Catalytic system for polymerization of olefins, for and the method of polymerization of propylene

 

(57) Abstract:

Describes a catalytic system and a method of preparation of the catalytic system on the media for the polymerization of olefins containing metallocene catalyst component, alumoxane and porous media, and this method involves the following stages: a) mixing the metallocene catalyst component with alumoxane in a solvent to obtain a solution, where the metallocene catalyst component corresponds to the formula I, where M denotes a metal of group 4, 5 or 6 of the Periodic table of elements; R1and R2the same or different and each denotes a hydrogen atom, a C1-C10alkyl group, a C1-C10alkoxygroup,6-C10aryl group6-C10alloctype,2-C10alkenylphenol group7-C40arylalkyl group7-C40alcylaryl group8-C40arylalkyl group or halogen atom; R3and R4denote hydrogen atoms; R5and R6the same or different, preferably same, and each represents a halogen atom, a C1-C10alkyl group which may be halogenated, a C6- 40alkenylphenol group7-C40arylalkyl group7-C40alcylaryl group8-C40arylalkyl group, a radical-NR215, -SR15, -OR15, -OSiR315or-PR215where R15denotes a halogen atom, a C1-C10alkyl group or a C6-C10aryl group; R7denotes the radical And where R11, R12and R13the same or different and each denotes a hydrogen atom, a halogen atom, a C1-C20alkyl group, a C1-C20alkyl fluoride group6-C30aryl group6-C30ferrillo group1-C20alkoxygroup,2-C20alkenylphenol group7-C40arylalkyl group8-C40arylalkyl group or7-C40alcylaryl group, or R11and R12or R11and R13together with the atoms connecting them may form a cyclic system; M2denotes a silicon, germanium or tin; R8and R9the same or different and have the meanings indicated for R11; m and n are the same or different and each represents zero, 1 or 2 and the sum of m plus n R11, R12and R13and additionally, two adjacent radicals R10can be linked with the formation of a cyclic system, and b) mixing the solution with a porous medium, provided that the ratio of total solution volume to the total volume of pores of a porous medium is less than three. Describes the method of polymerization of propylene. The technical result is to simplify the process by reducing clogging of the reactor and education in its layers. 3 S. and 6 C.p. f-crystals, 3 PL.

< / BR>
R7denotes the radical

< / BR>
< / BR>
< / BR>
< / BR>
= BR11, =AlR11, -Ge-, -Sn-, -O-, -S-, -SO-, =SO2, =NR11, A =CO, PR11or = P(O)R11;

This patent application is partially continuing the application for U.S. patent 08/265532 filed June 24, 1994

THE TECHNICAL FIELD TO WHICH THE INVENTION RELATES

The present invention relates to catalytic systems, methods for their preparation and use in the polymerization of olefins. The invention in particular relates to a method for the catalytic system on the media for use in gas phase, slurry phase or liquid phase/solution with improved operability of the reactor.

BACKGROUND WITH the or in the gas phase, it is advisable to use a catalytic system on the media. Typically, these catalytic systems include metallocene and alumoxane supported on a carrier such as silica. For example, in U.S. patent 4937217 presents a General description of the mixture of trimethylaluminum and triethylaluminum added to neobezjirennogo the silicon dioxide, which then add metallocene catalyst component. In European application 308177-B1 mainly described the addition of wet monomer into the reactor containing metallocene, trialkylaluminium and diabetogenic silicon dioxide. In U.S. patent 4912075, 4935397 and 4937301 described the addition of trimethylaluminum to neobezjirennogo the silicon dioxide and the subsequent addition of metallocene with getting dry catalytic system on the media. In U.S. patent 4914253 described the addition of trimethylaluminum to neobezjirennogo the silicon dioxide, adding metallocene, followed by drying the resulting catalytic system on the carrier together with a certain amount of hydrogen, resulting in a polyethylene wax. In U.S. patent 5008228, 5086025 and 5147949 describes the preparation of dry catalytic system on the media by the addition of trimethylaluminum in impregnated in the 4808561, 4897455 and 4701432 describes how to prepare the catalytic system on the media, in which the inert carrier, typically silicon dioxide, calicivirus and enter into contact with metallocenes (metallocene) and activator-socialisticheskom component. In U.S. patent 5238892 describes the preparation of dry catalytic system on the media mix of metallocene with alkylamines and then adding neobezjirennogo silicon dioxide. In U.S. patent 5240894 described getting deposited on the carrier metallocen/alumoxane catalytic system by cooking metallocen/alumoxane reaction solution, adding a porous medium and evaporation of the resulting suspension to removal of the carrier residual solvent.

Although all of these catalysts on a carrier suitable for use, however, there is a need for an improved metallocene catalyst system, which upon receipt of the polymers does not contaminate the reactor.

Thus, in particular, in the process of polymerization in suspension or in the gas phase with the use of these catalytic systems there is a tendency to the emergence of technological problems in the reactor during peoplepets and is glued or sticks to the walls of the reactor. This phenomenon is often called "lacing" or "layering". The accumulation of polymer particles on the reactor walls, the recirculation lines and cooling systems raises many issues, including poor heat transfer during the polymerization process. Polymer particles, which stick to the walls of the reactor can continue to cure and often fused, forming clumps that may have a negative impact on the continuous polymerization process. Similarly, during the polymerization of propylene in the mass of the liquid medium in which the use of such catalytic systems, there is a tendency to agglomerate the polymer particles and their gluing or sticking to the walls of the reactor. It may also have a negative impact on such a continuous process.

Thus, there is a need for an improved polymerization catalyst system in the polymerization process substantially improve the efficiency of the reactor and ensures a higher quality of the polymer product.

SUMMARY OF THE INVENTION

The object of the present invention are the CoE.

In one embodiment, the invention features an improved method for the catalytic system on the media based on the volume of the ligand with the transition metal by introducing a porous medium in contact with the product of the interaction metallocene catalyst component with alumoxane in the solution, and the total amount of the reaction product of no more than approximately four times the total pore volume of the porous media, preferably less than that quantity at which the suspension is formed, and moreover, the metallocene catalyst component is a substituted chiral associated bridge bicentenial with transition metal of group 4, 5 or 6.

Another object of the invention is a method of obtaining a polypropylene polyolefin by introducing propylene monomer optionally together with the co monomer in contact with a catalytic system described above.

DETAILED DESCRIPTION OF THE INVENTION

Introduction

The object of the present invention is a catalytic system on the media, which can be used for the polymerization of olefins. Method of preparation of this catalytic system according to the invention includes the first activator or acetalization.

