DE2729196C2 - - Google Patents

Description

The invention relates to the subject matter of the claims. It is an improved manufacturing process a highly stereoregular polymer or copolymers of an olefin with at least 3 carbon atoms in high yields.

There are various recommendations for polymerization or Copolymerization of olefins in the presence of a catalyst, consisting of (A) a solid containing magnesium Titanium composition and (B) an organometallic compound a metal from groups I to III of the periodic table, known. In many of these recommendations, magnesium is used containing solid titanium compound obtained by chemical Deposition of a titanium compound on a halogen compound of magnesium, such as magnesium dihalide, magnesium hydroxychloride or a magnesium alkoxy halide as a catalyst component, used. [See e.g. B. JA patent publication published No. 16,986 / 73 (DE-OS 22 30 672), published patent application JA No. 1 26 590/75 (DE-OS 25 04 036) and published JA Patent Publication No. 28,189 / 76 (U.S. Patent No. 4,076,924)].

It is also known that halogen-free magnesium compounds in possible magnesium-containing solid titanium compositions can be converted by using suitable halogenating agents or halogen-containing titanium compounds during a catalyst formation reaction used [see e.g. B. JA patent publication No. 34 098/71 (DE-AS 17 95 197), JA patent publication No. 34 084/75 (DE-AS 23 29 641) and JA patent publication No. 42 137/72 (FR-PS 20 27 788)].  

Compared to the catalysts known from DE-OS 21 11 455, consisting of an organometallic compound of group I to III of the periodic table and a titanium-containing catalyst component, with the implementation of magnesium alcoholates 4-valent halogen-free titanium alcoholates and acid halides formed by elements of groups III to VI of the periodic table the catalysts used according to the invention are distinguished by a surprisingly higher capacity.

Many of the conventional catalysts that contain a magnesium contain solid titanium compound, have the deficiency, that they have little activity in the polymerization propylene and copolymerization of a monomer mixture, which contains a predominant proportion of propylene, show while having a pretty good polymerization activity in the polymerization of ethylene or the copolymerization a monomer mixture that is predominant Ethylene contains, show, or that they are not to any great extent can result in stereoregular polypropylene. So these are Catalysts for achieving highly stereoregular Polymers or copolymers of olefins with at least 3 carbon atoms not suitable in high yields.  

Generally, when using catalysts of halogen compounds of magnesium the compounds are exposed to moisture and even if all precautions are taken there is a tendency for faults to occur due to the presence of moisture during storage or during catalyst manufacture. Therefore there is increasingly the possibility of causing non-uniformity in terms of catalyst properties and consequently it is difficult to make highly stereoregular polypropylene in high yields and with good reproducibility to build. On the other hand, this lack could be with catalysts Avoid the halogen-free magnesium compounds included, however, it is still difficult to a great extent stereoregular polymers or copolymers of olefins with to form at least 3 carbon atoms in high yields.

It got intense after one improved method sought that with the use the halogen-containing magnesium compound and so far recommended halogen-free magnesium compounds Defects can be remedied and to a large extent stereoregular polymers or copolymers of olefins with at least 3 carbon atoms in high yields and with good reproducibility can result. This led to the discovery of the invention Process as it is in the claims and in the following description is explained in more detail.  

It is therefore an object of the invention to provide an improved method for Production of a highly stereoregular polymer or copolymer of an olefin with at least 3 carbon atoms in high To provide yields.

The foregoing and other objects and advantages of the invention will become apparent from the following description.  

The organic magnesium compound (1) is a compound which is obtained by reacting metallic magnesium or an alkyl magnesium with a suitable compound, which contains a hydroxyl group in the molecule, such as one aliphatic alcohol, an aromatic alcohol or a Phenol.

One through an exchange reaction between the magnesium compound of the above formula, wherein this magnesium compound does not necessarily contain an aromatic residue must, and the described compound, which has a hydroxyl group contains in the molecule, compound obtained can also can be used as an organic magnesium compound (1).

Specific examples of the halogen-free magnesium compound (1) are given below.

