DE2755529C2 - - Google Patents

Description

The invention relates to a method for producing a Polyolefins according to the preamble of claim 1.

Such a method is already known from JP-OS 75 44 273 known. The catalyst system used from (A) one titanium-containing component and (B) an organoaluminum Compound, and (C) an electron donor, its component (A) by reacting Mg (OH) Cl with a carboxylic acid ester and TiCl₄ has been obtained, however, regarding its catalytic activity or in terms of achievable isotactic index in the manufacture of stereoregular polyolefins unsatisfactory.

According to the older patent DE-PS 27 24 971, a process for the homopolymerization of α-olefins having 3 to 6 carbon atoms and for their copolymerization with one another or with up to 10 mol% of ethylene and / or a diolefin is carried out in the presence of a catalyst system, the Magnesium-containing solid titanium catalyst component (A) has been prepared using a halogen-containing magnesium compound of the formula Mg (OR) _n X _2-n , which magnesium compound can be obtained by reacting a Gringard compound of the formula R′′MgX, where R ′ 'Represents an alkyl group or an aryl group and X is a halogen atom with, inter alia, an aryl alcohol or an arylalkyl alcohol. In the process according to DE-PS 27 24 971, the halogen-containing magnesium compound is brought into contact with an organic acid ester without mechanical pulverization and the resulting product is brought into contact with a tetravalent titanium compound.

Furthermore, DE-OS 20 00 566 describes a process for the polymerization of, in particular, ethylene, but also propylene, using a catalyst system composed of an organoaluminum compound and a solid component containing magnesium and titanium, which can be obtained by reacting magnesium compounds of the formula X _2-n Mg (OR ) _n , in which X represents a halide radical and R represents an alkyl or aryl group and n is 1 or 2, has been obtained with titanium (IV) halides or alkoxyhalides.

Furthermore, e.g. B. proposed for the polymerization of α-olefins to use a catalytic solid component which was made by reacting a titanium halide on a carrier material made of a divalent metal hydroxychloride, which in turn was produced under Use of a divalent metal chloride and an oxide or Hydroxides (Japanese Patent No. 13 050/1968 and 5 547/1969). If However, if these catalysts are used, they are stereo specific properties of the polymers formed, in particular in the case of propylene or butene-1, quite low, so this Process is not suitable for industrial implementation.

It is therefore an object of the present invention to provide a method for the production of a polyolefin with excellent stereospecific properties using a To create a catalyst with high catalytic activity. It is also an object of the invention to provide a method for Manufacture of a polyolefin with an isotactic index create, which because of the high catalyst activity without Separation of the catalyst residue can be used.

This object is achieved according to the invention in claim 1 defined procedures solved.  

Preferred configurations of the method according to the invention are characterized in the subclaims.

In the process according to the invention, polyolefin is also obtained excellent stereospecific properties. Since the Stereospecificity of the polyolefin obtained can be high Separation of an amorphous polymer (atactic polymer) from the formed polyolefin. The invention used titanium-containing catalyst solid component has a very high polymerization activity. Accordingly, the level of Removal of the catalyst residue from the formed Also avoid polyolefin.

The titanium-containing solid Catalyst component can be made by contact ren of

• (a) water and / or a hydroxy compound (hereinafter referred to as OH compound),
• (b) a Grignard reagent,
• (c) a titanium tetrahalide and
• (d) a specific electron donor.

These connections will be explained below.

(a) OH compound

You can only use water in liquid form. It is however preferred the water in an ether solvent, such as diethyl ether, dibutyl ether and tetrahydrofuran. Water can also be used in the form of steam. In this case you can use an inert gas such as Dilute nitrogen or argon.  

One can use a hydroxy compound with preferably the following general formula

R (OH) _n

insert, where n is an integer from 1-6 and R is one Hydrocarbon residue, preferably a hydrocarbon radical with 1 to 35 carbon atoms, or wherein R a remainder of the formula

means, where Z is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms and 1 an integer from 1 to 30 mean.

Suitable hydroxy compounds are monohydric alcohols and polyhydric alcohols and phenols. As monohydric alcohols alkyl alcohols are possible, such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, octyl  alcohol, 2-ethylhexyl alcohol, nonyl alcohol and decyl alcohol; Aralkyl alcohols such as benzyl alcohol; alicyclic alcohols, such as cyclohexyl alcohol. Coming as polyhydric alcohols Alkylene glycols in question, such as ethylene glycol, propylene glycol, and butylene glycol; Polyalkylene glycols, such as polyethylene glycol and polypropylene glycol; Glycerin; Pentaerythritol etc. Phenol, cresol, pyrocatechol or resorcinol come as phenols in question.

In addition to the compounds of the formula R (OH) _n , hydroxyl-containing hydrocarbon polymers with a molecular weight above 500, for. B. polyvinyl alcohol, hydrolyzed ethylene-vinyl acetate copolymers. These compounds can be used with or without dilution with a diluent. Suitable diluents are aromatic hydrocarbons, such as benzene and toluene; saturated aliphatic hydrocarbons such as n-heptane, n-hexane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and ethers such as diethyl ether and dibutyl ether. It is preferred to use water, monohydric alcohols and phenols and especially water and alkyl alcohols.

(b) Grignard reagent

One can Grignard reagents preferably with the following general formula

R¹MgX

use, where R¹ is a hydrocarbon radical and X a Halogen atom mean. Suitable hydrocarbon residues R¹ are alkyl, aryl and aralkyl groups with up to 20 preferably up to 10 carbon atoms and in particular Alkyl groups, such as methyl, ethyl, propyl, butyl, amyl and hexyl groups, as well as aryl groups such as phenyl groups; Aralkyl groups, e.g. B. benzyl groups. Suitable halogen atoms X are chlorine, bromine and iodine.  

The Grignard reagent is usually in the form of an ethereal Solution or an ether adduct used. Suitable ether are diethyl ether, dibutyl ether, dihexyl ether, dioctyl ether, Tetrahydrofuran, tetrahydropyran, dioxane, diethyl thioether etc. Suitable solvents, which in addition to the ether solvents can be used are aromatic Hydrocarbons such as benzene and toluene; heterocyclic Compounds like pyridine and thiophene.

(c) Titanium tetrahalides

The titanium tetrahalides include titanium tetrachloride, Titanium tetrabromide, titanium tetraiodide, etc. It is preferred Use titanium tetrachloride.

(d) electron donors

Suitable electron donors are amines, carboxamides, Phosphines, phosphine oxides, phosphoric acid esters, phosphorous acid esters, phosphoric acid amides, ketones and carboxylic acid esters. One or more electron donors can be used. The carboxylic acid esters have a hydrocarbon residue, which by an amino group or an alkoxy group may be substituted so that it is an amino acid ester can act.

Suitable electron donors are amines, such as tetramethyl ethylenediamine, tetraethylethylenediamine; Carboxamides, such as benzoic acid amide, acetamide; Phosphines, such as tris (nonyl phenyl-) phosphine, triphenylphosphine; Phosphine oxides, such as triethylphosphine oxide, triphenylphosphine oxide; Phosphorus acid esters such as triethyl phosphate, tributyl phosphate, etc .; Phosphorous acid esters, such as triphenyl phosphite, tris (nonylphenyl) phosphite; Phosphoric acid amides such as hexamethylphosphorus acid triamide; Carboxylic acid esters, such as methyl benzoate, Ethyl benzoate, propyl benzoate, butyl benzoate, phenyl benzoate, Methyl p-methoxybenzoate, ethyl p-methoxybenzoate, propyl p- methoxybenzoate, methyl p-methylbenzoate, ethyl p-methylbenzoate,  Butyl-m-methoxybenzoate, phenyl-o-methoxybenzoate, methyl-p- ethoxybenzoate, ethyl p-ethoxybenzoate, butyl p-methoxybenzoate, Methyl p-ethylbenzoate, ethyl p-ethylbenzoate, butyl p-ethoxy benzoate, methyl p-butoxybenzoate, ethyl p-butoxybenzoate, Butyl p-butoxybenzoate, phenylacetate, phenylpropionate, Ethyl acrylate, methyl methacrylate, ethyl crotonate, propyl crotonate, butyl crotonate, ethyl cinnamate, propyl cinnamate, Butylcinnamate, dimethylglycine ethyl ester, dimethylglycine propyl esters, dimethylglycine butyl ester, diphenylglycine ethyl ester, Diphenylglycine propyl ester, diphenylglycine butyl ester, Ethyl p-dimethylaminobenzoate; Ketones, such as acetone, Methyl ethyl ketone, benzophenone, acetophenone.

It is preferred to use carboxylic acid esters, and in particular their ethyl benzoate, methyl p-methyl benzoate and ethyl p-methyl benzoate.

The electron donors can be in pure form or with diluted with a diluent. Suitable Diluents are aromatic hydrocarbons, such as Benzene and toluene; saturated aliphatic hydrocarbons, such as n-pentane, n-hexane, n-heptane, n-octane, n-dodecane and liquid paraffin; alicyclic hydrocarbons such as Cyclohexane and methylcyclohexane; Ether, like diethyl ether, Dibtuyl ether, tetrahydrofuran and tetrahydropyran.

In the method according to the invention, the four components ten (a), (b), (c) and (d) in an appropriate Order contacted with each other, taking the titanium contains solid component. Preferably the Component (c), namely the titanium tetrahalide, the Added reaction mixture, which was obtained by Reaction of the OH compound (a) with the Grignard reagent (b) or the reaction mixture obtained by Reaction of the OH compound (a) with the Grignard reagent (b) and the electron donor (d). It is therefore preferred that React OH compound (a) with the Grignard reagent (b), before contacting the titanium tetrahalide (c) makes.  

The electron donor (d) is preferably the reaction gene mixed added, which by reaction of the OH compound (a) with the Grignard reagent (b) or by Reaction of the OH compound (a) with the Grignard reagent (b) and the titanium tetrahalide (c). The following are some typical examples of the order of contacting the Components (a), (b), (c) and (d) indicated:

• 1) The OH compound (a) is with the Grignard reagent (b) contacted and in the presence of the electron donor (d) implemented and then the titanium tetrahalide (c) to the reaction mixture.
• 2) The OH compound (a) is with the Grignard reagent (b) contacted and implemented and then the electron donor (d) added and then the titanium tetra is added halide (c) to the reaction mixture.
• 3) The OH compound (a) is with the Grignard reagent (b) contacted and implemented and then you give the titanium tetrahalide (c) to the reaction mixture and then added finally add the electron donor (d).
• 4) This by contacting the OH compound (a) with the Grignard reagent (b) is obtained simultaneously with the titanium tetrahalide (c) and the electron donor (d) treated.

Methods (2) and (4) are preferred. If you go through Reaction of the OH compound (a) with the Grignard reagent (b) obtain a compound of the following formula

Mg (OR⁸) XnE,

where R⁸ is a hydrogen atom or a hydrocarbon radical means; where X is a halogen atom and E is a Ether molecule means and where n is a number from 0.4 to 25 means and if you go according to the procedures (1) to (4)  works, you get a catalyst with an elevated catalytic activity.