It was found that the catalytic system prepared with a high molar ratio between the metal component alumoxane and transition metal metallocene compounds are characterized by high activity, but also exhibit a tendency to clogging of the equipment when carrying out polymerization. The decrease in the ratio between the quantities alumoxane and transition metal allows to weaken this tendency to clogging, but also reduces the catalytic activity. It was found that, when the preparation of the catalytic system according to the invention the volume of solution of metallocene catalyst compounds and alumoxane not more than four times the pore volume of the porous media, preferably less than that quantity which is necessary for the suspension, but more than a single volume of pores of the porous carrier, the catalytic activity is retained, and in many cases increases, whereas the formation of impurities is slowing down, and in many cases eliminated. The preparation of the catalytic system according to the invention thus results in a simple, suitable for technical use and value the more effective catalytic alimamy product of high bulk density, with improved morphology of the particles.

Metallocene catalyst component according to the invention

Metallocene components used in the implementation of the present invention include the transition metals of groups 4, 5 and 6, dicyclopentadienyl derivatives, preferably bicentenary metallocene components corresponding to the following General structural formula:

< / BR>
where M denotes a metal of group 4, 5 or 6 of the Periodic table of elements, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, preferably zirconium, hafnium and titanium, most preferably zirconium;

R1and R2the same or different and each denotes a hydrogen atom, a C1-C10alkyl group, preferably C1-C3alkyl group, a C1-C10alkoxygroup, preferably C1-C3alkoxygroup, C6-C10aryl group, preferably C6-C8aryl group, a C6-C10alloctype, preferably C6-C8alloctype, C2-C10alkenylphenol group, preferably C2-C4alkenylphenol group, C7-C40arylalkyl group, PR is about C7-C12alcylaryl group, C8-C40arylalkyl group, preferably C8-C12arylalkyl group, or a halogen atom, preferably chlorine;

R3and R4denote hydrogen atoms;

R5and R6the same or different, preferably same, and each represents a halogen atom, preferably fluorine, chlorine or bromine, C1-C10alkyl group, preferably C1-C4alkyl group which may be halogenated, a C6-C10aryl group which may be halogenated, preferably C6-C8aryl group, a C2-C10alkenylphenol group, preferably C2-C4alkenylphenol group, C7-C40arylalkyl group, preferably C7-C10arylalkyl group, C7- C40alcylaryl group, preferably C7-C12alcylaryl group, C8-C40arylalkyl group, preferably C8-C12arylalkyl group, a radical-NR215, -SR15, -OR15, -OSiR315or-PR215where R15denotes a halogen atom, preferably a chlorine atom, a C1-C10acilitate C6- C9aryl group;

R7denotes the radical

< / BR>
< / BR>
< / BR>
< / BR>
= BR11, =AIR11, -Ge-, -Sn-, -0-, -S-, =SO, =SO2, =NR11, A =CO, PR11or = P(O)R11;

where R11, R12and R13the same or different and each denotes a hydrogen atom, a halogen atom, a C1-C20alkyl group, preferably C1-C10alkyl group, a C1-C20alkyl fluoride group, preferably C1-C10alkyl fluoride group, a C6-C30aryl group, preferably C6-C20aryl group, a C6-C30ferrillo group, preferably C6-C20ferrillo group, C1-C20alkoxygroup, preferably C1-C10alkoxygroup, C2-C20alkenylphenol group, preferably C2-C10alkenylphenol group, C7-C40arylalkyl group, preferably C7-C20arylalkyl group, C8-C40arylalkyl group, preferably C8-C22arylalkyl group, or C7- C40alcylaryl group, preferably C7-C20alcylaryl group, or R11and R12or R11and R13together Soi or tin, preferably silicon or germanium, most preferably silicon;

R8and R9the same or different and have the meanings indicated for R11;

m and n are the same or different and each represents zero, 1 or 2,

preferably zero or 1, and the sum of m plus n is zero, 1 or 2, preferably zero or 1; and

R10are the same or different radicals and are shown for R11, R12and R13.

Two adjacent radicals R10can be linked with the formation of a cyclic system, preferably a cyclic system containing 4-6 carbon atoms.

The term "alkyl" denotes remotemachine or branched substituents. The term "halogen" ("halogenated" refers to fluorine atoms, chlorine, bromine or iodine, preferably fluorine or chlorine.

Especially preferred metallocenes are compounds of structural formula

< / BR>
< / BR>
where M1represents Zr or Hf,

R1and R2each represents methyl or chlorine, and

R5, R6, R8, R9, R10, R11and R12have the above values.

Chiral metallocene used is to use pure R - or S-shape. Using these pure stereoisomeric forms can be obtained optically active polymers. To ensure that the center (i.e., the metal atom) provides stereoregular polymerization, mesoform metallocene it is preferable to remove.

Separation of stereoisomers can be produced by known literature methods. For specific products can also be used racemic mesosoma.

Metallocene usually get by using a multi-stage process involving re-phase deprotonation/metallation of aromatic ligands and the introduction of the bridge and the Central atom through their halogenated derivatives. This General approach is illustrated in the following diagrams reactions:

< / BR>
X=Cl, Br, I or 0-tosyl;

< / BR>
Regarding obtaining described metallocene you can refer to Journal of Organometallic Chem. volume 288 (1958), pages 63-67, and in European patent application A-320762, both of these publications are included in this description in full as references.

Illustrative, but non-limiting scope of the invention examples metallocenes are:

dimethylselenide(2-methyl-4-phenyl-1-indenyl)ZrCl2;

dimethylselenide(2-micelangelo(2-ethyl-4-phenyl-1-indenyl)ZrCl2;

dimethylselenide(4-naphthyl-1-indenyl)ZrCl2;

phenyl(methyl)Silantieva(2-methyl-4-phenyl-1-indenyl)ZrCl2;

dimethylsilane[2-methyl-4-(1-naphthyl)-1-indenyl] ZrCl2;

dimethylsilane[2-methyl-4-(2-naphthyl)-1-indenyl] ZrCl2;

dimethylselenide (indenyl) ZrCl2;

dimethylselenide(2-methyl-4,5-aminobutiramida 1-indenyl)ZrCl2;

dimethylselenide (2,4,6-trimethyl-1-indenyl) ZrCl2;

phenyl(methyl)Silantieva(2-methyl-4,6-aminobutiramida 1-indenyl)ZrCl2;

1,2-atanderson(2-methyl-4,6-aminobutiramida 1-indenyl)ZrCl2;

1,2-BUTADIENES(2-methyl-4,6-aminobutiramida 1-indenyl)ZrCl2;

dimethylselenide(2-methyl-4-ethyl-1-indenyl)ZrCl2;

dimethylselenide(2-methyl-4-isopropyl-1-indenyl)ZrCl2;

dimethylselenide(2-methyl-4-tert-butyl-1-indenyl)ZrCl2;

phenyl (methyl) Silantieva(2-methyl-4-isopropyl-1-indenyl) ZrCl2;

dimethylselenide(2-ethyl-4-methyl-1-indenyl)ZrCl2;

dimethylselenide(2,4-dimethyl-1-indenyl)ZrCl2;

dimethylselenide(2-methyl-4-ethyl-1-indenyl)ZrCl2;

dimethylselenide(2-methyl-acenet-1-indenyl)ZrCl2;

phenyl (methyl)Silantieva(2-methyl-4,5-benzo-1-indenyl)ZrCl22;

phenyl(methyl)Silantieva(2-methyl-acenet-1-indenyl)ZrCl2;