Aryloxy-containing halogen-free magnesium compounds, such as Mg (OCH₃) (OC₆H₅), Mg (OCH₃) (OC₆H₄CH₃), Mg (OCH₃) (OC₆H₄C₂H₅), Mg (OCH₃) (OC₆H₄C₃H₇), Mg (OCH₃) [OC₆H₃ (CH₃) ₂], Mg (OCH₃) (OC₆H₄C₄H₉), Mg (OC₂H₅) (OC₆H₅), Mg (OC₂H₅) (OC₆H₄CH₃), Mg (OC₂H₅) (OC₆H₄C₂H₅), Mg (OC₂H₅) (OC₆H₄C₃H₇), Mg (OC₂H₅) [OC₆H₃ (CH₃) ₂], Mg (OC₂H₅) (OC₆H₄C₄H₉),  Mg (OC₃H₇) (OC₆H₄CH₃), Mg (OCH₃) (OC₆H₄OCH₃), Mg (OC₂H₅) (OC₆H₄OCH₃), Mg (OC₈H₁₇) (OC₆H₄OCH₃), Mg (OCH₃) (OC₁₀H₇), Mg (OC₂H₅) (OC₁₀H₇), Mg (OC₃H₇) (OC₁₀H₇), Mg (OC₆H₁₀) (OC₆H₅), Mg (OC₆H₁₀) (OC₆H₄CH₃), Mg (OC₆H₅) ₂, Mg (OC₆H₄CH₃), Mg (OC₆H₄C₂H₅) ₂, Mg (OC₆H₄C₃H₇) ₂, Mg (OC₆H₄C₄H₉) ₂, Mg (OC₆H₄C₈H₁₇) ₂, Mg (OC₆H₄C₉H₁₉) ₂, Mg [OC₆H₄C (CH₃) C₆H₅] ₂, Mg [OC₆H₃ (CH₃) ₂] ₂, Mg [OC₆H₂ (CH₃) ₂ (C₄H₉)] ₂, Mg (OC₆H₄OCH₃) ₂, Mg (OC₁₀H₇) ₂, Mg (OC₁₀H₆CH₃) ₂, Mg (OC₁₀H₆C₂H₅) ₂, Mg [OC₁₀H₅ (CH₃) ₂] ₂, and Mg (OC₁₀H₆OCH₃) ₂; and containing alkoxy halogen-free magnesium compounds, such as Mg (OCH₃) (OCH₂C₆H₅), Mg (OCH₃) (OC₂H₄C₆H₅), Mg (OCH₃) [OCH (CH₃) C₆H₅], Mg (OCH₃) [OC (CH₃) ₂C₆H₅], Mg (OCH₃) (OCH₂C₆H₄C₃H₇), Mg (OCH₃) [OC (CH₃) ₂ C₆H₄C₃H₇], Mg (OCH₂H₅) (OCH₂C₆H₅), Mg (OC₂H₅) (OC₂H₄C₆H₅), Mg (OC₂H₅) [OCH (CH₃) C₆H₅], Mg (OC₂H₅) [OC (CH₃) ₂C₆H₅], Mg (OC₂H₅) (OCH₂C₆H₄C₃H₇), Mg (OC₃H₇) (OCH₂C₆H₅), Mg (OCH₂C₆H₅) ₂, Mg (OC₂H₄C₆H₅) ₂, Mg [OCH (CH₃) C₆H₅] ₂, Mg [OC (CH₃) ₂C₆H₅] ₂, Mg (OCH₂C₆H₄C₃H₇) ₂, and Mg [OC (CH₃) ₂C₆H₄C₃H₇] ₂.  

Organic acid esters as electron donors (2) that help to form the catalyst forming solid titanium component, which in the invention is used are aliphatic acid esters (2-a), alicyclic acid esters (2-b) and aromatic Acid esters (2-c).

Examples of aliphatic esters (2-a) are esters that are formed are between carboxylic acids or their halogen substitution products, selected from the group consisting of saturated or unsaturated aliphatic carboxylic acids 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms, and their halogen substitution products and alcohols or phenols selected from the group consisting of saturated or unsaturated aliphatic primary alcohols with 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms, saturated or unsaturated alicyclic alcohols with 3 to 8 carbon atoms, preferably 5 to 6 Carbon atoms, phenols with 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and C₁- to C₄-saturated or unsaturated aliphatic primary alcohols, to the ring carbon atom of a C₃- to C₁₀ aliphatic or aromatic ring, and lactones with 3 to 10 carbon atoms.

