Catalytic systems for polymerisation processes, their production and application

The present invention relates to a method for producing a supported catalyst system and a supported catalyst system. It is used in the olefin polymerization process. In particular, the invention relates to a method for producing a supported catalyst system for use in the gas phase, in the suspension phase or in the liquid / solution phase, providing a more favorable operation of the reactor in which the metallocene catalyst component is selected from the group consisting of:

rac-dimethylsilandiylbis (2-methyl-4,5-benzindenyl) zirconium dichloride; rac-dimethylsilylbis (2-methylindenyl) zirconium dichloride rac-dimethylsilandiylbis (2-methyl-4,6-diisopropylindenyl) racyl-dimethylsilandiylbis (2-methyl-4-phenylindenyl) zirconyl-ethyl-zirconyl-dimethyl-zirconium-dimethyl-zirconium-dimethyl -fenyloindenylo) zirconium.

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State of the art of the invention

In many polymerization processes, especially in the slurry or gas phase, it is desirable to use a supported catalyst system. Typically, such catalyst systems contain metallocene and alumoxane supported on a support such as silica. For example, U.S. Patent 4,937,217 generally describes a mixture of trimethylaluminum and triethylaluminum added to anhydrous silica, to which a metallocene catalyst component is then added. EP-308177-B1 generally describes the addition of a wet monomer to a reactor containing metallocene, trialkylaluminum and anhydrous silica. U.S. Patent Nos. 4,912,045, 935,397 and 4,937,301 generally relate to the addition of trimethylaluminum to anhydrous silica, followed by the addition of metallocene to provide a dry supported catalyst system. U.S. Patent 4,914,253 describes the addition of trimethylaluminum to anhydrous silica, the addition of a metallocene, followed by drying of the resulting supported catalyst system with an amount of hydrogen to obtain polyethylene wax. US Patent Nos. 5 008 228.5 086 025 and 5 147 949 generally describe the preparation of a supported dry catalyst system by adding trimethylaluminum to water impregnated silica to produce alumoxane in situ followed by the addition of metallocene. U.S. Patent Nos. 4,808,561, 4,897,455 and 4,701,432 describe methods for producing a supported catalyst system by which an inert support, typically silica, is calcined and contacted with bw and contacted with metallocene (metallocenes) and a component activator / catalyst. U.S. Patent No. 5,238,892 describes the preparation of a supported dry catalyst system by mixing metallocene with aluminum alkyl followed by the addition of dehydrated silica. U.S. Patent No. 5,240,894 generally discloses the preparation of a supported metallocene / alumoxane catalyst system by preparing a metallocene / alumoxane reaction solution, adding a porous carrier, and evaporating the resulting suspension to remove residual solvent from the carrier.

Although such supported catalysts are useful, it is desirable to provide an improved metallocene catalyst system that would not cause reactor fouling in the production of the polymer. In particular, in the slurry or gas phase polymerization process using the prior art catalytic systems there is a tendency to cause problems with the reactor during polymerization. In a typical gas phase polymerization process, fine particles in the reactor often accumulate hanging down or sticking to the reactor walls. This phenomenon is often referred to as "layering". The accumulation of polymer particles on the walls of the reactor, in the circulation lines and in the cooling system creates many problems such as poor heat transfer during polymerization. Polymer particles that adhere to the walls of the reactor and can further polymerize, often clump together to form lumps, which can adversely affect the continuous polymerization process. Also in the process of mass polymerization of propylene in the liquid phase using the prior art catalysts there is a tendency to join the polymer particles and to hang them or stick to the reactor walls. It may also adversely affect the continuous polymerization process.

In accordance with the invention, a polymerization catalyst system has been developed which, in the polymerization process, significantly improves the operation of the reactor and provides an improved polymeric product and a method for producing this catalyst system.

The present invention relates to a process for the production of a new supported catalyst system for polymerization. This is an improved method of producing a supported catalyst system that is used in the polymerization process, especially of olefins.

The improved method of producing the supported metal-containing catalyst system according to the invention is to contact the porous support with a reaction product of a metallocene catalyst component and alumoxane in solution, the total volume of the reaction product being less than four times the total pore volume in each

182 074 a squared support, preferably less than the amount at which the suspension is prepared, and the metallocene catalyst component is a chiral bisindenyl transition metal compound from the 4, 5 or 6 group with a bridge.

The system prepared according to the invention is used in the production of polypropylene polyolefins by contacting the propylene monomer, optionally together with a comonomer, in the presence of the catalyst system described above.

Detailed description of the invention

The invention relates to a supported catalyst system for olefin polymerization. The method of producing a catalyst system of the invention includes supporting a metallocene catalyst component or compound with an alumoxane activator or catalyst.

It was found that catalytic systems produced at a higher molar ratio of the metal contained in alumoxane to the transition metal in the metallocene compound show greater activity, but also tend to induce fouling during polymerization. By lowering the ratio of alumoxane to transition metal, not only the tendency to fouling decreases, but also the activity of the catalyst. It has been surprisingly found that by producing a supported catalyst system according to the invention, when the volume of the metallocene solution and the alumoxane compound is less than four times the total pore volume of the porous carrier, preferably in the range from less than necessary to make up the suspension to a volume greater than the volume the pores in the porous carrier are preferably smaller than three times, more preferably less than twice and most preferably in the range from 2.5 to 1.05, catalyst activity is maintained, and in many cases it is increased by simultaneous reduction and in many cases the elimination of overgrowth. Preparation of the catalyst system according to the invention in this way provides a simple, technically useful and economical supported catalyst system. In addition, the catalyst system of the invention allows the production of a high bulk density polymer with improved particle morphology.

The metallocene catalyst component used according to the invention.

The metallocene components of the invention used as metallocene components are biscyclopentadienyl derivatives of the 4,5 or 6 transition metal group. The metallocene components of the catalyst are selected from the group consisting of:

rac-dimethylsilandiylbis (2-methyl-4,5-benzindenyl) zirconium dichloride; rac-dimethylsilylbis (2-methylindenyl) zirconium dichloride rac-dimethylsilandiylbis (2-methyl-4,6-diisopropylindenyl) racyl-dimethylsilandiylbis (2-methyl-4-phenylindenyl) zirconyl-ethyl-zirconyl-dimethyl-zirconium-dimethyl-zirconium-dimethyl -fenyloindenylo) zirconium.