1,2-atanderson (2-methyl-4,5-benzo-1-indenyl)ZrCl2;

1,2-BUTADIENES(2-methyl-4,5-benzo-l-indenyl)ZrCl2;

dimethylselenide(2-methyl-4,5-benzo-1-indenyl)ZrCl2;

1,2-atanderson(2,4,7-trimethyl-1-indenyl)ZrCl2;

dimethylselenide(2-methyl-1-indenyl)ZrCl2;

1,2-atanderson(2-methyl-1-indenyl)ZrCl2;

phenyl(methyl)Silantieva(2-methyl-1-indenyl)ZrCl2;

diphenylsilanediol(2-methyl-1-indenyl)ZrCl2;

1,2-BUTADIENES(2-methyl-1-indenyl)ZrCl2;

dimethylselenide(2-ethyl-1-indenyl)ZrCl2;

dimethylselenide(2-methyl-5-isobutyl-1-indenyl)ZrCl2;,

phenyl(methyl)Silantieva(2-methyl-5-isobutyl-1-indenyl)ZrCl2;

dimethylselenide(2-methyl-5-tert-butyl-1-indenyl) ZrCl2;

dimethylselenide(2,5,6-trimethyl-1-indenyl)ZrCl2etc.

Metallocene catalyst components of the present invention are described in U.S. patents 5149819, 5243001, 5239022, 5296434 and 5276208, all of which are in full included in this description as a reference.

Activator component according to the invention

Activator or socialisticheski component this is Sana and

< / BR>
for oligomeric cyclic alumoxane, where n and m denote 1-40, most preferably 3-20 and R is a C1-C8alkyl group or R represents C6-C18aryl group or hydrogen, preferably methyl group, or R may denote a mixture of alkyl and aryl substituents.

There are different ways of cooking alumoxane, examples of which are described, but not limited to, U.S. patents NN 4665208, 4952540, 5091352, 5206199, 5204419, 4874734, 4924018, 4908463, 4968827, 5308815, 5329032, 5248801, 5235081, 5157137, 5103031, in the European applications A-0561476, B1-0279586, A-0594218 and in the international application 94/10180, all of which are in full included in this description as a reference. It may be preferable to use a visually transparent methylalumoxane. To obtain a clear solution is turbid or gelatinizing alumoxane can be filtered or transparent alumoxane can be decanted from the surface of the turbid solution.

Environment media according to the invention

In the context of this description, the terms "media" and "substrate" are used interchangeably and may designate any material medium, preferably a porous carrier, such as talc, jinene, or any other organic material media, etc., the average particle size exceeds 10 μm.

Preferred materials carriers are inorganic oxide materials, which include those consisting of oxides of metals of groups 2, 3, 4, 5, 13 and 14 of the Periodic table of elements. In a preferred embodiment, the carriers for the catalysts are silicon dioxide, aluminum oxide, kranidioti-aluminiumoxid and mixtures thereof. Other inorganic oxides that may be used either individually or in combination with silicon dioxide, aluminum oxide or kremmidiotis-aluminiumoxide include magnesium oxide, titanium dioxide, zirconium dioxide, etc.

In a preferred embodiment, the specific surface area of the carrier for the catalyst of the present invention is from about 10 to about 700 m2/g, its pore volume is from about 0.1 to about 4.0 CC/g and average particle size is from about 10 to about 500 microns. More preferably, the specific surface area is from about 50 to about 500 m2/g, the porosity is from about 0.5 to about 3.5 CC/g and average particle size costal is about 100 to about 400 m2/g, the porosity is from about 0.8 to about a 3.0 CC/g and average particle size is from about 30 to about 100 microns. Typically, the pore size of the carrier according to the invention is from 10 to preferably from 50 to about and most preferably from 75 to approximately

The method of preparation of the catalytic system according to the invention

There are many different options for preparation of the catalytic system on the media according to the invention.

In the context of this description and the accompanying claims, the term "solution" includes a suspension, a suspension and the mixture. You can use any compatible solvent suitable for solution or so on at least one metallocene catalyst component and/or at least one alumoxane according to the invention. Non-limiting examples of solvents are aliphatic, aromatic and saturated hydrocarbons, and cyclic hydrocarbons such as isopentane, heptane, toluene, etc., the preferred solvents are cyclic aliphatic and aromatic hydrocarbons, most preferred of which is toluene.

Commonly used methods of applying NGO catalytic component, as described above, in contact with alumoxane or methylalumoxane (MAO) obtaining a soluble reaction product. Further, this soluble reaction product is introduced into contact with a porous medium, where the total amount of soluble reaction product is added to the carrier, not more than four times the pore volume of the carrier, preferably less than the volume required for suspension. The resulting catalytic system on the media can be dried in such a way as to ensure the destruction of almost the whole or the greater part of the residual solvent from the pores of the carrier. In this way receive engineering catalytic system on the media.

In one embodiment, the present invention proposes a method of preparation of engineering, optional prepolymerisation catalytic system on the media, including stage a) preparation of a suitable solvent metallocen/alumoxane mixture, where metallocene described above; b) introducing the mixture from stage (a) into contact with a porous medium, where the total amount of the mixture added to the porous carrier, less the amount that is required for suspension, but once more the total volume of pores Ele and (d) the optional prepolymerisation such catalytic systems on the medium using one or more olefinic monomers, resulting in forprimary catalytic system on the media for polymers of propylene or copolymers, the molecular weight of which is approximately 50,000 or more, preferably 100000 or more, a melting temperature which is equal to approximately 135oC or higher, preferably about 140oC or higher and more preferably about 145oC or higher and a volume weight of approximately between 0.30 g/cm3or more. The average particle size of the finished granular polymer is from about 500 to about 1000 microns or more. In the most preferred embodiment, metallocene and alumoxane the components are mixed, obtaining a solution which is then added to the porous media.

In another embodiment, the dried catalytic system on the media is washed or treated in any other way to remove weakly bound (s) with her catalytic (s) component (s). For washing the catalyst system can be any hydrocarbon, however, the hydrocarbon must be able to dissolve this catalytic component and should be easily removed from the carrier during drying. Preferred tomaxaewsa solution is not more than four times the pore volume of the porous media, preferably not more than three times, more preferably not more than twice, and most preferably is not more than a single total pore volume of the porous media.

