GB2047718A - Supported titanium components of olefine polymerisation catalysts - Google Patents

Abstract

A catalytic titanium component for the polymerization of alkenes-1 particularly propylene contains a halogenated titanium compound, an electron donor, and a mixture of a magnesium halide and an aluminium halide, characterized in that the titanium component contains 0.1 - 10% by wt. of titanium and the titanium : magnesium : aluminium weight ratio amounts to 1 : (0.5-20): (0.05-2.5), while the magnesium : aluminium weight ratio is at least 3 : 1. With such very specific weight ratios, the aluminium halide does not act as an inert filler, but has a very special action, reflected in a particular high activity and good stereospecificity of a catalyst system containing such a titanium component. The carrier is prepared by grinding the magnesium halide and aluminium halide in the absence of the electron donor.

Description

SPECIFICATION Catalytic titanium component, process for the manufacture thereof, and process for the polymerization of alkenes-1 using such a titanium component The invention relates to a catalytic titanium component useful for the polymerization of alkenes-1 i.e.

for homopolymerization of alkenes-1 or copolymerization of alkenes-1 with for example ethylene, which titanium component contains a halogenated titanium compound, an electron donor and a mixture of a magnesium halide and an aluminium halide as carrier.

A similar titanium component is known from the Dutch patent application No. 7610267, laid open for public inspection, which describes a catalyst system forthe polymerization of alkenes-1 with a titanium component which contains the product of a reaction between a magnesium halide, a titanium (IV) compound and an electron donor, and which may contain, for instance, 80% by wt. or more of an inert filler, for instance aluminium chloride.

According to this publication, the presence of, for instance, aluminium chloride as filler has the drawback that the specific surface of the titanium component is only moderately large, while the properties of the catalyst system are not particularly good.

It has now been found by the applicant that an aluminium halide in a mixture with a magnesium halide in a carrier for a complex of a halogenated titanium compound with a Lewis base, with very specific weight ratios, does not act as an inert filler, but has a very particular effect which is reflected in a particularly high activity at good stereospecificity of a catalyst system containing such a titanium component. It is assumed that with these very specific weight ratios, a specific conversion of the complex titanium compound, magnesium halide and aluminium halide takes place. However, the invention is not restricted by any theoretical consideration.

According to the invention, a catalytic titanium component useful for the polymerization of alkenes1 andforthecopolymerization of alkenes-1 with each other or with ethylene contains a halogenated titanium compound, an electron donor, and a mixture of a magnesium halide and an aluminium halide as carrier, characterized in that the titanium component contains 0.1-10% by wt. of titanium and in that the titanium : magnesium : aluminium weight ratio amounts to 1: (0.5-20): (0.05-2.5), while the magnesium : aluminium weight ratio amounts to at least3: 1.

The titanium component according to the invention improves the activity of the polymerization catalyst, with good stereospecificity. With this catalyst, polymers can be obtained -for instance, polypropylene, polybutylene-1, poly-4-methyl pentylene-1 or other polyalkylenes-1 - with a very low halogen content, a very low titanium content, good particle size and good particle size distribution. The polymer therefore has good processing properties and is little corrosive for the processing equipment.

More in particular, the titanium : magnesium aluminium weight ratio in the titanium component is 1 : (1-5): (0.2-1), while the titanium content preferably amounts to 2-10 % by wt. The magnesium aluminium weight ratio preferably is 3:1 to 100:1, more in particular4: 1 to 20:1.

The halogenated titanium compound used in the manufacture of the catalyst component can be any halogenated compound of bi-, tri-, or tetravalent titanium, including compounds in which some of the titanium valencies have been taken up by atoms other than halogen atoms. The halogen in the halogenated titanium compound is preferably chlorine, but may also be bromine and/or iodine, for instance. Examples of halogenated titanium compounds are TiCI3, TiCI4, TiBr4, Til4, Ti(isobutoxy)2C12, Ti(phenoxy)C13 and Ti(o-methyl phenoxy)C13.

