The solid precursor of a catalytic system for the polymerization of olefins, process for its production, the catalytic system for polymerization of olefins and polymerization of olefins

 

(57) Abstract:

Describes a new solid precursor of a catalytic system for the polymerization of olefins, obtained using neutral metallocene containing a transition metal of group IV that is associated with at least one halogen atom, and at least one ionizing agent, characterized in that the corresponding metallocene treated with ionizing agent in a heterogeneous environment. Also describes the method of its production, the catalytic system for polymerization of olefins and polymerization of olefins. The technical result is to simplify the process and increase the stability of the catalytic system. 4 C. and 24 C.p. f-crystals.

The present invention relates to a solid precursor of a catalytic system used for the polymerization of olefins, in particular to a solid precursor, including metallocene It also relates to a method for obtaining this solid precursor to a catalytic system for polymerization of olefins comprising the precursor, and the method of polymerization of olefin using the catalyst system.

In European patent application EP-426639 [FINA CHNOL OGY IN the NR condition, obtained by mixing a solution of an ionizing agent such as a solution of triphenylcarbenium - tetrakis/pentafluorophenyl/borate, with a solution of neutral and alkylated derivative of a transition metal metallocene [for example, as a solution of bis/cyclopentadienyl/dimethylsilane in toluene]. These neutral alkylated metallocene have the disadvantage that they are unstable, they are difficult to get and keep. In addition, these known catalysts are particularly volatile and during their use for the polymerization of olefins have activity, which decreases rapidly from the moment of their receipt.

These catalysts can be simplified, as described in European patent application EP-0500944-A1 (MITSUI TOATSU CHEMICALS INC.), selecting from the neutral metallocenes such that galogenirovannyie, entering into interaction first alyuminiiorganicheskikh connection with neutral halogen-containing metallocenes in aromatic solvent and ionizing then the thus obtained product with ionizing agent. To this end, in the polymerization reactor is injected in series:

(a) the product of the alkylation reaction between alyuminiiorganicheskikh connection and neutral and (b) the ionizing agent. In this way, the preliminary alkylation reaction neutral halogenated metallocene using alyuminiiorganicheskikh compounds in aromatic solvent is essential to obtain a stable and active catalyst. This known method has the disadvantage that the necessary pre-processing of the neutral halogenated metallocene using alyuminiiorganicheskikh connections before putting it in contact with the agent. In addition, as the reaction product of alkylation neutral halogenated metallocene very unstable, putting it in contact with the agent must necessarily be implemented in situ in the polymerization reactor.

The aim of the present invention is to avoid these above-mentioned disadvantages due to the use of new solid precursor of a catalytic system, the receipt of which is simplified and there is no need for pre-treatment of the neutral halogenated metallocene. Another advantage of the invention is to provide a stable solid predecessor, which you can prepare in advance and be stored for at least one day (usually longer) before the use of the doctrine of the solid precursor of a catalytic system, which allows you to obtain polyolefins with a high average molecular weight, broad molecular massivem distribution and high apparent specific gravity.

The invention relates to a solid precursor of a catalytic system for the polymerization of olefins, and this precursor contains at least one neutral metallocene derived transition metal, and at least one ionizing agent, characterized in that the neutral metallocene is essentially in halogenated state, and the transition metal is associated with at least one halogen atom.

The main characteristic of the solid precursor according to the invention is a halogenated neutral state metallocene forming part of the predecessor. In the solid precursor according to the invention the neutral metallocene is usually selected from the formula (Cp)a(C'p)bMXxZZwhere:

Cpand C'peach refers to an unsaturated hydrocarbon radical, coordinated atom M, and group Cpand C'pcan be linked by covalent bridge;

M denotes a transition metal of choice is La, such that (a+b=x=Z)=m; x>0; Z0 and ' a 'and/or' b ' 0;

"m" denotes the valence of the transition metal M;

X denotes halogen and

Z denotes a hydrocarbon radical, in certain cases may include oxygen or a radical of the formula (Rt-Si-R R"R"'), where

R denotes alkyl, alkenylphenol, aryl, CNS or cycloalkyl group, in some cases replaced, including up to 20oC-atoms;

R', R" and R"' are the same or different and represent each a halogen or alkyl, alkenylphenol, aryl, CNS or cycloalkyl group, in some cases substituted, containing up to 20oC-atoms;

"t" denotes 0 or 1.

Preferably the transition metal is chosen from the group of scandium, titanium, zirconium, hafnium and vanadium. Particularly well suitable zirconium. Group Cpand C'peach represent preferably a mono - or polycyclic group, in some cases substituted, containing 5-50 C-atoms connected conjugated double bonds. As typical examples, cyclopentadienyls, intenally or fluorenyl radical or a substituted derivative of this radical in which at least one atom l, derived element chosen in the group VA of the periodic system, for example, nitrogen or phosphorus.