In the formula, R⁸ represents a hydrogen atom or a Hydrocarbon residue with up to 20 carbon atoms, e.g. B. an alkyl group, such as methyl, ethyl, propyl, butyl, amyl, Hexyl, octyl, nonyl or decyl; an aryl group such as phenyl, or an arylkyl group such as benzyl; X means Cl, Br or J and in particular Cl; E means an ether, a poly ether, a glycol ether or dioxane of the formula R²-O-R³, where R² and R³ each have a hydrocarbon residue 1 to 30 carbon atoms and where R² and R³ can be connected to each other and form a ring can. Examples include dialkyl ethers such as Diethyl ether, di-n-butyl ether, di-iso-propyl ether, Di-n-butyl ether, di-iso-butyl ether, di-t-butyl ether, Di-n-amyl ether, di-iso-amyl ether, di-n-hexyl ether and Di-n-octyl ether; Diaryl ethers such as diphenyl ether and di benzyl ether; Diaralkyl ether; Alkyl aryl ethers such as phenethole and anisole; Alkylcycloalkyl ethers such as methylcyclohexyl ether; Alkylaralkyl ethers, such as methylbenzyl ether; Polyether, like Polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, Polyethylene oxide and polypropylene oxide; Glycol ether like Ethylene glycol dimethyl ether and ethylene glycol diethyl ether; Propylene oxide; cyclic ethers, such as tetrahydrofuran, dioxane, 4-methyl-1,3-dioxane and tetrahydropyran, especially tetra hydrofuran; n means a number from 0.4 to 10 and in particular special from 0.4 to 5.

The catalysts of extremely high activity can be used with us extension of the compound mentioned can be obtained.

The compounds are made by adding a stoichiometric amount or excess ether a reaction product obtained by Um setting component (a) with component (b) and Um setting them at room temperature up to 100 ° C during 0.1 to 10 h and separation of the ether excess in  suitably, e.g. B. by heating, distilling under reduced pressure, extracting or washing. It is preferred an inert hydrocarbon solution in this reaction tel, such as hexane or heptane.

The connections can also be made by Preparation of an ether solution or an ether adduct Compound (b) and addition of compound (a) to the ether solution or to the ether adduct or by adding the ether solution or the ether adduct to compound (a), wherein in both Cases working near room temperature and afterwards at 50 to 200 ° C and preferably 50 to 150 ° C during 0.1 to 10 hours. After that, the ether excess is through Filter or evaporate separated from the reaction mixture. The amount of ether in the starting material is more than 0.3 times the molar amount based on the Grignard reagent. The amount of the compound (a) is in the range of 0.01 to 2 and preferably 0.5 to 1.5 and especially 0.7 to 1.3 as Molar ratio of the OH compound to the alkyl group in the Grignard reagent. When the ether excess is separated after the reaction the molar ratio of the complexed ether is to the magnesium at least 0.4, so that a separation of the complexed ether is prevented. So if the surplus of tetrahydrofuran is removed by evaporation, so this separation should be close to room temperature respectively.

The following are suitable methods of contacting of the components to form the titanium-containing catalyst solid component with regard to cases (1) to (4) explained.

(1) The OH compound (a) and the Grignard reagent (b) the electron donor (d) at -50 to 100 ° C and preferably -30 ° C to room temperature added. The Mixture is at 20 to 200 ° C and preferably 20 to 150 ° C and especially 20 to 100 ° C heated and during  0.1 to 10 h implemented. It is preferred to react the Grignard reagent with the electron donor before the reaction of the Grignard reagent with the OH compound. Accordingly, it is preferred to use the OH compound and the Grignard reagent to mix at low temperature if the Electron donor easily reacts with the Grignard reagent, so that the reaction of the electron donor with the Grignard reagent is absent and only the reaction of the OH compound with the Grignard reagent.

The reaction mixture can be used without separation. However, it is preferred to use the reaction product as a solid by decanting, filtering or evaporating the solution by means of separation from the reaction mixture. If the separation of the reaction product by decanting or filtering takes place, the solid obtained with an inert Washed hydrocarbon solvent and the obtained Solids are then added to the titanium tetrahalide and the mixture is at 60 to 350 ° C for more than 1 min and preferably treated for 0.1 to 10 hours. After Treatment is the solid catalyst component from Separated reaction mixture, preferably at 50 to 140 ° C. and washed with an inert hydrocarbon solvent. Suitable inert hydrocarbon solvents are aromatic hydrocarbons such as benzene, toluene; saturated aliphatic hydrocarbons, such as n-pentane, n-hexane, n-heptane, n-octane, n-dodecane, liquid paraffin; alicyclic Hydrocarbons such as cyclohexane, methylcyclohexane.

(2) The Grignard reagent (b) becomes the OH compound (a) given or vice versa, at -50 to 100 ° C and preferably at -20 ° C to near room temperature. Then the reaction at 20 to 200 ° C and preferred wise at 20 to 150 ° C and especially at 20 to 100 ° C carried out for 0.1 to 10 h. The reaction obtained mixture or that of the reaction mixture by filtration, Decant or evaporate the solvent Solid is with the electron donor (d) or one  Solution of the same mixed. The mixture is preferred at 60 to 200 ° C for more than 0.1 h and preferably Treated 0.1 to 10 h and especially 1 to 5 h.

If you use toluene, xylene or kerosene as a diluent used for the electron donor in this process, this step is particularly convenient because you can can work at the boiling point of the solvent. It is further possible to add the product at this temperature of the electron donor and treat the dilution distill off to dry the product. Then the product with the titanium tetrahalide (c) treated further according to method (1). The conditions for treatment with the titanium tetrahalide and for separating and washing the product following the procedure (1).

(3) The reaction of the OH compound with the Grignard reagent is carried out according to method (2). That he held product is treated with the titanium tetrahalide, namely after the method (1) and then the loading act with the electron donor according to method (2).

(4) According to process (2), the OH compound (a) contacted with the Grignard reagent (b) and then gives the titanium tetrahalide (c) and the electron donor (d) becomes the product and the mixture simultaneously treated further according to method (1). In this case the complex can be formed beforehand by contacting of the titanium tetrahalide (c) with the electron donor (d).

One can in the preparation of the catalyst component a treatment with a halo at a desired level Make genizing agent (s), e.g. B. with a halogen containing silicon compound. The halogenating agent (s) is usually added to a product made by Reaction of the OH compound (a) with the Grignard reagent (b) and possibly the electron donor (d) was obtained  and the mixture is at a temperature below Zer setting temperature of the halogenating agent during min treated for at least 0.1 h and preferably for 0.1 to 1 h.

The halogenating agent is usually a chlorinating agent, a brominating agent or a Iodine. It can all known halogenation means are used. Suitable halogenating agents are halogens such as chlorine, bromine and iodine; Hydrogen halide, such as hydrogen chloride, hydrogen bromide or hydrogen iodide; Haloalkanes, such as carbon tetrachloride, chloroform, dichloro ethane, tetrachloroethane, methylene chloride, trichlorethylene, Methyl chloride, ethyl chloride, n-butyl chloride, n-octyl chloride, non-metallic oxyhalides, such as sulfuryl chloride, thionyl chloride, nitrosyl chloride, phosphorus oxychloride, phosgene; non-metallic halides, such as phosphorus trichloride, Phosphorus pentachloride, halogen-containing silicon compounds; Metal halides or ammonium halides, such as aluminum halides, ammonium halides, except titanium tetrahalides. It is preferred to use chlorination as the halogenating agent medium to use. It is particularly preferred to use one halogen-like silicon compound of the formula

R _n ⁴SiX _4-n

where R⁴ is a hydrocarbon residue with 1 to 6 carbons atoms or a halogenated hydrocarbon residue and where X is a halogen atom and where n is Be drawing 0 ≦ n ≦ 3 applies. Typically acts the radical R⁴ is an alkyl group, a cycloalkyl group or an aryl group. X means chlorine, bromine, iodine or fluorine. In the case of n = 0, it is tetra halosilanes of the formula

SiX₄.

The halogen atoms can be the same or different.  Suitable tetrahalosilanes are tetrachlorosilane, tetra bromosilane, tetraiodosilane, tetrafluorosilane, trichlorobromosilane, Trichloroiodosilane, trichlorofluorosilane, dichlorodibromosilane, Dichlorododosilane, dichlorodifluorosilane, chlorotribromosilane, Chlorotrÿodsilan, Chlortrifluorsilan, Bromtrÿodsilan, Bromotrifluorosilane, dibromododosilane, dibromodifluorosilane, Tribromoiodosilane, tribromofluorosilane, iodotrifluorosilane, Dÿoddifluorsilan and Trÿodfluorsilan.

It is preferred to use tetrachlorosilane, tetrabromosilane, Trichlorobromosilane, dichlorodibromosilane or chlorotibromosilane to use. The use of tetrachlorosilane is optimal.

If n = 1, the compounds have the formula

R⁴SiX₃.

Suitable compounds of this formula are
Alkyltrichlorosilanes with saturated C _1-16 -alkyl groups, such as methyltrichlorosilane, ethyltrichlorosilane, n- and i-propyl trichlorosilanes, n-, i- and tert-butyltrichlorosilanes, n- and i-amyltrichlorosilanes, n-hexyltrichlorsylanilane, n-hexane Octyltrichlorosilane, n-dodecyltrichlorosilane, n-tetradecyltrichlorosilane, n-hexadecyltrichlorosilane; unsaturated alkyltrichlorosilanes with unsaturated C _1-4 alkyl groups, such as vinyltrichlorosilane, isobutenyltrichlorosilane; Haloalkyltrichlorosilanes or unsaturated haloalkyl trichlorosilanes, such as chloromethyltrichlorosilane, dichloromethyl trichlorosilane, trichloromethyltrichlorosilane, (2-chloroethyl) trichlorosilane, (1,2-dibromethyl) trichlorosilane, trifluoromethyl-trichlorosilane (trichlorosilane); saturated and unsaturated cycloalkyltrichlorosilanes such as cyclopropyltrichlorosilane, cyclopentyltrichlorosilane, cyclohexenyltrichlorosilane and 3-cyclohexenyltrichlorosilane; Aryl or aralkyltrichlorosilanes, such as phenyltrichlorosilane, 2-, 3- or 4-tolyltrichlorosilanes and benzyltrichlorosilane; mixed trihalosilanes with saturated alkyl groups or saturated haloalkyl groups such as Methyldifluorchlorsilan, Methylfluordichlorsilan, Äthyldifluorchlorsilan, Äthylfluor dichlorosilane, n- and i-Propyldifluorchlorsilane, n-butyl difluorchlorsilan, n-Butylfluordichlorsilan, chlorosilane Phenyldifluor, Methyldichlorbromsilan, Äthyldichlorbromsilan, Methyldichlorjodsilan and (trifluoromethyl) silane -difluorbrom .

If n = 2, the compounds have the formula

R₂⁴SiX₂.

Suitable compounds of this formula are dialkyldihalosilanes, such as dimethyldichlorosilane, diethyldichlorosilane, di-n- and i-propyldichlorosilanes, di-n-, i- and tert-butyldichlorosilanes, Di-n- and i-amyldichlorosilanes, di-n-hexyldichlorosilane, Di-n-heptyldichlorosilane and di-n-octyldichlorosilane; Dicycloalkyldihalosilanes, such as dicyclopentyldichlorosilane, Dicyclhexyldibromosilane, dicyclohexyldodosilane, Dicyclohexyldifluorosilane; Diaryl or diaralkyl dihalogen silane, such as diphenyldichlorosilane, di-2-, -3- or -4-tolyl dichlorosilane and dibenzyldichlorosilane.

If n = 3, it is a compound of the formula

R₃⁴SiX.