TiCI4 is particularly suitable.

For application in multi-stage polymerization processes, especially those in which more than half an hour is normally required for polymerization in the first stage before a second stage is started, it is of special advantage if the halogenated titanium compound used is a titanium halide phenolate of the formula TinXaAb, in which X represents a halogen atom and Athe acid radical of a phenol, n is a whole number of at least 1, and a and b are such numbers that a/n and b/n both amount to 1-3, on the understanding that (a+b)/n is equal to 3-4.The rate of decline in the activity of the catalyst system is then substantially reduced, so that multi-stage polymerization processes, for instance so-called block copolymerizations, in which in a first stage, for instance, for half an hour propylene, butylene-1, 4-methyl pentylene-1 or another alkene-1 with at least 3 carbon atoms per molecule is polymerized, possibly in the presence of a minor quantity of ethylene, after which in a second stage another monomer or a monomer mixture of a different composition is polymerized in the presence of the polymer formed in the first stage, so that blocks differing in monomer composition may be present in one polymer molecule, give considerably higher proportions of such block copolymer.

The phenolate may be, for instance, the acid radical derived from unsubstituted phenol or from a phenol in which one or more alkyl groups or alkoxy groups with, for instance, 1-6 carbon atoms per group have been substituted, for instance cresol, methoxy phenol, xylenol, ethyl phenol, propyl phenol, octyl phenol, dibutyl phenol, cumyl phenol or napthol. Cresolates and methoxy phenolates are particularly suitable, while cresolates offer the advantage of particularly high stereospecificity of the catalyst system. The benzene nucleus of the phenolate may contain other substituents which are non-detrimental in the polymerization reaction, such as one or more halide substituents. The phenolate group may have, for instance, 6 to 18 carbon atoms, preferably 6-12 atoms.

The halide : phenolate ratio in the titanium halide phenolate is preferably from 1:1 to 3:1. Besides the titanium halide phenolate, a phenolate-free titanium halide can be used in the halogenated titanium compound, if so desired. Preferably, a halide phenolate of tetravalent titanium is used. The value of n is mostly 1, but may also be 2 or higher, especially if a polyphenolate is used.

Specific examples of titanium halide phenolates to be used in the method according to the invention are titanium(lV) trichloride monophenolate, titanium(lV) dichloride di-phenolate, titanium(lV) trichloride mono-p-cresolate, titanium(lll)dichloride mono-ocresolate, titanium(lV) monochloride tri-1 - naphtholate, titanium(lV) trichloride mono-(pchlorophenolate), titanium(lV) tribromide mono-pcresolate, titanium(lV) tribromide mono(xylenolateisomer mixture) and titanium(lV) monoiodide trianisolate. Such compounds can be obtained, for instance, through conversion of the relevant titanium halide with the stoechiometric quantity of the relevant phenol, in which reaction the relevant hydrogen halide is liberated, or th rough double conversion of a titanium halide with a metal phenolate, for instance an alkali metal phenol ate.

As electron donor in the titanium component one or more of the compounds used in a known manner in similar catalyst systems may be used, for instance oxygen-containing electron donors, such as water, alcohols, phenols, ketones, aldehydes, acid halides, carboxylic acids, esters, ethers and acid am ides, or nitrogenous electron donors such as ammonia, amines, nitriles, isocyanates and nitro compounds.