Specific examples of aliphatic esters (2-a) include primary alkyl esters of saturated fatty acids such as methyl formate, ethyl acetate, n-amyl acetate, 2-ethyl hexyl acetate, n-butyl formate, ethyl butyrate or ethyl valerate; Alkenyl esters of saturated fatty acids such as vinyl acetate and allyl acetate; primary alkyl esters of unsaturated fatty acids such as methyl acrylate, methyl methacrylate or n-butyl crotonate; Alkyl esters of halogenated aliphatic monocarboxylic acids such as methyl chloroacetate or ethyl dichloroacetate; and lactones such as propiolactone, γ- butyrolactone or δ -valerolactone.

Examples of alicyclic esters (2-b) are esters that are formed  are between alicyclic carboxylic acids with 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms, and saturated or unsaturated aliphatic primary alcohols with 1 to 8 carbon atoms, preferably 1 to 4 Carbon atoms. Specific examples include methylcyclohexane carboxylate, Ethylcyclohexane carboxylate, methylmethylcyclohexane carboxylate and ethyl methylcyclohexane carboxylate.

Examples of aromatic esters (2-c) are esters that are formed are between aromatic carboxylic acids with 7 to 18 Carbon atoms, preferably 7 to 12 carbon atoms, and alcohols or phenols selected from the group consisting of from saturated or unsaturated aliphatic primary Alcohols, saturated or unsaturated alicyclic Alcohols with 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms, phenols with 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and C₁- to C₄-saturated or unsaturated aliphatic primary alcohols, to the ring carbon atom of a C₃- to C₁₀ aliphatic or aromatic ring are bound; and aromatic Lactones with 8 to 12 carbon atoms.

Specific examples of aromatic esters (2-c) are methyl benzoate, Ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, Chlorophenyl benzoate, methyl toluate, ethyl toluate, propyl toluate, Butyl toluate, amyl toluate, allyl toluate, methyl ethyl benzoate, Ethyl ethyl benzoate, ethyl xylol carboxylate, methyl anisate, ethyl anisate, Propyl anisate, butyl anisate, methyl ethoxybenzoate, ethyl ethoxybenzoate, Methyl hydroxybenzoate, ethyl hydroxybenzoate, Methylaminobenzoate, ethylaminobenzoate, methylchlorobenzoate, Ethyl chlorobenzoate, coumarin and phthalide.

Among the aromatic esters (2-c) as illustrated above were esters of benzoic acid, alkyl or Alkenylbenzoic acids and alkoxybenzoic acids are preferred. Especially  preferred species are C₁ to C₄ alkyl esters, for example Methyl or ethyl ester of benzoic acid, o- or p- Toluic acid and p-anisic acid.

The titanium halide compounds (3) used to form the solid titanium component for the used according to the invention Catalyst used are tetravalent titanium compounds of the formula

Ti (OR ′) _g X₄ _{- g}

wherein R 'is an alkyl group having 1 to 8 carbon atoms, X is a halogen atom, such as chlorine, bromine or iodine, and g is a number from 0 ≦ g <4, preferably 0 ≦ g ≦ 3, in particular 0 ≦ g ≦ 2.

Specific examples of these titanium compounds are titanium tetrahalides, such as TiCl₄, TiBr₄ or TiJ₄; Alkoxytitanium trihalides, such as Ti (OCH₃) Cl₃, Ti (OC₂H₅) Cl₃, Ti (O n-C₄H₉) Cl₃, Ti (OC₂H₅) Br₃ or Ti (O iso-C₄H₉) Br₃; Alkoxy titanium dihalides, such as Ti (OCH₃) ₂Cl₂, Ti (OC₂H₅) ₂Cl₂, Ti (O n-C₄H₉) ₂Cl and Ti (OC₂H₅) ₂Br₂; Trialkoxytitanium monohalides, such as Ti (OCH₃) ₃Cl, Ti (OC₂H₅) ₃Cl, Ti (O n-C₄H₉) ₃Cl and Ti (OC₂H₅) ₃Br. Among these, the titanium tetrahalides are special prefers. Most preferred is titanium tetrachloride.  