Suitable compounds of this formula are trialkyl halides silanes, such as trimethylchlorosilane, triethylchlorosilane, Tri (n- and i-propyl) chlorosilanes, tri (n- and i-butyl) - chlorosilanes, tri (n-hexyl) chlorosilane, tri (n-heptyl) chlorine silane, tri (n-octyl) chlorosilane, dimethyl (ethyl) chlorosilane, Methyl (diethyl) chlorosilane; Triaryl or triaralkyl halosilanes, such as triphenylchlorosilane, tri (2-, 3- or 4-tolyl) chlorosilane and tribenzylchlorosilane.

It is preferred to use silicon tetrachloride and mono-, di- or  Use tri-chlorosilanes in which R⁴ in the formula is a methyl, ethyl or phenyl group.

It is possible to use several halogenating agents.

The treatment with the halogenating agent can be carried out in Presence of an inert solvent or an inert one Perform gas. Suitable inert solvents are aromatic hydrocarbons such as benzene and toluene and liquid saturated aliphatic hydrocarbons, such as n-pentane, n-hexane, n-heptane, n-octane, n-dodecane, liquid Paraffin; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Nitrogen comes as inert gases and argon in question.

The amounts of the components in the process according to the invention are chosen in the following areas. The molar ratio the OH connection to the alkyl group is in the Grignard reagent in the range of 0.01 to 2 and preferably 0.5 to 1.5 and especially 0.7 to 1.3. If you ver as an OH compound water turns, the molar ratio is preferably below 1.0, so that a precipitate is obtained without free water. The molar ratio of the electron donor to the Grignard reagent is in the range of 0.01 to 10 and preferably 0.1 to 2. The molar ratio of titanium tetrahalide to Grignard Reagent is in the range of 0.1 to 50 and preferably 1 to 30. The molar ratio of the halogenating agent to Grignard reagent ranges from 0.01 to 50 and specifically 0.1 to 5.

If you have the compound of the formula

Mg (OR⁸) XnE,

the titanium tetrahalide (c) and the electron donor (d) contacted, the proportions in the following Areas selected.  

The molar ratio of the electron donor to the compound of the formula (Mg (OR⁸) X in the complex Mg (OR⁸) X · nE is in Range of 0.2 to 10, and preferably 0.4 to 4. That Molar ratio of titanium tetrahalide to Mg (OR⁸) X im Complex Mg (OR⁸) X · nE is in the range of 0.1 to 50 and especially 1 to 30. Thus, a pale yellowish brown can Solid with a titanium content of 0.01 to 20 wt .-% and preferably 0.1 to 10% by weight and especially 0.5 to 10% by weight obtained by contacting the OH compound, the Grignard reagent of titanium tetrahalide and electron donators.

You can the solid catalyst component with high cataly activity for the polymerization of an olefin single to form a highly stereospecific polymer Lich already obtained by having the product formed washes with the hydrocarbon solvent. If but washes the product formed with titanium tetrachloride, so you get a solid catalyst component with a even higher catalytic activity. If you look at the Titan containing solid catalyst component, produced by Contacting the OH compound (a), the Grignard reagent (b), of the titanium tetrahalide (c) and the electron donor (d) and washing the product formed with titanium tetrachloride di mixes with an organoaluminum compound and for used the polymerization of the olefin, so you get an extraordinarily high catalytic activity and extraordinarily high stereospecific properties of the formed polyolefin. The washing can be done in this way be that titanium tetrachloride to the titanium-containing solid there catalyst component and the mixture during 0.1 until 10 h, preferably with stirring, and then separates the product from titanium tetrachloride. The washing process can be done near room temperature and preferred as at an elevated temperature in the range of 50 ° C to to the boiling point of titanium tetrachloride. It is preferred the wash solution from the solid catalyst component  at a higher temperature in the range of 50 to 140 ° C cut off. Accordingly, it is preferable to use a continuous one High temperature extractor, e.g. B. a Soxhlet extractor use. The washing operation can be carried out in one step leads. However, it is preferred the washing process to be repeated until the titanium content of the titanium-containing Solid catalyst component is constant. You can do that Use titanium tetrahalide alone for washing or but also in a mixture with an inert hydrocarbon solvent. Suitable inert hydrocarbon solution aromatic hydrocarbons such as benzene and Toluene; saturated aliphatic hydrocarbons, such as n-pentane, n-hexane, n-heptane, n-octane, n-dodecane, liquid Paraffin; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. The amount of titanium tetrachloride, which one is used for a washing stage is not critical table. The molar ratio of titanium tetrachloride for the Washing stage for the magnesium compound in the solid catalyst gate component is preferably 1 to 30.

After washing with titanium tetrachloride, the solid becomes catalyst component with an inert hydrocarbon solvent washed. Suitable inert hydrocarbon solvents for this purpose are the above aromatic hydrocarbons, the aforementioned saturated aliphatic hydrocarbons and the alicycli mentioned hydrocarbons.

In olefin polymerization, the titanium-containing solid Catalyst component with an organic aluminum Mixed compound, whereby the catalyst system is formed. The organoaluminum compound preferably has the formula

AlR _m ⁵X _3-m

where R⁵ is a C _1-8 alkyl group and where m is a number from 1 to 3 and X is a halogen atom and where the same or different alkyl groups may be present in the molecule. Suitable organoaluminum compounds which can be used as auxiliary catalysts are: trialkyl aluminum, such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum; Dialkyl aluminum monohalides such as dimethyl aluminum monochloride, diethyl aluminum monochloride; Alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride; Dialkylaluminum monoalkoxides, such as diethylaluminum monoethoxide, diethylaluminum monomethoxide. It is preferred to use trialkyl aluminum such as triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum or trioctyl aluminum, etc. The molar ratio of the organoaluminum compound to the Ti in the titanium-containing solid catalyst component is in the range from 1 to 500 and preferably 1 to 100 and especially 2 to 50.

The process according to the invention, namely the polymerization an olefin, is in the presence of the catalyst system with the organoaluminum compound and the titanium content carried out gene solid catalyst component and, if required, you can use known additives for improvement the stereospecific properties. As additives electron donors come into question, e.g. B. the above Component (d) and preferably carboxylic acid ester, phosphorus acid esters and phosphoric acid esters. It is special preferred a carboxylic acid ester of the following general formula

use, where R⁶ and R⁷ each represent C _1-10 alkyl groups. In this case, polyolefins with excellent stereospecific properties are obtained at an extremely high polymerization rate.

Suitable carboxylic acid esters of the above formula are methyl p-methylbenzoate, ethyl p-methylbenzoate, propyl p-methylbenzoate, butyl p-methylbenzoate, hexyl p-methylbenzoate, octyl p-methylbenzoate, methyl p-ethylbenzoate, ethyl p-ethylbenzoate, propyl-p-ethylbenzoate, butyl-p-ethylbenzoate, hexyl-p-ethylbenzoate, octyl-p-ethylbenzoate, methyl-p-butyl benzoate, ethyl-p-butylbenzoate, propyl-p-butylbenzoate, butyl-p -butyl benzoate, hexyl p-butyl benzoate, octyl p-butyl benzoate, methyl p-hexyl benzoate, ethyl p-hexyl benzoate, propyl p-hexyl benzoate, butyl p-hexyl benzoate, hexyl p-hexyl benzoate, octyl p- hexyl benzoate, methyl p-octyl benzoate, ethyl p-octyl benzoate, propyl p-octyl benzoate, butyl p-octyl benzoate, hexyl p-octyl benzoate, octyl p-octyl benzoate etc. The benzoates in which R⁶ and R⁷ C _{1 -4-} alkyl groups are particularly suitable.

The process of adding the additive is not subject to any Restrictions. The additive can be the aluminum organi added or the titanium-containing compound Solid catalyst component or a mixture thereof. The molar ratio of the additive to Ti in the titanium content gene catalyst component is in the range of preferably 0.1-200 and especially 0.1 to 40 and especially special 1 to 10.

As olefins, one can use α-olefins, such as ethylene, propylene, butene-1 etc. use. The polyolefins can advantageously are obtained by homopolymerization, statistical copolymerization tion or block copolymerization of two or more olefins using the catalyst system according to the invention. When carrying out a copolymerization, it is preferred use less than 10 wt .-% of a comonomer. The Catalyst system of the invention is preferably used in the Homopolymerization of propylene used or in the Copolymerization of propylene and one of the other α-olefins. In the method according to the invention, homopolymerization or copolymerization as a solution polymerization in an inert hydrocarbon or liquefied  Propylene carried out or as precipitation polymerization or as gas phase polymerization without any solvent. If desired, you can use any conventional Add additive.

The polymerization can be at 20 to 100 ° C and preferably 50 to 80 ° C under a pressure from atmospheric to 100 atm. be performed. The molecular weight of the formed Polyolefins can be caused by the presence of hydrogen in the Polymerization zone are regulated.

In the following the invention is based on exemplary embodiments play explained in more detail.

In the examples and comparative examples, the isotactic index (I.I.) the amount of solid residue after extraction with boiling heptane for 6 h in an improved Soxhlet extractor (wt%). The Melt index (MFI) is measured according to ASTM D-1238.  

example 1 (I) Preparation of the titanium-containing catalyst solid component

In a 500 ml four-necked flask, which with a dry stick Was flushed gas gas, 32 ml of a solution of Chlorine-n-butyl magnesium in di-n-butyl ether in one conc tration of 2.3 mmol / ml and a solution of 100 mmol water in 160 ml of ethyl ether is added dropwise at 25 ° C added vigorous stirring to the solution, a white Precipitation arises. After the addition, the mixture becomes Stirred at 25 ° C for 1 h and the temperature is raised to 45 ° C increased and the mixture continues for 1 h touched. During this process, ethyl ether is distilled off. The reaction mixture is passed through under reduced pressure Distilling off the solvent, drying 7.55 g of a white powder is obtained. The atomic ratio Cl / Mg in the powder formed is 0.90.

Then 20 ml of a solution of ethyl benzoate are added Toluene at a concentration of 1 mmol / ml to the powder and after this addition the mixture is stirred while Heated to 110 ° C for 1.5 h. Then 220 ml of titanium tetra are added add chloride and the mixture is still on for 1 h Heated 130 ° C and the suspension of the reaction mixture is decanted without cooling and the product is Repeatedly washed with heptane until you are in the wash solution can no longer detect chlorine. A pale yellow is obtained Solid catalyst component. The titanium content in the festival body is 6.2% by weight.

(II) olefin polymerization

The polymerization of the olefin is carried out using the catalyst component prepared in step (I). 500 ml of n-heptane, 0.22 mmole of triethylaluminum and 42.0 mg of the titanium-containing solid catalyst according to step (I) are placed in a 1 liter four-necked flask which is flushed with dry nitrogen gas. The Al / Ti molar ratio is 4. Then the mixture is heated to 70 ° C. with stirring and propylene gas is introduced under atmospheric pressure, the polymerization taking place for 2 hours. The polymerization is stopped by adding a small amount of isopropyl alcohol. The contents are placed in methanol and the precipitate is separated off and dried. 16.0 g of a white powdery poly propylene are obtained. The polymerization activity of the catalyst (K _cat ) is according to the formula

K _cat = polymer (g) / Ti cat. Component (g) × time (h) × propylene pressure (kg / cm²)

given and is 317. The polymerization activity, based on the titanium content (K _Ti ) is from the formula

K _Ti = polymer (g) / titanium (g) × time (h) × propylene pressure (kg / cm²)

calculated and is 5110. The isotactic Index (I.I.) is 72.5% and the melt index (MFI) is 2.2. The results are summarized in Table 1 poses.