The carrier preferably be processed containing catalyst (s) component (s) solution so as to obtain a homogeneous catalytic system, i.e. a system in which such an(s) component(s) evenly distributed (s) on the particles of the carrier and inside them. In a preferred embodiment, the total volume of solution containing metallocene and activator and added to the carrier is in the range of from not more than is required for the formation of a suspension volume to volume, which is approximately equal to the total pore volume of the carrier is preferably from 2.5 times the total pore volume of the carrier to approximately 1,05 times the total pore volume of the carrier, more preferably from about 2.4-fold to about 1.1 times the total pore volume of the carrier, more preferably from approximately 2.3-fold to about 1.2 times the total pore volume of the carrier, more preferably from about 2.2-fold to approximately 1.25 times the total pore volume of the carrier, more preferably from example is go up to about 1.3 times the total pore volume of the carrier, most preferably from about 2.0 to fold to about 1.5 times the total pore volume of the carrier. In a preferred embodiment, the solution is added either dropwise or in aerosol form while mixing media or thoroughly mix in some other way.

Typically, a suspension is formed when one can observe two phases, one of which contains all or most of the media. The volume of solution required to reach this stage, usually varies depending on, among other things, the type of media and type of the components of the catalytic system. The moment of suspension immediately preceding stage, which in this description is defined as "slurry" stage. At this stage slurry volume of solution is that, although the two phases and indistinguishable, the material of the carrier is saturated, and the particles of the medium are tightly combined with each other. Before the slurry phase volume of the solution is such that in appearance the material of the carrier is in a state of dry and engineering (even though the media may include a solution, the volume of which is close to the single volume of pores) to dry but slightly sticky material of varying degrees of moisture and clumping, which is Khabibullina, is in the range of values from values larger than a single pore volume, to the value, which is necessary for the suspension, preferably from values larger than a single pore volume, to the value that you want to achieve a slurry phase. It should be borne in mind that the catalytic system formed at the slurry stage, it becomes more difficult mixing, and they require a longer drying period in comparison with those prepared with a smaller amount of solution. When less than a single volume of pores achieve uniform coating of the carrier components of the catalytic system can be difficult. This can result in blockage.

According to the present invention it is assumed that in the preparation of the catalytic system the total amount of solution added to the porous media at the same time or added to the porous media in individual portions should be such that at any point in time in the process of formation of the catalytic system solution volume remained the same as indicated above.

The catalytic system according to the invention can be dried and may still contain some Kudarat almost all of the solvent. In the context of this description and the accompanying claims the term "remove almost all solvent" means that during the drying of the catalytic system on the media out of it removed about 90% of the total solvent.

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

Methodology to measure the total volume of pores of porous media are well known in the art. Detail one of such methods is described in Experimental Methods in Catalytic Research (Academic Press, 1968), so 1 (first of all see the pages 67-96). This preferred method provides for the application of the classical BET unit for absorption of nitrogen. Another method well known in the art, described by Innes in Total Porosity and Particle Density of Fluid Catalyst by Liquid Titration, T. 28, N 3, Analytical Chemistry 332-334 (March, 1956).

In another embodiment, the molar ratio between the metal of the activator component and the transition metal metallocene comp is.

The catalytic system on the media according to the invention may include a surface modifier, such as described in application for U.S. patent 08/322675 (in full included in the present description by reference), and/or antistatic agent, for example, such as described in U.S. patent 5283278 fully included in the present description by reference. Non-limiting examples of antistatic agents include alcohols, thiols, silanol, diols, esters, ketones, aldehydes, acids, amines and ethers. The preferred tertiary amine compounds. Such an antistatic agent can be added at any stage of the process of preparation of the catalytic system on the media according to the invention, however, it is preferably added after the preparation of the catalytic system on the media according to the invention either in the form of a mist, or in the dried state. In another embodiment, a catalytic system on the media according to the invention includes a polyolefin wax, a substance for increasing the adhesiveness or etc.

The method of polymerization according to the invention

The catalytic system of the present invention is suitable for polymerization of the monomers and optional comonomers in any polymerization process or prepisanim pressure in the autoclave.

In a preferred embodiment, applying the processes in the gas phase or in suspension phase, and the most preferred polymerization of propylene in the mass of the liquid phase. In a preferred embodiment, the present invention relates to a suspension (liquid weight) and gas-phase reactions of polymerization and copolymerization of propylene, including the polymerization of propylene with one or more alpha-olefin monomers containing 4-20, preferably 4-12 carbon atoms, for example, alpha-olefin of the comonomers of ethylene, butene-1, pentene-1, 4 - methylpentene-1, hexene-1, octene-1, mission-1, and cyclic olefins such as styrene. Other monomers can include polar vinyl monomers, diolefin, such as diene, norbornene, acetylene and aldehyde monomers. The present invention is most suitable for polymerization reactions involving the polymerization of propylene. To increase the catalytic activity of all the catalytic systems according to the invention can be prepolymerized, polymerized or used in combination with additive or impurity binding component.

The catalytic system on the media according to the invention may not necessarily be prepolymerisation. It was the mouth of the German entities of the present invention, including its characteristic advantages and its limits.

In all examples as the material of the upper layer solution was used methylalumoxane in toluene concentration of 30 wt.%, supplied to the market by the company Albemarle Corporation, Baton Rouge, PCs Louisiana. Specialists in the art it is known that methylalumoxane is a colloidal suspension in toluene, the consistency of which is in the range from transparent, i.e. free from gel, to opaque gelatinizing liquid, however, in accordance with the present invention the preferred methylalumoxane free from gel.

Example 1

Catalyst 1

The solution of the precursor was prepared under stirring by mixing 11,858 g not containing gel solution methylalumoxane in toluene concentration of 30 wt.% (61,05 mmole Al) and 0,0747 g dimethylsilane(2-methylindenyl)zirconiated (0,156 mmole Zr). This solution of the precursor was added to 8,433 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical. Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica sostav RT.CT.) and when the 40oC for 16 h in This way received 11,147 g of catalyst. Elemental analysis showed the presence of 0.12 wt.% Zr and 15,30% wt. Al.

Example 2

Catalyst 2

The solution of the precursor was prepared under stirring by mixing 4,060 g not containing gel solution methylalumoxane in toluene concentration of 30 wt.% (20,90 mmole Al) and 0,0252 g dimethylsilane(2-methylindenyl)zirconiated (0,053 mmole Zr). To dilute this solution of the precursor was added 2,318 g of toluene. In a small chemical beaker was loaded 2,868 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2and one portion was added all predecessor. The value of the ratio between the liquid volume and the total pore volume of the silica was 1,53. For mixing, which in appearance resembled wet sand, using a putty knife. This mixture was then dried under reduced pressure (in vacuo 28+ inches of RT.CT.) and when the 40oC for 16 h in This way received 3,908 g engineering catalyst. Elemental analysis showed the presence of 0.12 wt.% Zr and 14,34% wt. Al.

