DE19623225A1 - Supported metallocene catalyst system giving narrow molecular weight distribution in alkene polymerisation - Google Patents

Abstract

A catalyst systems for the polymerisation of 2-12C alk-1-enes comprises: (A) an inorganic oxide carrier with a pH of 1-6 which comprises 5-30 vol.% voids and channels; (B) at least one metallocene complex; (C) at least one metallocenium ion-forming compound; and optionally (D) at least one alkali(ne earth) or Group III metal organic compound. Also claimed are (i) the preparation of 2-12C alk-1-ene polymers at -50 to +300 deg.C and 0.5-3000 bar using these catalyst systems, (ii) 2-12C alk-1-ene polymers prepared by this method, (iii) the use of these polymers for the preparation of fibres, films or moulded articles and (iv) fibres, films or moulded articles made from these polymers.

Description

The present invention relates to catalyst systems for Polymerization of C₂ to C₁₂-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 method for Preparation of polymers from C₂ to C₁₂-alk-1-enes with the help of these catalyst systems, the polymers obtainable hereafter as well as 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 (SiO₂) also in propylene polymerization with the help of Ziegler-Natta Catalyst systems used (US-A 4 857 613, US-A 5 288 824). The propylene polymers obtained in this way can be used with a right high productivity, but they are mostly through characterized a broad molecular weight distribution and beyond  they still have disadvantages such as unequal moderate comonomer installation.

The present invention was therefore based on the object Catalyst systems for the polymerization of C₂ to C₁₂ alk-1-enes to develop with polymers from C₂ to C₁₂-alk-1-enes a narrow molecular weight distribution, which the described Do not have disadvantages and get with high productivity be.

Accordingly, catalyst systems for the polymerization of C₂ to C₁₂-alk-1-enes found that

• 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 was found from C₂ to C₁₂-alk-1-enes, furthermore the ones obtained therefrom Polymers and their use as fibers, films and shapes body.

The catalyst system according to the invention becomes a polymerization from C₂ to C₁₂-alk-1-enes used. As C₂ to C₁₂-alk-1-ene are ethylene, propylene, but-1-ene, pent-1-ene, 4-methyl-pent-1-ene, Hex-1-ene, hept-1-ene or oct-1-ene and mixtures thereof C₂- to C₁₂-alk-1-enes preferred. Homo- or copolymers of propylene and ethylene, the Proportion of ethylene or propylene in the copolymers min is at least 50 mol%. In the copolymers of propylene those are preferred which are ethylene or as further monomers But-1-enes or mixtures thereof. For the copolymers Ethylene is particularly such a copolymer  sate, the further monomers propylene or 1-butene or Contain hex-1-ene or oct-1-ene or mixtures thereof.

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 C₄ to C₁₂-alk-1-ene
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 C₄ to C₁₂-alk-1-ene
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 Surfaces," 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%.

In particular, they are also used as inorganic carriers uses inorganic oxides, which are a medium particle diameter from 5 to 200 µm, in particular from 20 to 90 µm, and an average particle diameter of the primary particles of 1 to 20 µm, in particular 1 to 5 µm. Both so-called primary particles are porous, granular particles. The primary particles have pores with a Diameter from 1 to 1000 Å in particular. Furthermore are the inorganic oxides to be used according to the invention u. a. also still characterized in that they have cavities and channels with an average diameter of 0.1 to 20 microns, in particular from 1 to 15 µm. The inorganic oxides also have in particular still a pore volume of 0.1 to 10 cm³ / g, preferred from 1.0 to 5.0 cm³ / g, and a specific surface area from 10 to 1000 m² / g, preferably from 100 to 500 m² / 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 the 1st or 2nd main group of the periodic table. As a whole preferred inorganic oxide is in addition to aluminum oxide or Magnesium oxide or a layered silicate also silica gel (SiO₂) used, this in particular by spray drying can be obtained.

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.

