationship O = m = 4, is available.

The invention is explained in more detail below.

As magnesium halides used for the purposes of the invention and / or Manganese halides can be used essentially anhydrous compounds, such as magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, Manganese chloride or mixtures of such compounds, magnesium chloride being particularly is preferred.

As a compound of the general formula used according to the invention Al (OR) nX n r in which R is a hydrocarbon radical with 1 to 24, preferably 1 to 12 carbon atoms, such as an alkyl, aryl or aralkyl group, with alkyl groups with 1 to 4 carbon atoms are particularly preferred, X denotes a halogen atom and n stands for a number corresponding to 0 <n - 3, for example aluminum trimethoxide, Aluminum triethoxide, diethoxymonochloraluminum, monoethoxydichloraluminum, monomethoxydiethoxyaluminum, Aluminum tri-n-propoxide, aluminum triisopropoxide, diisopropoxymonochloroaluminum, Monoisopropoxydichloraluminum, monomethoxydiisopropoxyaluminum, aluminum tri-n-butoxide, Aluminum tri-sec.-butoxide and aluminum tri-t-butoxide are used, with aluminum trimethoxide and aluminum triethoxide are particularly preferred.

As a titanium compound and / or vanadium compound are suitable for For purposes of the invention, for example, halides, alkoxy halides, alkoxides and halogenated Oxides of titanium and / or vanadium. Compounds of the Trivalent and tetravalent titanium are preferred, and tetravalent are particularly preferred Titanium compounds of the general formula Ti (OR) X4, in which R is a hydrocarbon radical with 1 to 20 carbon material atoms, such as an alkyl, aryl or aralkyl group, <<X is a halogen atom and n is a number corresponding to o = n = 4, such as for example titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, Dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxydichlorotitanium, Diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, Diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, Dibutoxydichlortitan, Monopentoxytrichlortitan, Monophenoxytrichlortitan, Diphenoxydichlortitan, Triphenoxymonochloro titanium and tetraphenoxytitanium. Suitable examples of trivalent Titanium compounds include titanium trihalides, which are produced by the reduction of titanium tetrahalides, such as titanium tetrachloride and titanium tetrabromide, with hydrogen, aluminum, or titanium Organometallic compounds of metals in groups I to III of the periodic table of the elements are formed, as well as trivalent titanium compounds that are formed by reduction of tetravalent alkoxytitanium halides of the general formula Ti (OR) mX4 in in the R is a hydrocarbon radical with 1 to 20 carbon atoms, such as an alkyl, aryl or aralkyl group, X is a halogen atom and m is a number according to the relationship O <m <4 mean with organometallic compounds of metals of the groups I to III of the Periodic Table of the Elements are formed. Examples of suitable Vanadium compounds include tetravalent vanadium compounds, such as vanadium tetrachloride, Vanadium tetrabromide, vanadium tetraiodide and tetraethoxy vanadium, pentavalent vanadium compounds, such as vanadium oxytrichloride, ethoxydichlorvanadyl, triethoxyvanadyl and tributoxyvanadyl, and trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide.

In order to increase the effectiveness according to the invention, are often a Titanium compound and a vanadium compound used in combination and in this In this case, the molar ratio V / Ti is preferably in the range from 2 1 to 0.01: 1.

As a compound of the general formula used according to the invention Si (OR ') x m 4-m' in which R 'is a hydrocarbon radical with 1 to 24 carbon atoms, such as an alkyl, aryl or aralkyl group, X a halogen atom and m a number correspondingly 0 = m = 4, preferably 0 <m <= 4, can be, for example, silicon tetrachloride, Monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, Mono-n-butoxytrichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, Monophenoxytrichlorosilane, mono-p-methylphenoxytrichlorosilane, dimethoxydichlorosilane, Diethoxydichlorosilane, diisopropoxydichlorosilane, di-n-butoxydichlorosilane, dioctoxydichlorosilane, Trimethoxymonochlorosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane, Tri-n-butoxymonochlorosilane, tri-sec, -butoxymonochlorosilane, tetraethoxysilane and Tetraisopropoxysilane can be used.

As already stated, according to the present invention (1) a magnesium halide and / or manganese halide (hereinafter often simplified as component (I) - (l) referred to), (2) a compound of the general formula Al (OR) nX3 3-n (hereinafter simply referred to as component (I) - (2)) and (3) a titanium compound and / or a vanadium compound (hereinafter simply referred to as component (I) - (3)) with each other brought into contact and implemented, the method of bringing into contact with each other and converting is not particularly limited. These components can be through a so-called co-pulverization treatment, i.e. a common pulverization treatment in Can be brought into contact or in the presence or absence of an inert Solvents are brought into contact with one another and reacted.

