DE19720980A1 - Supported metallocene catalyst system giving narrow molecular weight distribution in alkene polymerisation - Google Patents

Abstract

Catalyst systems for the polymerisation of 2-12C alk-1-enes contain (a) an inorganic support (I), (b) metallocene complex(es) (II), (c) compound(s) (III) forming metallocenium ions, and optionally (d) organometallic compound(s) (IV) of alkali(ne earth) and/or group IIIB metal(s). (I) is an inorganic oxide with a pH of 1-6, which has pores and channels, the macroscopic volume fraction of which comprises 5-30% of the total particle. Also claimed are (i) preparation of alk-1-ene polymers using the catalyst systems; and (ii) the polymers per se. Polymerisation of 2-12C alk-1-enes, especially propylene or ethylene, is carried out at -50-300 deg C and 0.5-3000 bar, preferably in liquid monomers or in the gas phase. Prepolymerisation in suspension or in liquid monomers may be carried out first.

Description

The present invention relates to catalyst systems for the polymerization of C ₂ - to C ₁₂ -alk-1-enes containing

• A) an inorganic carrier,
• B) at least one metallocene complex,
• C) at least one compound forming metallocenium ions and
• D) optionally at least one organic metal compound an alkali or alkaline earth metal or a metal of III. Main group of the periodic table,

an inorganic oxide being used as the inorganic carrier which has a pH of 1 to 6 and cavities and channels has their macroscopic volume fraction of the total particle is in the range of 5 to 30%.

Furthermore, the present invention relates to a process for the preparation of polymers of C ₂ -C ₁₂ -alk-1-enes with the aid of these catalyst systems, the polymers obtainable hereafter, and also films, fibers and moldings made from these polymers.

Metallocene catalysts are complex compounds of metals from Subgroups of the periodic table with organic ligands, the together with compounds forming metallocenium ions result in complete catalyst system. They allow production novel polyolefins. For commercial use of such Metallocene catalysts in common technical processes Usually a support is required, as this will cause polymer sate with improved morphology can be obtained, as in the EP-A 294 942. Inorganic are often used as carriers or organic oxides used. The productivity of the supported metallocene catalysts is still unsatisfactory.

Inorganic oxides, such as silica gel (SiO ₂ ), are also used in the propylene polymerization with the aid of Ziegler-Natta catalyst systems (US Pat. Nos. 4,857,613, 5,288,824). The propylene polymers obtained in this way can be produced with a very high level of productivity, but they are usually characterized by a broad molar mass distribution and, moreover, they have disadvantages such as, for example, uneven comonomer incorporation.

The object of the present invention was therefore to develop catalyst systems for the polymerization of C ₂ -C ₁₂ -alk-1-enes which lead to polymers of C ₂ -C ₁₂ -alk-1-enes with a narrow molar mass distribution, which do not have the disadvantages described and which are obtained with high productivity.

Accordingly, catalyst systems for the polymerization of C ₂ -C ₁₂ -alk-1-enes have been found which

• A) an inorganic carrier,
• B) at least one metallocene complex,
• C) at least one compound forming metallocenium ions and
• D) optionally at least one organic metal compound an alkali or alkaline earth metal or a metal of III. Main group of the periodic table

contain,
an inorganic oxide is used as the inorganic carrier, which has a pH of 1 to 6 and cavities and channels, the macroscopic volume fraction of the total particle in the range of 5 to 30%.

In addition, a process for the preparation of polymers of C ₂ - to C ₁₂ -alk-1-enes was found, furthermore the polymers obtained therefrom and their use as fibers, films and moldings.

The catalyst system according to the invention is used for the polymerization of C ₂ -C ₁₂ -alk-1-enes. As C ₂ to C ₁₂ alk-1-enes are ethylene, propylene, but-1-ene, pent-1-ene, 4-methyl-pent-1-ene, hex-1-ene, hept-1- s or oct-1-enes and mixtures of these C ₂ - to C ₁₂ -alk-1-enes are preferred. Homopolymers or copolymers of propylene and of ethylene are particularly preferred, the proportion of ethylene or of propylene in the copolymers being at least 50 mol%. In the copolymers of propylene, preference is given to those which contain ethylene or 1-butene or mixtures thereof as further monomers. The copolymers of ethylene are, in particular, those copolymers which contain propylene or but-1-ene or hex-1-ene or oct-1-ene or mixtures thereof as further monomers.

The catalyst systems according to the invention are preferably used to prepare those polymers which
50 to 100 mol% propylene,
0 to 50 mol%, in particular 0 to 30 mol% of ethylene and
0 to 20 mol%, in particular 0 to 10 mol% of C ₄ to C ₁₂ alk-1-enes
contain.

Also preferred are those polymers that
50 to 100 mol% of ethylene,
0 to 50 mol%, in particular 0 to 30 mol%, propylene and
0 to 50 mol%, in particular 0 to 30 mol% of C ₄ to C ₁₂ alk-1-enes
exhibit.

The sum of the mol% always results in 100.

The polymerization using the catalyst according to the invention systems is available at temperatures in the range of -50 to 300 ° C preferably in the range from 0 to 150 ° C, and at pressures in the range from 0.5 to 3000 bar, preferably in the range from 1 to 80 bar, carried out. In this method also according to the invention should the residence times of the respective reaction mixtures 0.5 to 5 hours, especially 0.7 to 3.5 hours be put. It can u. a. also anti statics and molecular weight regulators, for example hydrogen, with be used.

The polymerization can be in solution, in suspension, in liquid Monomers or be carried out in the gas phase. Prefers the polymerization takes place in liquid monomers or in the Gas phase, the stirred gas phase being preferred.

The method according to the invention can also be continuous Lich as well as be carried out discontinuously. Suitable Reactors are u. a. continuously operated stirred kettle, whereby if necessary, a series of several in a row switched stirred tanks can use (reactor cascade).

The catalyst systems according to the invention contain as a compo nente A) an inorganic carrier. As an inorganic carrier uses an inorganic oxide that has a pH value,  determined according to S.R. Morrison, "The Chemical Physics of Surf aces," Plenum Press, New York [1977], pages 130ff, from 1 to 6 and Hohl spaces and channels, their macroscopic volume fraction of the total particle is in the range of 5 to 30%. Prefers In particular, such inorganic oxides are used their pH, d. H. whose negative decimal logarithm is the Proton concentration, in the range from 2 to 5.5 and in particular can be found in the range from 2 to 5. Furthermore, as inorganic carriers, in particular those inorganic oxides used, which have cavities and channels, the macro Scopic volume fraction of the total particle 8 to 30%, preferred 10 to 30% and particularly preferably 15 to 25%.