Comparative Examples 1 and 2

The production of the titanium-containing catalyst solid component is repeated according to stage (I) of Example 1, however, using magnesium hydroxychloride, which was prepared by preheating MgCl₂ · 6H₂O 200 ° C for 20 h and pulverization in one vibration mill for 72 h, followed by heating 285 ° C under dry nitrogen gas in a quartz tube. This product is used instead of the reaction product of Water and chlorine-n-butyl magnesium are used.

The polymerization of propylene is carried out after stage (II) of Example 1 repeated, the molar ratio Al / Ti changes to 4 or 30. The results are in Table 1 compiled. It is found that the polymerization activity and the isotactic index I.I. to a great extent depend on the solid support material which for  Production of the titanium-containing catalyst component is used.

Table 1

As Example 1 and Comparative Examples 1 and 2 show, is when using the catalyst of the invention Polymerization activity is much greater and further also the isotactic index of the polyolefin formed much higher than when using a catalyst, which was made from magnesium hydroxychloride. This fact shows that the magnesium compound which by reacting water with the Grignard reagent will hold, and in the manufacture of the titanium-containing Catalyst solid component is used behaves differently from magnesium hydroxychloride. The x-ray Scatter diagram of the magnesium compounds according to the invention does not show the scattering peaks of the magnesium hydroxychloride according to ASTM-24-725. Rather, it is magnesium compound around an amorphous substrate.

Examples 2 to 3

The polymerization of propylene according to stage (II) of Example 1 is repeated, the molar ratio Al / Ti varies according to Table 2. The results are in Table 2 compiled.  

Table 2

Example 4

The production of the titanium-containing catalyst solid component according to stage (I) of Example 1, is repeated, whereby 80 ml of a solution of 100 mmoles of water in Tetrahydrofuran instead of the water-containing ethyl ether used. The propylene polymerization is carried out in accordance with stage (II) of Example 1, wherein the obtained uses catalytic component. The results are in Table 3 compiled.

Example 5

The production of the titanium-containing solid catalyst compo nente is repeated after step (I) of Example 1, taking 100 ml of a solution of chlorine-n-butylmagnesium in di-n-butyl ether with a concentration of 1 mmol / ml used and taking 100 mmole of water instead of water-containing ethyl ether solution. The polymerization of the propylene is again according to stage (II) of Example 1 fetches, using the catalyst component obtained. The results are summarized in Table 3.

Table 3

Examples 6 to 7

The production of the titanium-containing catalyst solid component according to stage (I) of Example 1 is repeated, whereby the molar ratio of ethyl benzoate / Mg according to Table 4 varies. The polymerization of propylene will according to stage (II) of Example 1 with this catalyst solid component repeated. The results are in Table 4 compiled.

Table 4

Example 8

The preparation of the titanium-containing catalyst solid component according to step (I) of Example 1 is repeated, but changing the amount of the solution of ethyl benzoate in toluene (1 mmol / ml) from 20 ml to 80 ml and 220 ml of titanium tetrachloride after decanting is added to the suspension of the reaction mixture and before washing with heptane, and the suspension formed is stirred at 130 ° C. for 1 h and then decanted off. The titanium content is 2.9% by weight. The polymerization of propylene is repeated according to step (II) of Example 1, using 53.8 mg of the catalyst component and 0.11 mmol of triethyl aluminum. 43.3 g of the white powdery polypropylene are obtained. The polymerization activity of the catalyst K _cat is 671 and K _Ti is 23 140 and the isotactic index is 80.3% and the melt index MFI is 3.0.

Examples 9 to 11

The process of producing the titanium-containing catalyst Solid component is repeated according to Example 8, wherein one twice after treatment with titanium tetrachloride washes. The titanium content is 2.4% by weight. The polymerization of the propylene is repeated according to Example 8, wherein the catalyst component obtained is used and wherein the Al / Ti molar ratio is varied according to Table 5. The results are summarized in Table 5.

Table 5

Examples 12 to 14

The production of the titanium-containing catalyst solid Component is again according to the procedure of Example 8 fetches, the molar ratio of ethyl benzoate / Mg according to Table 6 varies. The polymerization of propylene will repeated according to Example 8, wherein the Kata obtained uses lysator component. The results are in Table 6 compiled.

Example 15

The process of producing the titanium-containing catalyst Solid component is repeated according to Example 8, wherein the amount of toluene solution of ethyl benzoate of 80 ml increased to 100 ml and after adding the toluene solution of ethyl benzoate, the mixture was heated to 110 ° C. for 1.5 h and washing the product formed with n-heptane and  dries before treatment with titanium tetrachloride carries out. The polymerization of propylene takes place in accordance with Example 8.

Table 6

Example 16

In a 500 ml four-necked flask, which is flushed with dry nitrogen, 32 ml of di-n-butyl ether solution of chlorine-n-butyl magnesium with a concentration of 3.2 mmol / ml are added and the temperature is raised to -20.degree cooled down. 100 mmoles of ethyl benzoate are added dropwise, the temperature being maintained and the mixture is stirred and then added dropwise with 160 ml of a solution of 100 mmoles of water in ethyl ether, the temperature being kept at -20 ° C. There is a white precipitate. After the addition, the mixture is stirred at -20 ° C. for 2 hours and heated to 45 ° C. and then stirred for a further 1 hour. The supernatant liquid is decanted off and the precipitate is washed with n-heptane and dried. A solid is obtained, to which 220 ml of titanium tetrachloride are added, whereupon the mixture is heated at 130 ° C. for 1 h. The suspension of the reaction mixture is decanted without cooling and the precipitate is washed with n-heptane. The solid catalyst component formed contains 6.3% by weight of titanium. The polymerization of the propylene is repeated according to step (II) of Example 1, using 40.0 mg of the solid catalyst component and using 0.21 mmole of triethylaluminum and obtaining 14.0 g of the white powdery polypropylene. A polymerization activity of the catalyst K _cat of 292 and K _Ti of 4640 is found. The isotactic index II is 72.8% and the melt index MFI is 2.5.

Examples 17 to 20

The production of the titanium-containing catalyst solid component according to step (I) of Example 1 is repeated, where different electron donors according to Table 7 instead of ethyl benzoate. Polymerization of propylene is repeated according to step (II) of Example 1. The results nisse are summarized in Table 7.

Table 7

Example 21 (I) Preparation of the titanium-containing catalyst solid component

150 ml of toluene and 40 ml of a solution of chloro-n-butylmagnesium (n-C₄H₉MgCl) in di-n-butyl ether with a concentration of 2.5 mmol are placed in a 500 ml four-necked flask, which is flushed with dry nitrogen gas / ml. 5.8 ml of ethanol (1000 mmoles) are also added dropwise at 25 ° C. with vigorous stirring. The molar ratio of EtOH / n-BuMgCl is 1.0. After this addition, the mixture is further stirred at 25 ° C. for 1 h and heated to 80 ° C. and then stirred for a further 1 h. The reaction product is washed 5 times with 150 ml of heptane each time and the heptane is distilled off under reduced pressure and the product is dried. A white powder of (C₂H₅O) _0.98 MgCl _{0.93 is obtained} .

Then 150 ml of toluene and 2.9 ml (20 mmoles) of ethyl are added benzoate at 25 ° C to the powder formed. The atomic ver Ratio Mg / ethyl benzoate is 0.2. After this encore the mixture is heated to 110 ° C. and stirred for 1 h. The reaction mixture is dried under reduced pressure net, the toluene being distilled off. It stays behind White dust. Then 220 ml (2 moles) of titanium tetra are added chlordi (TiCl₄) at 25 ° C with stirring. The Molver Ratio TiCl₄ / Mg is 20. After the addition, the mixture heated to 130 ° C and stirred for 1 h. Then will decane the suspension of the reaction mixture without cooling tiert and the remaining solid is repeated washed with heptane until the wash solution contains no chlorine ions contains. A pale yellow solid catalyst is obtained component. The titanium content is 2.4% by weight.

(II) olefin polymerization

The olefin polymerization is carried out using the solid catalyst component of step (I). For this purpose, a 1 l four-necked flask is sprayed with dry nitrogen gas, whereupon 500 ml of n-heptane, 0.10 mmole of triethylaluminum and 50.0 mg of the titanium-containing solid catalyst component of stage (I) are introduced. The Al / Ti molar ratio is 4. Then the mixture is heated to 70 ° C. with stirring, whereupon propylene gas is introduced under atmospheric pressure. The polymerization takes place for 2 hours. The polymerization is stopped by adding a small amount of isopropyl alcohol. The contents of the reaction vessel are poured into methanol. The precipitate is separated off and dried. 19.4 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 323 and K _Ti of 13 470 is measured. The isotactic index II is 85.2% and the melt index MFI is 2.6.

Comparative Example 3

The process for the preparation of the titanium-containing catalyst solid component of step (I) of Example 21 is repeated, using no ethyl benzoate. A catalyst component with 3.3% by weight of titanium is obtained. The polymerization of the propylene is repeated according to step (II) of Example 21, using the catalyst component obtained. 27.8 g of polypropylene are obtained. A polymerization activity of the catalyst K _cat of 463 and T _Ti of 14 040 is measured. The isotactic index II is 29.3%.

Examples 22 to 26 and Comparative Examples 4 to 8

The preparation of the catalyst component is according to Step (I) of Example 21 is repeated, except that it is different whose alcohols are used instead of ethanol. The polymerization of propylene is carried out according to stage (II) of Example 21 repeated, whereby the catalyst component obtained starts. The results are summarized in Table 8 provides, together with the results, which without the use of ethyl benzoate in the manufacture of Solid catalyst component can be achieved.  

Table 8

Examples 27 to 30

The preparation of the catalyst solid component is according to Step (I) of Example 21 is repeated using the Molar ratio of ethyl benzoate / Mg varies (EB / Mg). The polymerization of propylene is according to stage (II) of the case game 21 repeated, giving the catalyst obtained uses solid component. The results are in Table 9 compiled.

Table 9

Examples 31 to 37

The process of producing the catalyst solid component according to stage (I) of example 21 is repeated, with different electron donors according to Table 10 used instead of ethyl benzoate. The propylene polymer tion is according to step (II) of Example 21 with this Repeated catalyst component. The results are in Table 10 compiled.

Table 10

Example 38

In a 500 ml four-necked flask, which is dry Was flushed with nitrogen gas, 150 ml of toluene and 32.3 ml of a solution of chlorine-n-butyl magnesium (n-C₄H₉MgCl) in tetrahydrofuran with a concentration of 3.1 mmol / ml. The contents are then cooled to -30 ° C and 14.3 ml (100 mmoles) of ethyl benzoate are added dropwise  added at -30 ° C with stirring. Then you give 5.8 ml (100 mmoles) of ethanol dropwise at -30 ° C below Stir in, creating a white precipitate. The molar ratio of ethyl benzoate / Mg is 1.0 and the mol ratio ethanol / Mg is also 1.0. After this Addition, the mixture is stirred at -30 ° C. for 3 h and then heated to 60 ° C and stirred for a further 2 h. The supernatant liquid is decanted off and the The precipitate is washed 5 times with 150 ml of heptane and dried under reduced pressure, with heptane being distilled off. A white powder is obtained.