For example, a method can be used according to which the Component (I) - (1) and component (I) - (2) together at one temperature in the range from 20 to 400 "C, preferably from 50 to 3000C, in the presence or absence an inert solvent are brought into contact with one another and reacted and then the reaction product thus obtained with the component (I) - (3) at a Temperature in the range from 50 to 3000C, preferably 100 to 1500C, in the presence or in the absence of an inert solvent, a method after which component (I) - (3) to the above-mentioned reaction product from the Components (I) - (1) and (I) - (2) is added and then a copulverization after a known method is used to cause the reaction to proceed, a method according to which the component (I) - (1) with the component (I) - (2) together is pulverized and the product obtained is then mixed with component (I) - (3) at a temperature in the range from 50 to 3000C, preferably 100 to 1500C, in The presence or absence of an inert solvent is brought into contact, a method according to which the components (I) - (3) become the product of co-pulverization of components (I) - (1) and (I) - (2) is given and then another Copulverization is carried out, or a method according to which the components (I) - (1), (I) - (2) and (I) - (3) are copulverized at the same time.

Inert solvents for those exemplified above Reactions are used are not particularly limited. Usually are coal hydrogen solvents that do not inactivate lead from Ziegler catalysts and / or their derivatives. For examples for such inert solvents include various saturated aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons, such as propane, Butane, pentane, hexane, heptane, octane, benzene, toluene, xylene and cyclohexane.

It is desirable that components (I) - (1), (I) - (2) and (I) - (3) in an inert gas atmosphere free of oxygen and moisture Are brought into contact and that the contact time for each component is normal is not less than 5 minutes. A longer contact time, for example 5 minutes to 20 hours does not cause any trouble, but it is not necessary. After the reaction has ended, an unreacted portion of the component can (I) - (3) washed out several times with a solvent which is inert to Ziegler catalysts and the washing liquid can be evaporated under reduced pressure, a method that is preferred to be used.

As for the quantitative ratio of components (I) - (1) and (I) - (2), so both too small and too large proportions of component (I) - (2) the Decrease polymerization activity. To produce a catalyst with high Activity, it is desirable that the quantitative ratio, expressed as a molar ratio, from component (I) - (1) to component (I) - (2) in the range from 1: 0.001 to 20, preferably 1: 0.01 to 1 and in particular 1: 0.05 to 0.5. The component (I) - (3) can be in an amount accordingly 0.01 to 50 times Amount by weight of component (I) - (1) are used; however, it is desirable adjust the proportions so that the amount of titanium and / or vanadium contained in contained in the reaction product (hereinafter referred to simply as "Component (I)") in the sum of components (I) - (1), (I) - (2) and (I) - (3) in the range of 0.5 to 20, preferably 1 to 10% by weight.

The component (I) thus obtained is then with a compound of general formula Si (OR ') mX4 m (hereinafter referred to simply as "component (II)") implemented, the solid catalyst component used according to the invention being obtained will.

The method of implementation of components (I) and (II) is subject no particular restriction. Both components can pass through a co-pulverization treatment be reacted or can in the presence or absence of an inert solvent implemented together. It is desirable that this reaction should take place during 5 Minutes to 20 hours at a temperature in the range from 20 to 4000C, preferably from 50 to 300bC.

What is the reaction ratio between components (I) and (II) concerns, 0.05 to 50 g, preferably 0.1 to 30 g, of component (II) reacted with 100 g of component (I).

As the organometallic compound used in the present invention, organometallic compounds can be used of metals of groups I to IV of the periodic table that are considered a component of a Ziegler catalysts are known, vel-welltltt wiiiii.

Among these compounds are organoaluminum compounds and organozinc compounds preferred. Suitable examples thereof include organoaluminum compounds of general formulas R3Al, R2AlX, RAlX2, R2AlOR, RAl (OR) X and R3Al2X3, wherein R is a Denotes an alkyl or aryl group with 1 to 20 carbon atoms and the radicals R are the same or can be different and X represents a halogen atom, and organozinc compounds of the general formula R2 Zn, where R is an alkyl group having 1 to 20 carbon atoms means and the radicals R can be the same or different, such as triethylaluminum, Triisopropyl aluminum, triisobutyl aluminum, tri-sec.-butyl aluminum, tri-tert.-butyl aluminum, Trihexyl aluminum, trioctyl aluminum, diethyl aluminum chloride, diisopropyl aluminum chloride, Ethyl aluminum sesquichloride, diethyl zinc, and mixtures of such compounds. These organometallic compounds can also be used together with organocarboxylic acid esters, such as ethyl benzoate, ethyl o- or p-toluylate and ethyl p-anisate can be used.