Specific examples of suitable electron donors are alcohols with 1-18 carbon atoms per molecule, for instance methanol, ethanol, propanol, hexanol, stearyl alcohol, benzyl alcohol, phenyl ethyl alcohol orcumyl alcohol; phenols with 6-18 carbon atoms per molecule, for instance phenol, cresol, xylenol, ethyl phenol, propyl phenol, octyl phenol, dibutyl phenol,cumyl phenol ornaphthol; ketones with 3-15 carbon atoms per molecule, for instance acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone or benzophenone; aldehydes with 2-15 carbon atoms per molecule, for instance ethanal, propanal, heptanal, benzaldehyde, tolualdehyde or naphthaldehyde; acid halides with 2-15 carbon atoms per molecule, for instance acetyl chloride, benzoyl chloride ortoluyl chloride; acid amides with 2-15 carbon atoms per molecule, for instance formamide, acetamide, benzamide ortoluamide; amines with 2-18 carbon atoms per molecule, for instance methylamine, ethylamine, diethylamine, triethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline or ethylene diamine; nitriles with 2-15 carbon atoms per molecule, for instance acetonitrile, benzonitrile ortolunitrile; or nitro compounds, for instance nitrobenzene. Preference is given to ethers with 2-20 carbon atoms per molecule, for instance dim ethyl ether, diethyl ether, di-n-butyl ether, di-iso-amyl ether, tetrahydrofuran, anisole or diphenyl ether, and in particular organic esters with 2-40, in particular 2-18, carbon atoms per molecule.The acid component of the ester mostly contains 1-9 carbon atoms per molecule or is a natural fatty acid, while the alcohol component mostly contains 1-6 carbon atoms per molecule.

Examples of suitable esters are methyl formate, cyclohexyl formate, ethyl acetate, vinyl acetate, amyl acetate, 2-ethyl hexyl acetate, cyclohexyl acetate, ethyl propionate, amyl propionate, methyl butyrate, ethyl valeriate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, ethyl crotonate, dimethyl maleate, ethyl cyclohexane carboxylate, methyl benzoate, ethyl benzoate, i-butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzo- ate, phenyl ethyl benzoate, methyl toluate, ethyl toluate, i-amyl toluate, methyl anisate, ethyl anisate, y-butyrolactone, E-caprolactone, coumarin, phthalide and ethylene carbonate.Particular preference is given to esters derived from aromatic acids, in particular esters of benzoic acid, substituted or not with alkyl or alkoxy groups. Alkyl esters with 1-4 carbon atoms per alkyl group, in particular methyl or ethyl esters of benzoic acid, o- or p-toluene carboxylic acid, p-methoxy benzoic acid or phthalic acid, are preferred in particular.

Besides the halogenated titanium compound and the Lewis base, the catalytic titanium component according to the invention contains a mixture of a magnesium halide and an aluminium halide as carrier material. Preferably, this carrier is at least virtually anhydrous and also virtually free of magnesium oxide. Also aluminium oxide is preferably substantially absent.

The expressions 'at least virtually anhydrous' and 'at least virtually free of magnesium oxide' are understood to mean here that the concentration of water and magnesium oxide, respectively, in the carrier material is insignificant, i.e. as regards water at any rate less than 0.2 % by wt., preferably at most 0.1 % by wt., and as regards magnesium oxide as any rate less than 0.1, preferably at most 0.01, mgeq of base per g of carrier material determined by titration with a dilute strong acid, for instance 0.1 N hydrochloric acid.

The carrier material may further contain minor quantities of other metal ions, for instance sodium, tin, silicon or germanium. The halide ion is, in particular, bromide, preferably chloride.

It is remarked that the Japanese patent publication 54033578 (Derwent abstract 30894 B) describes a catalyst for the polymerization of alkenes-1, which contains in the titanium component a mixture of an inorganic magnesium compound and an electron donor-aluminium halide-complex. Such a catalyst shows however only moderate performance. Apparently said complex does not have that particular effect on the performance of the titanium component that the aluminium halide does have.

The carrier material may have been manufactured by any suitable method, preferably by grinding together ofthe magnesium halide and the aluminium halide, for instance in a ball mill, a vibration mill or a beatermill.

The various constituent elements ofthe titanium component may be combined in any known manner.

Preferably, first a complex of the titanium halide compound and the electron donor is prepared.

The complexes of the titanium halide compound and the electron donor may be obtained in any known manner, for instance by bringing the components of the complex into contact with each other.