The catalyst system according to the invention contains component B) at least one or more metallocene complexes. As a metallocene complexes are particularly suitable for those of the general formula IV

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, C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl, alkylaryl having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, -OR¹⁰ or -NR¹⁰R¹¹ ,
n is an integer between 1 and 3, where n corresponds to the valency of M minus the number 2,
in which
R¹⁰ and R¹¹ are C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each with
1 to 10 carbon atoms in the alkyl radical and
6 to 20 carbon atoms in the aryl radical,
R⁵ to R⁹ are hydrogen, C₁ to C₁₀ alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a C₁ to C₁₀ alkyl as a substituent, C₆ to C₁₅ aryl or arylalkyl, optionally also two adjacent residues together for 4 to 15 carbon atoms pointing to saturated or unsaturated cyclic groups or Si (R¹²) ₃ with
R¹² is C₁ to C₁₀ alkyl, C₃ to C₁₀ cycloalkyl or C₆ to C₁₅ aryl,
Z for X or

stands,
being the leftovers
R¹³ to R¹⁷ are hydrogen, C₁- to C₁₀-alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a C₁- to C₁₀-alkyl as a substituent, are C₆- to C₁₅-aryl or arylalkyl and optionally also two adjacent radicals together for 4 to 15 carbon atoms having saturated or unsaturated cyclic groups can stand, or Si (R¹⁸) ₃ with
R¹⁸ C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl or C₃ to C₁₀ cycloalkyl,
or wherein the radicals R⁸ and Z together form a group -R¹⁹-A- in which

= BR²⁰, = AlR²⁰, -Ge-, -Sn-, -O-, -S-, = SO, = SO₂, = NR²⁰, = CO, = PR²⁰ or = P (O) R²⁰,
in which
R²⁰, R²¹ and R²² are the same or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ fluoroalkyl group, a C₆-C₁₀ fluoro aryl group, a C₆-C₁₀ aryl group, a C₁-C₁₀ -Alkoxy group, a C₂-C₁₀ alkenyl group, a C₁-C₁ Ar arylalkyl group, a C₈-C Ar-aryl alkenyl group or a C₇-C₄₀-alkylaryl group be or where two adjacent radicals each form a ring with the atoms connecting them, and
M² is silicon, germanium or tin,
A is -O -, - S-, NR²³ or PR²³,
With
R²³ C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl, C₃ to C₁₀ cycloalkyl, alkylaryl or Si (R²⁴) ₃,
R²⁴ is hydrogen, C₁- to C₁₀-alkyl, C₆- to C₁₅-aryl, which in turn can be substituted with C₁- to C₄-alkyl groups or C₃- to C₁₀-cycloalkyl
or wherein the radicals R⁸ and R¹⁶ together form a group -R¹⁹-.

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, C₁ to C₄ alkyl or phenyl,
n is the number 2 and
R⁵ to R⁹ are hydrogen or C₁ to C₄ 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, C₁ to C₄ alkyl or phenyl,
n is the number 2,
R⁵ to R⁹ are hydrogen, C₁ to C₄ alkyl or Si (R¹²) ₃,
R¹³ to R¹⁷ are hydrogen, C₁- to C₄-alkyl or Si (R¹⁸) ₃
mean.

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
R⁵ and R¹³ are the same and represent hydrogen or C₁ to C₁₀ alkyl groups,
R⁹ and R¹⁷ are the same and represent hydrogen, a methyl, ethyl, iso-propyl or tert-butyl group,
R⁶, R⁷, R¹⁴ and R¹⁵ the meaning
R⁷ and R¹⁵ C₁ to C₄ alkyl
R⁶ and R¹⁴ are hydrogen
have or two adjacent radicals R⁶ and R⁷ and R¹⁴ and R¹⁵ together represent 4 to 12 carbon atoms pointing to cyclic groups,
R¹⁹ for

stands,
M for titanium, zirconium or hafnium and
X represents chlorine, C₁ to C₄ 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 (ind enyl) 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, C₁ to C₄ alkyl or phenyl.
R¹⁹ for

stands,
A for -O-, -S-, NR²³
and
R⁵ to R⁷ and R⁹ are hydrogen, C₁- to C₁₀-alkyl, C₃- to C₁₀-cycloalkyl, C₆- to C₁ (-aryl or Si (R¹²) ₃, or two adjacent radicals for 4 to 12 carbon atoms having cyclic Groups stand.

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, compounds of the general my Formula V

M³X¹X²X³ V

preferred in the
M³ an element of III. Main group of the periodic table means, in particular B, Al or Ga, preferably B,
X¹, X² and X³ 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.

Compounds of the general formula V are particularly preferred, in which X¹, X² and X³ are the same, preferably tris (pentafluor phenyl) borane.