The amount of the organometallic compound present in the catalyst of the invention is not particularly limited, but it can usually be 0.1 to 1,000 Moles per mole of the titanium compound and / or vanadium compound.

The olefin polymerization using the catalyst of the present invention can be in the form of suspension polymerization, solution polymerization or vapor phase polymerization be performed. The polymerization reaction is carried out in the same way as the conventional olefin polymerization reaction using a Ziegler catalyst, i.e. in a substantially oxygen and anhydrous environment and in presence or absent absence of an inert hydrocarbon solvent, carried out. Suitable conditions for olefin polymerization include temperatures in the range from 20 to 1200C, preferably 50 to 1000C, and pressures in the range of Atmospheric pressure up to 70 bar (70 kg / cm2), preferably from 2 to 60 bar. The molecular weight can to a certain extent by changing the polymerization conditions, such as the The polymerization temperature and the molar ratio of the components of the catalyst, be adjusted, the addition of hydrogen to the polymerization system is however, more effective for this purpose. Using the catalyst according to the invention Of course, two- or multistage polymerization reactions can also be carried out without difficulty carried out, with different hydrogen concentrations in the various stages and different polymerization temperatures can be used.

The polymerization process of the present invention can be used for polymerization of all olefins which can be polymerized in the presence of Ziegler catalysts are, especially for the homopolymerization of α-olefins, such as ethylene, propylene, Butene-1, hexene-1, 4-methylpentene-1 and octene-1, for the copolymerization of ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-1, Ethylene and octene-1 and propylene and butene-1, and for the copolymerization of Ethylene and two or more other oc-olefins.

The copolymerization of olefins with dienes is also preferred Modification of polyolefins, for example with butadiene, 1,4-hexadiene, ethylidene-norbornene and dicyclopentadiene.

The polymerization catalyst according to the invention has a very high polymerization activity, so that the partial pressure of the monomers is low during the polymerization and a polymer having a high bulk density is formed, so that an improvement in Productivity is achieved, and moreover the amount of after the completion of the Polymerization in the polymer formed, the catalyst residue remained very much is small. As a result, the catalyst removal step in the Manufacturing processes for polyolefins are omitted, so that work-up of polymers is simplified and the production of polyolefins as a whole in can be done extremely economically.

According to the method according to the invention, polymers with such a high level are obtained Bulk density obtained that the amount of polymer formed per polymerization unit is great.

The inventive method is also with regard to the Particle size of the polymer formed is advantageous. The proportion of coarse particles and fine particles of less than 50 µm is small in spite of the high bulk density and therefore, it is not only easy to carry out a continuous polymerization reaction carry out, but also the centrifugal separation in the work-up stage of the polymer and the handling of the polymer particles, such as powder transport relieved.

Further advantages of the invention are that using of the catalyst according to the invention produced polyolefins, as already indicated, have high bulk density and that to achieve a poly- meren with the desired melt index, the required hydrogen concentration is lower than with conventional methods and, as a result, the total pressure during the polymerization can be kept at relatively low levels, thereby providing an effective improvement profitability and productivity is achieved.

It is also used in the polymerization of ethylene of the catalyst according to the invention, the reduction in the rate of ethylene absorption small even with the lapse of time and the polymerization can therefore last for a long time Duration can be carried out with a smaller amount of catalyst.

In addition, polymers made using the invention Catalyst produced, very narrow molecular weight distribution and her The proportion extracted by hexane is low. This means that the formation of low polymers is suppressed to a minimum as a by-product. As a result, it is for example possible in the production of a polymer suitable for films and foils To achieve high quality product that has superior antiblocking properties.

According to the invention, a new catalyst system is made available, which has the advantages explained above and with the help of which the with known processes and catalysts associated disadvantages can be eliminated. It is surprising that the advantages of the invention are easily reduced Use of this catalyst can be achieved.

The following examples are provided for further illustration given the invention without this should be limited thereto.

