DE3340754A1 - METHOD AND CATALYST COMPONENT FOR PRODUCING POLYOLEFINES - Google Patents

Description

PATENT LAWYERS

STREHL SCHÜBEL-HOPF SCHULZ

WIDENMAYEKSTKASSE 17. ü-8000 MUNICH 22

DIPL. ING PETER STREHI.

DlPL -CIlICM. I) K. URSULA SCHÜBEL-HOPF

DIPL.-PIIYS. DR RÜTGER SCHULZ

ALSO LAWYER HEl DKN LANDGERICHTEN MÜNCHEN 1 UND U

SO EUROPEAN PATENT ATTORNEYS

TELEPHONE I0H9I 223911 TELEX 5214 (KlIi SSSM D TELECOPIER IOH9I 223915

DEA-13 84 9

Process and catalyst component

The invention relates to a process for the polymerization or copolymerization of α-olefins using of a new catalyst with high polymerization activity.

Catalysts containing titanium halides and organoaluminum compounds are already known as catalysts for the production of polymers with high stereospecificity from α-olefins. When polymerizing under Using such a catalyst, a highly stereospecific polymer is actually formed, it is however, required because of the low catalyst activity that remained in the polymer formed Remove catalyst residues.

Recently, numerous proposals have been made for improving the catalyst activity. These Proposals show that a catalyst with high activity can be obtained by adding a catalyst component is used, which is an inorganic solid carrier, for example MgCl «, and on this applied titanium

tetrachloride includes.

In the manufacture of polyolefins, however, it is desirable that the catalyst activity be as high as is possible. For this reason, higher activity catalysts are desired. In the case of a stereospecific For polymers, it is also important that the lowest possible atactic fraction is formed.

In addition, in conventional processes, the average particle diameter of the polymer formed is relative small, the grain size distribution is generally broad and there is a large proportion of finely divided powdery Polymers formed. With regard to the production efficiency and handling of the polymer slurry there is therefore a strong need for improvement. They also occur when deforming of such a polymer has difficulties such as dusting and deterioration in effectiveness the molding process. For this reason, there is a strong demand for an increase in bulk density and a Reduction of the proportion of finely divided powdery polymer. In addition, it has recently been desired omit the pelletizing stage and the powdery one To feed polymers directly to the processing device. In order to meet this requirement, however further improvements deemed necessary.

The above difficulties are to be eliminated by the subject of the application. The invention lies therefore the object of the invention is a process for the production of highly stereospecific polyolefins with high activity to provide by using a new catalyst, the application of which enables a

Short-term polymerization at low partial pressure des or the monomers, the amount of catalyst remaining in the polymer formed should be extremely low. In this way, various beneficial effects can be achieved: for example, the step of catalyst removal from the manufacturing process for polyolefins can be omitted and the proportion of atactic polymer in the polymer formed is extraordinary small amount.

With the help of the method according to the invention, polyolefins with high stereospecificity, large average particle size, narrow particle size distribution and obtained with a small proportion of finely divided powdery polymer. They also have polyolefins formed in this way have a high bulk density. These properties are extremely beneficial to the polymerization process. The polymers obtained in this way can also not only be in the form of pellets, but can also be subjected to a molding process directly as a powder without causing serious problems will. The inventive method therefore enables an extremely advantageous production of Polyolefins.

On the other hand, attempts have recently been made to incorporate soft or semi-hard olefin copolymers Use of Ziegler catalysts to manufacture. In this regard, too, show the usual procedures however disadvantages. For example, the procedure is complicated and the quality of the polymer formed is complicated bad.

The invention is therefore also based on the object of providing a process for the production of new, soft or semi-hard olefin copolymers having a density in the range from 0.860 to 0.910 g / cm ³ with the aid of a new catalyst of the Ziegler type. With the aid of this process according to the invention, olefin copolymers of this type can be produced with extremely low density in a stable process, the copolymers being less sticky and having good particle properties and high bulk density, as a result of which they adhere less to the reactor walls and show less agglomeration of the polymer particles, even if the process is carried out continuously for a long period of time.

The invention is therefore a method for Production of polyolefins by polymerization or copolymerization of olefins in the presence of a one solid catalyst component and a catalyst comprising an organometallic compound, characterized in that is that the polymerization is carried out in the presence of a catalyst / which consists essentially of consists of the following components:

I. a solid catalyst component obtained by contacting and reacting the the following components (1) to (4):

(1) a silica and / or alumina,

(2) the reaction product obtained by reacting a magnesium halide and a compound of the general formula Me (OR) X

is obtained in which Me is an element of groups I to VIII of the periodic table of Elements other than silicon, titanium and vanadium represents, R is a hydrocarbon radical with 1 to 24 carbon atoms,

X is a halogen atom, ζ the valence of Me and η a number corresponding to 0 <η <ζ mean

(3) a compound of the general formula

R ³ - f-Si - 0 4 - R ⁴ , in which R ¹ , R ² and R ³

each for hydrocarbon radicals with up to 24 carbon atoms, alkoxy groups,

Are hydrogen atoms or halogen atoms,

4th
R denotes a hydrocarbon radical with 1 to carbon atoms and η a number

corresponding to 1 <η ^ 30, and

(4) a titanium compound and / or a vanadium compound;

II. A compound of the general formula

R ¹

I 4 12 3

R - {- Si - 0- ^ R, in which R, R and R, respectively

for hydrocarbon residues with 1 to 24 carbon atoms / Alkoxy groups, hydrogen atoms

or halogen atoms, R is a hydrocarbon radical having 1 to 24 carbon atoms and η denotes a number corresponding to 1 <η <30;

and
III. an organometallic compound.

The invention also relates to a catalyst component a catalyst for the polymerization or copolymerization of olefins obtainable by contacting and implementing the following components (1) to (4):

(1) a silica and / or Aluininiuni-OXJ ds ;,

(2) the reaction products obtained by reaction of a magnesium halide and a compound of the al J qoracine formula Me (OR) X

η ζ-η

get] tcn wire, in the Me en η element of the Groups I to VI] of the Periodic Table of the Elements, excluding silicon, titanium and Represents vanadium, R is a hydrocarbon residue with 1 to 24 carbon atoms,

X is a halogen atom, ζ the valence of Me and η a number corresponding to 0 <η <ζ mean

(3) a compound of the general formula

R ¹
R ³ - (- Si - 0-r - R ⁴ , in which R ¹ , R ² and R ³

each for hydrocarbon residues with 1 up to 24 carbon atoms, alkoxy groups, Are hydrogen atoms or halogen atoms,

4th
R is a hydrocarbon radical with 1 to

20 'means carbon atoms and η a number corresponding to 1 <η <30, and

(4) a titanium compound and / or a vanadium compound.