Then there are 220 ml (2 moles) of TiCl₄ at 25 ° C with stirring to the powder. The molar ratio TiCl₄ / Mg is 20. After the addition, the mixture is heated to and at 130 ° C Temperature stirred for 1 h. The suspension of the reaction the mixture is decanted without cooling and the lead remains The solid is washed 5 times with 150 ml of heptane. A solid catalyst component with 3.2% by weight is obtained. Ti.

The polymerization of propylene is repeated according to step (II) of Example 21, using 40 mg of the catalyst component and 0.107 mmole of triethylaluminum. 12.7 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 265 and K _Ti of 8270 is measured. The isotactic index II is 82.5% and the melt index MFI is 3.1.

Example 39 (I) Preparation of the titanium-containing catalyst solid component (I) - (A) magnesium hydroxychloride ether complex

A 500 ml four-necked flask is filled with dry nitrogen gas rinsed and with 87 ml of a solution of chlorine-n-butyl magnesium  in tetrahydrofuran (2.3 mmole / ml) and 150 ml of one Solution of 220 mmoles of water in tetrahydrofuran dropwise at 25 ° C over 30 min with stirring given. The mixture is heated to 60 ° C and during Stirred for 1 h and then the product with three times 250 ml each of n-heptane washed. The solvent is at Room temperature removed. A white powder remains. The atomic ratio Cl / Mg of the powder is 0.93. The powder is taken up with ethanol and the content of tetrahydro furan in the ethanol is determined by gas chromatography. It is found that in the complex of magnesium hydroxychlorids the molar ratio of tetrahydrofuran to magnesium (THF / Mg) is 1.37.

(I) - (B) Preparation of the titanium-containing catalyst solid component

2.2 g of the powder formed are mixed with 23 ml of toluene and 35.2 mmoles of ethyl benzoate are mixed and the mixture is heated to 60 ° C during 2 h and then the product washed with n-heptane and the solvent is washed under distilled off under reduced pressure. Then add 28 ml Titanium tetrachloride to the residue and the mixture heated to 130 ° C for 1 h. Then the product washed twice with 50 ml of toluene and then with Washed n-heptane. A gray-green solid is obtained with a titanium content of 3.29% by weight.

(II) Polypropylene production

The polymerization of the olefin is carried out with the solid catalyst component of stage (I) - (B). 200 ml of n-heptane, 0.10 mmole of triethylaluminum and 20 mg of the titanium-containing solid catalyst according to step (I) - (B) are placed in a 500 ml four-necked flask. The mixture is heated to 70 ° C. with stirring and propylene gas is introduced under atmospheric pressure and the polymerization is carried out for 2 hours. The polymerization is then stopped by adding a small amount of isopropyl alcohol. The contents of the reaction vessel are poured into methanol and the precipitate formed is separated off and dried. 28 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 1167 and K _Ti of 35 500 is measured and the isotactic index II is 77.3%.

Comparative Example 9

The preparation of the titanium-containing catalyst solid component by the process (I) - (B) of Example 39 is repeated, using magnesium hydroxychloride, which was obtained by heating MgCl₂ · 6H₂O during 20 h at 200 ° C and pulverization for 72 h in a vibration mill and subsequent heating to 285 ° C in the presence of dry nitrogen gas in a quartz tube. This solid product is used instead of the tetrahydrofuran complex of the reaction product of water and chlorine-n-butylmagnesium. The polymerization of propylene is repeated according to step (II) of Example 39. There is a polymerization activity of the catalyst K _cat of 25 and K _Ti from 1920 and the isotactic index II is 45.3%.

Examples 40 to 42

The production of the titanium-containing catalyst solid Component according to process (I) - (B) of Example 39 is repeated, the tetrahydrofuran complex of Magnesium hydroxychloride of stage (I) - (A) of Example 39 treated under reduced pressure or wherein Tetra hydrofuran in toluene adds to the tetrahydrofuran complex (THF / Mg) according to Table 11. The poly merization of propylene is carried out according to stage (II) of the case game 39 performed. The results are in Table 11 compiled.  

Table 11

Example 43

The polymerization of propylene is used a titanium-containing catalyst solid component carried out, which in step (I) - (B) of Example 39 arises.

200 ml of n-heptane, 0.20 mmole of triethylaluminum, 0.0310 mmole of ethylbenzoate and 26 mg of the titanium-containing catalyst solid component are placed in a 500 ml four-necked flask which has been flushed with dry nitrogen gas. Then the mixture is heated to 70 ° C with stirring and propylene gas is introduced under atmospheric pressure and the polymerization is carried out for 2 hours. The polymerization is stopped by adding a small amount of isopropyl alcohol. The contents of the reaction vessel are poured into methanol and the precipitate is separated off and dried. 23.8 g of a white powdery polypropylene are obtained. On the basis of the product, a polymerization activity of the catalyst K _cat of 763 and K _Ti of 23 200 is determined. The isotactic index II is 91.6%.

Example 44

25 ml of titanium tetrachloride are added to 2.0 g of the reaction product of water and chloro-n-butylmagnesium from stage (I) - (A) of Example 39 and the mixture is heated at 130 ° C. for 1 h and then with n- Wash heptane and 31.9 mmoles of ethyl benzoate are added and the mixture is heated to 60 ° C. for 1 h and then washed with n-heptane. A solid catalyst component containing 3.02% by weight of titanium is obtained. The polymerization of propylene is repeated according to step (II) of Example 39, using the catalyst solid component obtained. A polymerization activity of the catalyst K _cat of 938 and K _Ti of 31 100 is determined. The isotactic index II is 79.1%.

Example 45

A mixture of 28 ml of titanium tetrahalide and 35.2 mmole of benzoic acid is added to 2.2 g of the reaction product of water and chloro-n-butylmagnesium, which is obtained according to step (I) - (A) of Example 39 and the mixture becomes heated to 130 ° C for 1 h and then washed twice with 50 ml of toluene each and then washed with n-heptane, giving a solid catalyst component with 3.44% by weight of Ti. The polymerization of the propylene is repeated according to step (II) of Example 39, using the catalyst component obtained. A polymerization activity of the catalyst K _cat of 728 and K _Ti of 21 200 is found. The isotactic index II is 82.0%.

Examples 46 to 50

The preparation of the catalyst component and the polymerization of propylene are carried out according to Example 39, but with different ethers according to Table 12 instead of the tetrahydrofuran. The results are compiled in Table 12.

Table 12

Examples 51 to 53

The preparation of the catalyst component and the polymerization of propylene are repeated according to Example 39, with different electron donors according to Table 13 instead of the ethyl benzoate used in step (I) - (B). The results are summarized in Table 13.

Table 13

Example 54 (I) Preparation of the titanium-containing catalyst solid component (I) - (A) Magnesium Ethoxy Chloride Ether Complex

In a 500 ml four-necked flask, which is dry Was flushed with nitrogen gas, 43 ml of a tetra are added hydrofuran solution of 2.3 mmol / ml chlorine-n-butyl magnesium. Then 150 ml of a tetrahydrofuran solution of 100 mmoles of ethanol dropwise at 25 ° C for 30 min with stirring and the mixture is then brought to 60 ° C heated and stirred for 1 h and then three times with 250 ml each of n-heptane washed. The solvent is at Distilled room temperature. You get a white one Powder. The atomic ratio Cl / Mg of the powder is 0.93. The powder is dissolved in ethanol and the tetrahydro furan in ethanol is analyzed by gas chromatography. It is found that in the complex of magnesium ethoxychloride (THF / Mg) per 1 mole of magnesium 1.3 moles of tetra hydrofuran come.  

(I) - (B) Preparation of the titanium-containing catalyst solid component

25 ml of toluene and 35.3 mmole of ethyl benzoate become 2.5 g of the powder obtained and the mixture is during Heated to 60 ° C for 2 h and washed with n-heptane. The Solvent is distilled off under reduced pressure. Then 28 ml of titanium tetrachloride are added to the residue and the mixture is heated to 130 ° C for 1 h and with Washed n-heptane. A gray-green solid is obtained with a titanium content of 3.0% by weight.

(II) olefin polymerization

The polymerization of the olefin is carried out with the catalyst component of stage (I) - (B). 200 ml of n-heptane, 0.10 mmole of triethyl aluminum and 20 mg of the titanium-containing catalyst solid component of stage (I) - (B) are placed in a 500 ml four-necked flask which has been flushed with dry nitrogen gas. Then the mixture is heated to 70 ° C with stirring and propylene gas is introduced under atmospheric pressure and the polymerization is carried out for 2 hours. The polymerization is stopped by adding a small amount of isopropyl alcohol. The contents of the reaction vessel are then poured into methanol and the precipitate is separated off and dried. 14.8 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 617 and K _Ti of 20 560 is found. The isotactic index II is 85.3%.

Examples 55 to 57

The production of the titanium-containing catalyst solid component according to step (I) - (B) of Example 54 is repeated, where the amount of tetrahydrofuran in the complex (THF / Mg) according to Table 14 by treatment of the tetrahydrofuran Complex of stage (I) - (A) magnesium ethoxychloride  by reduced pressure or by adding tetrahy drofuran sets. The polymerization of propylene will repeated according to step (II) of Example 54. The results nisse are summarized in Table 14.

Table 14

Example 58

The polymerization of propylene is repeated using the titanium-containing catalyst solid component of step (I) - (B) of Example 54. For this purpose, 200 ml of n-heptane, 0.15 mmole of triethylaluminum and 0.025 mmole of methyl p-methylbenzoate and 20 mg of the titanium-containing catalyst solid component are added to a 500 ml four-necked flask which has been flushed with dry nitrogen gas. The mixture is then heated to 70 ° C. with stirring and propylene gas is introduced under atmospheric pressure and the polymerization is carried out for 2 hours. The polymerization is stopped by adding a small amount of isopropyl alcohol. The contents are poured into methanol and the precipitate is separated and dried. 10.3 g of a white powdery polypropylene are obtained. A polymerisation activity of the catalyst K _cat of 429 and K _Ti of 14 310 is determined. The isotactic index II is 93.5%.

Example 59

20 ml of titanium tetrachloride are added to 2.0 g of the reaction product of ethanol and chloro-n-butylmagnesium from stage (I) - (A) of Example 54 and the mixture is heated at 130 ° C. for 1 h and then with n-heptane washed, whereupon 30 mmoles of ethyl benzoate are added and the mixture is heated at 60 ° C. for 1 h and then washed with n-heptane. This gives a catalyst solid component with 2.0% by weight of titanium. The polymerization of propylene is repeated according to step (II) of Example 54, using the component obtained. A polymerization activity of the catalyst K _cat of 510 and K _Ti of 17 590 is determined. The isotactic index II is 86.5%.

Example 60

The mixture of 20 ml of titanium tetrachloride and 30 mmole of ethyl benzoate is added to 2.0 g of the reaction product of ethanol and chloro-n-butylmagnesium from stage (I) - (A) of Example 54 and the mixture is heated to 130 ° C. for 1 h heated and then washed with n-heptane to obtain a catalyst solid component containing 3.2% by weight of titanium. The polymerization of propylene is repeated in accordance with step (II) of Example 54, using the catalyst component. A polymerization activity of the catalyst K _cat of 620 and K _Ti of 19 380 was determined and the isotactic index II was 85.1%.