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

[(Y ^{a +} ) Q₁Q₂. . .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
Q₁ to Q _z for single negatively charged radicals such as C₁- to C₂₈-alkyl, C₆- to C₁₅-aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl, each with 6 to 20 carbon atoms in the aryl and 1 to 28 carbon atoms in the Alkyl radical, C₃- to C₁₀-cycloalkyl, which can optionally be substituted with C₁- to C₁₀-alkyl groups, halogen, C₁- to C₂₈-alkoxy, C₂- to C₁₅-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.

Particularly suitable as compound C) forming metallocenium ions are open chain or cyclic alumoxane compounds of all general formula II or III

wherein R⁴ is a C₁ to C₄ alkyl group, preferred a methyl or ethyl group and m for one integer from 5 to 30, preferably 10 to 25 stands.

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 advantageous to use the metallocene complexes and to use the oligomeric alumoxane compound in such amounts that the atomic ratio between aluminum from the oligomer Alumoxane compound and the transition metal from the metallocene complexes in the range from 10: 1 to 10⁶: 1, especially in the range from 10: 1 to 10⁴: 1.

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

M¹ (R¹) _r (R²) _s (R³) _t I

in the
M¹ is an alkali, an alkaline earth metal or a metal of III. Main group of the periodic table, ie boron, aluminum, gallium, indium or thallium,
R¹ is hydrogen, C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl, alkylaryl or arylalkyl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
R² and R³ are hydrogen, halogen, C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl, alkylaryl, arylalkyl or alkoxy each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical,
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 M¹,
contain.

Of the metal compounds of the general formula I, those are preferred in which
M¹ means lithium, magnesium or aluminum and
R¹ to R³ are C₁ to C₁₀ 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 in an amount of 800: 1 to 1: 1, in particular 500: 1 to 50: 1 (molar ratio of M¹ from I to transition metal M from IV) contained in the catalyst system.

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 particularly suitable for the preparation of polymers of C₂ to C₁₂-alk-1-enes, the yourself u. a. due to a narrow molecular weight distribution and very low Mark xylene-soluble components. Because of the very low xylene-soluble portions can also be the fiction contemporary polymers of C₂ to C₁₂-alk-1-enes in particular use as packaging materials in the food sector.

The method according to the invention, in which the be Catalyst systems are used is u. a. by a relatively low procedural effort and through characterized high productivity. The ones obtained from it Polymers of C₂ to C₁₂-alk-1-enes can in particular Fibers, foils and moldings are processed.

Examples Comparative Example A I. Production of the carrier material

20 g of silica gel (particle diameter: 20 to 45 µm; spec cal surface: 280 m² / g; Pore volume: 1.7 cc / g; Volume proportions of voids and channels in the total particle: 15%; pH: 7.0) were in vacuo at 180 ° C for 8 hours dehydrated, then suspended in 250 ml of toluene and then with 160 ml of 1.53 molar methylalumoxane (company Witco) at room temperature. After 12 hours it was filtered off silica gel deactivated with methylalumoxane, two times washed with 100 ml of toluene and dried in vacuo. The yield was 27.9 g of methyl-supported silica gel alumoxan.

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 that of Comparative Example A, except that the supported catalyst based on a granular, acidic Silica gel (particle diameter: 20 to 45 µm; specific upper area: 320 m² / g; Pore volume: 1.75 cm³ / g; Volume fractions of Voids and channels in the total particle: <5%; pH value: 5.5) produced. 830 mg of supported catalyst gave the  Polymerization of propylene 1360 g of polymer powder, which one Productivity corresponds to 1050 g PP / g catalyst / hour. The associated polymer data are listed in Table 1.

example 1

The procedure was analogous to that of Comparative Example A, except that the supported catalyst based on an acidic silica gel an increased volume of voids and channels (particles diameter: 20 to 45 µm; specific surface area: 325 m² / g; Pore volume: 1.50 cm³ / g; Volume fraction of cavities and channels in the total particle: 15%; pH value: 5.5). 445 mg supported catalyst provided in the polymerization of Propylene 1500 g polymer grits, which is a productivity of 2200 g PP / g catalyst / hour corresponds. The associated poly Further data are listed in Table 1.

Example 2

The procedure was analogous to that of Comparative Example A, except that the supported catalyst based on an acidic silica gel (Particle diameter: 20 to 45 µm; specific surface: 325 m² / g; Pore volume: 1.50 cm³ / g; Volume fraction of voids and channels in the total particle: 15%, pH: 5.0). 445 mg of supported catalyst gave the polymerization of propylene 1655 g polymer grit, which is a productivity of 2400 g PP / g catalyst / hour corresponds. The associated poly Further data are listed in Table 1.