The term "mechanical pulverization" as used herein used means a mechanical pulverization process, because of the powerful mechanical pulverization effect, which can be illustrated by pulverization in a ball mill, in a vibration mill or in a beater mill while contacting it Components is effected. An ordinary stirring process To ensure good contact, the definition "Mechanical pulverization" is not included.

The reaction of components (1) and (2) by mechanical Powdering is preferably done essentially in the absence performed by oxygen and water. The powdering time is about 1 hour to about 10 days and that Temperature is room temperature or a temperature close to it and there is cooling or heating specifically not required. This procedure leads to the Broadening the half-peak width of the most intense diffraction line of the parent magnesium compound. The degree of broadening is at least, for example 1.05 times the half-peak width of the magnesium compound before pulverization. The structure of the product obtained is not fully known, but its composition changes by washing with an inert diluent etc. not.

In this reaction, the electron donor (2) is in one Amount of preferably about 0.1 to 2 moles, in particular approx. 0.05 to 1 mol per magnesium atom of the halogen-free organic  Magnesium compound (1) used.

The reaction of the titanium halide compound (3) with a solid Product of the reaction between the compound (1) and the compound (2) can be present in the presence or absence of an inert Diluent are carried out. Preferably the product in the absence of mechanical pulverization brought into contact with the compound (3) in the liquid phase. To contact the titanium halide compound (3) in the liquid phase a liquid titanium compound, such as titanium tetrahalide, used alone or the titanium halide compound is in an inert solvent such as hexane, Heptane or kerosene, dissolved before contact.

There is no particular limitation on the Contacting temperature, however, is preferred contacting at about 0 to about 200 ° C for at least about 0.5 hours. After the reaction, it will Product preferably with an inert solvent, for example a hydrocarbon (e.g. hexane, heptane or Kerosene), washed and then used for the polymerization.

According to the solid titanium composition (A), the was prepared in the above manner, and a halogen / titanium molar ratio from at least 6, preferably 6 to 50, and an electron donor / titanium molar ratio of at least 0.1, preferably 0.1 to 1, as one component of the catalyst used. Usually the halogen in the solid titanium composition (A) the halogen in the titanium halogen compound (3).

The weight ratio of magnesium / titanium / halogen / electron donor in a typical solid titanium composition (A) is 1 / 0.05 to 0.5 / 1 to 5 / 0.1 to 1.5, although according to the type of halogen or electron donor varies.  

The composition changes when washed with hexane Room temperature essentially not. Generally possesses the titanium composition (A) has a specific surface area of at least 10 m² / g, preferably at least 20 m² / g.

The catalyst used in the process according to the invention consists of the magnesium-containing solid titanium composition (A) and the organoaluminum compound one Metal of groups I to III of the periodic table (B).

The organoaluminum compound (B) is selected from alkyl aluminum compounds, Alkenyl aluminum compounds, alkyl aluminum alcoholates, Alkyl aluminum hydrides and alkyl aluminum halides.

The alkyl groups can be C₁ to C₁₃ alkyl groups. The alkenyl groups can be C₂ to C₁₃ alkenyl groups. The alkoxy groups can be C₁ to C₁₃ alkoxy groups. Specific examples of organoaluminum compounds (B) include trialkyl or trialkenyl aluminum compounds such as Al (C₂H₅) ₃, Al (CH₃) ₃, Al (C₃H₇) ₃, Al (C₄H₉) ₃ or Al (C₁₂H₂₅) ₃; Alkyl aluminum compounds in which the majority of the aluminum atoms are bonded via an oxygen or nitrogen atom, such as (C₂H₅) ₂AlOAl (C₂H₅) ₂, (C₄H₉) ₂AlOAl (C₄H₉) ₂ or Dialkylaluminium hydrides such as (C₂H₅) ₂AlH or (C₄H₉) ₂AlH; Dialkylaluminium halides, such as (C₂H₅) ₂AlCl, (C₂H₅) ₂AlJ or (C₄H₉) ₂AlCl; and dialkyl aluminum alcoholates or phenolates, such as (C₂H₅) ₂Al (OC₂H₅) or (C₂H₅) ₂Al (OC₆H₅). The trialkyl aluminum compounds are most preferred.

In the process according to the invention, at least one olefin  polymerized or copolymerized with at least 3 carbon atoms or it is with up to 10 mole percent ethylene and / or a diolefin copolymerized in the presence of a catalyst, from (A) the magnesium-containing solid Titanium composition and (B) the organoaluminum compound.