Examples 61 to 63

The preparation of the catalyst component and the polymerization of propylene are repeated according to Example 54, using different ethers instead of Table 15 of tetrahydrofuran in stage (I) - (A). The Results are summarized in Table 15.  

Table 15

Examples 64 to 67

The preparation of the catalyst solid is repeated component and the polymerization of propylene according to game 54, according to different electron donors Table 16 instead of ethyl benzoate in step (I) - (B) starts. The results are summarized in Table 16.

Table 16

Examples 68-71

The preparation of the catalyst solid component and the Polymerization of propylene is carried out according to Example 54 repeated, using various alcohols in Table 17 instead of ethanol in stage (I) - (B). The results are summarized in Table 17.  

Table 17

Example 72 (I) Preparation of the titanium-containing catalyst solid component

In a 500 ml four-necked flask, which is dry Nitrogen gas has been purged, 32 ml of a solution are added of chlorine-n-butyl magnesium in di-n-butyl ether with one Concentration of 3.2 mmole / ml and then added dropwise 150 ml of a solution of 100 mmoles of water in tetrahydrofuran at 25 ° C for 30 min with stirring. The mixture will heated to 60 ° C and then stirred for 1 h. The white precipitate is washed with n-heptane and dried under reduced pressure, the solvent distilled off. 7.8 g of dry powder are obtained. The Atomic ratio Cl / Mg of the powder is 0.92. Then there 18 ml of n-heptane to 1.00 g of the powder and 6.8 mmoles Ethyl benzoate and 13.6 mmole silicon tetrachloride added to the solution and the mixture is at 60 ° C during Stirred for 1 h. Then the reaction product with 5 times washed 100 ml of n-heptane and the solvent is distilled off under reduced pressure. You get one White dust. The atomic ratio Cl / Mg of the powder is 1.56. Then 30 ml of titanium tetrachloride are added to the powder and the mixture is heated to 130 ° C and for 1 h implemented. After the reaction, the reaction product washed twice with 100 ml of toluene and then  washed three times with 100 ml of n-heptane each. You get one pale yellowish green catalyst solid component with 2.8 wt% titanium.

(II) olefin polymerization

The polymerization of the olefin is carried out using the catalyst solid component of step (I). 500 ml of n-heptane, 0.15 mmole of triethyl aluminum and 26 mg of the titanium-containing catalyst solid component of stage (I) are placed in a 1 liter four-necked flask which has been flushed with dry nitrogen gas. The molar ratio Al / Ti is 9.9. The mixture is then heated to 70 ° C. with stirring and propylene gas is introduced under atmospheric pressure, the polymerization taking place for 2 hours. The polymerization is stopped by adding a small amount of isopropyl alcohol. The contents of the reaction vessel are poured into methanol and the precipitate is separated off and dried. 31.1 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 998 and K _Ti of 35 600 is determined. The isotactic index II is 80.3% and the melt index of the MFI is 1.8. The results are summarized in Table 18.

Examples 73 to 78

The preparation of the titanium-containing solid catalyst component of stage (II) of example 72 is repeated, using the chlorosilanes of Table 78 instead of Silicon tetrachloride uses. Propylene polymerization is repeated according to step (I) of Example 72. The results are summarized in Table 18.  

Table 18

Examples 79 to 81

The polymerization of propylene is carried out according to Example 75 repeated, using different electron donors according to Table 19 instead of ethyl benzoate. The results are summarized in Table 19.

Table 19

Example 82

The polymerization of the olefin is carried out using the titanium-containing solid catalyst component of Example 75 carried out. In a 1 l four-necked flask, which with 500 ml of dry nitrogen gas has been purged n-heptane, 0.27 mmole triethyl aluminum, 0.033 mmole Ethyl benzoate and 26 mg of the titanium-containing solid catalyst sator component.  

The mixture is then heated to 70 ° C. with stirring and propylene gas is introduced under atmospheric pressure and the polymerization takes place for 2 hours. The polymerization is stopped by adding a small amount of isopropyl alcohol and the contents of the reaction vessel are poured into methanol and the precipitate is separated off and dried. 26.8 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 859 and K _Ti of 29 600 is determined. The isotactic index II is 93.2%.

Example 83

In a 500 ml four-necked flask, which was flushed with dry nitrogen gas, 32 ml of a solution of chlor-n-butylmagnesium in di-n-butyl ether with a concentration of 3.2 mmole / ml are added and the contents are then - Cooled 20 ° C and 100 mmole of ethyl benzoate are added dropwise with stirring. Then 160 ml of a solution of 100 mmoles of water in ethyl ether are added dropwise at -20 ° C. with stirring, a white precipitate being formed. After the addition, the mixture is stirred at -20 ° C for 2 h and then stirred at 45 ° C for 1 h. The supernatant liquid is decanted off and the precipitate is washed with n-heptane and dried. Then 200 mmoles of trimethylchlorosilane are added and the mixture is treated for 1 h at 60 ° C. with stirring. The product is washed with heptane and dried. Then 220 ml of titanium tetrachloride are added to the product and the mixture is heated at 130 ° C. for 1 hour. The product is washed with n-heptane, giving a solid catalyst component with 3.56% by weight of titanium. The polymerization of propylene is repeated according to step (II) of Example 72, using 25.0 mg of the catalyst component and 0.12 mmole of triethylene aluminum. 27.8 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 927 and K _Ti of 26,000 is determined. The isotactic index II is 73.8%.

Example 84

A solution of 100 mmoles of chlorine-n-butylmagnesium in di-n-butyl ether and a solution of 100 mmoles of water in ethyl ether is added dropwise at room temperature with stirring to a 500 ml four-necked flask which has been flushed with dry nitrogen gas. After this addition, the mixture is stirred at room temperature for 1 h and then stirred at 45 ° C. for 1 h. The reaction mixture is washed with n-heptane and dried, a white powder being obtained. Then 200 mmoles of trimethylchlorosilane are added to the powder and the mixture is stirred at 60 ° C. for 1 h and then washed with n-heptane and dried. Then 220 ml of titanium tetrachloride are added and the mixture is heated to 130 ° C. for 1 h. The product is washed with n-heptane and 20 mmoles of ethyl benzoate are added and then the mixture is heated to 60 ° C for 1 h. The product is then washed with n-heptane and a catalyst solid component with 2.2% by weight of titanium is obtained. The polymerization of propylene is repeated in accordance with stage (II) of Example 72, using 25 mg of the catalyst component obtained and 0.08 mmole of triethylaluminum. 26.3 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 877 and K _Ti of 39,800 is determined and the isotactic index II is 76.3%.

Example 85

A solution of chlorine-n-butyl magnesium in di-n-butyl ether with a concentration of 100 mmoles and a solution of 100 mmoles of water in ether are added to a 500 ml four-necked flask which has been flushed with dry nitrogen Dripped in room temperature while stirring. After this addition, the mixture is stirred at room temperature for 1 h and then stirred at 45 ° C. for 1 h. The reaction mixture is washed with n-heptane and dried. To the white powder obtained are added 20 mmoles of ethyl benzoate and the mixture is stirred at 100 ° C. for 1 hour and washed with n-heptane and dried, whereupon 200 ml of silicon tetrachloride are added and the mixture is heated at 60 ° C. for 1 hour. Then 220 ml of titanium tetrachloride are added and the mixture is heated at 130 ° C. for 1 h and the product is washed with n-heptane. The catalyst solid component obtained contains 3.6% by weight of titanium. The polymerization of the propylene is repeated according to step (II) of Example 72, using 23 mg of the catalyst solid component and 0.11 mmole of triethyl aluminum. 33.8 g of the white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 1225 and K _Ti of 34 000 is determined. The isotactic index II is 82.0%.

Example 86

1.00 g of the hydrolyzed product of the Grignard reagent according to Example 72 is placed in a flask and this is mixed with 18 ml of n-heptane and 6.2 mmoles of ethyl benzoate are added and the mixture is heated to 60 ° C. for 1 h and the product is washed five times with 100 ml of n-heptane each. The solvent is distilled off under reduced pressure and 13.6 mmoles of dichlorodimethylsilane and 30 ml of titanium tetrachloride are added at the same time, whereupon the mixture is heated to 60 ° C. for 1 h. The product is washed with n-heptane. A catalyst solid component with 2.4% by weight of titanium is obtained. The polymerization of propylene is repeated according to step (II) of Example 72, 25 mg of the catalyst component and 0.090 mmole of triethylaluminum being added. 28.5 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 950 and K _Ti of 39 600 is determined. The isotactic index II is 76.8%.

Example 87 (I) Preparation of the titanium-containing solid catalyst component

In a 500 ml four-necked flask, which is dry If nitrogen gas is flushed, 40 ml of a solution are added of chlorine-n-butyl magnesium in di-n-butyl ether with one Concentration of 2.5 mmole / ml and 150 ml of a solution of 100 mmoles of water in tetrahydrofuran is added dropwise 25 ° C with vigorous stirring, a white Precipitation is formed. After this addition, the Ge mix at 50 ° C for 1 h and then Distilled off solvent under reduced pressure, wherein 7.9 g of a white solid powder are obtained. The atomic ratio nis Cl / Mg is 0.98. Then 4 mmoles of ethyl benzoate are added, 20 ml of n-heptane, 40 mmole of thionyl chloride to 1.54 g of the powder and the mixture is heated to 60 ° C over 2 hours and then washed five times with 100 ml of n-heptane, after which the Solvent is distilled off and a white powder with an atomic ratio Cl / Mg of 1.75 remains. To this are added 20 ml of titanium tetrachloride, whereupon the mixture during Is heated to 130 ° C for 1 h and seven times with 100 ml each n-heptane is washed. You get a titanium-containing Catalyst solid component with 3.0 wt% titanium.

(II) olefin polymerization

The olefin polymerization is carried out using the catalytic component of step (I). In a 1 liter four-necked flask, which was flushed with dry nitrogen gas, 500 ml of n-heptane, 0.12 mmole of triethylaluminum and 35.0 mg of a titanium-containing catalyst solid component of stage (I). The molar ratio Al / Ti is 5.5. The mixture is then heated to 70 ° C. with stirring and propylene gas is introduced under atmospheric pressure, the polymerization taking place for 2 hours. The polymerization is stopped by adding a small amount of isopropyl alcohol. The contents of the reaction vessel are poured into methanol and the precipitate is separated off and dried. 25.0 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 595 and K _Ti of 19 830 is determined. The isotactic index II is 85.6% and the melt index MFI is 1.6.

Example 88

The preparation of the titanium-containing catalyst solid component is repeated after step (I) of Example 87, using phosphorus trichloride instead of thionyl chloride. The atomic ratio Cl / Mg after the halogenation is 1.65 and the titanium content is 3.7% by weight. The polymerization of propylene is repeated according to step (II) of Example 87, using the catalyst component obtained. A polymerization activity of the catalyst K _cat of 415 and K _Ti of 11 200 is determined and the isotactic index II is 78.2%.