With the aid of the process according to the invention, a soft copolymer with a density in the range from 0.860 to 0.910 g / cm ³ can be prepared by carrying out the polymerization of propylene in a first stage and then in the second stage a copolymerization of ethylene and propylene and / or Butene-1 is carried out in the presence of the polypropylene obtained in the first stage under essentially solvent-free conditions.

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The invention is hereinafter referred to as more preferred

ι forms of management described.

The silica used for the purposes of the invention is silica or a double oxide of silicon and at least one metal from Groups I to VIII of the Periodic Table of the Elements.

The aluminum oxide used according to the invention is aluminum oxide (Al ₂ O ₃ ) or a double oxide of aluminum and at least one other metal from groups I to VIII of the Periodic Table of the Elements.

Typical examples of such double oxides of silicon or aluminum and at least one other metal from groups I to VIII of the Periodic Table of the Elements are various natural and synthetic double oxides, such as Al ₃ O ₃ -MgO, Al ₂ O ₃ -CaO, Al ₃ O ₃ -SiO ₂ , Al ₂ O ₃ -MgO-CaO, Al ₂ O ₃ -MgO-SiO ₂ , Al ₂ O ₃ -CuO, Al ₂ O ₃ -Fe ₂ O ₃ , Al ₂ O ₃ -NiO and SiO ₂ -MgO. These formulas are not molecular formulas, they only indicate the composition. The structure and the ratio of the components in the double oxides to be used according to the invention are not subject to any particular restriction. The silicon oxide and / or aluminum oxide used according to the invention can also contain small amounts of adsorbed water and impurities.

The magnesium halide used for the purposes of the invention is essentially anhydrous. Examples of this include magnesium fluoride, magnesium chloride, magnesium bromide and magnesium iodide, with magnesium chloride being particularly preferred. These magnesium halides can be used beforehand with electron donors, for example alcohols, esters, ketones, carboxylic acids, ethers, amines and phosphines, be treated.

ORtGiWAL

As examples of the compound of the general formula Me (OR) X, in which Me is an element from Groups I to VIII of the Periodic Table of the Elements, excluding silicon, titanium and vanadium, R is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, ζ the valence of Me and η mean a number corresponding to 0 <η <ζ, which is used according to the invention, includes the following compounds: NaOR, Mg (OR) ₉ , Mg (OR) X, Ca (OR) ₂ , Zn (OR) ₂ , Zn (OR) X, Cd (OR) ₂ , Al (OR) ₃ , Al (OR) ₂ X, B (OR) ₃ , B (OR) ₂ X, Ga (OR) ₃ , Ge (OR) ₄ , Sn (OR) ₄ , P (OR) ₃ , Cr (OR) ₂ , Mn (OR) ₂ , Fe (OR) ₂ , Fe (OR) ₃ , Co (OR) ₂ and Ni (OR) ". The following compounds are preferred as more specific examples: NaOC ₂ H ₁ -, NaOC ₄ H ₁ ,, Mg (OCH ₃ ) ", Mg (OC ₂ H ₅ ) ₂ , Mg (OC ₃ H ₇ I ₂ , Ca (OC ₂ H ₅ ) ₂ , Zn Zn (OC ₂ H ₅ ) Cl, Al (OCH ₃ J ₃ , Al (OC ₂ H ₅ ) ₃ , Al Al (OC ₃ H ₇ ) ₃ , Al (OC ₄ Hg) ₃ , Al (OC ₆ H ₅ J ₃ , B (OC ₃ H ₅ J ₃ , P (OC ₂ H ₅ J ₃ , P (OC ₆ H ₅ J ₃ and Fe (OC ₄ H ₉ J ₃ .

For the purposes of the invention, compounds of the general formulas Mg (OR) X ₀ , Al (OR) X ₀ and B (OR) X-,

η ζ-η η J-η η J-η

particularly preferred. The substituent R is alkyl groups with 1 to 4 carbon atoms and the phenyl group particularly preferred.

The method of reacting the magnesium halide with the compound of the general formula Me (OR) X _ is not subject to any particular restriction. Both compounds can be mixed and reacted with heating to a temperature of 20 to 400 ^° C., preferably 50 to 300 ^° C., for 5 minutes to 10 hours in an organic solvent such as an alcohol, ether, ketone or an ester. Optionally, both compounds can also be combined with one another by applying a treatment of pulverizing or milling together

implemented.

The reaction method using a common pulverization treatment becomes special in the present invention preferred- The device to be used for co-grinding is not particularly limited. Ball mills, vibration mills, rod mills or hammer mills can normally be used. the Conditions such as the temperature and duration of milling can easily be determined by those skilled in the art, depending on the type of pulverization or grinding can be determined. In general, the grinding temperature is Range from 0 to 200 ° C, preferably 20 to 100 ° C, and the grinding time in the range from 0.5 to 50 hours, preferably 1 to 30 hours. The process of co-milling should of course be under an inert gas atmosphere and under extensive exclusion of moisture.

The conversion ratio of the magnesium halide and the compound of the general formula Me (OR) X _ is in the range from 0: 0.01 to 1:10, preferably 1: 0.1 to 1: 5, given as the atomic ratio Mg: Me (molar ratio) .

As examples of the inventive method used

binding the general formula R ¹ 3 ι
R t-Si - 0 + -R ⁴ , '2 η R.

12 3
in which R, R and R each represent hydrocarbon radicals having 1 to 24, preferably 1 to 18 carbon atoms, alkoxy groups, hydrogen atoms or halogen atoms,

4th
R is a hydrocarbon radical with 1 to 24, preferably 1 to 18 carbon atoms and η is a number corresponding to 1 <η <30, the following compounds can be mentioned:

BATH ORIGINAL

Monomethyltrimethoxysilane, monomethyltriethoxysilane, Monomethyltri-n-butoxysilane, monomethyltri-sec.-butoxysilane, Monomethyltriisopropoxysilane, monomethyltripentoxysilane, Monomethyltrioctoxysilane, monomethyltristearoxysilane, Monomethyltriphenoxysilane, dimethyldimethoxysilane, Dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiphenoxysilane, Trimethylmonomethoxysilane, trimethylmonoethoxysilane, Trimethylmonoisopropoxysilane, trimethylmonophenoxysilane, Monomethyldimethoxymonochlorosilane, Monomethyldiethoxymonochlorosilane, monomethylmonoethoxydichlorosilane, Monomethyldiethoxymonochlorosilane, monomethyldiethoxymonobromosilane, Monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, monoethyltrimethoxysilane, Monoethyltriethoxysilane, monoethyltriisopropoxysilane, Monoethyltriphenoxysilane, diethyldimethoxysilane, Diethyldiethoxysilane, diethyldiphenoxysilane, triethylxnonomethoxysilane, triethylmonoethoxysilane, Triethylmonophenoxysilane, monoethyldimethoxymonochlorosilane, Monoethyldiethoxymonochlorosilane, monoethyldiphenoxymonochlorosilane, Monoisopropyltrimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, Mono-sec-butyltriethoxysilane, monophenyltriethoxysilane, Diphenyldiethoxysilane, Diphenylmonoethoxymonochlorosilane, Monomethoxytrichlorosilane, monoethoxytrichlorosilane, Monoisopropoxytrichlorosilane, mono-n-butoxytrichlorosilane, Monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenoxytrichlorosilane, Mono-p-methylphenoxytrichlorosilane, dimethoxydichlorosilane, Dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, Triisopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, Tri-sec-butoxymonochlorosilane, tetraethoxysilane, Tetraisopropoxysilane and chain or cyclic Polysiloxanes, which were named by condensation of the compounds just mentioned by way of example for polysiloxanes,

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COPY

R ¹ the repeating units of the formula - (- Si - O -) -

R ²

exhibit. Mixtures of these compounds can also be used.

Examples of titanium compounds and / or vanadium compounds to be used according to the invention include Halides, alkoxy halides, alkoxides and halogenated oxides of titanium and / or vanadium.

Suitable examples of titanium compounds suitable according to the invention are tetravalent and trivalent titanium connections

TO gen. Compounds of the general formula Ti (OR) X._ , where R is an alkyl, aryl or aralkyl group with 1 to 20 carbon atoms, X is a halogen atom and η is a number corresponding to the relationship 0 <η <4, are used as tetravalent titanium compounds mean, preferred. Examples are titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium and tetraphenoxytitanium. As examples of trivalent titanium compounds, titanium trihalides, which are obtainable by reducing titanium tetrahalides, such as titanium tetrachloride and titanium tetrabromide, with hydrogen, aluminum, titanium or an organometallic compound of a metal from groups I to III of the Periodic Table of the elements, as well as trivalent titanium compounds can be mentioned, which can be mentioned by Reduction of tetravalent alkoxy titanium halides of the general formula

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Ti (OR) X. with an organometallic compound of a metal of groups I to III of the periodic table are, where in the formula R is an alkyl, aryl or aralkyl group having 1 to 20 carbon atoms, X for a halogen atom and m for a number corresponding to O <m < 4 stand.

As examples of vanadium compounds suitable according to the invention can tetravalent Vanadiuray bonds, such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide and tetraethoxy vanadium, pentavalent vanadium compounds, such as vanadium oxytrichloride, ethoxydichlorvanadyl, triethoxyvanadyl and tributoxyvanadyl; and trivalent Mention vanadium compounds such as vanadium trichloride and vanadium triethoxide.

In order to achieve an increased effect according to the invention, the titanium compound and the vanadium compound are often used in combination. In this case lies preferably the V / Ti molar ratio in the range of 2: 1 up to 0.01: 1.

Examples of the organometallic compound used according to the invention are organometallic compounds of metals of groups I to IV of the periodic table, which are known as the catalyst component of Ziegler catalysts. Organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples are organoaluminum compounds of the general formulas R ₃ Al, R ₃ AlX, RAlX ₃ , R ₃ AlOR, RAl (OR) X and R ₃ Al ₃ X ₃ , in which the radicals R can be identical or different and each represent alkyl - Or aryl groups with 1 to 20 carbon atoms and X denotes a halogen atom, as well as organozinc compounds of the general formula R ₃ Zn, in which the radicals R can be identical or different and each represent an alkyl group with 1 to 20 carbon atoms

atoms, such as triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-sec.-butyl aluminum, Tri-tert-butyl aluminum, trihexyl aluminum, trioctyl aluminum, Tridecyl aluminum, diethyl aluminum chloride, diisopropyl aluminum chloride, diethyl aluminum monoethoxide, Ethyl aluminum sesquichloride, diethyl zinc and mixtures of such compounds.

The amount of the organometallic compound used in the present invention is not particularly limited, but it is usually in the range of 0.1 to 1000 moles per mole of the transition metal compound (s).

Together with the organometallic compound, an ester an organocarboxylic acid can be used, for example benzoic acid, o- or p-toluic acid or p-anisic acid.

The order and method in which the following are also not particularly limited Components (1) to (4) are brought into contact with one another and reacted: (1) A silicon oxide and / or a Alumina, hereinafter referred to simply as component I- (1); (2) the reaction product from the reaction of a magnesium halide and a compound of the general formula Me (OR) X, hereinafter referred to simply as

η z-n

Component I- (2) is designated; (3) a compound of the general formula

R ¹

3 '4

R - (- Si - 0-4-- R, hereinafter referred to simply as a component

i ²

nente I- (3) is denoted; and (4) a titanium compound and / or a vanadium compound, hereinafter referred to simply as component I- (4).

BATH ORIGINAL

The order in which these compounds are brought into contact is not subject to any special restriction. For example, components I- (1) and I- (2) can first be brought into contact then component I- (.3) and finally component I- (4) are added, or first the contact treatment between components I- (1) and I- (3) can be carried out, after which finally the Components I- (2) and I- (4) are added.

The method by which the contact treatment is carried out is also not particularly limited and usual methods can be used. For example, the ingredients in the presence or absence of an inert solvent usually for 5 minutes to 20 hours at a temperature im In the range from 20 to 400 ° C., preferably 50 to 300 ° C., are brought into contact with one another and reacted, or the components can be prepared by co-milling treatment or a combination of the above specified two methods are implemented together.

The inert solvent is also not subject to any particular restriction. Usually can hydrocarbons and / or their derivatives, which do not lead to the deactivation of Ziegler catalysts, are used. Examples these are saturated aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic ones Hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, benzene, toluene, xylene and cyclohexane, as well as alcohols, ethers and esters such as ethanol, diethyl ether, tetrahydrofuran, ethyl acetate and ethyl benzoate.