Example 1 (a) Preparation of the solid catalyst component In a 300 ml three-necked flasks equipped with a magnetic induction stirrer 100 ml of ethanol, 20 g of anhydrous magnesium chloride and 12 g of aluminum tri-sec.-butoxide given and reacted for 3 hours under reflux of ethanol. Then 150 ml n-hexane added to precipitate the product. After standing it was then the supernatant liquid removed and dried at 2000C under vacuum, whereby a white dry powder was obtained. Then 60 ml of titanium tetrachloride were added added and the reaction carried out at 130.degree. C. for one hour. Finally it was excess titanium tetrachloride removed and the product repeated with n-hexane washed until no more titanium tetrachloride can be found in the washing liquid to give a white solid powder (A).

10 g of the white powder (A) and 2 g of tetraethoxysilane were put into a Stainless steel vessel with a capacity of 400 ml, the 25 stainless Containing steel balls with a diameter of 1.27 cm each, and grinding in the Ball mills were operated for 16 hours at room temperature under a nitrogen atmosphere carried out. Thus there was obtained a solid powder (B) containing 15 mg of titanium per g of powder.

(b) Polymerization A stainless steel autoclave was used as the device used for vapor phase polymerization and a loop was made from a blower, a controller for the Flow rate and a dry cyclone. The temperature of the autoclave was determined by bubbling warm water through the jacket set. In the autoclave set to 800C, the solid powder (B) added at a rate of 50 mg / h and triethylaluminum at a rate of 5 mmol / h, after which butene-1 ', ethylene and hydrogen were fed in gaseous form, the Molar ratio of butene-1 / ethylene in the vapor phase in the autoclave at 0.25 and the Hydrogen concentration were maintained at 15% of total pressure. The polymerization was carried out under a total pressure of 10 bar (10 kg / cm2) while the gases were circulated in the polymerization system with the aid of the blower. The ethylene copolymer formed had a bulk density of 0.39, a melt index (MI) of 1.2 and a density of 0.9203.

The catalyst activity was 564,000 g polymer / g Ti, which is very high.

After operating continuously for 10 hours, the autoclave became opened and checked its inside. It was found that the inner wall and the stirrer was clean and that no polymer was adhering to it.

The F.R. value (F.R. = MI / MI) of this polymer, expressed as 10 2.16 as the ratio of the melt index Mm10, measured under a load of 10 kg, to the melt index Mm21161 measured under a load of 2.16 kg at 190OC according to the ASTM-D 1238-65T method, was 7.1, indicating that the molecular weight distribution was very narrow.

A film formed from this copolymer was in extracted boiling hexane. It was found den that the through Hexane extracted amount was 1.3% by weight, which is very low.

Comparative Example 1 Using those described in Example 1 Apparatus, the below-mentioned vapor phase polymerization was carried out.

In the autoclave set to 800C, this was done in Example 1 obtained solid powder (A) at a rate of 50 mg / h and triethylaluminum in one Rate of 5 mmol / h introduced. Then butene-1, ethylene and hydrogen became gaseous fed in, the feed being adjusted so that the molar ratio of butene-1 / Ethylene in the vapor phase in the autoclave was 0.27 and that the hydrogen concentration 15% of the total pressure, and the polymerization was under a total pressure of 10 bar carried out while the gases within the polymerization system with With the help of the fan. The ethylene copolymer formed had a bulk density of 0.31, a melt index (MI) of 1.2 and a density of 0.9195.

The catalyst activity was 315,000 g copolymer / g Ti.

After operating continuously for 10 hours, the autoclave became opened and checked the inside. The polymer became easy to adhere to the inner wall and the stirrer observed.

The F.R. value of this copolymer was 8.1, that is, the molecular weight distribution is wider than in the case of the polymer according to Example 1.

A film formed from the copolymer was left in boiling for 10 hours Hexane extracted. It was fraudulent.

the fraction extracted in hexane was 3.7% by weight.

In game 2 2 g of the solid powder obtained in Example 1 (A) and 0.4 g of tetraethoxysilane was added to 100 ml of hexane and refluxed for one hour of hexane to obtain a catalyst slurry (C).

The catalyst slurry was placed in the autoclave set at 80 "C (C) at a rate of 2.5 ml / h and triethylaluminum at a rate of 5 mmol / h given. Then butene-1, ethylene and hydrogen were fed in gaseous form, whereby the adjustment was made so that the molar ratio of 1-butene / ethylene in the vapor phase in the autoclave was 0.27 and the hydrogen concentration was 15% of the total pressure, and the polymerization was carried out under a total pressure of 10 bar while the gases in the polymerization system are circulated with the aid of the blower became. The formed ethylene copolymer had a bulk density of 0.38, one Melt index (MI) of 1.1 and a density of 0.9203.