Example 3

Catalyst 3

The solution of the precursor was prepared under stirring by a cm who emailservice(2-methylindenyl)zirconiated (0,078 mmole Zr). This solution of the precursor was added to 4,250 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0.68. Fine engineering solid material was dried under reduced pressure (in vacuo 28+ inches of RT.CT.) and when the 40oC for 16 h in This way received 5,209 g of catalyst. Elemental analysis showed the presence of 0.12 wt.% Zr and is 10.68% wt. Al.

Example 4

Catalyst 4

The solution of the precursor was prepared under stirring by mixing 4,205 g not containing gel solution methylalumoxane in toluene concentration of 30 wt.% (21,65 mmole Al) and 0,0367 g dimethylsilane(2-methylindenyl)zirconiated (0,077 mmole Zr). This solution precursor was diluted 1,648 g of toluene. The precursor was added to 4,125 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0.97. Fine engineering solid material was dried under reduced pressure (in vacuo 28+ inches of RT.CT.) and when the 40o<% wt. Al.

Example 5

Catalyst 5

The solution of the precursor was prepared under stirring by mixing 3,106 g not containing gel solution methylalumoxane in toluene concentration of 30 wt.% (15,99 mmole Al) and 0,0401 g dimethylsilane(2-methylindenyl)zirconiated (0,084 mmole Zr). To dilute this precursor was added 2,516 g of toluene. The solution of the precursor was added to 4,024 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co. ) previously heated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0.97. Drying the fine engineering of solid material began in vacuum at 25 inches of RT.article and the 35oC. for 2.5 h in a vacuum and the temperature was increased to bring the vacuum to 29+ inch RT.article and temperatures up to 60oC. Elemental analysis showed the presence of 0.13 wt.% Zr and 7,93% wt. Al. The additional drying was continued for 1.0 hours the way it was received 4,862 g engineering catalyst.

Example 6

Catalyst 6

The solution of the precursor was prepared under stirring by mixing 1,560 g not containing gel solution methylalumoxane in toluene concentration of 30 wt.% (8.03 mmole Al) and 0,0201 g dimethyltin the small chemical beaker was loaded 2,005 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2and one portion was added all predecessor. The value of the ratio between the liquid volume and the total pore volume of the silica was 2,48. For mixing, which in appearance resembled very wet sand or mud, using a putty knife. Next, this mixture was dried in vacuum at 25 inches of RT.article and at the 50oC to remove all liquid, then within 0,75 h vacuum and the temperature was increased to bring the vacuum to 29+ inch RT.article and temperatures up to 60oC. Elemental analysis showed the presence of 0.15 wt.% Zr and 8,63% wt. Al. The additional drying was continued for 1.0 hours the way it was received 2,444 g engineering catalyst.

Example 7

Catalyst 7

The solution of the precursor was prepared under stirring by mixing 1,563 g not containing gel solution methylalumoxane in toluene concentration of 30 wt.% (8,05 mmole Al) and 0,0209 g dimethylsilane(2 - methylindenyl)zirconiated (0,044 mmole Zr). To dilute this solution of the precursor was added 17,402 g of fresh toluene. In a small chemical beaker was loaded 2,011 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), p is. The value of the ratio between the liquid volume and the total pore volume of the silica was $ 6,70. For mixing the mixture using a putty knife and the suspension was dried in vacuum at 25 inches of RT. Art. and at the 25oC to remove all liquid, then for 1.25 h the vacuum and the temperature was increased to bring the vacuum up to 28+ inches of RT.article and temperatures up to 60oC. Drying was continued for another 1,0 h under vacuum 28+ inches of RT.article and at 60oC. in This way received 2,395 g engineering catalyst.

Comparative example 8

Catalyst 8

The solution of the precursor was prepared under stirring by mixing 6,932 g not containing gel solution methylalumoxane in toluene concentration of 30 wt.% (35,68 mmole Al) and 0,0227 g dimethylsilane(2-methylindenyl)zirconiated (0,048 mmole Zr). To dilute this solution of the precursor was added 12,384 g of toluene. In the solution of the precursor was carefully added 2,007 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was $ 6,70. This suspension was dried in vacuum at 25 inches of RT.article and at the 50oC to remove sun and temperatures up to 60oC. Drying was continued for another 1,0 h in vacuum at 28+ inches of RT. Art. and at 60oC. in This way received 4,100 g engineering catalyst. Elemental analysis showed the presence of 0,091 wt.% Zr and 20,48% wt. Al.

Example 9

Catalyst 9

The solution of the precursor was prepared under stirring by mixing 5,809 g of the solution methylalumoxane in toluene concentration of 30 wt.% (29,91 mmole Al) and 0,0365 g dimethylsilane(2-methylindenyl)zirconiated (0,076 mmole Zr). This solution of the precursor was added to 4,225 g of silicon dioxide (MS948, the porosity of 1.6 CC/g, the company, Davison Chemical Co.), pre-heated to 200oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0,93. Fine engineering solid material was dried in vacuum at 28+ inches of RT.article and when the 40oC for 16 h in This way received 4,909 g of catalyst. Elemental analysis showed the presence of 0.12 wt.% Zr and 15,98% wt. Al.

Example 10

The catalyst 10

The solution of the precursor was prepared under stirring by mixing 5,692 g of the solution methylalumoxane in toluene concentration of 30 wt.% (29,31 mmole Al) and 0,0358 g dimethylsilane(2 - methylindenyl)zirconiated (of 0.075 mmole Zr). Using EQ the lead of 1.6 CC/g, the company, Davison Chemical Co.), preheated to 600oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0,93. Fine engineering solid material was dried in vacuum at 22 inches RT.article and if 30oC for 1.5 h and then for 2 h at 28+ inches of RT.article and at 60oC. in This way received 5,344 g of catalyst. Elemental analysis showed the presence of 0.10 wt.% Zr and 15,58% wt. Al.

Examples 9 and 10 illustrate the catalyst according to the present invention and show that the temperature of the hydrated silica not decisive.

Example 11

Catalyst 11

The solution of the precursor was prepared under stirring by mixing 4,339 g of the solution methylalumoxane in toluene concentration of 30 wt.% (22,34 mmole Al) and 0,0273 g dimethylsilane(2-methylindenyl)zirconiated (0,057 mmole Zr). This solution of the precursor was added to 3,079 g of silicon dioxide (MS3040, the porosity of 3.0 CC/g, the firm Philadelphia Quartz), preheated to 700oC in air and then at 50oC in vacuum blew N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0,51. Fine easy is SUP>C for 16 h in This way received field are estimated at 4.054 g of catalyst. Elemental analysis showed the presence of 0.10 wt.% Zr and 13,92% wt. Al. This example illustrates the obtaining of a catalytic system according to the invention using other media porosity.