Inorganic oxides which have an average particle diameter from 5 to 200 μm, in particular from 20 to 90 μm, and an average particle diameter of the primary particles from 1 to 20 μm, in particular from 1 to 5 μm, are used in particular as inorganic carriers . The so-called primary particles are porous, granular particles. The primary particles have pores with a diameter of in particular 1 to 1000 Å. Furthermore, the inorganic oxides to be used according to the invention are also characterized, inter alia, by the fact that they have cavities and channels with an average diameter of 0.1 to 20 μm, in particular 1 to 15 μm. The inorganic oxides also have, in particular, a pore volume of 0.1 to 10 cm ³ / g, preferably 1.0 to 5.0 cm ³ / g, and a specific surface area of 10 to 1000 m ² / g, preferably 100 up to 500 m ² / g.

Because of the presence in the finely divided inorganic oxides Cavities and channels are clearly visible in the carrier material better distribution of the active catalyst components. The cause acidic centers on the surface of the inorganic oxide In addition, homogeneous loading of the catalyst inventory divide. In addition, such acts with cavities and channeled material positive on the diffusions controlled supply of monomers and cocatalysts and thus also on the polymerization kinetics.

Such a finely divided inorganic oxide is u. a. available by spray drying of ground, appropriately sieved Hydrogels, which for this with water or an aliphatic Alcohol to be mashed. During spray drying, the required pH from 1 to 6 also by using ent speaking acidic primary particle suspensions are set. Such a fine-particle inorganic oxide is also in the Available commercially.  

Preferred inorganic carriers are, in particular, oxides of silicon, aluminum, titanium or one of the metals of main group I or II of the periodic table. In addition to aluminum oxide or magnesium oxide or a layered silicate, silica gel (SiO ₂ ) is also used as a very preferred inorganic oxide, which can be obtained in particular by spray drying.

So-called Cogele, ie. H. Mixtures of at least two different inorganic oxides used will.

Preferably, per gram of carrier, i.e. H. component A), 0.1 to 10000 µmol, especially 5 to 200 µmol, of the metallocene complex, d. H. of component B) used.

As component B), the catalyst system according to the invention contains at least one or more metallocene complexes. Complexes of the general formula IV are particularly suitable as metallocene complexes

in which the substituents have the following meaning:
M titanium, zirconium, hafnium, vanadium, niobium or tantalum, as well as elements of III. Subgroup of the periodic table and the lanthanoids,
X fluorine, chlorine, bromine, iodine, hydrogen, C ₁ to C ₁₀ alkyl, C ₆ to C ₁₅ aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, OR ¹⁰ or -NR ¹⁰ R ¹¹ ,
n is an integer between 1 and 3, where n corresponds to the valency of M minus the number 2,
in which
R ¹⁰ and R ^{11 are} C ₁ to C ₁₀ alkyl, C ₆ to C ₁₅ aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical ,
R ⁵ to R ^{9 are} hydrogen, C ₁ to C ₁₀ alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a C ₁ to C ₁₀ alkyl as a substituent, C ₆ to C ₁₅ aryl or arylalkyl, where optionally two adjacent residues may together represent 4 to 15 carbon atoms pointing to saturated or unsaturated cyclic groups or Si (R ¹² ) ₃ with
R ¹² C ₁ to C ₁₀ alkyl, C ₃ to C ₁₀ cycloalkyl or C ₆ to C ₁₅ aryl,
Z for X or

stands,
being the leftovers
R ¹³ to R ^{17 are} hydrogen, C ₁ to C ₁₀ alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a C ₁ to C ₁₀ alkyl as a substituent, are C ₆ to C ₁₅ aryl or arylalkyl and where optionally two adjacent radicals together can represent 4 to 15 carbon atoms-saturated or unsaturated cyclic groups, or Si (R ¹⁸ ) ₃ with
R ^{18 is} C ₁ to C ₁₀ alkyl, C ₆ to C ₁₅ aryl or C ₃ to C ₁₀ cycloalkyl,
or wherein the radicals R ⁸ and Z together form a group -R ¹⁹ -A- in which

= BR ²⁰ , = AlR ²⁰ , -Ge-, -Sn-, -O-, -S-, = SO, = SO2, = NR ²⁰ , = CO, = PR ²⁰ or = P (O) R ²⁰ ,
in which
R ²⁰ , R ²¹ and R ^{22 are the} same or different and represent a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ fluoroalkyl group, a C ₆ -C ₁₀ fluoro aryl group, a C ₆ -C ₁₀ aryl group, a C ₁ -C ₁₀ alkoxy group, a C ₂ -C ₁₀ alkenyl group, a C ₇ -C ₄₀ arylalkyl group, a C ₈ -C ₄₀ aryl alkenyl group or a C ₇ -C ₄₀ -Alkylarylgruppe be or where two adjacent radicals each form a ring with the atoms connecting them, and
M ^{2 is} silicon, germanium or tin,
A is -O-, -S-, NR²³ or PR²³,
With
R ²³ C ₁ to C ₁₀ alkyl, C ₆ to C ₁₅ aryl, C ₃ to C ₁₀ cycloalkyl, alkylaryl or Si (R ²⁴ ) ₃ ,
R ^{24 is} hydrogen, C ₁ to C ₁₀ alkyl, C ₆ to C ₁₅ aryl, which in turn can be substituted by C ₁ to C ₄ alkyl groups or C ₃ to C ₁₀ cycloalkyl
or wherein the radicals R ⁸ and R ¹⁶ together form a group -R ¹⁹ .

Of the metallocene complexes of the general formula IV are

prefers.  

The radicals X can be the same or different, are preferred them right away.

Of the compounds of the formula IVa, those are particularly preferred in which
M titanium, zirconium or hafnium,
X is chlorine, C _{1 to} C ₄ alkyl or phenyl,
n is the number 2 and
R ⁵ to R ^{9 are} hydrogen or C ₁ - to C ₄ -alkyl.

Of the compounds of the formula IVb, preference is given to those in which
M stands for titanium, zirconium or hafnium,
X is chlorine, C _{1 to} C ₄ alkyl or phenyl,
n is the number 2,
R ⁵ to R ^{9 are} hydrogen, C ₁ to C ₄ alkyl or Si (R ¹² ) ₃ ,
R ¹³ to R ^{17 are} hydrogen, C ₁ to C ₄ alkyl or Si (R ¹⁸ ) ₃ .

The compounds of the formula IVb are particularly suitable in which the cyclopentadienyl radicals are the same.