The catalyst activity was 436,000 g polymer / g Ti, which is very high.

After operating continuously for 10 hours, the autoclave became opened and checked its inside. It was found that the inner wall and the stirrer was acidic and had no polymer attached.

The F.R. value of this copolymer was 7.2; the molecular weight distribution was therefore very narrow.

A film formed from this copolymer was 10 hours in extracted boiling hexane. It was found that the portion extracted in hexane Was 1.1% by weight and thus was very small.

Example 3 In the ball mill vessel described in Example 1 were 10 g of anhydrous magnesium chloride, 4.3 g of aluminum triethoxide and 2.7 g of titanium tetrachloride and ball milling was carried out for 16 hours in a nitrogen atmosphere. Then 2 g of tetraethoxysilane was added, followed by a further 16 hours in the ball mill was ground to obtain a solid powder containing 35 mg of titanium per g.

Then the above-described were set to 800C Autoclave the solid powder obtained above at a rate of 50 mg / h and triethylaluminum introduced at a rate of 5 mmol / h, after which butene-1, ethylene and hydrogen were supplied in gaseous form in such a way that the molar ratio of butene-1 / ethylene in the vapor phase in the autoclave 0.27 and the hydrogen concentration 15% des Total pressure, and the polymerization was carried out at a total pressure of 10 bar carried out while the gases in the polymerization system with the help of the blower were circulated. The formed ethylene copolymer had a bulk density of 0.41, a melt index (MI) of 0.9 and a density of 0.9210.

The catalyst activity was 625,000 g copolymer / g Ti and was thus very high.

After continuous operation for 10 hours, the autoclave became opened and checked its inside. It was found that the inner wall and the stirrer was clean and free of adhering polymer.

The F.R. value of this copolymer was 6.9; the molecular weight distribution was therefore very narrow.

A film formed from the copolymer was left in boiling for 10 hours Hexane extracted. It was found that the fraction extracted in hexane was 0.8 % By weight and thus was very low.

Example 4 In the ball mill vessel described in Example 1 were 10 g of anhydrous magnesium chloride, 4.3 g of aluminum triethoxide and 2.7 g of titanium tetrachloride and ball milling was carried out for 16 hours in a nitrogen atmosphere. Then 2 g of triethoxymonochlorosilane were added, followed by a further 16 hours in the ball mill was ground. In this way a solid powder was obtained, which contained 36 mg of titanium per g.

In the autoclave set at 80 "C, the above-obtained solid powder at a rate of 50 mg / h and triethylaluminum at a rate of 5 mmol / h initiated. Then butene-1, ethylene and hydrogen in gaseous form in the Way initiated that the molar ratio of butene-1 / ethylene in the vapor phase im Autoclave was 0.27 and the hydrogen concentration was 15% of the total pressure, and the polymerization was carried out under a total pressure of 10 bar while the gases in the polymerization system are circulated with the aid of the blower became. The ethylene polymer formed had a bulk density of 0.39, a melt index (MI) of 1.0 and a density of 0.9211.

The catalyst activity was 716,000 g copolymer / g Ti and was thus very high.

After operating continuously for 10 hours, the autoclave became opened and checked its inside. It was found that the inner wall and the stirrer was clean and free of adhering polymer.

The F.R. value of this copolymer was 7.2; the molecular weight distribution was therefore very narrow.

A film formed from this copolymer was left in boiling for 10 hours Hexane extracted. It was found that the portion extracted in hexane was 1.2 % By weight and thus was very small.

Example 5 A 2 stainless steel autoclave fitted with an induction stirrer was provided was flushed with nitrogen. 1000 ml of hexane were placed in the autoclave and then 1 mmol of triethylaluminum and 10 mg of the solid obtained in Example 1 Powder (B) was added and the temperature was increased to 90 ° C. with stirring. By the vapor pressure of hexane, the system was under a pressure of 2 bar above atmospheric pressure. Then hydrogen was released up to a total pressure of 4.8 bar above atmospheric pressure and finally ethylene up to a total pressure of 10 bar above atmospheric pressure initiated and the polymerization started. The polymerization was one hour carried out for a long time while continuously introducing ethylene to the total pressure to be maintained at 10 bar above atmospheric pressure. Finally the polymer slurry transferred to a beaker and hexane removed under reduced pressure, whereby 196 g white polyethylene with a melt index of 1.1, a density of 0.9635 and a bulk density of 0.39.