In the case in which components I- (1) to I- (4) with the help of a common grinding treatment (copulverization

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J ό 4 U I b

treatment) are reacted with each other, the conditions, such as the temperature and duration of the grinding can easily be adjusted by the person skilled in the art as a function of the copulverization method used. In general, the milling temperature is in the range of

0 to 200 ^° C., preferably 20 to 100 ^° C., and the duration of the grinding in the range from 0.5 to 50 hours, preferably 1 to 30 hours. The co-milling operation should of course be carried out under an inert gas atmosphere and moisture should be excluded as far as possible.

Most preferred are the order and method of contact treatment of the components given below I- (1) to I- (4):

First, components I- (1) and I- (2) are in a solvent which is component I- (2), i.e. the reaction product of a magnesium halide and a compound of the general formula Me (OR) X _, dissolves, at a

Xl Z "~ I1

Temperature from 0 to 300 ⁰ C, preferably 10 to 200 ⁰ C and in particular 20 to 100 ⁰ C for a period of

1 minute to 48 hours, preferably 2 minutes to

10 hours, brought into contact with each other and implemented. Preferred examples of the aforementioned solvent are alcohols, tetrahydrofuran and ethyl acetate. The relationship, by bringing both components into contact is in the range from 0.01 to 5 g, preferably 0.1 to 2 g of component I- (2) per g of component I- (1). After the reaction, the solvent is removed, to obtain a reaction product with both components.

With the reaction product thus obtained, component I- (3), i.e. a compound of the general formula

E ¹

3 '4

R - (- Si - O -) - R at a temperature of 20 to 40O ⁰ C,

preferably 50 to 300 ° C., for preferably 5 minutes up to 20 hours directly or in the presence of an inert solvent, for example hexane, heptane, octane, Benzene or toluene, brought into contact and reacted. The magnesium halide, the compound of the general Formula Me (OR) X and component I- (3) can

η zn ^c

are added and implemented at the same time. The ratio in which the reaction product from the components I- (1) and I- (2) is brought into contact with component I- (3), corresponds to 0.01 to 5 g, preferably 0.1 to 2 g of component I- (3) per g of said reaction product.

Thereafter, the component becomes I- (4), that is, a titanium compound and / or vanadium compound, with the reaction product from components I- (1), I- (2) and I- (3) with heating to a temperature of 20 to 300 ° C, preferably 50 to 150 ° C, for 5 minutes to 10 hours directly or in Presence of an inert solvent, for example hexane, heptane, octane, benzene or toluene, mixed, whereby the titanium compound and / or the vanadium compound is applied to said reaction product. This reaction is preferably carried out in the absence of a solvent. The component I- (4) becomes used in such an amount that in the thus prepared solid catalyst component 0.5 to 50 wt .-%, preferably 1 to 20% by weight of the titanium compound and / or vanadium compound are contained. After the reaction the unreacted portion of the titanium compound and / or vanadium compound is removed by repeated washing with a solvent which is inert to Ziegler catalysts is removed. The solvent will then

evaporated under reduced pressure to give a powdery solid.

As for the amount of the catalyst component used according to the invention II relates, i.e. the compound of the general formula

R ¹

3 '4

R - {- Si - O -} - R, then would be both too large and too ι ~ π

small amounts of this compound are not effective. Usually their amount in the range of 0.1 to 100 moles, preferably 0.3 to 20 moles, per mole of the titanium compound and / or vanadium compound in the catalyst component I. is present.

Component II can also be used in the form of a reaction product resulting from the reaction of this component with the organometallic compound results. In this case, the reaction ratio is in the range from 1: 500 to 1: 1, preferably 1: 100 to 1: 2, given as the molar ratio of component II to the organometallic compound. The reaction product produced by the reaction of the component II and the organometallic compound is given in an amount of preferably 0.1: 1 to 100: 1, in particular 0.3: 1 to 20: 1, as the ratio Si: Ti and / or V (molar ratio), based on the titanium compound present in catalyst component I and / or vanadium compound.

The polymerization or copolymerization of olefins using the catalyst of the present invention can be in the form of suspension polymerization, solution polymerization or vapor phase polymerization can be carried out. The inventive Catalyst is particularly well suited for that

BATHROOM LOCAL GINAL

Vapor phase polymerization. The polymerization reaction is carried out in the same manner as the usual olefin polymerization reaction using a Ziegler catalyst. This means that the reaction is carried out under essentially oxygen-free and anhydrous conditions and in the presence or absence of an inert hydrocarbon. Conditions for olefin polymerization include temperatures in the range from 20 to 120 ° C., preferably 50 to 100 ° C., and a pressure in the range from atmospheric pressure to 70 bar (70 kg / cm ² ), preferably 2 to 60 bar (2nd up to 60 kg / cm ² ). The adjustment of the molecular weight can be made to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the addition of hydrogen to the polymerization system is more effective for this purpose. Using the catalyst according to the invention, two- or multistage polymerization reactions can of course also be carried out without difficulty, in which different polymerization conditions, such as different types and concentrations of the monomers, different hydrogen concentrations and different polymerization temperatures are used. For example, the catalyst according to the invention is extremely well suited for the production of so-called block copolymers, for carrying out the polypropylene production process, etc.

The process according to the invention is suitable for polymerization all olefins that can be polymerized with the help of Ziegler catalysts. Particularly preferred become ot-olefins with 2 to 12 carbon atoms. So suitable the process according to the invention, for example, for the homopolymerization of α-olefins, such as ethylene, propylene, Butene-1, hexene-1 and 4-methylpentene-1, the copolymerization

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of ethylene and propylene, ethylene and butene-1, ethylene and hexene-1 and propylene and butene-1, and for the
Copolymerization of ethylene with two or more other α-olefins.

The copolymerization with dienes to modify polyolefins is preferred, for example the
Copolymerization with butadiene, 1,4-hexadiene, ethylidene norbornene and dicyclopentadiene.

The method according to the invention is particularly effective for the production of highly stereospecific homopolymers or copolymers of α-olefins with 3 to 8 carbon atoms and for making soft, extremely low density copolymers.

In the manufacture of such soft copolymers is

first the polymerization of propylene by means of a conventional polymerization method, for example by
Suspension polymerization, bulk polymerization or vapor phase polymerization. In this case, propylene can be copolymerized with small amounts of other α-olefins such as ethylene and butene-1. The conditions for the polymerization are not subject to any
special restriction. The polymerization can be carried out under conditions which are customary for
Polymerization of propylene with the help of a Ziegler

Catalyst are applied. In this first stage, propylene is used in an amount of 0.0001 to 80% by weight, preferably 0.001 to 70% by weight and in particular 0.01 to 60% by weight, based on the final polypropylene
amount of polymer formed.