Examples of particularly suitable compounds include:
Bis (cyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride,
Bis (methylcyclopentadienyl) zirconium dichloride,
Bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dichloride and
Bis (trimethylsilylcyclopentadienyl) zirconium dichloride
as well as the corresponding dimethyl zirconium compounds.

Of the compounds of the formula IVc, those in which
R ⁵ and R ^{13 are the} same and represent hydrogen or C ₁ - to C ₁₀ -alkyl groups,
R ⁹ and R ^{17 are the} same and represent hydrogen, a methyl, ethyl, isopropyl or tert-butyl group,
R ⁶ , R ⁷ , R ¹⁴ and R ^{15 have} the meaning
R ⁷ and R ^{15 are} C ₁ to C ₄ alkyl
R ⁶ and R ^{14 are} hydrogen
have or two adjacent radicals R ⁶ and R ⁷ and R ¹⁴ and R ¹⁵ together stand for 4 to 12 carbon atoms pointing to cyclic groups,
R ¹⁹ for

stands,
M for titanium, zirconium or hafnium and
X represents chlorine, C ₁ -C ₄ -alkyl or phenyl.

Examples of particularly suitable complex compounds include
Dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (indenyl) zirconium dichloride,
Dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride,
Ethylene bis (cyclopentadienyl) zirconium dichloride,
Ethylene bis (indenyl) zirconium dichloride,
Ethylene bis (tetrahydroindenyl) zirconium dichloride,
Tetramethylethylene-9-fluorenylcyclopentadienylzirconium dichloride,
Dimethylsilanediylbis (-3-tert.butyl-5-methylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (-3-tert.butyl-5-ethylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (-2-methylindenyl) zirconium dichloride,
Dimethylsilanediylbis (-2-isopropylindenyl) zirconium dichloride,
Dimethylsilanediylbis (-2-tert.butylindenyl) zirconium dichloride,
Diethylsilanediylbis (-2-methylindenyl) zirconium dibromide,
Dimethylsilanediylbis (-3-methyl-5-methylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (-3-ethyl-5-isopropylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (-2-ethylindenyl) zirconium dichloride,
Dimethylsilanediylbis (-2-methylbenzindenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethylbenzindenyl) zirconium dichloride,
Methylphenylsilanediylbis (2-ethylbenzindenyl) zirconium dichloride,
Methylphenylsilanediylbis (2-methylbenzindenyl) zirconium dichloride,
Diphenylsilanediylbis (2-methylbenzindenyl) zirconium dichloride,
Diphenylsilanediylbis (2-ethylbenzindenyl) zirconium dichloride, and
Diphenylsilanediylbis (-2-methylindenyl) hafnium dichloride
as well as the corresponding dimethyl zirconium compounds.

Other examples of suitable complex compounds include
Dimethylsilanediylbis (-2-methyl-4-phenylindenyl) zirconium dichloride,
Dimethylsilanediylbis (-2-methyl-4-naphthylindenyl) zirconium dichloride,
Dimethylsilanediylbis (-2-methyl-4-isopropylindenyl) zirconium dichloride and
Dimethylsilanediylbis (-2-methyl-4,6-diisopropylindenyl) zirconium dichloride and the corresponding dimethylzirconium compounds.

In the case of the compounds of the general formula IVd, those in which
M for titanium or zirconium,
X represents chlorine, C ₁ -C ₄ -alkyl or phenyl.
R ¹⁹ for

stands,
A for -O-, -S-, NR²³
and
R ⁵ to R ⁷ and R ^{9 are} hydrogen, C ₁ to C ₁₀ alkyl, C ₃ to C ₁₀ cycloalkyl, C ₆ to C ₁₅ aryl or Si (R ¹² ) ₃ , or two adjacent ones Residues represent cyclic groups containing 4 to 12 carbon atoms.

The synthesis of such complex compounds can in itself known methods take place, the implementation of the ent appropriately substituted, cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum is preferred.  

Examples of corresponding manufacturing processes include. a. in the Journal of Organometallic Chemistry, 369 (1989), 359-370 described.

Mixtures of different metallocene complexes can also be used be set.

The catalyst system according to the invention contains component C) a compound forming metallocenium ions.

Suitable metallocenium ion-forming compounds are strong, neutral Lewis acids, ionic compounds with Lewis acids Cations and ionic compounds with Bronsted acids as Cation.

As strong, neutral Lewis acids are compounds of the general formula V

M ³ X ¹ X ² X ³ V

preferred in the
M ^{3 is} an element of III. Main group of the periodic table means, in particular B, Al or Ga, preferably B,
X ¹ , X ² and X ³ for hydrogen, C1 to C10 alkyl, C6 to C15 aryl, alkyl aryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical or fluorine, chlorine, bromine or iodine, in particular for haloaryls, preferably for pentafluorophenyl.

Particularly preferred are compounds of the general formula V in which X ¹ , X ² and X ^{3 are the} same, preferably tris (pentafluorophenyl) borane.

Compounds of the general formula VI are ionic compounds with Lewis acid cations

[(Y ^{a +} ) Q ₁ Q ₂ . . . Q _z ] ^{d +} VI

suitable in which
Y is an element of I. to VI. Main group or the I. to VIII. Subgroup of the periodic table means
Q ₁ to Q _z for single negatively charged radicals such as C ₁ to C ₂₈ alkyl, C ₆ to C ₁₅ aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having 6 to 20 C atoms in the aryl and 1 to 28 C atoms in the alkyl radical, C ₃ - to C ₁₀ -cycloalkyl, which may optionally be substituted with C ₁ - to C ₁₀ -alkyl groups, halogen, C ₁ - to C ₂₈ -alkoxy, C ₆ - to C ₁₅ Aryloxy, silyl or mercaptyl groups
a for integers from 1 to 6 and
z represents integers from 0 to 5,
d corresponds to the difference az, but d is greater than or equal to 1.

Carbonium cations, oxonium cations and Sulfonium cations and cationic transition metal complexes. Ins special are the triphenylmethyl cation, the silver cation and to name the 1,1'-dimethylferrocenyl cation. Prefer to own they do not coordinate counterions, especially boron compounds gene, as they are also mentioned in WO 91/09882, preferred Tetrakis (pentafluorophenyl) borate.

Ionic compounds with Bronsted acids as cations and before counterions, which are likewise not coordinating, are in the WO 91/09882 called, preferred cation is the N, N-dimethyl anilinium.

The amount of compounds forming metallocenium ions is preferably 0.1 to 10 equivalents, based on the metallocene complex IV.

Open-chain or cyclic alumoxane compounds of the general formula II or III are particularly suitable as compound C) forming metallocenium ions

where R ^{4 is} a C ₁ to C ₄ alkyl group, preferably a methyl or ethyl group and m is an integer from 5 to 30, preferably 10 to 25.