The POLYMERIZATION TEST of CATALYSTS 1-11 (see table. 1).

A sample of each of the catalysts on a carrier prepared in the above examples 1-11, suspended in 2 ml of hexane and a strong jet of 250 ml of propylene was blown away in 2-liter autoclave, purged with nitrogen and containing 0.5 ml of 1 M solution of triethylaluminum in hexane and 1000 ml of propylene, after which the reactor was heated to a temperature of 65oC. the Reaction was conducted for 1 h, after which the reactor was cooled, was ventolinbuy and within 20 minutes was purged with nitrogen. After nitrogen purge, the reactor was opened, the product was collected and dried in vacuum for at least 2 h at 75oC. If the mixer or thermocouple detect any residual product (the polluter), it was collected and weighed separately.

Example 12

Catalyst 12

The solution of the precursor was prepared under stirring by mixing 3,5022 g not containing gel solution methylalumoxane in toluole Zr). Then added 1,9488 g of toluene. This solution of the precursor was added to 4,00 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 600oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0.95. Fine engineering solid material was dried for 2.5 h under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of about 50oC. in This way received 5,12 g of catalyst. Elemental analysis showed the presence of 0.07 wt.% Zr and 8.98 wt.% Al.

Example 13

The catalyst 13

The solution of the precursor was prepared under stirring by mixing 3,4997 g not containing gel solution methylalumoxane in toluene concentration of 30 weight. % (18,02 mmole Al) and 0,0648 g dimethylsilane(2-methyl-4 - phenylindane)zirconiated (0,103 mmole Zr). Then added 3,6798 g of toluene. This solution of the precursor was added to 4,00 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 600oC current N2. The value of the ratio between the material predetermined resembled wet sand, and it was dried for 2.5 h under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of about 50oC. in This way received at 4.99 g of finely ground engineering of the solid catalyst. Elemental analysis showed the presence of 0.07 wt.% Zr and 8,64% wt. Al.

Example 14

The catalyst 14

The solution of the precursor was prepared under stirring by mixing 3,5017 g not containing gel solution methylalumoxane in toluene concentration of 30 weight. % (18,03 mmole Al) and 0,0653 g dimethylsilane(2-methyl-4 - phenylindane)zirconiated (0.104 g mmole Zr). Then added 9,3018 g of toluene. This solution of the precursor was added to 4,00 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 600oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 2,25. According to its consistency, this solid material was reminiscent of wet sand, and it was dried for 2.5 h under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of about 50oC. in This way received of 5.11 g of the catalyst in the form of fine engineering of solid material. Elements is destinia was prepared under stirring by mixing 5,0489 g not containing gel solution methylalumoxane in toluene concentration of 30 weight. % (25,992 mmole Al) and 0,0649 g dimethylsilane(2-methyl-4-phenylindane)zirconiated (0,103 mmole Zr). Then added 0,5014 g of toluene. This solution of the precursor was added to 4,00 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 600oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0.95. Fine engineering solid material was dried for 2.5 h under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of about 50oC. in This way received the 5.65 g of the catalyst. Elemental analysis showed the presence of 0,098% wt. Zr and 13,17 wt.% Al.

Example 16

The catalyst 16

The solution of the precursor was prepared under stirring by mixing 5,0476 g not containing gel solution methylalumoxane in toluene concentration of 30 weight. % (25,986 mmole Al) and 0,0652 g dimethylsilane(2-methyl-4 - phenylindane)zirconiated (0.104 g mmole Zr). Then added 2,1983 g of toluene. This solution of the precursor was added to 4,00 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Da and total pore volume of the silica was 1.25. According to its consistency, this solid material was reminiscent of wet sand, and it was dried over 2.6 hours under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of about 50oC. Thus was obtained the ceiling of 5.60 g of the catalyst in the form of fine engineering of solid material. Elemental analysis showed the presence of 0,089 wt.% Zr and 13,43% wt. Al.

Example 17

The catalyst 17

The solution of the precursor was prepared under stirring by mixing 5,0552 g not containing gel solution methylalumoxane in toluene concentration of 30 weight. % (26,025 mmole Al) and 0,0654 g dimethylsilane(2-methyl-4-phenylindane)zirconiated (0.104 g mmole Zr). Then added 7,8602 g of toluene. This solution of the precursor was added to 4,00 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 600oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 2,25. According to its consistency, this solid material was reminiscent of wet sand, and it was dried for 2,3 hours under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of about 50oC. in This way, given the presence of 0,088 wt.% Zr and 13,59% wt. Al.

Example 18

The catalyst 18

The solution of the precursor was prepared under stirring by mixing 13,3840 g not containing gel solution methylalumoxane in toluene concentration of 30 wt.% (68,90 mmole Al) and 0,1014 g dimethylsilane(2-methyl-4,5-benzhydryl)zirconiated (0,176 mmole Zr). Then added 1,4120 g of toluene. This solution of the precursor was added to 9,4953 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0.97. Fine engineering solid material was dried overnight under reduced pressure (in a vacuum of 28 inches of RT.CT.) and at a temperature of about 40oC. in This way received 13,183 g of catalyst. Elemental analysis showed the presence of 0.09 wt.% Zr and 13.25 wt.% Al.

Example 19

The catalyst 19

The solution of the precursor was prepared under stirring by mixing 4,2500 g not containing gel solution methylalumoxane in toluene concentration of 30 wt.% (21,88 mmole Al) and 0,0432 g dimethylsilane(2-methyl-4,5 - benzhydryl)zirconiated (of 0.075 mmole Zr). Then d is b. cm/g supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0.97. Fine engineering solid material was dried for 2.5 h under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of about 60oC. in This way received 5,185 g of catalyst. Elemental analysis showed the presence of 0.10 wt.% Zr and 10.64% wt. Al.

Example 20

The catalyst 20

The solution of the precursor was prepared under stirring by mixing 3,5902 g not containing gel solution methylalumoxane in toluene concentration of 30 weight. % (18,48 mmole Al) and 0,0262 g dimethylsilane(2-methyl-4,5 - benzhydryl)zirconiated (0,045 mmole Zr). Then added 1,8979 g of toluene. This solution of the precursor was added to 4,0055 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0,94. Fine engineering firm mA is o
C. in This way received 4,901 g of catalyst. Elemental analysis showed the presence of 0.06 wt.% Zr and by 8.22% wt. Al.

Example 21

The catalyst 21

The solution of the precursor was prepared under stirring by mixing 1,7072 g not containing gel solution methylalumoxane in toluene concentration of 30 weight. % (8,79 mmole Al) and 0,0257 g dimethylsilane(2-methyl-4,5-benzhydryl)zirconiated (0,045 mmole Zr). Next was added 3,5518 g of toluene. This solution of the precursor was added to 3,9309 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 0,94. Fine engineering solid material was dried for 3.2 h under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of about 60oC. in This way received 4,400 g of catalyst. Elemental analysis showed the presence of 0.07 wt.% Zr and 4.76 wt.% Al.