As examples of neutral metallocene formula (Cp)a(C'p)bMXXZZin the case where "Z" is 0, can be called mono - and dihalogenoalkane metallocene scandium, such as chlorine di(cyclopentadienyl)scandium; and dichloro(indenyl)scandium; mono-, di - and trihalomethane metallocene titanium, such as chlorine-three(pentamethylcyclopentadienyl)titanium, dibromide(methylcyclopentadienyl)-titanium and trichloro(cyclopentadienyl)titanium; mono-, di - and trihalomethane metallocene zirconium, such as ITRI (cyclopentadienyl)zirconium, dibromo(cyclopentadienyl-1-indenyl) zirconium, trichloro(fluorenyl)-zirconium; mono-, di - and trihalomethanes metallocene hafnium, mono-, di - and trihalomethane metallocene vanadium, such as Hartry (cyclopentadienyl)vanadium, dichloride (ethylcyclopentadienyl)vanadium and trichloro(ethyl-indenyl)vanadium; mono - and dihalogenoalkane metallocene tervalent chromium, such as dichloro(cyclopentadienyl)-chromium.

In the case when Z is not zero, and when Z is a hydrocarbon radical, neutral metallocene formula (Cp)a(C'

In the case when Z is not zero, and when Z represents silylene a radical of the formula (Rt-Si-R', R", R"'), neutral metallocene formula (Cp)a(C'p)bMXXZZcan be selected, for example, among those, including as a silyl radical allylimidazole, allylmethylamine, 5- (bicycloheptene)trichlorosilyl, 2-bromo-3-trimethylsilyl-1-propenyl, 3-chloropropionitrile, 2-(3-cyclohexenyl)ethyltrimethoxysilane and diphenyldichlorosilane.

Metallocene containing covalent bridge linking both groups Cpand C'pcan be selected from among those of General formula:

< / BR>
in which A denotes alkylenes group, which in certain cases may include oxygen, albaniles, arylalkyl, alkylaryl, arylalkyl, in known cases, halogenated, or a radical derived element selected among elements of IIIA, IVA, VA and VIA groups of the periodic system, such as boron, aluminum, silicon, germanium, tin, nitrogen, phosphorus, and sulfur. As an example, containing bridges metallocenes can be called medianly radical and Cyc*means pentamethylene-pentadienyl radical.

The preferred metallocene formula (Cp)a(C'p)bMXXZZare those in which the group Cpand C'pselected among cyclopentadienyls, ingenering and fluoroanilino radicals. Good results are obtained with such metallocene, groups Cpand C'p, which are connected by covalent bridge alkyl type. Metallocene, transition metal selected from titanium, zirconium and hafnium, very good fit. Particularly satisfactory results are obtained with metallocene, derivatives of zirconium.

According to the invention, under ionizing agent understand the connection comprising a first part which has the properties of a Lewis acid and which is able to ionize neutral metallocene and the second part, which is inert with respect to the ionized metallocene and which is capable of stabilizing ionized metallocene. Ionizing agent may be an ionic compound comprising a cation having the properties of a Lewis acid and the anion constituting the above-mentioned second part of the ionizing agent. Anions, leading to very good cut is, the which the boron atom is associated with 4 organic substituents. As examples of ionizing ionic agents include triphenyl - carbene-tetrakis(pentafluorophenyl)borate, N,N-dimethyl-aniline - tetrakis(pentafluorophenyl)-borate, and three(n-butyl)ammonium tetrakis(pentafluorophenyl)borate. Preferred cationic Lewis acids are carbene, sulfone and hydronium.

Especially preferred ionizing agents are those comprising the cation type carbene.

Alternatively, the ionizing agent may be a nonionic compound having the properties of a Lewis acid which is capable to transform neutral metallocene in cationic metallocene. To do this himself ionizing agent becomes inert to the cationic metallocene anion, which is able to stabilize. As examples of non-ionic ionizing agent can be called three (pentafluorophenyl) boron, triphenylboron, trimethylboron, three (trimethylsilyl) borate and organobromine.

The ionizing agent is preferably selected from triphenyl-carbene - tetrakis(pentafluorophenyl) borate and three(Penta-forfinal) boron.

Triphenyl-carbene-tetrakis(pentafluorophenyl)borate osobennogo metal, usually 0.2 to 20 wt.%, the most usual values are from 0.5 to 10 wt.%; - 1-50 wt.% halogen, preferably 5-30 wt.%.

The solid precursor according to the invention should contain the ionizing agent in a quantity sufficient to ionize most part [e.g., at least 80 wt.%], preferably the whole neutral metallocene. The optimal number corresponding halogenated neutral metallocene and ionizing agent in the precursor, depend on the chosen metallocene and ionizing agent. Almost solid precursor according to the invention preferably includes the number of neutral metallocene and ionizing agent in a molar ratio of 0.5 to 2; they are preferably in an appreciable degree of equimolar. Preferably, the weight ratio of the neutral metallocene to ionizing agent is 0.1-10, in particular from 0.2 to 2.