The titanium halide compound may be applied to the carrier material in any known manner, for instance by simple mixing, preferably by grinding together, for instance in a ball mill, a vibration mill or beater mill. The mixing may be done in the copresence of an inorganic or organic filler, for instance lithium chloride, calcium carbonate, calcium chloride, chromium(ll)chloride, barium chloride, sodium sulphate, sodium carbonate, titanium dioxide, sodium tetraborate, calcium orthophosphate, calcium sulphate, barium carbonate, aluminium sulphate, borium trioxide, aluminium oxide, silicon oxide, polyethylene, polypropylene or polystyrene.

The filler may also have been taken up in the carrier material beforehand. It is possible to first form a complex of the titanium halide compound and the electron donor and apply it to the carrier, or also to first apply the non-complexed titanium halide compound to the carrier and add the electron donor afterwards, either before or after addition of the organoaluminium component used in the finished catalyst It may be advantageous to treat the titanium component with a halogen or an interhalogen compound, for instance bromium, preferably in the absence of an inactive solvent.

The titanium content of the finished titanium component on the carrier normally amounts to between 0.1 and 10 % by wt. The electron donor in the titanium component is preferably present in a quantity of, for instance, 0.1 to 5 molecules per titanium atom. Atypical example of the composition of the titanium component, although varying in dependence on the conditions of the catalyst manufacture, is: 2-10 % by wt. of titanium, 16-25 % by wt.

of magnesium, 1.5-2.5 % by wt. of aluminium, 45-64 % bywt. of halogen and 5-25 % bywt. of the electron donor.

It is pointed out that after combining the titanium halide compound with the metal halide used as carrier, the tetravalent titanium may be reduced to a lower valency, for instance to bi- or trivalent titanium, if so desired, so that the finished titanium component need not necessarily contain tetravalent titanium.

In the finished polymerization catalyst, the titanium compound is used in combination with an organometal component derived from a metal of one of the groups-l-lll of the Periodic System, with a hydrocarbon group bonded direct to the metal.

Examples are trailkyl aluminium compounds, alkyl aluminium alkoxides, alkyl aluminium hydrides, alkyl aluminium halides, dialkyl zinc compounds and dialkyl magnesium compounds. Among these, the organoaluminium compounds are particularly suitable. Examples of the organoaluminium compounds are trialkyl ortrialkenyl aluminium compounds, for instance triethyl aluminium, tripropyl aluminium, triisobutyl aluminium, triisoprenyl aluminium, trihexyl aluminium and trioctyl aluminium; alkyl aluminium compounds in which a number of the aluminium atoms are connected via an oxygen or nitrogen atom, for instance (C2H5)2AlOAI(C2H5)2, (i-C4H9)2AlOAl(i-C4H9)2 or (C2H5)2AIN HAI(C2H5); dialkyl aluminium hydrides such as diethyl aluminium hydride or diisobutyl aluminium hydride; dialkyl aluminium halides, in particular a chloride or bromide, diethyl aluminium chloride and bromide being particularly suitable, while also other dialkyl aluminium halides with preferably 1-10 carbon atoms in the alkyl group, such as for instance di-n-butyl aluminium chloride and methyl-n-butyl aluminium chloride, can be used; and dialkyl aluminium alkoxides or phenoxides, for instance diethyl ethoxy aluminium or diethyl phenoxy aluminium. The trialkyl aluminium compounds deserve most preference.

The organometal compound may also contain a trialkyl aluminium compound as well as a dialkyl aluminium halide or a mixture of a dialkyl magnesium compound and a monoalkyl aluminium dihalide. The alkyl groups of the organoaluminium compounds preferably contain 1-10 carbon atoms each. The alkyl groups of the dialkyl magnesium compound preferably contain 1-10 carbon atoms each or are a palmityl or stearyl group. Examples of suitable dialkyl magnesium compounds are diethyl magnesium, di-n-butyl magnesium, di-n-hexyl magnesium and di-n-octyl magnesium. The monoalkyl aluminium dihalide preferably is a chloride or a bromide.Ethyl aluminium dichloride or dibromide is particularly suitable, but also other monoalkyl aluminium dihalogenides with preferably 1-10 carbon atoms in the alkyl group may be used, such as isopropyl aluminium dichloride, n-butyl aluminium dibromide or n-octyl aluminium dichloride. The molar ratio between the dialkyl magnesium compound and the monoalkyl aluminium dihalide may be between, for instance, 0.1 and 1, preferably between 0.3 and 0.6. Too high a molar ratio leads to insufficiently stereospecific catalysts, while insufficient catalyst activity results if it is too low.