These oligomeric alumoxane compounds are prepared usually by reacting a solution of trialkyl aluminum with water and is u. a. in EP-A 284 708 and US A 4,794,096.

As a rule, the oligomeric alumoxane verses obtained in this way bonds as mixtures of different lengths, both linear as well as cyclic chain molecules, so that m is the mean can be seen. The alumoxane compounds can also be mixed with other metal alkyls, preferably with aluminum alkyls lie.

Both the metallocene complexes (component B) are preferably as well as the compounds forming metallocenium ions (comp nente C) used in solution, wherein aromatic hydrocarbon substances with 6 to 20 carbon atoms, in particular xylenes and toluene, are particularly preferred.

Furthermore, as component C) aryloxyalumoxanes, as in No. 5,391,793, aminoaluminoxanes as described in US Pat US-A 5,371,260, aminoaluminoxane hydrochlorides, such as in EP-A 633 264, siloxyaluminoxanes, as in the EP-A 621 279 described, or mixtures thereof used will.

It has proven to be advantageous to use the metallocene complexes and the oligomeric alumoxane compound in amounts such that the atomic ratio between aluminum from the oligomeric alumoxane compound and the transition metal from the metallocene complexes is in the range from 10: 1 to 10 ⁶ : 1, in particular in the range Range from 10: 1 to 10 ⁴ : 1.

The catalyst system according to the invention can optionally also be a metal compound of the general formula I as component D)

M ¹ (R ¹ ) _r (R ² ) _s (R ³ ) _t I

in the
M ^{1 is} an alkali metal, an alkaline earth metal or a metal of III. Main group of the periodic table, ie boron, aluminum, gallium, indium or thallium,
R ^{1 is} hydrogen, C ₁ to C ₁₀ alkyl, C ₆ to C ₁₅ aryl, alkylaryl or arylalkyl, each having 1 to C atom in the alkyl radical and 6 to 20 C atoms in the aryl radical,
R ² and R ^{3 are} hydrogen, halogen, C ₁ - to C ₁₀ -alkyl, C ₆ - to C ₁₅ -aryl, alkylaryl, arylalkyl or alkoxy, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in Aryl residue,
r is an integer from 1 to 3
and
s and t are integers from 0 to 2, the sum r + s + t corresponding to the valence of M ¹ ,
contain.

Of the metal compounds of the general formula I, those are preferred in which
M ^{1 means} lithium, magnesium or aluminum and
R ¹ to R ^{3 are} C ₁ to C ₁₀ alkyl.

Particularly preferred metal compounds of the formula I are n-butyl lithium, n-butyl-n-octyl-magnesium, n-butyl-n-heptyl Magnesium, tri-n-hexyl aluminum, tri-iso-butyl aluminum, Triethyl aluminum and trimethyl aluminum.

If component D) is used, it is preferably present in the catalyst system in an amount of 800: 1 to 1: 1, in particular 500: 1 to 50: 1 (molar ratio of M ¹ from I to transition metal M from IV).

Components A), B), C) and optionally D) are combined used as a catalyst system according to the invention.  

The catalyst systems according to the invention are usually ana log EP-A 294 942 available.

A preferred production process for the catalyst systems according to the invention is characterized by the process steps

• a) contacting a solution of a metallocenium ion-forming Compound with a second solvent in which this Compound is only slightly soluble in the presence of the carrier materials,
• b) removing at least a portion of the solvents from the Backing material and
• c) contacting a solution of a mixture of a metalloce nium ion-forming compound and a transition metal com plexes with a second solvent in which this Mixture is only slightly soluble in the presence of the according to a) and
• b) carrier material obtained,

out.

This manufacturing process is in the older German patent registration 196 26 834.6, in particular page 12, line 15, to Page 15, line 27, and examples, as well as in the one cited there EP-A 295 312 described in detail.

The catalyst systems according to the invention are particularly suitable for the preparation of polymers of C ₂ -C ₁₂ -alk-1-enes which are distinguished, inter alia, by a narrow molar mass distribution and very low xylene-soluble fractions. Because of the very low xylene-soluble fractions, the polymers of C ₂ - to C ₁₂ -alk-1-enes, which are also according to the invention, can be used in particular as packaging materials in the food sector.

The process according to the invention, in which the catalyst systems described are used, is characterized, inter alia, by a relatively low outlay in terms of process engineering and by high productivity. The polymers of C ₂ - to C ₁₂ -alk-1-enes obtained therefrom can in particular be processed into fibers, films and moldings.

Examples Comparative Example A I. Production of the carrier material

20 g of silica gel (particle diameter: 20 to 45 µm; specific surface: 280 m ² / g; pore volume: 1.7 cm ³ / g; volume fraction of voids and channels in the total particle: 15%; pH value: 7.0 ) were dehydrated in vacuo at 180 ° C. for 8 hours, then suspended in 250 ml of toluene and then mixed with 160 ml of 1.53 molar methylalumoxane (Witco company) at room temperature. After 12 hours, the silica gel deactivated with methylalumoxane was filtered off, washed twice with 100 ml of toluene and dried in vacuo. The yield was 27.9 g of methyl alumoxane supported with silica gel.

II. Supporting the catalyst

4.9 g of the obtained under I., with methylalumoxane desakti fourth silica gel was added to a mixture of 28 mg Bis- [3,3 '- (- 2-methyl-benzo [e] indenyl)] dimethylsilanediyl zirconium dichloride, 6.3 ml 1.53 molar methylalumoxane solution (in toluene, Witco company) and 22 ml of toluene slowly added.

After 30 minutes the solvent became slow and con trolled to room temperature in a high vacuum. The Yield on the supported catalyst was 5.0 g.

III. Polymerization of propylene

In a dry 10 liter car purged with nitrogen 50 g of polypropylene powder and 10 ml were claves in succession Triisobutylaluminum (2 molar in a heptane solution) and stirred for 15 minutes. Then you filled the reactor in nitrogen countercurrent with 670 mg of the in II. obtained supported catalyst. The reactor was closed next closed again and then again with a stir speed of 350 revolutions / minute at room temperature with 1.5 l liquid propylene filled. After 30 minutes of prepoly temperature was first raised to 65 ° C, the internal pressure of the reactor gradually by automatic Pressure control was increased up to a final pressure of 25 bar. It was then 90 minutes at automatic Propylene gas control (25 bar) in the gas phase at 65 ° C poly merized. After the polymerization was over 10 minutes long relaxed to atmospheric pressure and the resulting poly  merisat discharged in a stream of nitrogen. 340 g were obtained Polypropylene semolina, which has a productivity of 650 g poly propylene / g catalyst / hour corresponds. The associated Polymer data are shown in Table 1 below listed.