In a second stage, a copolymerization of ethylene with propylene and / or butene-1 is then carried out. At this point, that is obtained in the first stage

Reaction mixture, which contains the polymer formed and unreacted monomer, directly or after a flash evaporation to remove volatile constituents, such as unreacted monomers! and solvent, introduced into the second stage polymerization system where a solid powdery polymer is formed. The first-mentioned process, ie the direct supply of the reaction mixture, is advantageous because the volatile constituents can be used in an effective manner in order to dissipate the heat of polymerization in the second polymerization stage by means of their evaporation. The polymerization temperature is usually in the range of 20 to 11O ⁰ C, preferably 40 to 100 ⁰ C and the polymerization pressure is in the range of atmospheric pressure to 70 bar above atmospheric pressure (7Q kg / cm ² .G), preferably 2 to 60 bar above atmospheric pressure ( 2 to 60 kg / cm ² .G).

The polymerization reaction of the first stage can be followed by multistage polymerization reactions in which different polymerization conditions such as different polymerization temperatures and different Hydrogen and comonomer concentrations, can be used. It is preferable for such a multi-stage Polymerization reactions the polymerization reaction in the last stage is carried out in the vapor phase.

In addition, such multistage polymerization reaction in the presence of dienes, for example butadiene, 1,4-hexadiene, 1,5-hexadiene, vinyl norbornene and ethylidene norbornene be performed.

The invention is illustrated in more detail by the following examples, but is not intended to be limited to them be limited.

example 1
(a) Preparation of the solid catalyst component

10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide were placed in a stainless steel vessel of 400 ml capacity containing 25 stainless steel balls, each 1.27 cm in diameter, and ball milling was performed Carried out for 16 hours at room temperature under a nitrogen atmosphere, whereby a reaction product was formed. A three-necked flask equipped with a stirrer and reflux condenser was then flushed with nitrogen and charged with 5 g of the reaction product prepared above and 5 g of silicon dioxide (No. 952, product of Fuji-Davison) which ^{had been calcined at 600 °} C., after which 100 ml Tetrahydrofuran was added and the reaction was carried out at 60 ° C for 2 hours. Then tetrahydrofuran was removed by drying at 120 ° C under reduced pressure. Thereafter, 50 ml of hexane was added, the mixture was stirred, and finally 1 ml of tetraethoxysilane was added and the reaction was carried out under reflux of hexane for 2 hours to obtain a solid powdery product (A).
The solid powdery product (A) thus obtained was put into 30 ml of titanium tetrachloride, and the reaction was carried out at 120 ° C. for 2 hours. Then the reaction mixture was washed with hexane until no titanium tetrachloride was found in the hexane, a solid catalyst component containing 70 mg of titanium per g being obtained.

(b) vapor phase polymerizon

As an apparatus for vapor phase polymerization, a 5 liter stainless steel autoclave equipped with an induction stirrer was used. In held at 60 ⁰ C autoclave 1OO were mg of the solid catalyst component described above, 2.5 mmol of triethylaluminum and 0.5 mmol of phenyltriethoxysilane was added and the polymerization was carried out for 8 hours while propylene was continuously fed so that the total pressure at 8 , 5 bar above atmospheric pressure (8.5 kg / cm ² .G) was maintained. There was thus obtained 450 g of polypropylene in the form of spherical particles having a bulk density of 0.40 and an average particle diameter of 1,000 µm. The catalyst activity was 64,000 g polypropylene / g Ti. The percentage residue of the polypropylene after extraction in boiling heptane was 87% by weight.

Comparative example 1

(a) Preparation of the solid catalyst component

A solid catalyst component was prepared in the same manner as in Example 1 except that no tetraethoxysilane was used. The titanium content was 35 mg per g of the catalyst component.

(b) vapor phase polymerizon

Using the solid catalyst component thus prepared the polymerization was carried out in the same manner as in Example 1, except that none Phenyltriethoxysilane was used. In this way

BATHROOM LOCAL GINAL

150 g of polypropylene with a bulk density of 0.35 and an average particle diameter of 700 μπι obtained. The catalyst activity was 4 3,000 g polypropylene / g Ti. The percentage residue of the polypropylene after extraction in boiling heptane was 40% by weight.

Example 2
(a) Preparation of the solid catalyst component

10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide were placed in the ball mill jar described in Example 1, and ball milling was carried out for 16 hours at room temperature under a nitrogen atmosphere to obtain a reaction product. In the three-necked flask described in Example 1, 2.5 g of the reaction product thus prepared and 7.5 g of silicon dioxide (No. 952, product of Fju-Davison) which had been calcined at 600 ° C. were placed. 100 ml of tetrahydrofuran were then added and the reaction was carried out ^{at 60 ° C. for 2 hours.} Thereafter, tetrahydrofuran was removed by drying at 120 ° C. under reduced pressure. Finally, 50 ml of hexane was added and, after stirring, 1 ml of diethyldiethoxysilane was added and the reaction was carried out under reflux of hexane for 2 hours to obtain a solid powdery product (B).

The solid powdery product (B) produced in this way was added to 30 ml of titanium tetrachloride and ^{reacted at 120 °} C. for 2 hours. The reaction mixture was then washed with hexane until no more titanium tetrachloride could be found in the hexane, a solid catalyst component being obtained which contained 60 mg of titanium per g.

held,
(b) vapor phase polymerization

Using the apparatus described in Example 1, vapor phase polymerization was carried out in the following manner. Into the autoclave kept at 60 ° C., 100 mg of the solid catalyst component prepared above, 2.5 mmol of triethylaluminum and 0.5 mmol of phenyltriethoxysilane were charged, and polymerization was carried out for 8 hours while propylene was continuously supplied so that the total pressure was 8 , 5 bar above atmospheric pressure (8.5 kg / cm ² .G) was maintained. In this way, 430 g of polypropylene were formed in the form of spherical particles with a bulk density of 0.45 and an average particle diameter of 900 μm.

The catalyst activity was 72,000 g polypropylene / g Ti. The percentage residue of the polypropylene after Extraction in boiling heptane was 89% by weight.

Example 3
(a) Preparation of the solid catalyst component

10 g of commercially available anhydrous magnesium chloride and 1.3 g of magnesium diethoxide were added to the ball mill vessel described in Example 1 and for 16 hours Room temperature under a nitrogen atmosphere in the Ball mill ground to obtain a reaction product. 5 g of the reaction product thus prepared and 5 g of alumina that had been calcined at 600 ° C was then placed in the same three-necked flask as in Example 1 after which 100 ml of tetrahydrofuran was added and the reaction was carried out at 60 ° C for 2 hours.