The organometal component preferably contains a complex of an organic metal compound, in particular a trialkyl aluminium compound, with an ester of an oxygen-containing organic acid. Suitable esters are the same esters as may be used in the titanium component, in particular again the esters of aromatic carboxylic acids. For brevity's sake, reference is made to the foregoing. Preferably, part of the organic metal compound, for instance 50-80 %, is present in a non-complexed condition.

The Al : Ti atom ratio is generally between 10 and 1000; the molecule-atom ratio of Lewis base bonded in total in the catalyst to Ti is in general between 5 and 500.

The process according to the invention is applied in particular in the stereospecific polymerization of alkenes-1 with 3-6 carbon atoms per molecule, such as propylene, butylene-1,4-methyl pentylene-1 and hexylene-1, and in the copolymerization of these alkenes-1 with each other and/or with ethylene.

Copolymers with a random arrangement of the various monomer units as well as block copolymers can be produced. If ethylene is taken as a comonomer, it is usual to incorporate minor quantities of it in the polymer, for instance at most 30 % by wt., more in particular between 1 and 15 % by wt. The process according to the invention is of importance in particular for manufacture of isotactic polypropylene, random copolymers of propylene with minor quantities of ethylene, and block copolymers of propylene and ethylene. For the manufacture of block copolymers, any desired sequence of monomer additions may be applied.

The circumstances under which the polymerization reaction with the titanium component according to the invention is carried out do not deviate from those known in the art. The reaction may be carried out in the gas phase or in the presence of a dispersant. The dispersant may be inert or also a monomer in liquid form. Examples of suitable dispersants are aliphatic, cycloaliphatic, aromatic and mixed aromatic/aliphatic hydrocarbons with 3-8 carbon atoms per molecule, for instance propylene, butylene-1, butane, isobutane, n-hexane, n-heptane, cyclohexane, benzene, toluene and the xylenes.

In the case of polymerization in the liquid phase, it is preferable for the concentration of the titanium component to be set at about 0.001-0.5 mmole, calculated as titanium atom, and the concentration of the organometal compound at about 0.1 -50 mmole, both per litre of liquid phase.

The polymerization temperature is normally between 190 and 475 K, preferably between 310 and 375 K. The pressure may be, for instance, between 100 and 3000 kPa.

If so desired, it is possible to regulate the molecu larweightofthe polymer during the polymerization process for instance by carrying out the reaction in the presence of hydrogen or with any other known molecular weight regulator.

The polymerization reaction may be carried out as a batch process or as a continuous process.

The invention will now be elucidated by means of the following non-restrictive examples and the comparative expertiments.

EXAMPLES AND COMPARATIVE EXPERIMENTS Example I A. Preparation ofthe titanium component At 273 K, 6.5 ml of water-free ethyl benzoate (EB), dissolved in 75 ml of water-free gasoline, is added to a solution of 5 ml of TiCI4 and 125 ml of gasoline, flushed with dry nitrogen. The resultant precipitate of TiC14.EB is separated off by filtration and subsequently dried.

At 970 K, commercially available MgC12 is dehydrated further in a flow of CO and Cl2 in order to remove the residual content of H2O and MgO. 3.0 g of this MgCl2, 0.210 g ofAICI3 and 3.4 g ofTiCl4.EB are ground together for 17 hours in a stainless steel ball mill in an atmosphere of dry nitrogen.