Chiral methanocenes are used in the form of a racemate for the production of high isotacticity polypropylene copolymers.

A pure R or S form can also be used. Using such pure stereoisomeric forms, an optically active polymer can be made. Preferably, the meso form of metallocenes is removed so that the center (or metal atom) will provide stereoregular polymerization. _ _. ...

Stereoisomers can be separated by known methods described in the literature. For some products, rac / meso mixtures may also be used.

Typically, metallocenes are produced by a multistage process involving repeated deprotonation / metalation of aromatic ligands and the introduction of a bridge and central atom through halogen derivatives. The following reaction diagram illustrates the general approach.

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H £ R^c + ButylLi

-7 HR^cLi

H₂R^d + ButylLi 7 HR^dLi

HRC- (CR⁸R⁹) R-R⁷- (CR^sR9n-R^dH

LiRC- (CR⁸R⁹) mR⁷- (CR⁸R 9) n._Rd_Land

X- (CR^sR⁹) M R 7 (CR⁸R⁹) nX ----------------------------_>

Butyl Li

M^:CL (R.⁸R⁹C)_m-_Rc (R8R⁹C) m - R.^c

Cl r⁷

M¹

R¹ Li

Cl (R⁸R⁹C)_n- R^d (R⁸R⁹C)_m-_Rc

R²Li I

- * R⁷ (R⁸R⁹C)_n X = Cl, Br, lor O-tosyl;

R⁷ (R⁸R⁹C)_n

HIM

L

R¹

cl

M¹'• R² • R²

<img file="PL182074B1_D0001.tif" />

The production of metallocenes is described in Journal of Organometallic Chem., 288 (1958), 63-67 and EP-A-320762, both publications incorporated as literature sources.

Analogous metal catalyst components of the invention are described in detail in US Patent Nos. 5,149,819.5 243 001.5 239 022.5 296 434 and 5,276 208, which are incorporated by reference.

Activator according to the invention

According to the invention, the activator or localizer is an alumoxane having the general formula R- (Al-O) n-AlR2

R for oligomeric, linear alumoxane and

R- (Al-O) mI

R

182 074 in the case of an oligomeric cyclic alumoxane, where n and m = 1-40, most preferably 3-20, and R is a C1-8 alkyl group or R is a Cs-Cn aryl group or a hydrogen atom, preferably a methyl group or R may be a mixture of alkyl and aryl substituents.

Many processes are known for the production of alumoxane, which, for example, but not exclusively, are described in US Patent Nos. 4,665,208.4 952 540, 5 091352,5 206 199.5 204 419.4 874 734, 4 924 018.4 908 463.4 968 827.5 308 815.5 329 032.5 248 801.5 235 0815 157 137.5 103 031 and wEP-A-0 561 476, EP-B1-0 279 586, EP-A-0-594 218 and WO 94/10180, which is incorporated as literature sources. The use of visibly clear alumoxane may be beneficial. Turbid or gelled alumoxane can be filtered to obtain a clear solution, or the clear alumoxane can be decanted from the cloudy solution.

Carrier according to the invention

In the description, the terms "support" or "support" are used interchangeably and may mean any support material, preferably a porous support such as talc, inorganic oxides, inorganic chlorides and resinous support materials such as polyolefin or polymeric compounds or any other organic carrier material, etc., with an average particle size of over 10 pm.

Preferred support materials include inorganic oxide materials including metal oxides from the 2,3,4,5 group 13 or 14 of the Periodic Table of Elements. In a preferred embodiment, the catalyst support material is silica, alumina, silica-alumina, or mixtures thereof . Other inorganic oxides, alone or in combination with silica, alumina or silica-alumina, such as magnesium oxide, titania, zirconia etc. can also be used.

The surface area of ​​the catalyst support according to the invention is from about 10 to about 700 m²/ g, pore volume from about 0.1 to about 4.0 cm³/ g and average particle size from about 10 to about 500 pm. Even more preferably, the specific surface area is from about 50 to about 500 m²/ g, pore volume from about 0.5 to about 3.5 cm3 / g and average particle size from about 20 to about 200 pm. Most preferably, the specific surface area is from about 100 to about 400 m2 / g, the pore volume from about 0.8 to about 3.0 cm3 / g, and the average particle size from about 30 to about 100 pm. The pore size of the carrier according to the invention is usually from 10 to 1000 A, preferably from 50 to about 500 A, and most preferably from 75 to about 350 A.

The method of producing a catalyst system according to the invention

In the description and claims, the term "solution" includes a suspension, paste or mixture. Any compatible solvent that can form a solution etc. with at least one metallocene catalyst component and / or with at least one alumoxane of the invention can be used. Examples of, but not the only, solvents include aliphatic, aromatic and saturated hydrocarbons and cyclic hydrocarbons such as isopentane, hexane, toluene, etc. Particularly preferred solvents include cyclic aliphatic and aromatic hydrocarbons, of which toluene is most preferred.

Generally, the supported deposition method involves contacting, in a suitable solvent or other liquid, the metallocene catalyst component as defined above with alumoxane or methylalumoxane (MAO) to obtain a soluble reaction product. The soluble reaction product is then contacted with the porous support, the total volume of soluble reaction product added to the support being less than four times greater than the total pore volume in the porous support, preferably less than the volume necessary to form a suspension, i.e. less than three times. The resulting supported catalyst system can be dried to ensure that substantially all or most of the residual solvent residue is removed from the pores of the support. A free-flowing supported catalyst system is obtained.