BATH ORIGINAL

The tetrahydrofuran was then obtained by drying at 120 ° C removed under reduced pressure. Then 50 ml Hexane was added and, after stirring, 2 ml of tetraethoxysilane was added and the reaction was continued for 2 hours carried out under reflux of hexane to form a solid powder (C).

The solid powder (C) produced in this way was placed in 30 ml of titanium tetrachloride and the reaction was carried out ^{at 120 ° C. for 2 hours.} The reaction mixture was then washed with hexane until no further titanium tetrachloride could be found in the hexane, a solid catalyst component containing 100 mg of titanium per g being obtained.

(b) vapor phase polymerization

Using the apparatus described in Example 1, vapor phase polymerization was carried out in the following manner. 100 mg of the above-described solid catalyst component, 2.5 mmol of triethylaluminum and 0.7 mmol of tetraethoxysilane were put into the autoclave kept at 60 ° C, and polymerization was carried out for 8 hours while continuously feeding propylene so that the total pressure was 8 , 5 bar above atmospheric pressure (8.5 kg / cm ² .G) was maintained. In this way, 500 g of polypropylene were obtained in the form of spherical particles with a bulk density of 0.41 and an average particle diameter of 950 μm. The catalyst activity was 50,000 g polypropylene / g Ti. The percentage residue of the polypropylene after extraction in boiling heptane was 92% by weight.

BAD ORfGINAL

Example 4

(a) Preparation of the solid catalyst component

10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide were placed in the ball mill jar described in Example 1, and ball milling was carried out for 16 hours at room temperature under a nitrogen atmosphere to prepare a reaction product. 5 g of the reaction product thus formed and 5 g of calcined at 600 ° C alumina was then added to those described in Example 1 three-necked flask, followed by 100 ml of tetrahydrofuran were added and the reaction was carried out at 60 ⁰ C for 2 hours. The tetrahydrofuran was then removed by drying at 120 ° C. under reduced pressure. Finally, 50 ml of hexane was added and, after stirring, 2 ml of diethyldiethoxysilane was added and the reaction was carried out under reflux of hexane for 2 hours to obtain a solid powdery product (D).

The solid powdery product (D) thus formed became placed in 30 ml of titanium tetrachloride, and the reaction was carried out at 120 ° C for 2 hours. After that it became Washed the reaction mixture with hexane until no more titanium tetrachloride could be found in the hexane, whereby a solid catalyst component containing 25 mg of titanium per g was obtained.

(b) vapor phase polymerization

Using the apparatus described in Example 1, vapor phase polymerization was carried out in the following manner carried out. 100 mg of the solid ca-

BAD ORIGINAL COPY

catalyst component, 2.5 mmoles of triethylaluminum and 0.5 mmoles of diethyldiethoxysilane were placed in the autoclave kept at 60 ° C, and the polymerization was carried out for 8 hours while propylene was fed continuously so that the total pressure was 5 bar above atmospheric pressure (5, 8 kg / cm ² .G) was maintained. In this way, 450 g of polypropylene were obtained in the form of spherical particles with a bulk density of 0.40 and an average particle diameter of 980 μm. The catalyst activity was 60,000 g polypropylene / Ti. The percentage residue of the polypropylene after extraction in boiling heptane was 90% by weight.

Example 5

A 2 liter stainless steel autoclave equipped with an induction stirrer was purged with nitrogen and then charged with 1000 ml of hexane, 2.5 mmol of triethylaluminum and 50 mg of the solid catalyst component obtained in Example 1, followed by 0.25 mmol of phenyltriethoxysilane was added and the temperature was raised to 50 ⁰ C. Propylene was then passed in up to a total pressure of 8.5 bar above atmospheric pressure (8.5 kg / cm ² .G) and the polymerization was started. The polymerization was continued for 8 hours while the internal pressure of the autoclave was maintained at 8.5 bar above atmospheric pressure (8.5 kg / cm ² .G). Then, the polymer slurry was transferred to a beaker and hexane was removed under reduced pressure to obtain 34.4 g of polypropylene having a bulk density of 0.41 and an average particle diameter of 1,300 µm. The catalyst activity was 98,000 g polypropylene / g Ti. The percentage residue of the polypropylene after extraction in boiling heptane was 75% by weight,

BAD ORiGiNAL

Example 6

(a) Preparation of the solid catalyst component

10 l of tetrahydrofuran, 500 g of a reaction product obtained by ball milling 1 kg of anhydrous magnesium chloride and 42O g of aluminum triethoxide, and 500 g of silicon dioxide (No. 952, product of Fuji-Davison) which had been calcined at 600 ° C were placed in a 30 liter stainless steel autoclave, and the reaction was carried out ^{at 60 ° C. for 5 hours.} The reaction mixture was then ^{dried at 120 °} C. under reduced pressure in order to remove the tetrahydrofuran. Finally, 5 liters of hexane was added and, after stirring, 100 ml of tetraethoxysilane was added and the reaction was carried out under reflux of hexane for 5 hours to obtain a solid powdery product (A). The solid, powdery product (A) produced in this way was added to 3 l of titanium tetrachloride and the reaction was carried out ^{at 120 ° C. for 5 hours.} The reaction mixture was then washed with hexane until no more titanium tetrachloride could be found in the hexane, a solid catalyst component being obtained which contained 70 mg of titanium per g.

(b) Polymerization of propylene in the vapor phase

As an apparatus for vapor phase polymerization, a stainless steel autoclave was used. In the at The autoclave kept at 60 ° C. was 100 g of the solid catalyst component described above, 2.5 mol of triethylaluminum and 0.25 mol of phenyltriethoxysilane and the polymerization was carried out for 6 minutes,

BATH ORIGINAL
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3 3 4 O 7 ο 4

while propylene was continuously introduced so that the total pressure was maintained at 4 bar above atmospheric pressure (4 kg / cm ² .G). In this way, 5 kg of polypropylene was formed.

(c) Copolymerization of ethylene and propylene in the vapor phase

A stainless steel autoclave was used as an apparatus for vapor phase polymerization and a Circulation was established including a blower, a flow control valve and a dry cyclone Separation of the polymer formed formed. The temperature of the autoclave was increased by running warm Water regulated by his coat. The copolymerization was carried out at 60 ° C during the above under

(b) Polypropylene formed at a rate of 5 grams per Hour was added to the autoclave and while the concentrations (molar proportions) of the with the help of the fan ethylene, propylene and hydrogen introduced into the autoclave were maintained at 44%, 44% and 12%, respectively.