Example 22

The catalyst 22

The solution of the precursor was prepared under stirring by mixing 106 g not containing gel solution methylalumoxane in toluene concentration 3 what does 40 g of toluene. This solution of the precursor was added to 100 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 1.0. The solid material which was not really engineering, dried over 3,25 h under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of about 60oC. the Catalyst was obtained in the form of fine engineering of solid material. Elemental analysis showed the presence of 0.11 wt.% Zr and 8,96% wt. Al.

Example 23

The catalyst 23

The solution of the precursor was prepared under stirring by mixing 108 g not containing gel solution methylalumoxane in toluene concentration of 30 weight. % (554 mmole Al) and 1.10 g of dimethylsilicone(2-methyl-4,5-benzhydryl)zirconiated (1,90 mmole Zr). Then added 72 g of toluene. This solution of the precursor was added to 100 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 800oC current N2. Velicina this solid material was reminiscent of wet sand, and it was dried over 3,25 h under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of about 60oC. the Catalyst was obtained in the form of fine engineering of solid material. Elemental analysis showed the presence of 0.12 wt.% Zr and 9,26% wt. Al.

Example 24

The catalyst 24

The solution of the precursor was prepared under stirring by mixing 1,7940 g not containing gel solution methylalumoxane in toluene concentration of 30 weight. % (9,236 mmole Al) and 0,0135 g dimethylsilane(2-methyl-4,5 - benzhydryl)zirconiated (0,023 mmole Zr). Then added 5,3578 g of toluene. This solution of the precursor was added to 2,0153 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 2.5. According to its consistency, this solid material was reminiscent of wet sand, and it was dried for 3 h under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of 60oC. 2,6172 g of catalyst was obtained in the form of fine engineering of solid material. Elemental analysis pacaveli under stirring by mixing 0,8765 g not containing gel solution methylalumoxane in toluene concentration of 30 weight. % (4,508 mmole Al) and 0,0146 g dimethylsilane(2-methyl-4,5 - benzhydryl)zirconiated (0,025 mmole Zr). Then added 6,2009 g of toluene. This solution of the precursor was added to 2,0015 g of silicon dioxide MS948 with porosity of 1.6 CC/g, supplied to the market by the firm of W. R. Grace, Davison Chemical Division, Baltimore, PCs Maryland (Davison Chemical Co.) and preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 2.5. According to its consistency, this solid material was reminiscent of wet sand, and it was dried for 3 h under reduced pressure (in vacuo 29+ inch RT.CT.) and at a temperature of about 60oC. in This way received 2,4446 g of the catalyst in the form of fine engineering of solid material. Elemental analysis showed the presence of 0.09 wt.% Zr and 5,11 wt.% Al.

Comparative example 26

The catalyst 26

The solution of the precursor was prepared under stirring by mixing 6,8627 g not containing gel solution methylalumoxane in toluene concentration of 30 weight. % (35,33 mmole Al) and 0,0277 g dimethylsilane(2-methyl-4,5-benzhydryl)zirconiated (0,048 mmole Zr). Then added 12,3745 g of toluene. This solution of the precursor was added to 2,0021 g of silicon dioxide MS9l Co.) and preheated to 800oC current N2. The value of the ratio between the liquid volume and the total pore volume of the silica was 6.7. The result has been a suspension, which was dried over 4,1 h under reduced pressure (in vacuo 29+ inch RT. Art. ) and at a temperature of about 60oC. in This way received 4,1414 g of the catalyst in the form of fine engineering of solid material. Elemental analysis showed the presence of 0.09 wt.% Zr and 18,82% wt. Al.

The POLYMERIZATION TEST of CATALYSTS 12-17 (see tab. 2).

A sample of each of the catalysts on the media (75 mg) prepared in the above examples 12-17, suspended in 2 ml of hexane and a strong jet of 250 ml of propylene was blown away in 2-liter autoclave, purged with nitrogen and containing 0.5 ml of 1 M solution of triethylaluminum in hexane and 1000 ml of propylene at a temperature of 70oC. the Reaction was conducted for 1 h, after which the reactor was cooled, was ventolinbuy and within 20 minutes was purged with nitrogen. After nitrogen purge, the reactor was opened, the product was collected and dried in vacuum for at least 2 h at 75oC.

The POLYMERIZATION TEST of CATALYSTS 18-Cf. 26 (see tab. 3).

A sample of each of the catalysts is on Elena blew off a 2-liter autoclave, purged with nitrogen and containing 0.5 ml of 1 M solution of triethylaluminum in hexane and 1000 ml of propylene, after which the reactor was heated to a temperature of 65oC. the Reaction was conducted for 1 h, after which the reactor was cooled, was ventolinbuy and within 20 minutes was purged with nitrogen. After nitrogen purge, the reactor was opened, the product was collected and dried in vacuum for at least 2 h at 75oC. If the mixer or thermocouple detect any residual product (the polluter), it was collected and weighed separately.

Although the present invention is described and illustrated with reference to specific ways of its implementation, for any expert in the art it is obvious that the invention can make various changes, which need not be illustrated in this description. For example, in the scope of the present invention includes mixing at least two of the catalysts according to the invention or the catalyst according to the invention together with another catalyst or catalyst system known in the art, for example with a conventional catalyst or catalytic system of the Ziegler-Natta. In addition, the catalytic the reactors. Thus, the scope of the present invention is defined only by the attached claims.

1. The method of preparation of the catalytic system on the media for the polymerization of olefins containing metallocene catalyst component, alumoxane and porous media, and this method involves the following stages: a) mixing the metallocene catalyst component with alumoxane in a solvent to obtain a solution, where the metallocene catalyst component corresponds to the formula

< / BR>
where M denotes a metal of group 4, 5 or 6 of the Periodic table of elements;

R1and R2the same or different and each denotes a hydrogen atom,

C1- C10alkyl group, a C1- C10alkoxygroup, C6- C10aryl group, a C6- C10alloctype, C2- C10alkenylphenol group, C7- C40arylalkyl group, C7- C40alcylaryl group, C8- C40arylalkyl group or a halogen atom;

R3and R4denote hydrogen atoms;

R5and R6the same or different, preferably same, and each represents a halogen atom, a C1- C10the alkyl group is th, C2- C10alkenylphenol group, C7- C40arylalkyl group, C7- C40alcylaryl group, C8- C40arylalkyl group, a radical-NR215, -SR15, -OR15, -OSiR315or-PR215where R15denotes a halogen atom, a C1- C10alkyl group or a C6- C10aryl group;