The catalyst activity was 251,300 g polyethylene / g Ti.

i.e. C2H4 pressure or 3770 g polyethylene / g solids, i.e. C 2H4 pressure. Consequently was able to achieve high bulk density polyethylene with extremely high catalyst activity can be obtained.

The F.R. value of the polyethylene was 8.3, which is compared to the comparative example 2 indicates a very narrow molecular weight distribution. The one extracted in hexane The proportion was 0.1% by weight.

Comparative Example 2 The polymerization was carried out for one hour in carried out the same way as in Example 5, with the modification that 10 mg of des Solid powder (A) used in Comparative Example 1 were used. To this Thus, 171 g of white polyethylene with a melt index of 1.3, density of 0.9638 and a bulk density of 0.31. The catalyst activity was 183 000 g polyethylene / g Ti.h.C2H4 pressure or

3300 g polyethylene / g solids, i.e. C2H4 pressure. The F.R. value of the polyethylene was 9.3 and the portion extracted into hexane was 0.8% by weight.

Claims (12)

PATENT CLAIMS 1. Process for the production of polyolefins by Polymerization of at least one olefin in the presence of a catalyst which is a Combination of a solid catalyst component and an organometallic compound represents, in that the solid catalyst component is a substance obtainable by reacting the following compounds I and II (I) of a reaction product is formed by reacting (1) at least one Compound from the group of magnesium halides and manganese halides, (2) one Compound of the general formula Al (OR) nX3 n t in which R is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom and n is a number corresponding to Mean relationship O <n = 3 and (3) at least one compound from the group of titanium compounds and vanadium compounds, and (II) a compound of the general formula Si (OR ') mX4 m' in which R 'is a hydrocarbon radical with 1 up to 24 carbon atoms, X a halogen atom and m a number corresponding to << the relationship O = m = 4. 2. The method according to claim 1, characterized in that g e k e n n -z e i c h n e t that a catalyst is used in which the quantitative ratio of the components (I) - (1): (I) - (2) in terms of the molar ratio is 1: 0.001 to 1:20. 3. The method according to claim 1 or 2, characterized in that g e -k e n n z e i c It should be noted that a catalyst is used in which the proportion by weight of Component (I) - (3) is 0.01 to 50 times the weight of Component (I) - (1). 4. The method according to any one of claims 1 to 3, characterized g e k e n n indicates that a catalyst is used for the production of which the Implementation of components (I) - (1), (I) - (2) and (I) - (3) was carried out so that first implemented any two components and then the remaining component is reacted with the reaction product obtained or by the three components implemented at the same time. 5. The method according to claim 4, characterized in that g e k e n n -z e i c h n e t that a reaction or the reactions by joint pulverization (copulverization) be performed. 6. The method according to any one of claims 1 to 5, characterized g e k e n n indicates that a catalyst is used for its production 0.05 up to 50 g of Component (II) reacted with 100 g of component (I) have been. 7. The method according to any one of claims 1 to 6, characterized in that z e i c ii n e t that the polymerization reaction takes place at a temperature in the range from 20 to 1200C and under a pressure in the range from atmospheric pressure to 70 bar is carried out. 8. The method according to any one of claims 1 to 7, characterized g e k e n n notices that the olefin used is ethylene. 9. The method according to any one of claims 1 to 8, characterized in that g e k e n n notices that anhydrous magnesium chloride is used as component (I) -S1) will. 10. The method according to one of claims 1 to 9, characterized g e k e n It is noted that a component (I) - (2) he given general formula is used in which R is an alkyl group having 1 to 4 carbon atoms. 11. The method according to any one of claims 1 to 10, characterized g e k e n It is noted that as component (I) - (3) a halide, alkoxy halide, alkoxide or halogenated oxide of titanium or vanadium is used. 12. Catalyst for the polymerization of olefins, consisting of the Combination of a solid catalyst component and an organometallic compound, in that the solid catalyst component is a substance which is formed by reacting the following compounds I and II (I) A reaction product formed by reacting (1) at least one compound from the group of the magnesium halides and manganese halides, (2) a compound of the general formula Al (OR) nX3 n, in which R is a hydrocarbon radical with 1 to 24 carbon atoms, X is a halogen atom and n is a number corresponding to the relationship O <n = 3 and (3) at least one compound from the group of titanium compounds and vanadium compounds, and (II) a compound of the general formula Si (OR ') mX4 m 'in which R' is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom and m is a number corresponding to the relationship O = m = 4.