In one embodiment, the invention relates to a method for producing a free-flowing, optionally prepolymerized supported catalyst system, consisting in

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a) a mixture of metallocene and alumoxane is prepared in a suitable solvent, in which the metallocene mentioned above is used, b) the mixture is contacted with (a) a porous carrier, the total volume of the mixture added to the porous carrier being in the range of smaller volume from the volume necessary for making the suspension to a volume equal to the total pore volume in the porous carrier, c) substantially all of the solvent is removed, d) a supported catalyst system is obtained and e) optionally, prepolymerization of one or more olefin monomers on a supported catalyst system is obtained to obtain a prepolymerized supported catalyst system for the production of propylene polymers or copolymers thereof with a molecular weight of about 50,000 or more, preferably 100,000 or above, with a melting point of about 135 ° C or above, preferably about 140 ° C or above, and most preferably about 145 ° C or above, and with a bulk density of about 0.30 g / cm3³ or above. The average particle size of the resulting granular polymer is from about 500 to about 1000 μ or above. In the most preferred embodiment, the metallocene and alumoxane are combined to form a solution, which is then added to the porous carrier.

The dried supported catalyst system can also be washed or otherwise treated to remove weakly bound one or more catalyst components. Any hydrocarbon may be used to wash the catalyst system, except that the hydrocarbon should dissolve the catalyst component and should be easily removed from the support. Toluene and hexane are preferably used.

In an embodiment of the invention, the total volume of the metallocene / alumoxane solution is less than threefold, particularly preferably, less than two-fold, and most preferably in the range of 2.5 to 1.05 of the total pore volume in the porous carrier.

Preferably, the solution containing the catalyst component (s) is applied to the support in such a way as to obtain a homogeneous catalyst system, i.e. one in which the component (s) are evenly distributed on and in the particles of the support material. In a preferred embodiment, the total volume of the metallocene-containing solution and activator is added to the carrier in an amount ranging from less than the volume at which the suspension forms to a volume greater than the volume equal to the total pore volume in the carrier, preferably from a volume of 2.5 total pore volume in the carrier to about 1.05 total pore volume in the carrier, even more preferably from a volume of from about 2.4 to about 1.1 of the total pore volume in the carrier, even more preferably from a volume of from about 2.3 to about

1.2 total pore volume in the carrier, even more preferably from a volume of about

2.2 to about 1.25 total pore volume in the carrier, even more preferably from a volume of about 2.1 to about 1.27 total pore volume in the carrier, even more preferably from a volume of about 2.0 to about 1.3 total pore volume in the carrier and particularly preferably from a volume of from about 2.0 to about 1.5 total pore volume in the carrier. Preferably, the solution is introduced dropwise or sprayed onto a carrier that is mixed or otherwise thoroughly homogenised.

Typically, a suspension is formed when two phases are observed, one of which contains all or part of the carrier. The volume of solution necessary to reach this stage will vary, among others, depending on the type of support material and the type of catalyst system components. Just before the point where the suspension forms, there is a stage, which in the description is called the "slime" stage. In the sludge stage, the volume of the solution is such that, although the two phases are not visible, the carrier material is saturated and the carrier particles are tightly packed. Before the sludge stage, the volume of the solution is such that the appearance of the carrier material varies from dry and loose (even if the carrier can contain a solution in an amount close to the pore volume) to dry, but slightly sticky, and then to varying degrees of moist and lumpy, similar to for the appearance of sand moistened to varying degrees.

The volume of solution added to the carrier material ranges from greater than the pore volume to the one required to form the slurry, preferably from greater than the pore volume to the one required to reach the sludge stage. It should be understood that the catalyst systems in the stage are more difficult to mix and require longer drying times compared to

182 074 with those obtained with less solution. Below one pore volume, it may be difficult to obtain an even coating of the support material with the components of the catalytic system. This can lead to overgrowth.

It is believed that in the production of the catalyst system of the invention, such a total volume of solution is added once to the porous carrier or individual portions of the solution are added to the porous carrier that at any time during the preparation of the catalyst system, the volume of the solution is as stated above.

The catalyst system according to the invention can be dried such that it will still contain some solvent, e.g. toluene, in a dried state, but preferably all of the solvent is removed. As used in the description and appended claims, the term "substantially all of the solvent is removed" means that upon drying, more than about 90% of all solvent is removed from the supported catalyst system.

According to the invention, the ratio of the total volume of metallocene component, catalyst, alumoxane and solvent to the total pore volume in the porous support material is from 5: 1 to 0.5: 1, preferably from 2.5: 1, to 0.8: 1, still more preferably from 2: 1 to 0.8: 1, and most preferably from 1: 1 to 0.85: 1.

The method of measuring the total pore volume in a porous carrier is well known. Details of one of the procedures are presented in volume I Esperimental Methods in Catalytic Research (Academic Press, 1968), (see especially pages 67-96). Such a preferred method involves the use of a classical BET apparatus for measuring nitrogen absorption. Another well-known method is described in Innes, Total porosity and Paricle Density of Fluid Catalyst By Liquid Titration, Vol, 28, No. 3, Analytical Chemistry 332-334 (March 1956).

In a preferred embodiment of the invention, the molar ratio of metal in the alumoxane component to the transition metal in the metallocene component is from 10: 1 to 800: 1, preferably from 20: 1 to less than 500: 1, and most preferably from 50: 1 to less than 400: 1.

The supported catalyst system of the invention may include a surface modifier as described in U.S. Patent Application No. 08/322 675 (which is incorporated by reference) and / or an antistatic agent, e.g. as described in U.S. Patent No. 5,283,278, which is introduced as a literature source. Examples of, but not the only, antistatic agents include alcohol, thiol, silanol, diol, ester, ketone, aldehyde, acid, amine and ether compounds. Tertiary amine compounds are preferred. The antistatic agent may be added at any stage of the preparation of the catalyst system on the carrier according to the invention, but it is preferred to add it after forming the catalyst system on the carrier according to the invention being in the form of a suspension or in a dry state. In another embodiment of the invention, the supported catalyst system according to the invention comprises a polyolefin wax or emollient etc.

The catalyst system of the invention is useful in the polymerization of monomers and optionally comonomers in any gas phase, suspension or solution polymerization or prepolymerization process; it can even be used in a process carried out in a high-pressure autoclave. In a preferred embodiment, the gas phase or suspension phase process is carried out, the most preferably being a process for the polymerization of liquid propylene in bulk.