Examples of olefins with at least 3 carbon atoms are Propylene, 1-butene and 4-methyl-1-pentene- Examples of this Diolefins are conjugated dienes such as butadiene and cyclopentadiene, and non-conjugated dienes such as 1,4-hexadiene, dicyclopentadiene and ethylidene norbornene.

The polymerization can be in the liquid phase or in the gas phase be performed. It will be in the liquid phase carried out, an inert solvent such as hexane, Heptane or kerosene, can be used as the reaction medium however, the olefin itself is used as the reaction medium can be.

In the case of liquid phase polymerization, it is preferred that Amount of the solid catalyst component (A) is 0.001 to 0.5 Millimoles, calculated as titanium atom per liter of liquid phase, and the amount of the organoaluminum compound (B) at 0.1 up to 50 millimoles, calculated as aluminum atom per liter of liquid Hold phase.

If the polymerization is carried out in the gas phase, so becomes the solid titanium catalyst component (A) in an amount from preferably 0.001 to 1.0 millimoles / liter gas phase, more preferably 0.01 to 0.5 millimoles / liter gas phase, calculated used as a titanium atom. The organoaluminum compound (B) is preferably used in an amount of 0.01 to 50 millimoles / Liter of gas phase, calculated as aluminum atom.

The polymerization according to the inventive method can in the presence of a molecular weight control agent such as  Hydrogen. For setting the stereo regularity the reaction is in simultaneous presence from an organic carboxylic acid ester carried out. The usage from aromatic carboxylic acid esters are preferred.

Such aromatic carboxylic acid esters can be selected among those that are useful in manufacturing the magnesium-containing solid titanium catalyst component, preferably among the benzoic acid esters and benzoic acid esters, which is ring-substituted by an electron donor substituent are. Examples of such esters are benzoic acid esters, unsubstituted or substituted by a substituent, selected from alkyl groups with 1 to 4 carbon atoms, Alkoxy groups with 1 to 4 carbon atoms, a hydroxy group and an amino group selected from C₁- to C₁₈ saturated or unsaturated aliphatic primary Alcohol esters, C₃- to C₈-saturated or unsaturated alicyclic Alcohol esters and C₆ to C₁₀ phenol esters. they include benzoic acid esters, toluic acid esters, anisic acid esters, Phthalic diesters, terephthalic diesters, hydroxybenzoic acid esters and aminobenzoic acid esters. Preferred esters are C₁ to C₄ alkyl esters of p-toluic acid, such as methyl p-toluate and ethyl p-toluate.

These aromatic carboxylic acid esters can be in the form of a Addition reaction product with the organoaluminum compound (B) be used.

The amount of connection to adjust the stereo regularity is about 0.001 to 10 moles, preferably about 0.01 to 2 moles, especially about 0.1 to 1 mole, per mole of organometallic Compound (B).  

The polymerization temperature is preferably about 20 up to 200 ° C, especially about 50 to 180 ° C. The polymerization pressure is preferably from normal atmospheric pressure to approx. 49 bar, in particular approx. 1.95 to 19.6 bar.

The polymerization can be carried out by a batch process, a semi-continuous process or a continuous one Procedures are carried out. It is also possible, them in two or more stages under different conditions perform.

The following examples illustrate the invention in greater detail.

example 1

A round-necked flask was charged with 0.3 mol of an im Commercially available Mg (OCH₃) ₂ and brought 0.6 moles of phenol, diluted with 200 ml of hexane into the flask. With stirring you raised the temperature and removed it because of the Distillate obtained by distillation under Achievement of Mg (OCc₆H₅) ₂. The half-peak width of a diffraction line, which is the maximum intensity of its x-ray spectrum showed was 0.49 °.

A ball mill cylinder with a capacity was charged of 800 ml and an inner diameter of 100 mm made of stainless Steel made with 100 stainless steel balls each contained a diameter of 15 mm, in one Nitrogen atmosphere with 0.2 mol of Mg (OC₆H₅) ₂ and 0.033 mol Ethyl benzoate as electron donor and brought during 100 Hours in contact with each other at 125 revolutions per minute, a halogen-free organic magnesium compound to obtain. The half-peak width of a diffraction line, the the maximum intensity of an X-ray spectrum of the obtained solid product showed was 5.83 °.