There was thus obtained a copolymer in the form of spherical particles which had a melt index (MI) of 0.82, a bulk density of 0.40 and a density of 0.883 g / cm ³ . The density was thus very low, but the copolymer was nonetheless tack-free.

The catalyst activity was very high and was 114 000 g copolymer / g Ti. The polypropylene content of the copolymer was 62 wt .-% O _7.

After continuous operation for 200 hours, the polymerization was interrupted and the interior of the autoclave checked. The polymer did not adhere to the inner walls, the stirrer and the removal line for the polymer, proving that

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BATH

34 - 3 3 4 0 7 5 A

continuous operation can be maintained extremely smoothly for long periods of time.

Comparative example 2

A solid catalyst component was prepared in the same manner as in Example 6 except that no tetraethoxysilane was used. Thereafter, the polymerization of propylene and the copolymerization of Ethylene and propylene carried out in the same way as in Example 6, but with the specified solid catalyst component was used and 0.5 mol of ethyl benzoate was used instead of the phenyltriethoxysilane became.

After 30 hours, stirring became impossible, so the polymerization reaction had to be stopped and the inside of the autoclave was checked. It was found that a large amount of the polymer adhered to the inner wall and to the shaft and blades of the stirrer. The copolymer thus formed had a melt index of 0.89 and a density of 0.883 g / cm ³ . It can be seen that the process of this comparative example, with regard to the continuous procedure, is significantly worse than example 6, in which tetraethoxysilane was used to prepare the solid catalyst component and both an organoaluminum component and phenyltriethoxysilane were used in the polymerization.

Example 7

Using the solid catalyst component prepared in Example 6, the polymerization of propylene was carried out carried out in the same way as in (b) of Example 6, with the modification that the amount of phenyl

BATH ORIGINAL

-Jd-

triethoxysilane changed to 0.5 mol and the polymerization time was changed in 1.5 minutes. In this way, 1 kg of polypropylene was obtained.

Using the polypropylene thus prepared, copolymerization of ethylene and propylene was then carried out in the same manner as in (c) in Example 6 except that the molar concentrations of ethylene, propylene and hydrogen were 38%, 56% and 6%, respectively % have been set. Thus, a copolymer in the form of spherical particles having a melt index of 0.32, a bulk density of 0.32 and a density of 0.875 g / cm ^{3 was} formed. The density was thus extremely low, but the copolymer was by no means sticky. The catalyst activity was high, 100,000 g copolymer / g Ti. The propylene content of the copolymer was 0.14% by weight.

After continuous operation for 200 hours, the polymerization was interrupted and the interior of the autoclave examined. The polymer did not adhere to the inner wall, the stirring blades or the Sampling line for the polymer established.

Example 8

Using the solid catalyst component prepared in Example 6, the polymerization of propylene was carried out carried out in the same manner as in section (b) of the example, with the modification that 0.2 mol of tetraethoxysilane was used in place of the phenyltriethoxysilane and that the polymerization time was changed to 1.6 hours became. In this way, 80 kg of polypropylene was obtained.

Using the polypropylene thus produced, the copolymerization of ethylene and propylene was then carried out in in the same way as in section (c) of Example 6 by ' guided. In this way, a copolymer in the form of

spherical particles with a melt index of 0.70, a bulk density of 0.45 and a density of 0.888 g / cm ^{3 were} obtained. The density was thus very low, but the copolymer was by no means tacky. The catalyst activity was high and was 107,000 g copolymer / g Ti. The polypropylene content of the copolymer was 10.6% by weight.

After continuous operation for 200 hours, the polymerization was interrupted and the interior of the autoclave examined. It was found that there was no polymer on the inner wall, on the paddles and the Sampling line for the polymer stuck.

Example 9

Using the solid catalyst component prepared in Example 6, the polymerization of propylene was carried out carried out in the same manner as in section (b) of Example 6, except that the polymerization time was changed to 1.8 hours. In this way 90 kg of polypropylene were obtained.

In the presence of the polypropylene thus prepared, the copolymerization of ethylene and propylene was then carried out in the same manner as in section (c> of Example 6, with the modification that no hydrogen was supplied and that the concentrations (molar concentrations) of ethylene and propylene were set to 25 % and 75% were adjusted, respectively, and thus there was obtained a copolymer in the form of spherical particles which had a melt index of 0.1, a bulk density of 0.42 and a density of 0.898 g / cm ^3. The density was thus very low, but the copolymer showed no stickiness. The catalyst activity was high and was 103,000 g copolymer / g Ti. The polypropylene content of the copolymer was 12.6% by weight. After the continuous operation for 200 hours, the polymerization was stopped and that Interior of the car

claves examined. It was found that none Polymer on the inner walls, the paddles and the Sampling line for the polymer stuck.

Example 10

Using the solid catalyst component prepared in Example 6, the polymerization of propylene was carried out carried out in the same manner as in (b) of Example 6, with the modification that the polymerization time in 12 Minutes was changed. In this way, 10 kg of polypropylene was obtained.

Using the polypropylene thus prepared, the copolymerization was then carried out in the same manner as under (c) of Example 6, with the modification that butene-1 was used as comonomer instead of propylene and that the concentrations (molar proportions) in the autoclave introduced reactants were adjusted to 44% ethylene, 44% butene-1 and 12% hydrogen. There was thus obtained a copolymer in the form of spherical particles which had a melt index of 1.0, a bulk density of 0.43 and a density of 0.880 g / cm ³ . The density was thus very low, but the copolymer was by no means tacky. The catalyst activity was high, corresponding to 103,000 g copolymer / g Ti. The polypropylene content of the copolymer was 1.3% by weight.

After the process has been carried out continuously for 200 hours the polymerization was stopped and the inside of the autoclave was examined. There was no adherence whatsoever Polymer on the inner wall, the paddles and the Sampling line found for the polymer.

Example 11

(a) Preparation of the solid catalyst component

10 l of tetrahydrofuran, 500 g of the reaction product, which had been obtained by grinding 1 kg of anhydrous magnesium chloride and 42O g of aluminum triethoxide in a ball mill, and 500 g of aluminum oxide (Ketjen B), which had been calcined at 600 ° C., were placed in a 30 1- Given autoclave made of stainless steel and ^{implemented at 60 0} C for 5 hours. Thereafter, the reaction mixture was dried at 120 ° C. under reduced pressure to remove the tetrahydrofuran. Thereafter, 5 liters of hexane was added and, after stirring, 100 ml of tetraethoxysilane was added and the reaction was carried out under reflux of hexane for 5 hours to obtain a solid powdery product (B). The solid powdery product (B) thus prepared was put in 3 liters of titanium tetrachloride, and the reaction was carried out at 120 ° C. for 5 hours. Thereafter, the reaction mixture was washed in hexane until no further titanium tetrachloride was found in the hexane, whereby a solid catalyst component containing 60 mg of titanium per g was obtained.