Liquid mass propylene polymerization reaction in gas phase suspension, or copolymerization involving the polymerization of propylene with one or more α-olefin monomers containing 4-20 carbon atoms, preferably 4-12 carbon atoms; examples of α-olefm comonomers include ethylene, butene-1, pentene-14-methylpentene-1, hexene-1, octene-1, decene-1 and cyclic olefins such as styrene. Other monomers may include polar vinyl compounds, diolefins such as dienes, norbomenes, acetylene and aldehyde monomers. The catalyst system of the invention is particularly useful for use in polymerization reactions involving propylene polymerization. All the processes of the invention can be used in polymerization or prepolymerization, optionally in combination with the use of an additive or scavenger to increase catalytic activity.

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The supported catalyst system can optionally be subjected to prepolymerization. Pre-polymerization has been found to improve particle morphology.

Examples

In order to provide a better understanding of the invention, including its basic advantages and limitations, the following examples are given.

All examples used a 30% by weight methylalumoxane supernatant in toluene (available from Albemarle Corporation, Baton Rouge, Louisiana). Those skilled in the art know that methylalumoxane forms a colloidal suspension in toluene with a consistency ranging from a clear, gel-free liquid to a cloudy, gelled liquid, except that the invention preferably uses non-gel methylalumoxane.

Example 1. Catalytic system 1

The precursor solution was obtained by combining with stirring 11.858 g 30% by weight of gel-free methylalumoxane in toluene (61.05 mmol A1) and 0.0747 dimethylsilylbis (2-methylindenyl) zirconium dichloride (0.156 mmol Zr). The precursor solution was added to 8.433 g of MS948 silica, 1.6 cm.3 / g pore volume, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davidson Chemical Co.) previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 0.95. The fine, loose powder was dried under reduced pressure 94818.87 Pascal (28 inch Hg vacuum) at 40 ° C for 16 hours. 11.1447 g of catalyst were obtained. Elemental analysis showed 0.12 wt% Zr and 15.30 wt% A1.

Example 2. Catalytic system 2

The precursor solution was obtained by mixing 4.060 g 30% by weight gel-free methylalumoxane in toluene (20.80 mmol A1) and 0.0252 dimethylsilylbis (2-methylindenyl) zirconium dichloride (0.053 mmol Zr) with stirring. 2.318 g of toluene to dilute the precursor solution. 2.868 g silica (MS948, 1.6 cm3 / g pore volume, Davison Chemical Co.) previously heated to 800 ° C under nitrogen was added to a small beaker, after which the precursor was added in one portion. The ratio of liquid volume to total silica pore volume was 1.53 cm3 / g. The mixture was dried under reduced pressure 94818.87 Pascal (28 inch Hg vacuum) at 40 ° C for 16 hours. 3.908 g of loose catalyst was obtained. Elemental analysis showed 0.12 wt% Zr and 14.34 wt% A1.

Example 3. Catalytic system 3

The precursor solution was obtained by combining with 4,268 g 30% by weight gel-free methylalumoxane in toluene (21.97 mmol A1) and 0.0374 dimethylsilylbis (2-methylindenyl) zirconium dichloride (0.078 mmol Zr). The precursor solution was added to 4.250 g silica (MS948, pore volume 1.6 cm3 / g, Davison Chemical Co.) previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 0.68. The finely divided, loose powder was dried under reduced pressure 94818.87 Pascal (vacuum 28 inches Hg) at 40 ° C for 16 hours. 5.209 g of catalyst was obtained. Elemental analysis showed 0.12 wt.% Zr and 10.68 wt.% A1.

Example 4. Catalytic system 4

The precursor solution was obtained by mixing 4.205 g 30% by weight gel-free methylalumoxane in toluene (21.65 mmol Al) and 0.0367 g dimethylsilylbis (2-methylindenyl) zirconium dichloride (0.077 mmol Zr). The precursor solution was diluted with 1.648 g toluene. The precursor was added to 4.125 g silica (MS948, 1.6 cm3 / g pore volume, Davison Chemical Co.) previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 0.97. The finely divided, loose powder was dried under reduced pressure 94818.87 Pascal (vacuum 28 inches Hg) at 40 ° C for 16 hours. 5.032 g of catalyst was obtained. Elemental analysis showed 0.12 wt.% Zr and 10.96 wt.% A1.

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Example 5. Catalytic system 5

The precursor solution was obtained by mixing 3.106 g 30% by weight of gel-free methylalumoxane in toluene (15.99 mmol A1) and 0.0401 g dimethylsilylbis (2-methylindenyl) zirconium dichloride (0.084 mmol Zr). 2.516 g toluene was added to dilute the precursor. The precursor solution was added to 4.024 g silica (MS948, 1.6 cm pore volume)³/ g, Davison Chemical Co.), previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 0.97. Drying of the finely divided, loose powder was started at 84,659.70 pascal (25 inches Hg) at 35 ° C. Vacuum and temperature were increased to 98,205.26 pascal (29 inches Hg) and 60 ° C over 2.5 hours. Elemental analysis showed 0.13 wt.% Zr and 7.93 wt.% Al. Drying continued for an additional hour. 4.862 g of loose catalyst was obtained.

Example 6. Catalytic system 6

The precursor solution was obtained by mixing 1.560 g 30% by weight gel-free methylalumoxane in toluene (8.03 mmol A1) and 0.0201 g dimethylsilylbis (2-methylindenyl) zirconium dichloride (0.042 mmol Zr) with stirring. 5.504 g of toluene was added to dilute the precursor solution. 2.005 g silica (MS948, 1.6 cc / g pore volume, Davison Chemical Co.), previously heated to 800 ° C under nitrogen, was added to a small beaker, after which the precursor was added in one portion. The ratio of liquid volume to total silica pore volume was 2.48. A paddle was used to mix the mixture, which looked like very wet sand or sludge. The mixture was then dried under 25 inches Hg vacuum at 50 ° C until all liquid was removed, then the vacuum and temperature were raised to 98 205.26 pascal (29 inches Hg) and 60 ° C for 0.75 hours. Elemental analysis showed 0.15 wt% Zr and 8.63 wt% Al. Drying continued for 1.0 hour. 2.444 g of loose catalyst were obtained.