The solid product obtained was in 200 ml of titanium tetrachloride  suspended and reacted for 2 hours at 80 ° C. with stirring. After the reaction, the solid portion was filtered collected and washed well with hexane to make a titanium containing solid titanium composition to give the 3.5 Weight percent titanium, 54 weight percent chlorine, 18.0 weight percent Magnesium and 11.1 weight percent ethyl benzoate contained.

A 2 liter autoclave was charged with 750 ml of hexane, from which all oxygen and moisture have been removed were. Propylene was introduced into the autoclave and one charged in an atmosphere of propylene at 40 ° C 5.0 millimoles of triethyl aluminum and 1.59 millimoles of methyl-p- toluate. 5 minutes later, the autoclave was charged 0.03 millimoles, calculated as the titanium atom, of those containing titanium solid catalyst composition. The system was heated to 60 ° C and increased the total pressure inside the autoclave to 6.86 bar with propylene. Then you headed 350 ml of hydrogen and polymerized propylene during 4 hours. After the polymerization, solid components were separated by filtration and received 244 g of polypropylene in Form of a white powder. The polymer had an extraction residue in boiling n-heptane of 96.2%, a bulk density of 0.36 and a melt index of 4.9. The narrowing the liquid portion gave 12.1 g of a solvent-soluble Polymers.

Examples 2 to 6

A titanium catalyst component was prepared in the same way as in Example 1 except that the organic magnesium compounds shown in Table I instead of Mg (OC₆H₅) ₂ used. It was polymerized under Use of the titanium catalyst component obtained in the same way as in Example 1 propylene. The results are given in Table I.  

Table I

Comparative Example 1

They suspended directly in 200 ml of TiCl₄ without prior treatment with an electron donor and with stirring, these components were placed at 80 ° C. for 2 hours. After the reaction, the solid portion was collected by filtration, washed with hexane, and dried. The obtained titanium-containing solid catalyst component contained 4.0% by weight of titanium, 59% by weight of chlorine and 18.0% by weight of magnesium.

Using the obtained titanium catalyst component polymerized propylene under the same conditions as in Example 1. Only 15.8 polypropylene was obtained in the form of a white powder and 1.7 g of a solvent-soluble Polymers. The powdery polymer had an extraction residue in boiling n-heptane of 90.8%.

Examples 7 to 10

Propylene was polymerized in the same manner as in Example 1 except that the ones synthesized in Example 2 were synthesized Titanium catalyst component used and the polymerization in the presence of everyone specified organic acid ester performed. The results are shown in Table II.  

Table II

Examples 11 to 19

A titanium-containing catalyst component was prepared in the same manner as in Example 1, except that and used any of the electron donors listed in Table III. Using the obtained titanium-containing catalyst component, propylene was polymerized under the same conditions as in Example 1. The results are shown in Table III.

Table III

Example 20

A 2 liter autoclave was charged with 750 ml of hexane, from which there is sufficient oxygen and moisture had been removed. You got into an atmosphere of Propylene at 40 ° C, 5.0 millimoles of triisobutyl aluminum and 1.67 Millimoles of methyl p-toluate. 5 minutes later the autoclave is 0.03 millimole, calculated as titanium atom, the titanium-containing solid catalyst component, which was obtained in Example 1. Immediately brought to it 100 ml of hydrogen were then added and the system was maintained a propylene pressure of 1.47 bar for 5 minutes. Man heated the system to 60 ° C and released the pressure with a gaseous propylene / ethylene mixture (molar ratio of 96/4) rise to 2.45 bar. Propylene was copolymerized with ethylene for 3 hours. Filtration of the solid Ingredients after polymerization gave 237 g propylene / Ethylene copolymer. The ethylene content of the copolymer was determined from its ethylene content was 4.1 mole percent. The Copolymers had a bulk density of 0.29 and one Melt index of 0.86.