Example 3

The procedure was analogous to that of Comparative Example A, except that the supported catalyst based on an acidic silica gel (Particle diameter: 20 to 45 µm; specific surface: 310 m² / g; Pore volume: 1.60 cm³ / g; Volume fraction of voids and channels in the total particle: 15%; pH value: 4.5). 410 mg of supported catalyst gave the polymerization of propylene 1620 g polymer grit, which is a productivity of Corresponds to 2550 g PP / g catalyst / hour. The associated poly Further data are listed in Table 1.

Example 4

The procedure was analogous to that of Comparative Example A, except that the supported catalyst based on an acidic silica gel (Particle diameter: 20 to 45 µm, specific surface: 315 m² / g; Pore volume: 1.50 cm³ / g; Volume fraction of voids  and channels in the total particle: 8%; pH value: 5.0). 565 mg of supported catalyst gave the polymerization of propylene 1580 g polymer grit, which is a productivity of Corresponds to 1580 g PP / g catalyst / hour. The associated poly Further data are listed in Table 1.

Example 5

The procedure was analogous to that of Comparative Example A, except that the supported catalyst based on an acidic silica gel (Particle diameter: 20 to 45 µm, specific surface: 325 m² / g; Pore volume: 1.50 cm³ / g; Volume fraction of voids and channels in the total particle: 24%; pH value: 5.0). 395 mg of supported catalyst gave the polymerization of propylene 1650 g polymer grit, which is a productivity of Corresponds to 2700 g PP / g catalyst / hour. The associated poly Further 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; spec cal surface: 280 m² / g; Pore volume: 1.56 cm³ / g; Volume proportion of voids and channels in the total particle: 15%; PH value: 7.0) were suspended in 90 ml of heptane and at 20 ° C thermostated. 33.9 ml a 1 molar solution of trimethyl aluminum (TMA) in heptane added, with a temperature not exceeding 4000 has been. After the TMA addition was complete, an additional 4 hours long stirred. The suspension was filtered off and twice washed with 20 ml of heptane each. 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 of 1.53 molar methylalumoxane solution was in toluene 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 that of Comparative Example C, except that the supported catalyst based on an acidic silica gel (Particle diameter: 20 to 45 µm; specific surface: 325 m² / g; Pore volume: 1.50 cm³ / g; Volume fraction of voids and channels in the total particle: 15%; pH value: 5.5). 265 mg of supported catalyst gave the polymerization of ethylene 1600 g polymer grit, which is a productivity of Corresponds to 4000 g polyethylene (PE) / g catalyst / hour. The associated polymer data are listed in Table 2.

Example 7

The procedure was analogous to that of Comparative Example C, except that the supported catalyst based on an acidic silica gel (Particle diameter: 20 to 45 µm; specific surface: 305 m² / g; Pore volume: 1.48 cm³ / g; Volume fraction of voids and channels in the total particle: 15%; pH value: 5.5). 215 mg of supported catalyst gave the polymerization of ethylene 1500 g polymer grit, which is a productivity of Corresponds to 4600 g PE / g catalyst / hour. The associated poly Further data are listed in Table 2.

Comparative Example D

The procedure was analogous to that of Comparative Example C, except that the supported catalyst based on a granular silica gel (Particle diameter: 50 µm; specific surface area: 320 m² / g; Pore volume: 1.75 cm³ / g; Volume fraction of cavities and channels in the total particle: <5%; pH value: 5.5). 440 mg supported catalyst provided in the polymerization of  Ethylene 1440 g polymer grit, which is a productivity of Corresponds to 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 (at 140 ° C for 7 hours in a vacuum heated) were suspended in 2000 ml of heptane and with 350 ml a 2 molar solution of triisobutylaluminum in heptane transferred. The silica gel was filtered off with heptane washed and dried in vacuo. You got the pre traded carriers as free-flowing powder. This showed one Particle diameter from 20 to 45 µm, a specific upper area of 320 m² / g, a pore volume of 1.75 cm³ / g, volume proportion of voids and channels in the total particle of <5.0% and a pH 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 that of Comparative Example F, except that the supported catalyst based on a spray-dried Silica gel (particle diameter: 20 to 45 µm; specific upper area: 325 m² / g; Pore volume: 1.50 cm³ / g; Volume fraction of hollow clearing and channels in the total particle: 15%; pH value: 5.5) posed. 68 mg of supported catalyst gave the Poly merization of ethylene 200 g polymer grit, which is a produktivi corresponds to 2000 g PE / g catalyst / hour. The supplied Relevant polymer data are listed in Table 3.