The particle diameter of the carrier was determined by Coulter counter analysis (grain size distribution of the Carrier particles), the pore volume and the specific Surface by nitrogen absorption according to DIN 66 131 or by mercury porosimetry according to DIN 66 133. The Determination of the average particle size of the primary particles, the diameter of the cavities and channels and their macro Scopic volume fraction was done with the help of scanning Electron microscopy (scanning electron microscopy) or the Electron Probe Micro Analysis (electron beam micro area analysis) on grain surfaces and grain cross sections of the carrier. The pH of the vehicle was changed to S.R. Morrison, "The Chemical Physics of Surfaces," plenum Press, New York [1977], page 130ff.

Comparative Example B

The procedure was analogous to Comparative Example A, but the supported catalyst was based on a granular, acidic silica gel (particle diameter: 20 to 45 μm; specific surface area: 320 m ² / g; pore volume: 1.75 cm ³ / g; volume fractions of Cavities and channels in the total particle: <5%; pH value: 5.5). 830 mg of supported catalyst gave 1360 g of polymer powder in the polymerization of propylene, which corresponds to a productivity of 1050 g PP / g catalyst / hour. The associated polymer data are listed in Table 1.

example 1

The procedure was analogous to Comparative Example A, but the supported catalyst was based on an acidic silica gel with an increased volume fraction of cavities and channels (particle diameter: 20 to 45 μm; specific surface area: 325 m ² / g; pore volume: 1.50 cm ³ / g; volume fraction of voids and channels in the total particle: 15%; pH value: 5.5). 445 mg of supported catalyst gave 1500 g of polymer powder in the polymerization of propylene, which corresponds to a productivity of 2200 g PP / g catalyst / hour. The associated polymer data are listed in Table 1.

Example 2

The procedure was analogous to Comparative Example A, but the supported catalyst was based on an acidic silica gel (particle diameter: 20 to 45 μm; specific surface area: 325 m ² / g; pore volume: 1.50 cm ³ / g; volume fraction of cavities and channels in the total particle: 15%, pH value: 5.0). 445 mg of supported catalyst gave 1655 g of polymer powder in the polymerization of propylene, which corresponds to a productivity of 2400 g PP / g catalyst / hour. The associated polymer data are listed in Table 1.

Example 3

The procedure was analogous to Comparative Example A, but the supported catalyst was based on an acidic silica gel (particle diameter: 20 to 45 μm; specific surface area: 310 m ² / g; pore volume: 1.60 cm ³ / g; volume fraction of cavities and channels in the total particle: 15%; pH value: 4.5). 410 mg of supported catalyst gave 1620 g of polymer powder in the polymerization of propylene, which corresponds to a productivity of 2550 g PP / g catalyst / hour. The associated polymer data are listed in Table 1.

Example 4

The procedure was analogous to Comparative Example A, but the supported catalyst was based on an acidic silica gel (particle diameter: 20 to 45 μm, specific surface area: 315 m ² / g; pore volume: 1.50 cm ³ / g; volume fraction of cavities and channels in the total particle: 8%; pH value: 5.0). 565 mg of supported catalyst gave 1580 g of polymer powder in the polymerization of propylene, which corresponds to a productivity of 1580 g PP / g catalyst / hour. The associated polymer data are listed in Table 1.

Example 5

The procedure was analogous to Comparative Example A, but the supported catalyst was based on an acidic silica gel (particle diameter: 20 to 45 μm, specific surface area: 325 m ² / g; pore volume: 1.50 cm ³ / g; volume fraction of cavities and channels in the total particle: 24%; pH value: 5.0). 395 mg of supported catalyst gave 1650 g of polymer powder in the polymerization of propylene, which corresponds to a productivity of 2700 g PP / g catalyst / hour. The associated polymer data are listed in Table 1.

Comparative Example C I. Production of the carrier material

12.1 g of silica gel (particle diameter: 20 to 45 µm; specific surface: 280 m ² / g; pore volume: 1.56 cm ³ / g; volume fraction of voids and channels in the total particle: 15%; pH value: 7 , 0) were suspended in 90 ml of heptane and thermostatted to 20 ° C. 33.9 ml of a 1 molar solution of trimethyl aluminum (TMA) in heptane were added within 90 minutes, a temperature of 40 ° C. not being exceeded. After the TMA addition was complete, stirring was continued for 4 hours. The suspension was filtered off and washed twice with 20 ml of heptane each time. After drying at 50 ° C, the modified carrier remained as a free-flowing powder.

II. Supporting the catalyst

To a solution of 131.3 mg bis (n-butylcyclopentadienyl) - zirconium dichloride in 56 ml 1.53 molar methylalumoxane Solution in toluene was at 20 ° C after stirring for 20 minutes Given 12.6 g of the carrier modified according to I. and others Stirred for 45 minutes. Then it was filtered off and then washed twice with heptane. After drying at 50 ° C, 15.1 g of the supported catalyst were obtained as free-flowing powder.

III. Polymerization of ethylene

Into a stirred 10 liter steel autoclave careful flushing with nitrogen and tempering on the Polymerization temperature of 70 ° C 4.5 liters of isobutane and 80 mg / liter n-butyl lithium submitted. Then 365 mg of the supported catalyst obtained from II. with further 0.5 liters of isobutane washed in and ethylene to a total pressure of 38 bar. The pressure in the autoclave was reduced kept constant by adding ethylene. After The polymerization was stopped for 90 minutes by relaxing the Autoclave broken off. 1660 g of polymer fell into shape of a free-flowing semolina. The corresponding poly Merization results are listed in Table 2.  

Example 6

The procedure was analogous to Comparative Example C, but the supported catalyst was based on an acidic silica gel (particle diameter: 20 to 45 μm; specific surface area: 325 m ² / g; pore volume: 1.50 cm ³ / g; volume fraction of cavities and channels in the total particle: 15%; pH value: 5.5). 265 mg of supported catalyst gave 1600 g of polymer powder in the polymerization of ethylene, which corresponds to a productivity of 4000 g of polyethylene (PE) / g of catalyst / hour. The associated polymer data are listed in Table 2.

Example 7

The procedure was analogous to Comparative Example C, but the supported catalyst was based on an acidic silica gel (particle diameter: 20 to 45 μm; specific surface area: 305 m ² / g; pore volume: 1.48 cm ³ / g; volume fraction of cavities and channels in the total particle: 15%; pH value: 5.5). 215 mg of supported catalyst gave 1500 g of polymer powder in the polymerization of ethylene, which corresponds to a productivity of 4600 g PE / g catalyst / hour. The associated polymer data are listed in Table 2.