Example 89

20 ml of n-heptane and 4 mmole of ethyl benzoate are added to 1.54 g of the hydrolyzed product from the Grignard reagent obtained according to Method 87, and hydrogen chloride gas is introduced into the liquid phase at a throughput of 10 l / h for 2 hours Stirring initiated. The temperature is kept at 25 ° C. The supernatant liquid is decanted off and the precipitate is washed with n-heptane and dried. A solid is obtained with the atomic ratio Cl / Mg of 1.56. Then 20 ml of titanium tetrachloride are added and the mixture is heated at 130 ° C. for 1 h and washed with n-heptane, the catalyst solid component being obtained with 4.1% by weight of titanium. The polymerization of propylene is repeated according to (II) of Example 87, using 40.0 mg of the catalyst solid component and 0.24 mmole of triethylaluminum. 24.5 g of a white powdery polypropylene lens are obtained. A polymerization activity of the catalytic converter K _cat of 510 and K _Ti of 12 400 is determined and the isotactic index II is 84.5%.

Example 90

The process for producing the titanium-containing catalyst solid component and the polymerization of propylene are repeated in accordance with Example 87, but using 20 ml of carbon tetrachloride instead of thionyl chloride without using 20 ml of n-heptane. The mixture is heated for 2 h in stage (II) to the boiling point of the carbon tetrachloride. A polymerization activity of the catalyst K _cat of 410 and K _Ti of 10 300 is determined. The isotactic index II is 71.5%. The results are summarized in Table 20.

Examples 91-94

The production of the titanium-containing catalyst solid component and the polymerization of propylene repeated according to Example 90, using different halo Generating agent according to Table 20 instead of tetrachlor carbon uses. The results are in Table 20 compiled.  

Table 20

Examples 95-97

The polymerization of propylene is carried out according to Example 87 repeated, using different electron donors according to Table 21 instead of ethyl benzoate. The results are summarized in Table 21.

Table 21

Example 98

The polymerization of propylene is repeated as follows with the titanium-containing catalyst solid component of Example 87: 500 ml of heptane, 0.263 mmole of triethylaluminum, 0.033 mmole of ethylbenzoate and 35.0 mg of the are added to a 1 liter four-necked flask which has been flushed with dry nitrogen gas Catalyst component. The mixture is then heated to 70 ° C. with stirring and propylene gas is introduced under atmospheric pressure, the polymerization being carried out for 2 hours. The polymerization is stopped by adding a small amount of isopropyl alcohol. The contents are poured into methanol and the precipitate is separated and dried. 12.0 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 285 and K _Ti of 9500 is determined. The isotactic index II is 93.5%.

Example 99

In a 500 ml four-necked flask, which was flushed with dry nitrogen gas, 32 ml of a solution of chlor-n-butylmagnesium in di-n-butyl ether with a concentration of 3.2 mmole / ml are added. The Inha 21623 00070 552 001000280000000200012000285912151200040 0002002755529 00004 21504lt is cooled to -20 ° C and 20 mmoles of ethylbenzoate are added dropwise with stirring. Then 160 ml of a solution of 100 mmoles of water in ethyl ether are added dropwise at -20 ° C., a white precipitate being formed. The mixture is then stirred at -20 ° C for 2 h and then 45 ° C for 1 h. The supernatant liquid is decanted off and the precipitate is washed with n-heptane and dried. Then 200 mmol of thionyl chloride and 100 ml of n-heptane are added, whereupon the mixture is heated to 60 ° C. with stirring for 1 h. The product is washed with n-heptane and dried. Then 220 ml of titanium tetrachloride are added to the mixture, which is heated at 130 ° C. for 1 h and washed with n-heptane. A catalyst solid component having a titanium content of 3.3% by weight is obtained. The polymerization of propylene is repeated according to step (II) of Example 87, using 30.0 mg of the catalyst component obtained and 0.14 mmole of triethylaluminum. 18.5 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 514 and K _Ti of 15 600 is determined. The isotactic index II is 75.0%.

Example 100

In a 500 ml four-necked flask, which with a dry stick was purged with gas, a solution of 100 mmoles is added Chlorine-n-butyl magnesium in di-n-butyl ether, whereupon one Solution of 100 mmoles of water in ethyl ether at room temperature drip in with stirring. After this addition, it will Mixture stirred at room temperature for 1 h and then Stirred at 45 ° C for 1 h. The reaction mixture is washed with n-heptane and dried. Man he holds a white powder. Then 200 mmoles of thionyl are added add chloride and the mixture is at 60 ° C for 1 h stirred and then washed with n-heptane and dried. Then add 220 ml of titanium tetrachloride, whereupon the Mixture is stirred for 1 h at 130 ° C and then is washed with n-heptane. Then give 20 mmoles Add ethyl benzoate and the mixture is left on for 1 h Heated 60 ° C and then washed with n-heptane. You get a catalyst solid component with 2.2 wt% titanium.

The polymerization of propylene is repeated according to step (II) of Example 87, using 25 mg of the catalyst component and 0.08 mmole of triethyl aluminum. 10.7 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 357 and K _Ti of 16 200 is determined. The isotactic index II is 84.6%.

Example 101

In a 500 ml four-necked flask, which is dry Nitrogen gas has been purged, a solution of 100 mmoles of chlorine-n-butyl magnesium in di-n-butyl ether, whereupon a solution of 100 mmoles of water in ethyl ether dripped in at room temperature with stirring. After this The mixture is added at room temperature for 1 h stirred and then stirred at 45 ° C for 1 h.  

The reaction product is washed with n-heptane and dried to give a white powder. Then 20 mmoles of ethyl benzoate are added and the mixture is stirred for a further hour at 100 ° C. and then washed with n-heptane and dried. Then 80 mmoles of thionyl chloride are added and the mixture is heated at 60 ° C. for 1 h and then mixed with 220 ml of titanium tetrachloride and heated at 130 ° C. for 1 h and then washed with n-heptane, whereby a catalyst solid component with 4 , 2 wt .-% titanium. The polymerization of the propylene is repeated in accordance with stage (II) of Example 87, 33.0 mg of the catalyst component obtained and 0.15 mmole of triethyl aluminum being used. 18.3 g of a white powdery polypropylene are obtained. A polymerization activity K _cat of 463 and K _Ti of 11,000 is determined and the isotactic index II is 82.0%.

Example 102 (I) Preparation of the titanium-containing catalyst solid component

In a 500 ml four-necked flask, which was flushed with dry nitrogen gas, 150 ml of toluene and 40 ml of a solution of di-n-butylmagnesium in di-n-butyl ether with a concentration of 2.5 mmole / ml are added, followed by 5.8 ml (100 mmoles) of ethanol are added dropwise at 25 ° C. with vigorous stirring. The molar ratio C₂H₅OH / n-BuMgCl is 1.0. After this addition, the mixture is stirred at 25 ° C for 1 h and then stirred at 80 ° C for 1 h. The reaction product is washed five times with 150 ml each of n-heptane and the heptane is distilled off under reduced pressure. The product is dried to give a white powder. This has the formula (C₂H₅O) _0.98 MgCl _0.93 . Then 150 ml of toluene, 2.9 ml (20 mmoles) of ethyl benzoate and 200 mmoles of thionyl chloride are added to the powder at 25 ° C. The mixture is then heated to 60 ° C. and stirred at this temperature for 2 h. The toluene is distilled off under reduced pressure and the product is dried, whereby a white powder with an atomic ratio Cl / Mg of 1.4 is obtained. Then 220 ml (2 moles) of titanium tetrachloride are added at 25 ° C. with stirring. The molar ratio TiCl₄ / Mg is 20. After the addition, the mixture is heated to 130 ° C and stirred at 130 ° C for 1 h and then the product is washed repeatedly with n-heptane until the washing liquid contains no chlorine. A pale yellow titanium-containing catalyst solid component with 2.8% by weight of titanium is obtained.

(II) olefin polymerization

The polymerization of the olefin is repeated using the catalyst solid component of step (I). 500 ml of n-heptane, 0.20 mmole of triethylaluminum and 50 mg of the titanium-containing catalyst solid component of stage (I) are placed in a 1 liter four-necked flask which has been flushed with dry nitrogen. The molar ratio Al / Ti is 7. Then the mixture is heated to 70 ° C. with stirring and propylene gas is introduced under atmospheric pressure and the polymerization is carried out for 2 hours. The polymerization is stopped by adding a small amount of isopropyl alcohol. The contents are poured into methanol and the precipitate is separated and dried. 31.2 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 520 and K _Ti of 18 570 is determined. The isotactic index II is 88.2% and the melt index MFI is 2.8.

Examples 103-107

The process of producing the titanium-containing catalyst Solid component is according to step (I) of Example 102 repeated, using the halogenating agents in Table 22 instead of thionyl chloride. The polymerization of the propylene is repeated according to Example 102. The results nisse are summarized in Table 22.

Table 22

Example 108 (I) Preparation of the titanium-containing catalyst solid component

In a 500 ml four-necked flask, which is dry Was flushed with nitrogen gas, 150 ml of toluene and 40 ml of a solution of chlorine-n-butyl magnesium in di-n- butyl ether with a concentration of 2.5 mmoles / ml. 5.8 ml (100 mmoles) of ethanol are then added dropwise at 25 ° C. with stirring into the solution. The molar ratio C₂H₅OH / n-BuMgCl is 1.0. The temperature will rise 80 ° C increased and the mixture is at this for 1 h Temperature stirred, whereupon the product with n-heptane will wash and the solvent under reduced pressure  distilled off. The dry white powder obtained has a Cl / Mg atomic ratio of 0.93. 150 ml toluene, 2.9 ml (20 mmoles) Ethyl benzoate and 200 mmoles of silicon tetrachloride become added to the powder and the mixture is left on for 2 h Heated to 60 ° C and the product is five times with 100 ml n- Washed heptane, whereupon the solvent under reduced Pressure is distilled off, so that a white powder with an atomic ratio Cl / Mg of 1.5 remains, to which one then add 220 ml (2 moles) of titanium tetrachloride, followed by heating the mixture to 130 ° C. for 1 h and washing the mixture five times with 100 ml of n-heptane each to form a pale yellowish green solid 2.8 wt% titanium.

(II) olefin polymerization

The polymerization of the propylene is repeated in accordance with step (II) of Example 102, the catalyst solid component being used and 40.8 g of a white powdery polypropylene being obtained. A polymerization activity of the catalyst K _cat of 680 and K _Ti of 24 290 and an isotactic index II of 88.5% and a melt index MFI of 3.7 are determined.

Examples 109 to 112

The production of the titanium-containing catalyst solid component is repeated according to stage (I) of example 108, taking the halogenating agents of Table 23 instead of silicon tetrachloride. The polymerization of propylene is carried out according to stage (II) of example 102 repeated. The results are summarized in Table 23 poses.  

Table 23

Examples 113-116

The production of the titanium-containing catalyst solid Component becomes again according to stage (I) of example 108 fetched using the electron donors in Table 24 used instead of ethyl benzoate. The polymerization of propylene is carried out according to stage (II) of example 102 repeated. The results are summarized in Table 24 poses.

Table 24

Examples 117-119

The production of the titanium-containing catalyst solid component according to stage (I) of Example 108 repeated, using the alcohols shown in Table 25.  The polymerization of propylene is carried out in accordance with stage (II) of example 102 repeated. The results are in Table 25 compiled.

Table 25

Example 120

The polymerization of propylene is repeated using the titanium-containing catalyst solid component of step (I) of Example 108. 500 ml of n-heptane, 0.322 mmole of triethyl aluminum, 0.058 mmole of methyl p-methylbenzoate and 50 mg of the titanium-containing catalyst solid component are placed in a 1 liter four-necked flask which has been flushed with dry nitrogen gas. Then the mixture is heated to 70 ° C with stirring and propylene gas is introduced under atmospheric pressure and the polymerization is carried out for 2 hours. The polymerization is stopped by adding a small amount of isopropyl alcohol. The content is poured into methanol and the precipitate is separated off and 24.9 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 415 and K _Ti of 14 820 and an isotactic index II of 94.0% are determined.