Comparative Example G

The procedure was analogous to that of Comparative Example F, the dreary The catalyst was based on a granular silica gel (Particle diameter: 20 to 45 µm; specific surface: 320 m² / g; Pore volume: 1.75 cm³ / g; Volume fraction of voids and channels in the total particle: <5%; pH value: 7.0), however, di-n-butylcyclopentadienyl was used as the metallocene component zirconium dichloride used. Deliver 66 mg of supported catalyst ten in the polymerization of ethylene 255 g of polymer powder, what a productivity of 2560 g PE / g catalyst / hour ent speaks. The associated polymer data are shown in Table 3 listed.

Example 10

The procedure was analogous to that of Comparative Example F, the dreary The catalyst was based on a spray-dried pebble gels (particle diameter: 20 to 45 µm; specific surface: 325 m² / g; Pore volume: 1.50 cm³ / g; Volume fraction of voids and channels in the total particle: 15%; pH value: 5.5), however, di-n-butylcyclopentadienyl was used as the metallocene component zirconium dichloride used. Deliver 81 mg of supported catalyst ten in the polymerization of ethylene 420 g of polymer powder, what a productivity of 3500 g PE / g catalyst / hour ent speaks. The associated polymer data are listed in Table 3 lists.

Comparative Example H

The procedure was analogous to that of Comparative Example F, the dreary The catalyst was based on a granular silica gel (Particle diameter: 20 to 45 µm; specific surface: 320 m² / g; Pore volume: 1.75 cm³ / g; Volume fraction of voids and channels in the total particle: <5%; pH value: 7.0),  however, as the metallocene component, dimethylsilylbis- (1- indenyl) zirconium dichloride used. 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 speaks. The associated polymer data are shown in Table 3 listed.

Example 11

The procedure was analogous to that of Comparative Example F, the dreary The catalyst was based on a spray-dried pebble gels (particle diameter: 20 to 45 µm; specific surface: 325 m² / g; Pore volume: 1.50 cm³ / g; Volume fraction of voids and channels in the total particle: 15%; pH value: 5.5), however, as the metallocene component, dimethylsilylbis- (1- indenyl) zirconium dichloride used. 72 mg of supported catalyst provided 240 g of polymer powder in the polymerization of ethylene, which corresponds to a productivity of 2200 g PE / g catalyst / hour speaks. The associated polymer data are shown in Table 3 listed.

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.

Claims (18)

1. Catalyst systems for the polymerization of C₂- to C₁₂-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,

an inorganic oxide as the inorganic carrier is used, which has a pH of 1 to 6 and hollow spaces and channels, their macroscopic volume proportion 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 it is inorganic carrier is silica gel (SiO₂). 6. Catalyst systems according to claim 5, wherein the used Silica gel (SiO₂) 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), M¹ (R¹) _r (R²) _s (R³) _t Iin the
M¹ is an alkali, an alkaline earth metal or a metal of III. Main group of the periodic table means
R¹ is hydrogen, C₁ to C₁₀ alkyl, C₆ to C₁₅ 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,
R² and R³ are hydrogen, halogen, C₁ to C₁₀ alkyl, C₆ to C₁₅ aryl, alkylaryl, arylalkyl or alkoxy each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical,
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 valency of M¹. 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 R⁴ is a C₁ to C₄ alkyl group and m is an integer from 5 to 30. 10. Process for the preparation of polymers from C₂ to C₁₂-alk-1-enes at temperatures in the range of -50 to 300 ° C. and pressures from 0.5 to 3000 bar, characterized in that a catalyst system according to one 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 characterized in that as C₂- to C₁₂-alk-1-ene propylene used. 14. The method according to any one of claims 10 to 12, characterized records that one uses as C₂- to C₁₂-alk-1-ene ethylene. 15. Polymers of C₂ to C₁₂-alk-1-enes, obtainable according to one Method according to one of claims 10 to 14. 16. Use of the polymers of C₂- to C₁₂-alk-1-enes according to the claim 15 for the production of fibers, films and mold bodies. 17. Fibers, films and moldings, available from the poly Merisates of C₂ to C₁₂-alk-1-enes according to Claim 15.