B. Polymerization Into a stainless steel reactor, flushed with dry nitrogen and provided with a mechanical agitator, 1.31 of gasoline, 2.5 ml of triisobutyl aluminium (TIBA), 0.25 ml EB and 0.068 g of the titanium component prepared as described under IA are introduced. By leading in propylene, the pressure is raised to and maintained at 700 kPa. The temperature is raised to and maintained at 333 K. After a polymerization time of 2 hours, the supply of propylene is stopped, the pressure is let off and the polymerization suspension is removed from the reactor. The polymer is separated off by filtration.

The polymerization activity amounts to 870 g of polypropylene (PP)/ mmole Ti.h; the soluble polymer content is 5.5 %. The average particle diameter (d50) is 550 microns.

Comparative experiment A A. Preparation of the titanium component The titanium component is prepared analogously to the procedure described in example IA, except for the omission of addition of AICI3.

B. Polymerization Polymerization is carried out in a manner analogous to that described in example IB, but now 0.065 g of the titanium component meant under point A of this comparative experiment is used. The polymerization activity amounts to 810 g PP/mmole Ti.h; the soluble polymer content is 5.3 %. The averga particle diameter of the polymer (d50) is 400 microns.

Example II A. Preparation of the titanium component The titanium component is prepared analogously to the procedure described in example IA, but now 0.270 g of AICI3 is added.

B. Polymerization Polymerization is carried out in a manner analogous to that described in example IB, but now 0.070 g of the titanium component of example IIA is used.

The polymerization activity now amounts to 920 g PP/mmole Ti.h; the soluble polymer content is 5.5 %.

The average particle diameter of the polymer is 575 microns.

Example Ill A. Preparation of the titanium component The titanium component is prepared analogously to the procedure described in example IA, but now 0.320 g of AICI3 is added.

B. Polymerization Polymerization is carried out in the same way as described in example IB, but now 0.067 g of the titanium component of example IIIA is used.

The polymerization activity amounts to 1080 g PP/mole Ti.h; the dissolved polymer content is 5.5 %.

The average particle diameter is 600 microns.

Example IV A. Preparation of the titanium component The titanium component is prepared analogously to the procedure described in example IA, but now 0.370 g of AICI3 is added.

B. Polymerization Polymerization is carried out in the same way as described in example IB, but now 0.071 g of the titanium component of example IVA is used.

The polymerization activity amounts to 1070 g PP/mmole Ti.h; the dissolved polymer content is 6.2 %. The average particle diameter is 650 microns.

Example V A. Preparation of the titanium component The titanium component is prepared analogously to the procedure described in example IA, but now 0.425 g of AICI3 is added.

B. Polymerization Polymerization is carried out in a manner analogous to that described in example IB, but now 0.072 g of the titanium component of example VA is used.

The polymerization activity amounts to 990 PP/ mmole Ti.h; the dissolved polymer content is 6.4 %.

The average particle diameter is 650 microns.

Comparative experiment B A. Preparation of the titanium component The titanium component is prepared analogously to the procedure described in example IA, but now 0.530 g of AICI3 is ground in.

B. Polymerization Polymerization is carried out in a manner analogous to that described in example IB, but now 0.74 g of the titanium component of comparative experiment B, part A, is used.

The polymerization activity amounts to 720 g PP/mmole Ti.h; the dissolved polymer content is 6.0 %. The average particle diameter is 675 microns.

A graphic representation of the polymerization results above is shown in the figure annexed hereto, in which the polymerization activity a in g of PP/mmole Ti.h has been plotted against the aluminium : magnesium weight ratio rofthetitanium component.

Comparative experiment C A. Preparation of the titanium component The titanium component is prepared analogously to the procedure described in example IA, but in stead of AICI3 now 2.85 g of AlCl3..ethyl benzoatecomplex is used.

B. Polymerization Polymerization is carried out in a manner analogous to that described in example IB, but now 0.069 g of the titanium component of comparative experiment C, part A, is used.

The polymerization activity amounts to 890 g PP/mmole Ti.h; the dissolved polymer content is 7.8 %, the average particle diameter is 675 microns.