R7denotes the radical

< / BR>
< / BR>
< / BR>
< / BR>
= BR11, = AlR11, -Ge -, - Sn -,- O-, -S-, =SO, =SO2, =NR11, =CO.PR11or = P(O)R11;

where R11, R12and R13the same or different and each denotes a hydrogen atom, a halogen atom, a C1- C20alkyl group, a C1- C20alkyl fluoride group, a C6- C30aryl group, a C6- C30ferrillo group, C1- C20alkoxygroup, C2- C20alkenylphenol group, C7- C40arylalkyl group, C8- C40arylalkyl group or a C7- C40arylalkyl group, or R11and R12or R11and R13together with the atoms connecting them may form a cyclic system;

M2denotes a silicon, germanium or tin;

R8and R9about the means zero, 1 or 2, and the sum of m plus n is zero, 1 or 2;

R10are the same or different radicals and are shown for R11, R12and R13and additionally, two adjacent radicals R10can be linked with the formation of a cyclic system,

and b) mixing the solution with a porous carrier, provided that the ratio of the total solution to the total volume of pores of a porous medium is less than three.

2. The method according to p. 1, where the ratio of the total solution volume to the total volume of pores of a porous medium is less than two.

3. The method according to p. 1, where the ratio of the total solution volume to the total pore volume of the porous media is 1.05 to 2.5.

4. The method according to any of the preceding paragraphs, where the metallocene catalyst component includes two or more metallocene catalyst components and/or where the molar ratio between the aluminum alumoxane and transition metal metallocene catalyst component is from 20 : 1 to 500 : 1.

5. The method according to any of the preceding paragraphs, where the method further includes a step of prepolymerisation catalytic system on the media ispolzovat silicon, R5and R6have the same value of C1- C10of alkyl, three of the radicals R10represent hydrogen, and one represents a C6- C30aryl group.

7. The method according to any of the preceding paragraphs, where the metallocene component is selected from a group consisting mainly of:

rat-dimethylanilines(2-methyl-4,5-benzhydryl)zirconiated;

rat-dimethylanilines(2-methylindenyl)zirconiated;

rat-dimethylanilines(2-methyl-4,6-diisopropylphenyl)-zirconiabased;

rat-dimethylanilines(2-methyl-4-phenyl-indenyl)zirconiated and

rat-dimethylanilines(2-methyl-4-phenyl-1-indenyl)zirconiated.

8. The method of polymerization of propylene individually or in combination with one or more other olefins comprising the polymerization in the presence of catalytic systems on a carrier prepared by the method according to p. 1.

9. The catalytic system on the media for the polymerization of olefins, obtained by the method according to PP.1 - 7.

 

Same patents:

The invention relates to new multi-core metallocene compounds of the formula I, in which M1denotes a metal of group IVб of the Periodic system of the elements; X is a halogen atom; L and L1are the same or different and represent a substituted cyclopentadienyl, optionally substituted indenyl and unsubstituted fluorenyl; denotes a group of formula (a), in which R1denotes a divalent hydrocarbon bridging group, the residues R2are the same and denote WITH1-C4is an alkyl group; M2denotes the silicon, as well as the way they are received, containing the catalytic system, a method for producing a polyolefin and a polymer molded product

The invention relates to a method for producing polyethylene by polymerization of ethylene at elevated temperature and pressure in the presence of a catalyst consisting of zirconocene and socializaton - methylalumoxane, while the polymerization of ethylene is carried out at a temperature of 100-150oC, a pressure of 4-8 bar in the presence of a catalyst containing as zirconocene a compound selected from the group including rat-dimethylsilane - bis-1-(2-methyl-4-phenylindane)zirconiated, rat - dimethylsilane-bis-1-(2-metalcrafter)zirconiated, rat - dimethylsilane-bis-1-(2-methyl-4,5-benzhydryl)zirconiated

The invention relates to metallocenes, which are preferably used for obtaining polyolefins with a wide range of properties

The invention relates to a solid titanium catalyst component for use as a catalyst in the production of homopolymers or copolymers of olefins and to a method for producing a solid titanium catalyst component

The invention relates to a method for ultracytochemical polyethylene (PE-UVMV) with a bulk density (apparent density of 350 - 460 g/l, particularly 430 - 460 g/l)

The invention relates to copolymers of ethylene with propylene, optionally with a minimum number of polyene and method of production thereof

The invention relates to a method for producing a catalyst used for the polymerization of olefins, by contacting compounds of magnesium with a halogenated titanium compound

The invention relates to new multi-core metallocene compounds of the formula I, in which M1denotes a metal of group IVб of the Periodic system of the elements; X is a halogen atom; L and L1are the same or different and represent a substituted cyclopentadienyl, optionally substituted indenyl and unsubstituted fluorenyl; denotes a group of formula (a), in which R1denotes a divalent hydrocarbon bridging group, the residues R2are the same and denote WITH1-C4is an alkyl group; M2denotes the silicon, as well as the way they are received, containing the catalytic system, a method for producing a polyolefin and a polymer molded product

The invention relates to a method for producing polyethylene by polymerization of ethylene at elevated temperature and pressure in the presence of a catalyst consisting of zirconocene and socializaton - methylalumoxane, while the polymerization of ethylene is carried out at a temperature of 100-150oC, a pressure of 4-8 bar in the presence of a catalyst containing as zirconocene a compound selected from the group including rat-dimethylsilane - bis-1-(2-methyl-4-phenylindane)zirconiated, rat - dimethylsilane-bis-1-(2-metalcrafter)zirconiated, rat - dimethylsilane-bis-1-(2-methyl-4,5-benzhydryl)zirconiated

The invention relates to a method for producing polyethylene by polymerization of ethylene at elevated temperature and pressure in the presence of a catalyst consisting of zirconocene and socializaton - methylalumoxane, while the polymerization of ethylene is carried out at a temperature of 100-150oC, a pressure of 4-8 bar in the presence of a catalyst containing as zirconocene a compound selected from the group including rat-dimethylsilane - bis-1-(2-methyl-4-phenylindane)zirconiated, rat - dimethylsilane-bis-1-(2-metalcrafter)zirconiated, rat - dimethylsilane-bis-1-(2-methyl-4,5-benzhydryl)zirconiated

The invention relates to metallocenes, which are preferably used for obtaining polyolefins with a wide range of properties

The invention relates to a solid titanium catalyst component for use as a catalyst in the production of homopolymers or copolymers of olefins and to a method for producing a solid titanium catalyst component

The invention relates to a method for ultracytochemical polyethylene (PE-UVMV) with a bulk density (apparent density of 350 - 460 g/l, particularly 430 - 460 g/l)

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The invention relates to a catalyst carrier and to a method for the media, it also relates to polymerization catalysts- olefins, obtained on the basis of these carriers, the method of production of these catalysts and to a method of polymerization- olefins in the presence of
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