Example 121

In a 500 ml four-necked flask, which was flushed with dry nitrogen gas, 32 ml of a solution of chlor-n-butylmagnesium in di-n-butyl ether with a concentration of 3.2 mmole / ml are added. 20 mmoles of methyl p-methyl benzoate are added dropwise to the solution with stirring at -20 ° C. and then 100 mmoles of ethanol are added dropwise to the mixture at -20 ° C. with stirring, a white precipitate being formed. The mixture is then stirred at -20.degree. C. for 2 h and then at 45.degree. C. for 1 h. The supernatant liquid is decanted off and the precipitate is washed with n-heptane and dried to give a solid. 200 mmoles of thionyl chloride and 100 ml of n-heptane are added to the solid and the mixture is heated to 60 ° C. for 2 hours with stirring, and the mixture is washed with n-heptane and dried. 220 ml of titanium tetrachloride are then added to the solid obtained and the mixture is heated at 130 ° C. for 1 h, after which the product is washed with n-heptane. A catalyst solid component with a titanium content of 3.4% by weight is obtained. The polymerization of propylene is repeated in accordance with stage (II) of Example 102, using 50 mg of the catalyst component obtained and 0.28 mmole of triethylaluminum. 30.3 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 505 and K _Ti of 14 850 is determined. The isotactic index II is 89.3%.

Example 122

A solution of 100 mmoles of chloro-n-butylmagnesium in di-n-butyl ether is added to a 500 ml four-necked flask, which has been flushed with dry nitrogen, after which 100 mmoles of ethanol are added dropwise at room temperature with stirring. The mixture is then stirred at room temperature for 1 h and then at 45 ° C. for 1 h, and the product is washed with n-heptane and dried. Then 200 mmoles of silicon tetrachloride are added to the white powder obtained, whereupon the mixture is stirred at 60 ° C. for 1 h and then washed with n-heptane and dried. 220 ml of titanium tetrachloride are added to the mixture and this is heated to 130 ° C. for 1 h. The product is washed with n-heptane and 20 mmoles of ethyl benzoate are added, whereupon the reaction mixture is heated at 60 ° C. for 1 h. The product is washed with n-heptane and a solid catalyst component with 3.3% by weight of titanium is obtained. The polymerization of propylene is repeated according to step (II) of Example 102, using 50 mg of the catalyst component and 0.28 mmol of triethyl aluminum. 24.8 g of a white powdery polypropylene are obtained. A polymerization activity of the catalyst K _cat of 413 and K _Ti of 12 530 is determined. The isotactic index II is 87.3%.

Example 123

A solution of 100 mmoles of chlorine-n-butylmagnesium in di-n-butyl ether and 100 mmoles of butanol are added dropwise at room temperature to a 500 ml four-necked flask which has been flushed with dry nitrogen. After this addition, the mixture is stirred at room temperature for 1 h and then stirred at 45 ° C. for 1 h. The product is washed with n-heptane and dried to give a white powder. Then 20 mmoles of ethyl benzoate are added to the solid and the mixture is stirred at 90 ° C. for 1 h and then 80 mmol of thionyl chloride are added. The mixture is heated to 60 ° C. for 1 h and then mixed with 220 ml of titanium tetrachloride. The mixture is heated at 130 ° C for 1 hour and then washed with n-heptane to give a catalyst solid component containing 3.0% by weight of titanium. The polymerization of propylene is repeated in accordance with stage (II) of Example 102, 55 mg of the catalyst solid component and 0.25 mmole of triethylaluminum being used. 29.2 g of a white powdery poly propylene are obtained. A polymerization activity of the catalyst K _cat of 486 and K _Ti of 16 220 was determined and the isotactic index II was 85.1%.

Example 124 (I) Preparation of the titanium-containing catalyst solid component

In a 500 ml four-necked flask, which is dry Nitrogen gas has been purged, 32 ml of a solution are added of chlorine-n-butyl magnesium in di-n-butyl ether with one Concentration of 3.2 mmoles / ml and a solution of 100 mmoles Water in 150 ml of tetrahydrofuran is stirred at 25 ° C added dropwise and the mixture is heated to 60 ° C and stirred for 1 h at this temperature. The received one The precipitate is washed with n-heptane and the solution medium is distilled off under reduced pressure, wherein 7.8 g of a dry powder with an atomic ratio Cl / Mg of 0.92 is obtained, followed by 6.8 mmoles of ethyl benzoate and 13.6 mmoles of silicon tetrachloride to a mixture of 18 ml of n-heptane and 1.00 g of the powder are added and the mixture heated to 60 ° C for 1 h and then five times with 100 ml each Washes n-heptane and the solvent under reduced Distilled off pressure, leaving a white solid with a Atomic ratio Cl / Mg of 1.56 remains, to which one then there are 30 ml of titanium tetrachloride, whereupon the mixture heated to 130 ° C for 1 h and then twice with each 100 ml of toluene and three washes with 100 ml of n-heptane each, where a pale yellowish green solid with 2.8% by weight Titan receives.

(II) olefin polymerization

The propylene polymerization is carried out with the catalyst component of step (I). 300 ml of n-heptane, 0.19 mmole of triethylaluminum and 0.03 mmole of methyl p-tolylate and 30.1 mg of the titanium-containing catalyst solid component of stage (I.) Are placed in a 500 ml four-necked flask which has been flushed with dry nitrogen gas ). The mixture is heated to 70 ° C with stirring and propylene gas is introduced under atmospheric pressure to carry out the polymerization for 2 hours, after which the polymerization is stopped by adding a small amount of methanol. The contents are poured into methanol and the precipitate is separated and dried. A white powdery polypropylene is obtained. A polymerization activity of the catalyst K _cat of 392 and K _Ti of 14,000 and an isotactic index II of 95.8% are determined.

Example 125 (I) Preparation of the titanium-containing catalyst solid component

150 ml of toluene and 40 ml of a solution of chlorine-n-butylmagnesium in di-n-butyl ether with a concentration of 2.5 mmoles / ml are placed in a 500 ml four-necked flask which has been flushed with dry nitrogen gas. 5.8 ml of ethanol are then added dropwise to the solution at 25 ° C. with vigorous stirring. The molar ratio C₂H₅OH / n-BuMgCl is 1.0. After the addition, the mixture is stirred for 1 h at 25 ° C, whereupon the temperature is raised to 80 ° C and the mixture is stirred for 1 h. The reaction product is washed five times with 150 ml of heptane each time and the reaction product is then dried under reduced pressure, with n-heptane being still. A white solid of the composition (C₂H₅O) _0.98 MgCl _{0.93 is obtained} .

150 ml of toluene and 2.9 ml (20 mmoles) of ethyl benzoate are added at 25 ° C to the mixture. The molar ratio of ethyl benzoate to Mg is 0.2. After the addition, the mixture heated to 110 ° C. with stirring for 1 h. The toluene will distilled off from the reaction mixture under reduced pressure, leaving a white solid. You give 220 ml (2 moles) of titanium tetrachloride at 25 ° C with stirring. The molar ratio TiCl₄ / Mg is 20. After the addition the mixture is heated to 130 ° C and at 1 h  this temperature stirred and the supernatant liquid is decanted when hot and the product is Repeatedly washed with n-heptane until the washing liquid no longer contains chlorine. A pale yellow is obtained Solid catalyst with 2.4% by weight of titanium.

(II) olefin polymerization

The polymerization of propylene is repeated in accordance with stage (II) of example 124, the catalyst solid obtained in stage (I) being used. A polymerization activity of the catalyst K _cat of 250 and K _Ti of 10 400 is determined. The isotactic index II is 92.4%.

Claims (16)

1. A process for producing a polyolefin by homopolymerization of an olefin or by copolymerization of two or more olefins in the presence of a catalyst system with an organoaluminum compound and a titanium-containing catalyst solid component, obtained from (a) water and / or a hydroxy compound, (b) a Grignard -Reagent and (c) a titanium tetrahalide, characterized in that a titanium-containing catalyst solid component is used, which was obtained by contacting components (a), (b) or (c) or the reaction mixture of two or three of these components with ( d) one or more electron donors from the following group: amines, carboxylic acid amides, phosphines, phosphine oxides, phosphoric acid esters, phosphoric acid esters, phosphoric acid amides, ketones and carboxylic acid esters, with the proviso that when component (d) is a carboxylic acid ester, the hydroxy compound (a ) not an aryl alcohol or an aralkylal is alcohol. 2. The method according to claim 1, characterized in that one propylene is used as olefin. 3. The method according to any one of claims 1 or 2, characterized characterized in that the olefin is a mixture of propylene with a other α-olefin. 4. The method according to any one of claims 1 to 3, characterized records that one as a component (d) a carboxylic acid ester puts.   5. The method according to any one of claims 1 to 4, characterized characterized in that a titanium-containing catalyst uses solid component, which was obtained by at the same time or in any order following displacement of the by contacting component (a) product obtained with component (b) with the components (c) and (d). 6. The method according to claim 5, characterized in that one makes contact in the presence of an ether leads. 7. The method according to claim 6, characterized in that the product the formula Mg (OR⁸) X · nEhat, where R⁸ is a hydrogen atom or a hydrocarbon means rest and where X is a halogen atom and E is a Ether molecule means and where n is a number from 0.5 to 25 is. 8. The method according to any one of claims 1 to 4, characterized ge indicates that you have a titanium-containing catalyst uses solid component, which was obtained by Adding component (c) to a product which obtained was by contacting component (a) with component (b) in the presence of component (d). 9. The method according to claim 8, characterized in that the contacting is carried out in the presence of ether. 10. The method according to any one of claims 8 or 9, characterized ge indicates that the product is the following general Formula Mg (OR⁸) X · nE, where R⁸ is a hydrogen atom or a hydrocarbon rest; X is a halogen atom; E is an ether and n is a number of 0.4 to 25 mean. 11. The method according to any one of claims 1 to 4, characterized ge indicates that one contains a titanium-containing catalyst uses material component which was obtained by Add component (d) to a contacting product component (a) with component (b), followed by one Add component (c) to the mixture. 12. The method according to any one of claims 1 to 4, characterized ge indicates that you have a titanium-containing catalyst uses solid component, which was obtained by Contacting components (a), (b), (c) or (d) or the reaction mixture of two, three or four components with (e) a halogenating agent other than titanium tetra halide 13. The method according to claim 12, characterized in that one contains a titanium-containing catalyst solid component which was obtained by simultaneous or consecutive in any order Add components (c), (d) and (e) to one Product obtained by contact of components (a) with component (b). 14. The method according to claim 12, characterized in that one contains a titanium-containing catalyst solid component which was obtained by simultaneous or consecutive in any order Adding components (c) and (e) to a product, which was obtained by contacting the component (a) with component (b) in the presence of the component (d).   15. The method according to any one of claims 1 to 14, characterized ge indicates that the titanium-containing catalyst solid component additionally treated with titanium tetrachloride becomes. 16. The method according to any one of claims 1 to 15, characterized in that in the olefin polymerization in addition to the titanium-containing catalyst solid component and the organoaluminum compound, a compound of the formula used, where R⁶ and R⁷ each represent a C _1-10 alkyl group.