Example 7. Catalytic system 7

The precursor solution was obtained by mixing 1.563 g 30% by weight gel-free methylalumoxane in toluene (8.05 mmol A1) and 0.0209 g dimethylsilylbis (2-methylindenyl) zirconium dichloride (0.044 mmol Zr) with stirring. 17.78 g of fresh toluene was added to dilute the precursor solution. 2.011 g silica (MS948, pore volume 1.6 cm3 / g, Davison Chemical Co.) previously heated to 800 ° C under nitrogen was added to a small beaker, after which the precursor was added in one portion. The ratio of liquid volume to total silica pore volume was 6.70. A paddle was used to mix the mixture, after which the suspension was dried under 8,4659.7 pascal (25 inches Hg) and 25 ° C vacuum until all liquid was removed, then the vacuum and temperature were raised to 94818.87 pascal (28 inches Hg) and 60 ° C within 1.25 hours. Drying was continued for an additional 1.0 hour at 94818.87 pascal (28 inches Hg) and at 60 ° C for 1.0 hour. 2.395 g of loose catalyst was obtained.

Comparative example 8. Catalytic system 8

The precursor solution was obtained by mixing 6.932 g 30% by weight gel-free methylalumoxane in toluene (35.68 mmol Al) and 0.0227 g dimethylsilylbis (2-methylindenyl) zirconium dichloride (0.048 mmol Zr). 12.384 g toluene was added to dilute the precursor solution. 2.007 g silica (MS948, pore volume 1.6 cm3 / g, Davison Chemical Co.) previously heated to 800 ° C under nitrogen atmosphere was slowly added to the precursor solution. The ratio of liquid volume to total silica pore volume was 6.70. The suspension was dried under 8,4659.7 Pascal (25 inches Hg) vacuum at 50 ° C until all liquid was removed, then the vacuum and temperature were raised to 94818.87 Pascal (28 inches Hg) and 60 ° C for 1.5 hours. Drying was continued for an additional 1.0 hour at 94818.87 pascal (28 inches Hg) and at 60 ° C for 1.0 hour. 4.100 g of loose catalyst was obtained. Elemental analysis showed a content of 0.091% by weight Zr and 20.48% by weight Al.

Example 9. Catalytic system 9

The precursor solution was obtained by mixing 5.809 g 30% by weight gel-free methylalumoxane in toluene (29.91 mmol A1) and 0.0365 g dichloride with stirring.

182 074 dimethylsilylbis (2-methylindenyl) zirconium (0.076 mmol Zr). The precursor solution was added to 4.225 g silica (MS948FF, 1.6 cm pore volume)³/ g, Davison Chemical Co.) previously heated to 200 ° C under a nitrogen atmosphere. The ratio of liquid volume to total silica pore volume was 0.93. The finely divided, free-flowing powder was dried in vacuo at 94818.87 pascali (28 inches Hg) at 40 ° C for 16 hours. 4.909 g of catalyst was obtained. Elemental analysis showed 0.126 wt% Zr and 15.98 wt% A1.

Example 10. Catalytic system 10

The precursor solution was obtained by mixing 5.692 g 30% by weight gel-free methylalumoxane in toluene (29.31 mmol A1) and 0.0358 g dimethylsilylbis (2-methylindenyl) zirconium dichloride (0.075 mmol Zr). Using the apparatus as in method 3, the precursor was added to 4.140 g silica (MS948FF, 1.6 cm pore volume)³/ g, Davison Chemical Co.), previously heated to 600 ° C under a nitrogen atmosphere. The ratio of liquid volume to total silica pore volume was 0.93. The finely divided, loose powder was dried under 7445.54 pascal (22 inches Hg) vacuum at 30 ° C for 1.5 hours, followed by 94818.87 pascal (28 inches Hg) at 60 ° C for 2 hours. 5.344 g catalyst was obtained. Elemental analysis showed 0.10 wt% Zr and 15.58 wt% A1.

Examples 9 and 10 illustrate the preparation of the catalyst system according to the invention and show that the silica dehydration temperature is not a decisive parameter

Example 11. Catalytic system 11

The precursor solution was obtained by mixing 4.339 g 30% by weight gel-free methylalumoxane in toluene (22.34 mmol A1) and 0.0273 g dimethylsilylbis (2-methylindenyl) zirconium dichloride (0.057 mmol Zr) with stirring. The precursor solution was added to 3.079 g silica (MS3040, 3.0 cm3 / g pore volume, Philadelphia Quartz), previously heated to 700 ° C in air and then at 50 ° C under vacuum with nitrogen purge. The ratio of liquid volume to total silica pore volume was 0.51. The finely divided, loose powder was dried under 94818.87 pascal (28 inches Hg) vacuum at 40 ° C for 16 hours. 4.054 g of catalyst was obtained. Elemental analysis showed 0.10 wt% Zr and 13.92 wt% Al. This example illustrates the preparation of the catalyst system of the invention using a different porosity support.

Polymerization test for catalytic systems 1-11

A sample of each of the supported catalysts obtained in Examples 1-11 above was suspended in 2 mL of hexane and flushed with 250 mL of propylene in a 2-liter reactor previously purged with nitrogen and containing triethylaluminum (0.5 mL of 1M solution in hexane) and 1000 mL of propylene after where the reactor was heated to 65 ° C. The reaction was carried out for 1 hour, after which the reactor was cooled, degassed and purged with nitrogen for 20 minutes. After purging with nitrogen, the reactor was opened and the product collected, and then dried under vacuum for at least 2 hours at 75 ° C. When any polymer remained on the agitator or thermocouple (fouling), it was collected and weighed separately.