Comparative Example D

The procedure was analogous to Comparative Example C, but the supported catalyst was based on a granular silica gel (particle diameter: 50 μm; specific surface area: 320 m ² / g; pore volume: 1.75 cm ³ / g; volume fraction of cavities and channels in the overall particle : <5% ,; pH value: 5.5). 440 mg of supported catalyst gave 1440 g of polymer powder in the polymerization of ethylene, which corresponds to a productivity of 2150 g PE / g catalyst / hour. The associated polymer data are listed in Table 2.

Comparative Example E I. Supporting the catalyst

5 g alumina with a pH of 7.5, a volume proportion of voids and channels in the total particle of <1.0% and an activity value of 1 slowly increased a 1.53 molar solution of methylalumoxane (from Witco) added in 80 ml of toluene at 0 ° C. After 12 hours filtered off the alumina, twice with 100 ml of toluene washed and directly to a mixture of 28.5 mg bis- [3,3'-  (2-methylbenzo [e] indenyl)] - dimethylsilanediylzirconiumdi chloride, 6.5 ml of a 1.53 molar solution of methylalumoxane in toluene and 25 ml of toluene are slowly added. After The solvent was slowly and controlled for 30 minutes removed at room temperature in a high vacuum. 5.1 g were obtained a free-flowing powder as a supported catalyst.

II. Polymerization of propylene

In a dry 10 liter car purged with nitrogen 50 g of polypropylene semolina were introduced into the clave. Subsequently 4 liters of liquid propylene, 10 ml of Triiso butyl aluminum (2 molar in heptane) and 975 mg catalyst (received according to I.) into the reactor via a lock. At a stirrer speed of 350 revolutions / minute at Room temperature of the autoclave with another 3 liters of propylene filled. Then the temperature was gradually increased 65 ° C increased, the internal pressure set to 26 bar. Polymerization was carried out at 65 ° C for 90 minutes. After finished Polymerization was at atmospheric pressure for 10 minutes relaxed and the polymer is discharged in the nitrogen atom. 255 g of polypropylene were obtained, which is a productivity of Corresponds to 140 g PP / g catalyst / hour.

Example 8

The procedure was analogous to that of comparative example E, except that the catalyst based on an acidic aluminum oxide (pH = 4.5; Activity: 1, total volume of voids and channels particles of 15%). 945 mg of supported catalyst gave 1050 g of polymer in the polymerization of propylene grits what a productivity of 700 g PP / catalyst / hour corresponds.

Comparative Example F I. Production of the carrier material

250 g of silica gel (heated in vacuo at 140 ° C. for 7 hours) were suspended in 2000 ml of heptane and mixed with 350 ml of a 2 molar solution of triisobutylaluminum in heptane. The silica gel was filtered off, washed with heptane and dried in vacuo. The pre-treated carrier was obtained as a free-flowing powder. This had a particle diameter of 20 to 45 µm, a specific surface area of 320 m ² / g, a pore volume of 1.75 cm ³ / g, volume fraction of cavities and channels in the total particle of <5.0% and a pH Value of 7.0.

II. Supporting the catalyst

A suspension of 0.5 mmol dicyclopentadienylzircondi chloride, 0.5 mmol N, N-dimethylanilinium tetrakis pentafluoro phenylborate and 5 g pretreated silica gel in 50 ml of toluene was heated to 80 ° C and at 30 minutes this temperature stirred. Then the toluene was in vacuo distilled off and the supported catalyst was obtained as a free-flowing powder.

III. Polymerization of ethylene

After stirring in a 10 liter steel autoclave flushing with nitrogen and tempering on the poly merisation temperature of 70 ° C 4.5 liters of isobutane and 150 mg Butyl-heptyl-magnesium submitted. Then 280 mg of the after II. Supported catalyst with a further 0.5 liters of isobutane washed in and ethylene to a total pressure of 38 bar pressed. The pressure in the autoclave was controlled by replenishing kept constant by ethylene. After 90 minutes the Polymerization terminated by relaxing the autoclave. 160 g of polymer fell in the form of a free-flowing Semolina with a productivity of 370 g PE / g Kataly sator / hour. The associated polymer data are listed in Table 3.

Example 9

The procedure was analogous to Comparative Example F, but the supported catalyst was based on a spray-dried silica gel (particle diameter: 20 to 45 μm; specific surface area: 325 m ² / g; pore volume: 1.50 cm ³ / g; volume fraction of cavities and channels in the total particle: 15%; pH value: 5.5). 68 mg of supported catalyst provided 200 g of polymer powder in the polymerization of ethylene, which corresponds to a productivity of 2000 g PE / g catalyst / hour. The associated polymer data are listed in Table 3.

Comparative Example G

The procedure was analogous to that of Comparative Example F, the supported catalyst was based on a granular silica gel (particle diameter: 20 to 45 μm; specific surface area: 320 m ² / g; pore volume: 1.75 cm ³ / g; volume fraction of cavities and channels in the total particle: <5%; pH value: 7.0), but di-n-butylcyclopentadienyl zirconium dichloride was used as the metallocene component. 66 mg of supported catalyst gave 255 g of polymer powder in the polymerization of ethylene, which corresponds to a productivity of 2560 g PE / g catalyst / hour. The associated polymer data are listed in Table 3.

Example 10

The procedure was analogous to Comparative Example F, the supported catalyst was based on a spray-dried silica gel (particle diameter: 20 to 45 μm; specific surface area: 325 m ² / g; pore volume: 1.50 cm ³ / g; volume fraction of cavities and Channels in the total particle: 15%; pH value: 5.5), but di-n-butylcyclopentadienyl zirconium dichloride was used as the metallocene component. 81 mg of supported catalyst gave 420 g of polymer powder in the polymerization of ethylene, which corresponds to a productivity of 3500 g PE / g catalyst / hour. The associated polymer data are listed in Table 3.

Comparative Example H

The procedure was analogous to that of Comparative Example F, the supported catalyst was based on a granular silica gel (particle diameter: 20 to 45 μm; specific surface area: 320 m ² / g; pore volume: 1.75 cm ³ / g; volume fraction of cavities and channels in the total particle: <5%; pH value: 7.0), but dimethylsilylbis (1-indenyl) zirconium dichloride was used as the metallocene component. 75 mg of supported catalyst gave 195 g of polymer powder in the polymerization of ethylene, which corresponds to a productivity of 1700 g PE / g catalyst / hour. The associated polymer data are listed in Table 3.