Claims (22)

1. Catalytic titanium component useful forthe polymerization of alkenes-1, which titanium component contains a halogenated titanium compound, an electron donor, and a mixture of a magnesium halide and an aluminium halide as carrier, characterized in that the titanium component contains 0.1-10 % by wt. of titanium and in that the titanium: magnesium : aluminium weight ratio amounts to 1 (0.5-20): (0.05-2.5), while the magnesium : aluminium weight ratio is at least :1.

2. Titanium component according to claim 1, characterized in that the titanium : magnesium aluminium weight ratio amounts to 1: (1-5) :(0.2-1).

3. Titanium component according to claim 1 or 2, characterized in that the titanium content amounts to 2-10% bywt.

4. Titanium component according to any one of the claims 1-3, characterized in that the magnesium aluminium weight ratio amounts to 4:1 to 20:1.

5. Titanium component according to any one of the claims 1-4, characterized in that the halogenated titanium compound is TiCI4.

6. Titanium component according to any one of the claims 1-4, characterized in that the halogenated titanium compound is a titanium halide phenolate of the formula TinXaAb, in which X represents a halogen atom and A the acid radical of a phenol, n is a whole number of at least 1, and a and b are such numbers that a/n and b/n both are 1-3, on the understanding that (a + b)/n is equal to 3-4.

7. Titanium component according to claim 6, characterized in that the titanium halide phenolate is a titanium(lV) trichloride monophenolate.

8. Titanium component according to any one of the claims 1-7, characterized in that the electron donor is an ether with 2-20 carbon atoms per molecule.

9. Titanium component according to any one of the claims 1-7, characterized in that the electron donor is an ester the acid component of which contains 1-9 carbon atoms per molecule, or is a natural fatty acid, while the alcohol component contains 1-6 carbon atoms per molecule.

10. Titanium component according to claim 9, characterized in that the ester is derived from an aromatic acid.

11. Titanium component according to claim 10, characterized in that the ester is an alkyl ester with 1-4 carbon atoms per alkyl group of benzoic acid, oor p-toluene carboxylic acid, p-methoxy benzoic acid or phthalic acid.

12. Titanium component according to any one of the claims 1-11, characterized in that the mixture of a magnesium halide and an aluminium halide is at least virtually anhydrous and also at least virtually free of magnesium oxide.

13. Titanium component according to any one of the claims 1 -12, characterized in that the carrier material used is a mixture of magnesium chloride and aluminium chloride.

14. Titanium component according to any one of the claims 1-13, characterized in that the carrier material is obtained by grinding together of a magnesium halide and an aluminium halide.

15. Titanium component according to claim 1, as substantially described in the specification and/or the examples.

16. Process for the preparation of a titanium component according to any of claims 1 to 15, which titanium component contains a halogenated titanium compound, an electron donor and a mixture of a magnesium halide and an aluminium halide, characterized in that a magnesium halide and an aluminium halide in a weight ratio, calculated as magnesium: aluminium, of3:1 to 400:1 are ground together in the absence of an electron donor, and the ground product is further manufactured into the finished titanium component.

17. Processforthe preparation of a titanium component according to claim 16, characterized in thatthetitanium component is manufactured by first forming a complex of the titanium halide component and the electron donor, and grinding this complex together with the mixture of a magnesium halide and an aluminium halide to be used as carrier.

18. Process for the polymerization of alkenes-1 using a catalyst system consisting of a titanium component containing a halogenated titanium compound, an electron donor and a mixture of a magnesium halide and an aluminium halide as carrier, and an organometal component derived from a metal of one of the groups I-Ill of the Periodic System of the Elements, characterized in that a titanium component according to any one of the claims 1-15 and/or manufactured by the process according to claim 16 or 17 is used.

19. Process according to claim 18, characterized in that the organometal component contains a complex of an organic metal compound with an ester of an oxygen-containing organic acid.

20. Process according to claim 16 or 18, as substantially described in the specification and/or the examples.

21. Polymer obtained with application of the process according to any one of the claims 18-20.

22. Shaped object, consisting in whole or in part of polymer according to claim 21.