Table 1

<td rowspan="2">Catalyst</td><td colspan="2">Metal content *</td><td rowspan="2">Ratio molar Al / Zr</td><td rowspan="2">% vol. pore</td><td rowspan="2">g polymer / g catalyst</td><td rowspan="2">g polymer / mg Zr</td><td rowspan="2">% overgrowth * *</td>

<td>Al</td><td>Zr</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td>

<td> 1</td><td> 7,24</td><td> 0,019</td><td> 381</td><td> 95</td><td> 2420</td><td> 2017</td><td> ~ 0,5</td>

<td> 2</td><td> 7,29</td><td> 0,018</td><td> 405</td><td> 153</td><td> 2767</td><td> 2306</td><td> ~ 0,5</td>

<td> 3</td><td> 5,17</td><td> 0,018</td><td> 287</td><td> 68</td><td> 2710</td><td> 2258</td><td> ~0,2</td>

<td> 4</td><td> 5,25</td><td> 0,019</td><td> 276</td><td> 97</td><td> 2865</td><td> 2388</td><td> 0,2</td>

<td> 5</td><td> 3,97</td><td> 0,021</td><td> 189</td><td> 97</td><td> 2642</td><td> -</td><td> 0</td>

<td> 6</td><td> 4,00</td><td> 0,021</td><td> 190</td><td> 250</td><td> 2554</td><td> -</td><td> 0</td>

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Table 1 - continued

<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td>

<td> 7</td><td> 4,02</td><td> 0,021</td><td> 191</td><td> 670</td><td> 1876</td><td> -</td><td> 0</td>

<td>C-8</td><td> 17,78</td><td> 0,024</td><td> 740</td><td> 670</td><td> 2320</td><td> 2549</td><td> 11,8</td>

<td> 9</td><td> 7,08</td><td> 0,021</td><td> 337</td><td> 93</td><td> 2417</td><td> 2014</td><td> &lt;0,1</td>

<td> 10</td><td> 7,08</td><td> 0,018</td><td> 393</td><td> 93</td><td> 2292</td><td> 2292</td><td> 0</td>

<td> 11</td><td> 7,26</td><td> 0,019</td><td> 382</td><td> 51</td><td> 2182</td><td> 2182</td><td> &lt;0,1</td>

* mmol / g silica ** g of layered polymer in relation to the total obtained polymer x 100%

Example 12. Catalytic system 12

The precursor solution was obtained by mixing 3.5022 g 30% by weight gel-free methylalumoxane in toluene (18.03 mmol A1) and 0.0654 g dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride (0.104 mmol Zr) with stirring. Then 1.9488 toluene. The precursor solution was added to 4.00 g MS948 silica, 1.6 cm3 / g pore volume, available from WR Grace, Davison Chmical Division, Baltimore, Maryland (Davison Chmemical Co.), previously heated to 600 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 0.95. The finely divided, loose powder was dried under reduced pressure 98,205.26 Pascal (vacuum 29 inches Hg) at a temperature up to 50 ° C for

2.5 hours. 5.12 g of catalyst were obtained. Elemental analysis showed a content of 0.07% by weight Zr and 8.98% by weight Al.

Example 13. Catalytic system 13

The precursor solution was obtained by mixing 3.4997 g 30% by weight gel-free methylalumoxane in toluene (18.02 mmol A1) and 0.0648 g dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride (0.103 mmol Zr) with stirring. 3.6798 g of toluene was then added. The precursor solution was added to 4.00 g silica MS948, pore volume

1.6 cm3 / g, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.), previously heated to 600 ° C under a nitrogen atmosphere. The ratio of liquid volume to total silica pore volume was 1.25. The wet sand solid was dried under 98205.26 Pascal (29 inch Hg vacuum) at 50 ° C for 2.5 hours. 5.11 g of finely divided, loose powder were obtained. Elemental analysis showed a content of 0.07% by weight Zr and 8.64% by weight Al.

Example 14. Catalytic system 14

The precursor solution was obtained by mixing 3.5017 g 30% by weight gel-free methylalumoxane in toluene (18.03 mmol A1) and 0.0653 g dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride (0.104 mmol Zr) with stirring. 9.3018 g of toluene was then added. The precursor solution was added to 4.00 g of MS948 silica, 1.6 cm3 / g pore volume, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.) previously heated to 600 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 2.25. The wet sand solid was dried under reduced pressure 98,205.26 pascal (29 inch Hg vacuum) at 50 ° C for 2.5 hours. 5.11 g of catalyst were obtained in the form of finely divided, loose powder. Elemental analysis showed 0.10 wt.% Zr and 9.21 wt.% Al.

Example 15. Catalytic system 15

The precursor solution was obtained by stirring 5.0489 g 30% by weight gel-free methylalumoxane in toluene (25.992 mmol Al) and 0.0649 g dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride (0.103 mmol Zr). Then 0.5014 g of toluene was added. The precursor solution was added to 4.00 g of MS948 silica, 1.6 cm3 / g pore volume, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.) previously heated to 600 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 0.95. The finely divided, loose powder was dried under reduced pressure 98,205.26 Pascal (vacuum 29 inches Hg) at a temperature up to 50 ° C for

2.5 hours. 5.65 g catalyst was obtained. Elemental analysis showed a content of 0.098% by weight Zr and 13.17% by weight Al.

Example 16. Catalytic system 16

The precursor solution was obtained by stirring 5.0476 g 30% by weight gel-free methylalumoxane in toluene (25.986 mmol A1) and 0.0652 g dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride (0.104 mmol Zr). Then 2.1983 g of toluene was added. The precursor solution was added to 4.00 g silica MS948, pore volume 1.6 cm³/ g, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.), previously heated to 600 ° C under a nitrogen atmosphere. The ratio of liquid volume to total silica pore volume was 1.25. The wet sand solid was dried under 98205.26 Pascal (29 inches Hg vacuum) at 50 ° C for 2.6 hours. 5.60 g of finely divided, loose powder were obtained. Elemental analysis showed 0.089 wt.% Zr and 13.43 wt.% Al.

Example 17. Catalytic system 17

The precursor solution was obtained by stirring 5.0552 g 30% by weight gel-free methylalumoxane in toluene (26.025 mmol Al) and 0.0654 g dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride (0.104 mmol Zr). 7.8602 g of toluene was then added. The precursor solution was added to 4.00 g silica MS948, pore volume

1.6 cm3 / g, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.), previously heated to 600 ° C under a nitrogen atmosphere. The ratio of liquid volume to total silica pore volume was 2.25. The wet sand consistency was dried under reduced pressure 98205.26 pascal (29 inch Hg vacuum) at 50 ° C for 2.3 hours. 5.54 g of finely divided, loose powder were obtained. Elemental analysis showed a content of 0.088% by weight Zr and 13.59% by weight Al.