Example 21

A glass ampoule was charged at 0.03 millimoles, calculated as the titanium atom, the titanium-containing obtained in Example 1 solid catalyst component and then brought in a 2 liter autoclave. The ampoule was arranged so that they start stirring the polymerization system would break. The inside of the autoclave was purged completely with nitrogen and 50 ml of hexane were added, 3 millimoles of triethyl aluminum and 1 millimole of methyl p-toluate to. Then 400 g of butene-1 were further introduced. One heated up the polymerization system to 40 ° C and started stirring, whereupon the glass ampoule broke and the polymerization started. The pressure of the polymerization system was at this Time 1.96 to 2.94 bar. 30 minutes later they relaxed  to end the polymerization. 215 g were obtained white powdered polybutene, which has an extraction residue in boiling diethyl ether of 92.1%.

Claims (4)

1. A process for the preparation of a polymer or copolymer of an olefin having at least 3 carbon atoms, which comprises polymerizing or copolymerizing at least one olefin having at least 3 carbon atoms or copolymerizing the olefin with up to 10 mol% of ethylene and / or a diolefin in the presence of a catalyst, consisting of (A) a magnesium-containing solid titanium composition, which is a reaction product of (1) a magnesium compound, (2) an electron donor and (3) a tetravalent titanium halogen compound of the formula Ti (OR ′) _g X₄ _{- g} , wherein R ′ is a Alkyl group having 1 to 8 carbon atoms, X represents a halogen atom and g represents a number of 0 g <4, and (B) comprises an organoaluminium compound selected from alkylaluminum compounds, alkenylaluminium compounds, alkylaluminium alcoholates, alkylaluminum hydrides and alkylaluminum halides, characterized in that to polymerization or copolym carried out in the presence of a catalyst which is formed by adding an organic acid ester to components (A) and (B) and in which component (A) is a reaction product which is formed by firstly acting as magnesium compound (1) a halogen-free organic magnesium compound of the formula Mg (OR) _n (OR ′) ₂ _{- n} wherein R and R ′, which may be the same or different, each have an alkyl group having 1 to 16 carbon atoms, which may be substituted by a member selected from the group Group consisting of phenyl, phenyl substituted by C₁ to C₅ alkyl and phenyl substituted by C₁ to C₄ alkoxy or a phenyl or naphthyl group, each of which may be substituted by a member selected from the group consisting of C₁ - to C₅-alkyl and C₁- to C₄-alkoxy, and n is a number from 0 to 2, where at least one of the radicals R and R 'is a phenyl or naphthyl group, which can each be substituted by a member, selected au s of the group consisting of C₁ to C Alkyl alkyl and C₁ to C₄ alkoxy, or an alkyl group having 1 to 16 carbon atoms, which is a radical selected from phenyl and by C₁ to C₅ alkyl or C₁ to C₄ -Alkoxy substituted phenyl, is substituted, with an organic acid ester optionally together with n-butyl ether, N, N, N ', N'-tetramethylethylenediamine or benzaldehyde as electron donor (2) by mechanical pulverization and then the product obtained in contact with the titanium compound (3) in the absence of mechanical pulverization, component (A) having a halogen / titanium molar ratio of at least 6 and an electron donor / titanium molar ratio of at least 0.1. 2. The method according to claim 1, characterized in that the organic acid ester representing the electron donor (2) a member is selected from the group consisting of from (a) esters formed between aromatic carboxylic acids with 7 to 18 carbon atoms and alcohols or phenols, selected from saturated or unsaturated aliphatic primary alcohols with 1 to 18 carbon atoms, saturated or unsaturated alicyclic alcohols with 3 to 8 Carbon atoms, phenols with 6 to 10 carbon atoms and C₁ to C₄ saturated or unsaturated aliphatic primary alcohols attached to the ring carbon atoms of a C₃- to C₁₀ aliphatic or aromatic ring bound and (b) aromatic lactones having 8 to 12 carbon atoms.   3. The method according to claim 1, characterized in that the organic added to components (A) and (B) Acid ester is a member selected from the group consisting of from esters, formed between benzoic acid, unsubstituted or substituted by a substituent, selected from the group consisting of alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, a hydroxyl group and an amino group and a member selected from the group consisting of C₁ to C₁₈ saturated or unsaturated aliphatic primary alcohols, C₃- to C₈-saturated or unsaturated alicyclic alcohols and C₆ to C₁₀ phenols. 4. The method according to claim 1, characterized in that polymerization or copolymerization at one temperature from 20 to 200 ° C under atmospheric pressure 49 bar is carried out.