Example 11

The procedure was analogous to Comparative Example F, the supported catalyst was based on a spray-dried silica gel (particle diameter: 20 to 45 μm; specific surface area: 325 m ² / g; pore volume: 1.50 cm ³ / g; volume fraction of cavities and Channels in the total particle: 15%; pH value: 5.5), but dimethylsilylbis (1-indenyl) zirconium dichloride was used as the metallocene component. 72 mg of supported catalyst gave 240 g of polymer powder in the polymerization of ethylene, which corresponds to a productivity of 2200 g PE / g catalyst / hour. The associated polymer data are listed in Table 3.

From Tables 1 to 3 u. a. indicates that use an inorganic carrier with a pH of 1 to 6 and a macroscopic volume fraction of cavities and channels on Total particles from 5 to 30% according to the inventive case play 1 to 11 in contrast to comparative examples A to H leads to polymers with reduced xylene-soluble fractions. Examples 1 according to the invention are also distinguished to 11 by significantly increased productivity.

Example 12 I. Production of the carrier material

100 g of granular silica gel (particle diameter 20 to 45 µm; specific surface 320 m ² / g; pore volume 1.75 cm ³ / g; channels in the total particle <5%; pH 5.5) were vacuumed at 180 for 8 hours ° C dehydrated, then suspended in 450 ml of toluene and then mixed with 775 ml of 1.53 molar methylalumoxane (in toluene, Witco) at room temperature. After 12 hours, the activated silica gel with methylalumoxane was mixed with 750 ml of isododecane and stirred for a further 1.5 hours at room temperature. The support material was then filtered off, washed twice with 150 ml of toluene and twice with 150 ml of pentane and dried in a nitrogen eddy current. The yield of deactivated methyl alumoxane silica gel was 146 g.

II. Supporting the catalyst

146 g of the obtained under I., with methylalumoxane des activated silica gel became a mixture of 5.25 g Bis- [3,3 '- (- 2-methyl-benzo [e] indenyl)] dimethylsilanediylzirko nium dichloride, and 1.2 l of 1.53 molar methylalumoxane solution (in toluene, Witco) added and ge at room temperature stirs. After 20 hours, 2.5 l was added within 4 hours Iso-dodecane added slowly and in a controlled manner and others Stirred for 1.5 hours at room temperature. Then was the solids content is filtered off, each with 150 ml of pentane and dried in a nitrogen eddy current. The yield on the supported catalyst was 154 g. Si content of the kata lysators: 25.42% by weight.  

Examples 13 to 15 Polymerization in a continuous 200 l gas phase reactor

The polymerizations were carried out in a vertically mixed gas phase reactor carried out with a useful volume of 200 l. Of the Reactor contained a moving fixed bed made of finely divided polymer sat. The reactor output was 20 kg polypropylene in all cases per hour. The polymerization results of Examples 13, 14 and 15 are listed in Table 4.

Example 13

Liquid propylene was depressurized in the gas phase reactor at a pressure of 24 bar and a temperature of 60 ° C. The dosing of the catalyst from Example 12 was carried out together with the propylene added for pressure control. The amount of catalyst added was measured so that the average output of 20 kg / h was maintained. Tri isobutylaluminum (TIBA) was also metered in in an amount of 30 mmol / h as a 1 molar solution in heptane. By briefly relaxing the reactor via a dip tube, successive polymer was removed from the reactor. Productivity was calculated from the silicon content of the polymer using the following formula:

P = Si content of the catalyst / Si content of the product

The procedural parameters and characteristic Product properties are shown in Table 4.

Example 14

Example 13 was repeated with the difference that as Molecular weight regulator hydrogen was used. The water concentration of the substance in the reaction gas was determined by gas chromatography averages. The procedural parameters and characteristics The product properties are shown in Table 4.

Example 15

Example 13 was repeated with the difference that 1-butene was used as Comonomeres was metered into the reactor. The butene concentration tion in the reaction gas was determined by gas chromatography. The procedural parameters and characteristic product properties are shown in Table 4.  

Example 16 I. Production of the carrier material

100 g of silica gel (particle diameter 20 to 45 µm; specific surface 325 m ² / g; pore volume 1.50 cm ³ / g; channels in the total particle 15%; pH 5.0) were in vacuo at 180 ° for 8 hours C dehydrated, then suspended in 450 ml of toluene and then mixed with 775 ml of 1.53 molar methyl alumoxane (in toluene, from Witco) at room temperature. After 12 hours, the silica gel deactivated with methylalumoxane was added to 750 ml of isododecane and the mixture was stirred for a further 1.5 hours at room temperature. The support material was then filtered off, washed twice with 150 ml of toluene and twice with 150 ml of pentane and dried in a nitrogen eddy current. The yield of deactivated methylalumoxane silica gel was 159 g.

II. Supporting the catalyst

159 g of the obtained under I., with methylalumoxane des activated silica gel became a mixture of 5.25 g Bis- [3,3 '- (- 2-methyl-benzo [e] indenyl)] dimethylsilanediylzirko nium dichloride, and 1.2 l of 1.53 molar methylalumoxane solution (in toluene, Witco) added and ge at room temperature stirs. After 20 hours, 2.5 l was added within 4 hours Iso-dodecane added slowly and in a controlled manner and others Stirred for 1.5 hours at room temperature. Then was the solids content is filtered off, each with 150 ml of pentane and dried in a nitrogen eddy current. The yield on the supported catalyst was 165 g. Si content of the kata lysators: 24.73% by weight.

Examples 17 to 19 Polymerization in a continuous 200 l gas phase reactor

The polymerizations were mixed in a vertical Gas phase reactor carried out with a useful volume of 200 l. The reactor contained a moving fixed bed made of finely divided poly merisat. The reactor output was 20 kg poly in all cases propylene per hour. The polymerization results from Example 17, 18 and 19 are listed in Table 4.  

Example 17

Liquid propylene was depressurized in the gas phase reactor at a pressure of 24 bar and a temperature of 60 ° C. The dosage of the catalyst from Example 16 was carried out together with the propylene added for pressure control. The amount of catalyst added was measured so that the average output of 20 kg / h was maintained. Tri isobutylaluminum (TIBA) was also metered in in an amount of 30 mmol / h as a 1 molar solution in heptane. By briefly relaxing the reactor via a dip tube, successive polymer was removed from the reactor. Productivity was calculated from the silicon content of the polymer using the following formula:

P = Si content of the catalyst / Si content of the product

The procedural parameters and characteristic Product properties are shown in Table 4.