Example 18. Catalytic system 18

The precursor solution was obtained by mixing 13.3840 g 30% by weight gel-free methylalumoxane in toluene (68.90 mmol A1) and 0.104 g dimethylsilylbis (2-methyl-4,5-benzindenyl) zirconium dichloride (0.176 mmol Zr) with stirring. Then, 1.4120 g of toluene was added. The precursor solution was added to 9.4953 g silica MS948, pore volume

1.6 cm3 / g, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.), previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 0.97. The finely divided, loose powder was dried under reduced pressure 94818.87 pascali (vacuum 28 inches Hg) at a temperature up to 40 ° C overnight. 13.183 g catalyst was obtained. Elemental analysis showed a content of 0.09% by weight Zr and 13.25% by weight Al.

Example 19. Catalytic system 19

The precursor solution was obtained by mixing 4.2500 g 30% by weight gel-free methylalumoxane in toluene (21.88 mmol Al) and 0.0432 g dimethylsilylbis (2-methyl-4,5-benzindenyl) zirconium dichloride (0.075 mmol Zr) ). Then 1.4120 g toluene was added. The precursor solution was added to 4.005 g silica MS948, pore volume

1.6 cm3 / g, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.), previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 0.97. The finely divided, loose powder was dried under reduced pressure 98,205.26 Pascal (29 inch Hg vacuum) at 60 ° C for 2.5 hours. 5.185 g of catalyst was obtained. Elemental analysis showed 0.10 wt.% Zr and 10.64 wt.% Al.

Example 20. Catalytic system 20

The precursor solution was obtained by mixing 3.5902 g 30% by weight gel-free methylalumoxane in toluene (18.48 mmol A1) and 0.0262 g dimethylsilylbis (2-methyl-4,5-benzindenyl) zirconium chloride (0.045 mmol) with stirring ). Then added

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1.8979 g toluene. The precursor solution was added to 4.0055 g silica MS948, pore volume

1.6 cm3 / g, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.), previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 0.94. The finely divided, loose powder was dried under reduced pressure 98,205.26 Pascal (29 inch Hg vacuum) at 60 ° C for 2.5 hours. 4.901 g of catalyst was obtained. Elemental analysis showed 0.06 wt% Zr and 8.22 wt% Al.

Example 21. Catalytic system 21

The precursor solution was obtained by mixing 1.7072 g 30% by weight gel-free methylalumoxane in toluene (8.79 mmol A1) and 0.0257 g dimethylsilylbis (2-methyl-4,5-benzindenyl) zirconium dichloride (0.045 mmol) Zr ). Then 3.5518 g of toluene was added. The precursor solution was added to 3.9309 g silica MS948, pore volume

1.6 cm3 / g, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.), previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 0.94. The finely divided, loose powder was dried under reduced pressure 98,205.26 Pascal (29 inch Hg vacuum) at 60 ° C for 3.2 hours. 4.400 g of catalyst was obtained. Elemental analysis showed a content of 0.07% by weight Zr and 4.76% by weight Al.

Example 22. Catalytic system 22

The precursor solution was obtained by mixing 106 g 30% by weight gel-free methylalumoxane in toluene (546 mmol A1) and 1.10 g dimethylsilylbis (2-methyl-4,5-benzindenyl) zirconium dichloride (1.90 mmol Zr) with stirring. Then 40 g toluene was added. The precursor solution was added to 100 g of silica MS948, 1.6 cm3 / g pore volume, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.) previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 1.0. The solid, which was not completely loose, was dried under reduced pressure 98,205.26 Pascal (29 inch Hg vacuum) at 60 ° C for 3.25 hours. A finely divided, free-flowing, solid catalyst was obtained. Elemental analysis showed 0.11 wt.% Zr and 8.96 wt.% A1.

Example 23. Catalytic system 23

The precursor solution was obtained by mixing 108 g 30% by weight gel-free methylalumoxane in toluene (554 mmol A1) and 1.10 g dimethylsilylbis (2-methyl-4,5-benzindenyl) zirconium dichloride (1.90 mmol Zr) with stirring. Then 72 g toluene was added. The precursor solution was added to 100 g of silica MS948, 1.6 cm3 / g pore volume, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.) previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 1.25. The wet sand solid was dried under reduced pressure 98,205.26 Pascal (29 inch Hg vacuum) at 60 ° C for 3.25 hours. A finely divided, free-flowing, solid catalyst was obtained. Elemental analysis showed 0.12 wt% Zr and 9.26 wt% A1.

Example 24. Catalytic system 24

The precursor solution was obtained by mixing 1.7940 g 30% by weight gel-free methylalumoxane in toluene (9.236 mmol Al) and 0.0135 g dimethylsilylbis (2-methyl-4,5-benzindenyl) zirconium dichloride (0.023 mmol Zr). Then 3.3578 g toluene was added. The precursor solution was added to 2.0153 g silica MS948, pore volume

1.6 cm3 / g, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.), previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 2.5. The wet sand solid was dried under 98205.26 Pascal (29 inch Hg vacuum) at 60 ° C for 3 hours. 2.6172 g of finely divided, loose, solid catalyst were obtained. Elemental analysis showed 0.11 wt.% Zr and 8.82 wt.% Al.

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Example 25. Catalytic system 25

The precursor solution was obtained by mixing 0.88765 g 30% by weight gel-free methylalumoxane in toluene (4.508 mmol A1) and 0.0146 g dimethylsilylbis (2-methyl-4,5-benzindenyl) zirconium dichloride (0.025 mmol Zr) with stirring. Then 6,2009 g of toluene was added. The precursor solution was added to 2.0015 g silica MS948, pore volume

1.6 cm³/ g, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.), previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 2.5. The wet sand solid was dried under 98205.26 Pascal (29 inch Hg vacuum) at 60 ° C for 3 hours. 2.4446 g of finely divided, loose, solid catalyst were obtained. Elemental analysis showed 0.09 wt% Zr and 5.11 wt% A1.