(b) Polymerization of propylene in the vapor phase

A stainless steel autoclave was used as an apparatus for vapor phase polymerization. Into the ^{autoclave kept at 60 °} C., 100 g of the solid catalyst component prepared above, 2.5 mol of triethylaluminum and 0.25 mol of phenyltriethoxysilane were placed, and the polymerization was carried out for 2 hours while propylene was continuously fed in so that the total pressure was 4 bar above atmospheric pressure

(4 kg / cm ² .G) was maintained. In this way, TOO kg of polypropylene were produced.

(c) Copolymerization of ethylene and propylene

A stainless steel autoclave was used as an apparatus for vapor phase polymerization and a cycle was using a blower, a flow control valve and a dry cyclone to separate the formed polymers formed. The temperature of the autoclave was adjusted by putting warm water through it his coat was passed.

The copolymerization was carried out at 6O ° C while the polypropylene prepared under (b) above was passed into the autoclave at a rate of 5 g per hour and ethylene, propylene and hydrogen fed into the autoclave in such molar ratios with the aid of the Gebiases were made that their concentrations (molar ratios) corresponded to 50% ethylene, 38% propylene and 12% hydrogen.

Thus, a spherical particle copolymer was obtained which had a melt index of 0.50, a bulk density of 0.42 and a density of 0.890 g / cm ³ . The density was thus low, yet the copolymer was not tacky. The catalyst activity was 103,000 g copolymer / g Ti. The polypropylene content of the copolymer was 16.2% by weight.

After the process had been carried out continuously for 200 hours, the polymerization was interrupted and the interior of the autoclave. The polymer did not adhere to the inner walls, the stirrer and the removal line noted for the polymer. It was thus demonstrated that the process was carried out continuously extremely smooth over long periods of time is possible.

Claims (4)

PATENT ADVOCATE ?:. "': STREHL SCHÜBEL-HOPF SCHULZ WIDENMAYERSTKASSE 17, I) -KOOO MÜNCHEN 22 DlIM. INi; I1KTKK STHKHl. IJlI1I. CHKM .. UK. UKSlH-A S (1IItIMKI. IU) I1I. KlHYSIK IJZIIM ALSO KKCHI SANWALl HKI DEN 1.ANIj (JEHICHTKN MlINCHKN I AND Il ALSO KUK (JI1ICAN ΡΛΤΚΝΊ AITOKNKYS TKLKKJN MJHiJI 22 3911 TKLKX Γ) 214 () 3 (, SSSM U TKLKC (JI1IKK HJK!) i DEA-13 84 9 November 10, 1983 CLAIMS 1. I Process for the preparation of polyolefins by polymerization or copolymerization of olefins in the presence of a catalyst comprising a solid catalyst component and an organometallic compound, characterized in that the polymerization is carried out in the presence of a catalyst which consists essentially of the following components: I. a solid catalyst component obtained by contacting and reacting the the following components (1) to (4): (1) a silica and / or alumina, (2} of the reaction product obtained by the reaction of a magnesium halide and a Ver bond of the general formula Me (OR) X Il £ t ™ "Xl is obtained in which Me is an element of groups I to VIII of the periodic table of R represents elements other than silicon, titanium and vanadium, R represents a hydrocarbon residual matter with 1 to 24 carbon atoms, X is a halogen atom, ζ the valence of Me and η a number corresponding to O <η <ζ mean ι (3) a compound of the general formula R ¹
R ³ - (- Si - O -) - R, in which R ¹ , R ² and R ³ k ² each for hydrocarbon radicals with 1 to 24 carbon atoms, alkoxy groups, Are hydrogen atoms or halogen atoms, 4th
R is a hydrocarbon radical with 1 to ^ ^{Means 0} carbon atoms and η a number corresponding to 1 <η <30, and (4) a titanium compound and / or a vanadium compound; II. A compound of the general formula R ¹ I 4 12 3 R - (- Si - 0 -H- R, in which R, R, and R, respectively for hydrocarbon residues with 1 to 24 carbon atoms, Alkoxy groups, hydrogen atoms or halogen atoms, R is a hydrocarbon radical having 1 to 24 carbon atoms and · Η is a number corresponding to 1 <η <30; and
III. an organometallic compound. 2. The method according to claim 1, characterized in that an ot-olefin with 2 to 12 carbon material atoms is polymerized. 3. The method according to claim 1, characterized in that propylene with the formation of high stereospecific polypropylene is polymerized. 4. The method according to claim 1, in which in a first stage the homopolymerization of propylene or the copolymerization of propylene and a small amount of another ct -olefin is carried out in the presence of the specified catalyst and in a second stage the copolymerization of ethylene and Propylene and / or butene-1 is carried out in the presence of the polypropylene formed in the first stage under essentially solvent-free conditions until a soft copolymer having a density in the range from 0.860 to 0.910 g / cm ^{3 is} formed. 5. The method according to claim 4, characterized in that in the first stage 0.0001 to 80% by weight of polypropylene based on the amount of final copolymer formed in the second stage and that the copolymerization in the second stage is carried out in the vapor phase. 6. Solid catalyst component of a catalyst for the polymerization or copolymerization of olefins, available by touching and converting the following components (1) to (4): (1) a silica and / or alumina, (2) the reaction product obtained by reacting a magnesium halide and a . binding of the general formula Me (OR) X η ζ — η is obtained in which Me is an element of groups I to VIII of the periodic table of Represents elements other than silicon, titanium and vanadium, R represents a hydrocarbon remainder with 1 to 24 carbon atoms, BAD ORlGlMAL X is a halogen atom, ζ the valence of Me and η a number corresponding to O <η <ζ mean (3) a compound of the general formula R ¹
R ³ - {- Si - 0-1 - R ⁴ , in which R ¹ , R ² and R ³ each for hydrocarbon radicals with 1 to 24 carbon atoms, alkoxy groups, Are hydrogen atoms or halogen atoms, 4th
R denotes a hydrocarbon radical with 1 to carbon atoms and η a number corresponding to 1 <η <30, and (4) a titanium compound and / or a vanadium compound,