Example 18

Example 17 was repeated with the difference that as Molecular weight regulator hydrogen was used. The water concentration of the substance in the reaction gas was determined by gas chromatography averages. The procedural parameters and characteristics The product properties are shown in Table 4.

Example 19

Example 17 was repeated with the difference that 1-butene was metered into the reactor as a comonomer. The butene concentration in the reaction gas was determined by gas chromatography. The process parameters and characteristic product properties are shown in Table 4.

Examples 20, 20V, 21 and 21V 1. Spin tests Examples 20, 20V

The spinning tests were carried out on a Barmag 4E / 1-Rieter J0 / 10 spinning and drawing machine. The spinning temperatures were 240 ° C, the stretching ratio 1: 3.4 at a stretching speed of 2,000 m / min. A titer of approximately dtex1220 f68 with a trilobal nozzle geometry was spun. A melt sieve pack of 6,000 / 1,500 / 300 mesh was used in front of the spinneret. The initial pressure before the screen packing was 60 bar. The blowing wind was 0.8 m / sec, the blowing temperature 18 ° C, the preparation order 0.8%. The spinning behavior and the fiber properties can be found in Table S1. A metallocene homopolymer with a flowability of 20 g / 10 min from Examples 14 (Example 20V) and 18 (Example 20) was used for the spinning experiments.
Example 20V: Catalyst on granular silica gel according to example 12;
Example 20: Catalyst on spherical silica gel according to example 16.

Table S1

As can be seen from Table S1, the polypropylene shows from example 20V significantly worse spinning and stretching behavior due to filament breaks and poorer filament properties such as lower filament strength and higher filament uneven Liquidity, expressed by the actual value, in comparison to the poly propylene from Example 20

2nd flat film test Examples 21 and 21V

For the experiments, films were placed on a flat film line produced. This consisted of a 90 mm bar extruder with a 25 D screw with mixing part and an 800 mm Johnson nozzle with a nozzle gap of 0.5 mm. The temperatures in the Ex ascending were 210 ° C to 255 ° C, the nozzle temperature at 250 ° C. The chill roll temperature was 20 ° C, the films train speed 14 m / min with a conveying capacity of 30 kg / h.

For the flat film tests, one metallocene homopoly mer each with a flowability of 7 g / 10 min, preparation analogous to Examples 14 and 18 was used.
Example 21V: Catalyst on granular silica gel according to Example 12;
Example 21: Catalyst on spherical silica gel according to example 16.

The film properties can be found in Table F2.  

Table F2

As can be seen from Table F2, the foils according to Bei game 21 better film properties, especially better opti properties such as lower resins or higher gloss than the films according to Example 21V.

The results from Examples 12 to 21 show that the Catalyst systems according to the invention have particularly good properties ten, for example, have high productivity values if they follow the manufacturing process according to the older German patent application 19626834.6 can be obtained. That gets with these catalysts Lichen polymers provide fibers or films, for example, u. a. with good mechanical and optical properties.

Claims (17)

1. Catalyst systems for the polymerization of C ₂ - to C ₁₂ -alk-1-enes, containing

• A) an inorganic carrier,
• B) at least one metallocene complex,
• C) at least one compound forming metallocenium ions and
• D) optionally at least one organic metal compound of an alkali or alkaline earth metal or a metal of III. Main group of the periodic table,

where an inorganic oxide is used as the inorganic carrier, which has a pH of 1 to 6 and cavities and channels, the macroscopic volume fraction of the total particle is in the range of 5 to 30%. 2. Catalyst systems according to claim 1, wherein the inorganic Carrier A) has a pH of 2 to 5.5 and cavities and Has channels whose macroscopic volume fraction on Total particles are in the range of 8 to 30%. 3. Catalyst systems according to one of claims 1 or 2, wherein the inorganic carrier has an average particle diameter from 5 to 200 µm, an average particle diameter of Primary particles from 1 to 20 µm and cavities and channels with has an average diameter of 0.1 to 20 microns. 4. Catalyst systems according to claims 1 to 3, wherein it is the inorganic carrier around an oxide of silicon, of aluminum, titanium or an oxide of a metal the 1st or 2nd main group of the periodic table. 5. A catalyst system according to claim 4, wherein the inorganic support is silica gel (SiO ₂ ). 6. Catalyst systems according to claim 5, wherein the silica gel used (SiO ₂ ) is spray dried. 7. Catalyst systems according to claims 1 to 6, wherein a Metallocene complex B) of titanium, zirconium or hafnium is used. 8. Catalyst systems according to claims 1 to 7, wherein a metal compound of the general formula I is used as the organic metal compound D),
M ¹ (R ¹ ) _r (R ² ) _s (R ³ ) _t I
in the
M ^{1 is} an alkali metal, an alkaline earth metal or a metal of III. Main group of the periodic table means
R ^{1 is} hydrogen, C ₁ to C ₁₀ alkyl, C ₆ to C ₁₅ aryl, alkylaryl or arylalkyl, each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical,
R ² and R ^{3 are} hydrogen, halogen, C ₁ - to C ₁₀ -alkyl, C ₆ - to C ₁₅ -aryl, alkylaryl, arylalkyl or alkoxy, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in Aryl residue,
r is an integer from 1 to 3
and
s and t are integers from 0 to 2, the sum r + s + t corresponding to the valence of M ¹ . 9. Catalyst systems according to claims 1 to 8, wherein open-chain or cyclic alumoxane compounds of the general formula II or III are used as the compound c) forming metallocenium ions,
wherein R ^{4 is} a C ₁ to C ₄ alkyl group and m is an integer from 5 to 30. 10. A process for the preparation of polymers of C ₂ - to C ₁₂ -alk-1-enes at temperatures in the range from -50 to 300 ° C and pressures from 0.5 to 3000 bar, characterized in that a catalyst system according to of claims 1 to 9 used. 11. The method according to claim 10, characterized in that the Polymerization in liquid monomers or in the gas phase he follows. 12. The method according to any one of claims 10 or 11, characterized characterized in that a prepolymerization in Suspension or in liquid monomers. 13. The method according to any one of claims 10 to 12, characterized in that one uses as C ₂ - to C ₁₂ -alk-1-ene propylene. 14. The method according to any one of claims 10 to 12, characterized in that ethylene is used as C ₂ - to C ₁₂ -alk-1-ene. 15. Polymers of C ₂ - to C ₁₂ -alk-1-enes, obtainable by a process according to any one of claims 10 to 14. 16. Use of the polymers of C ₂ - to C ₁₂ -alk-1-enes according to claim 15 for the production of fibers, films and moldings. 17. Fibers, films and moldings obtainable from the poly merisates of C ₂ to C ₁₂ alk-1-enes according to Claim 15.