Comparative example 26. Catalytic system 26 (C26)

The precursor solution was obtained by mixing 6.8627 g 30% by weight gel-free methylalumoxane in toluene (35.33 mmol Al) and 0.0277 g dimethylsilylbis (2-methyl-4,5-benzindenyl) zirconium dichloride (0.048 mmol Zr ). Then 12.3745 g of toluene was added. The precursor solution was added to 2.0021 g silica MS948, pore volume

1.6 cm³/ g, available from WR Grace, Davison Chemical Division, Baltimore, Maryland (Davison Chemical Co.), previously heated to 800 ° C under nitrogen. The ratio of liquid volume to total silica pore volume was 6.7. The wet sand consistency was dried under 98205.26 Pascal (29 inch Hg vacuum) at 60 ° C for 4.1 hours. 4.1414 g of finely divided, loose, solid catalyst was obtained. Elemental analysis showed a content of 0.09% by weight Zr and 18.82% by weight Al.

Polymerization test for catalytic systems 12-17.

A sample of each of the supported catalysts (75 mg) obtained in Examples 12-17 above was suspended in 2 mL of hexane and purged with 250 µl of propylene in a 2-liter reactor previously purged and containing triethylaluminum (0.5 mL of 1M solution in hexane) and 1000 mL propylene at 70 ° C. The reactions were carried out for 1 hour, after which the reactor was cooled, degassed and purged with nitrogen for 20 minutes. After purging with nitrogen, the reactor was opened and the product collected, and then dried under vacuum for at least 2 hours at 75 ° C.

Table 2

<td rowspan="2">Catalyst</td><td colspan="2">Metal content *</td><td rowspan="2">A1 / Zr molar ratio</td><td rowspan="2">% vol. pore</td><td rowspan="2">g polymer / g catalyst</td><td rowspan="2">g polymer / mg Zr</td><td rowspan="2">% overgrowing **</td>

<td>Al</td><td>Zr</td>

<td> 12</td><td> 4,50</td><td> 0,026</td><td> 175</td><td> 95</td><td> 2387</td><td> 3410</td><td> 0,2</td>

<td> 13</td><td>LL</td><td>LL</td><td></td><td> 125</td><td> 2253</td><td> 3219</td><td> 0</td>

<td> 14</td><td>LL</td><td>LL</td><td>LL</td><td> 225</td><td> 893</td><td> 893</td><td>small lumps</td>

<td> 15</td><td> 6,50</td><td>LL</td><td> 250</td><td> 95</td><td> 2813</td><td> 2870</td><td> 2,0</td>

<td> 16</td><td>LL</td><td></td><td>LL</td><td> 125</td><td> 2613</td><td> 2936</td><td> 0,2</td>

<td> 17</td><td>LL</td><td>LL</td><td>LL</td><td> 225</td><td> 2097</td><td> 2387</td><td>small lumps</td>

* mmol / g silica ** g of layered polymer in relation to the total obtained polymer x 100%

Polymerization test for catalytic system 18 - C26

A sample of each of the supported catalysts obtained in Examples 18-C26 was suspended in 2 mL of hexane and flushed with 250 mL of propylene in a 2-liter reactor previously purged with nitrogen and containing triethylaluminum (0.5 mL of 1M solution in hexane) and

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1000 ml of propylene, after which the reactor was heated to 65 ° C. The reaction was carried out for 1 hour, after which the reactor was cooled, degassed and purged with nitrogen for 20 minutes. After purging with nitrogen, the reactor was opened and the product collected, and then dried under vacuum for at least 2 hours at 75 ° C. When any polymer remained on the agitator or thermocouple (fouling), it was collected and weighed separately.

Table 3

<td rowspan="2">Catalyst</td><td colspan="2">Metal content *</td><td rowspan="2">Al / Zr molar ratio</td><td rowspan="2">% vol. pore</td><td rowspan="2">g polymer / g catalyst</td><td rowspan="2">g polymer / mg Zr</td><td rowspan="2">% overgrowing **</td>

<td>Al</td><td>Zr</td>

<td> 18</td><td> 7,26</td><td> 0,018</td><td> 392</td><td> 95</td><td> 1571</td><td> 1746</td><td> ~5</td>

<td> 19</td><td> 5,46</td><td> 0,019</td><td> 293</td><td> 97</td><td> 2505</td><td> 2087</td><td> 0,5</td>

<td> 20</td><td> 4,61</td><td> 0,011</td><td> 407</td><td> 94</td><td> 1000</td><td> 1099</td><td> 0,5</td>

<td> 21</td><td> 2,24</td><td> 0,011</td><td> 197</td><td> 94</td><td> 595</td><td> 495</td><td> 0</td>

<td> 22</td><td> 5,50</td><td> 0,019</td><td> 286</td><td> 100</td><td> 1841</td><td> 1674</td><td> 0,1</td>

<td> 23</td><td> 5,50</td><td> 0,019</td><td> 291</td><td> 125</td><td> 796</td><td> 796</td><td> 0,1</td>

<td> 24</td><td> 4,58</td><td> 0,012</td><td> 395</td><td> 250</td><td> 562</td><td> 562</td><td> 0</td>

<td> 25</td><td> 2,25</td><td> 0,013</td><td> 178</td><td> 250</td><td> 425</td><td> 472</td><td> 0,1</td>

<td>C-26</td><td> 17,65</td><td> 0,024</td><td> 737</td><td> 670</td><td> 2068</td><td> 2783</td><td> 100</td>

* mmol / g silica ** g of layered polymer in relation to the total obtained polymer x 100%

From tables 1 and 3 and from the comparative examples of catalyst systems - examples C-8 and C-26, it is clear that the catalyst systems according to the invention obtained by the method of the invention are surprisingly better than those known and especially if we compare the% fouling. This is very important in polymerization processes.

Although the invention has been described and illustrated with references to specific solutions, it will be understood by those skilled in the art that the invention also includes variants that are not illustrated and that are clear from the above invention. For example, the invention includes mixing at least two catalysts of the invention, or the use of the catalyst of the invention together with any other known catalyst or catalyst system, e.g. with traditional Ziegler-Natta catalyst or catalyst system. The catalyst system according to the invention can be used both in a single reactor and in a series of reactors.

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