The solid precursor according to the invention is typically in the form of powder granules, characterized in that:

- the average diameter D is 1-500 μm, usually 2-350 mcm, with the most common values are 5 to 200, for example, about 10 μm.

the standard is blowing dependencies

< / BR>
where "ni" indicates the weight the frequency of particles of diameter Di. The average diameter D and the standard deviation is measured by laser granulometry using a device MALVERNMSIZER 20. Usually, the solid precursor according to the invention is characterized, in addition, a specific surface area of 50-300 m3/g, typically 80-200 m2/g, for example, about 150, and pervym the amount of 0.1-3 cm3/g, for example, about 1.

According to a preferred variant of the solid precursor according to the invention, it also includes the media, which can be a polymer (such as, for example, polyethylene, polypropylene and their copolymers) or inorganic carrier. As examples of inorganic carrier can be called a metal halide such as magnesium chloride; metal oxides, such as oxides of silicon or aluminium [in known cases treated fluorine-containing compound], titanium, zirconium, thorium, and mixtures thereof, and mixed oxides of these metals, such as aluminum silicate and aluminum phosphate. Well suited silicon dioxide, aluminum oxide, magnesium chloride, aluminum phosphate and mixtures of silicon dioxide with magnesium chloride.

In this preferred embodiment, solid predestin the>- average diameter D 10-1000 microns, typically between 20 and 500 microns, with the most common values are 40-200 μm;

- standard deviation of 10-50 μm, preferably 20-40 μm.

In this preferred embodiment, the solid precursor according to the invention preferably includes a carrier in such quantity that the weight ratio of the carrier to the neutral metallocene amounted to 0.1, preferably 5; preferably, this ratio does not exceed 1000, in particular 100, with recommended values close to 10.

The solid precursor according to this variant of the invention has the advantage of giving the catalytic system, which, at the time of their use for the polymerization of olefins, reduce scum formation in the polymerization reactor and allow better control of the morphology of the obtained polymer.

According to another particular variant of the solid precursor according to the invention it includes, in addition to neutral metallocene and ionizing agent catalytic compound. This catalytic compound can be selected from halides or oxyhalogenation transition metal from groups IV and V of the periodic system and of compounds, including and which are obtained by mixing compounds of magnesium to transition metal compound and a halogenated compound. Halogen in certain cases may be part of the compounds of magnesium or compounds of the transition metal In the case where the halogen is not part of the magnesium compounds or transition metal compounds, halogen-containing compound may be selected from halogenated derivatives of aluminum, such as, for example, ethylaminoethanol, dipropyleneglycol, or trichloride aluminum. Catalytically-active compound preferably includes:

- 10-30 weight. % transition metal selected from among metals of groups IIIB, IV or VI of the periodic system, preferably 15-20 wt.%, usually about 17 wt.%;

- 20-50 weight. % halogen, and the preferred values of 30-40 wt.% (for example, about 40 wt.%),

- 0.5 to 20 wt.% magnesium, usually 0.5-20 wt.%, with the usual amount of 1-10 wt.%, for example, about 5%, and the solid is usually formed by elements originating from used for its products, such as carbon, hydrogen and oxygen.

Catalytically-active compound may also contain, in addition, 0.5 to 20 weight. % aluminum, usually 0.5-5 wt.%, with the usual amount of 1-3%. The transition metal and halogen preferably represents titanium and chlorine.

In this special Oba weight ratio of this catalytically-active connection to the neutral metallocene was at least 0,05, preferably equal to 0.5, preferably it does not exceed 1000, in particular 100.

Needless to say, that the solid precursor according to the invention may include more than one neutral metallocene, more than one ionizing agent and, if necessary, more than one carrier and/or more than one catalytically-active compounds.

The solid precursor according to the invention has a particularly high stability and can be obtained in advance and stored without danger of decontamination for at least 24 hours, usually at least a week, usually at least a month. The solid precursor according to the invention is particularly characterized by stability above 0.95, and this characteristic is the ratio between, on the one hand, the weight of the polyethylene obtained by polymerization of ethylene for 1 hour at a partial pressure of 1 bar in the presence of a catalytic system comprising in a weight ratio of 0.1-10 ORGANOMETALLIC compound and the above predecessor, which was stored after mixing neutral halogenated metallocene and ionizing agent within 48 hours at room temperature in a nitrogen atmosphere, and the other is AI 1 bar in the presence of the same catalyst system, in which the precursor is not subject to storage. According to the invention, thus there is no need for mixing of neutral halogenated metallocene with an ionizing agent in situ in the polymerization reactor at the time of polymerization.

The subject invention is also a method of obtaining a solid precursor of a catalytic system suitable for the polymerization of olefins, according to which at least one compound based on a neutral metallocene derived transition metal, is mixed at least one compound based on an ionizing agent; according to the invention, the neutral metallocene is halogenated, and the transition metal is associated with at least one halogen atom, and carry out the mixing in a heterogeneous environment.

Under heterogeneous environment see environment containing compound based on an ionizing agent and the compound based on a neutral metallocene, in which at least 80% [preferably at least 95%] but at least one of these two compounds are in solid state. This heterogeneous environment can be essentially solid and can be obtained by mixing, in the absence of erogena environment can contain liquid and may be formed by suspension, including organic liquid, in which at least 80% [preferably at least 95%] at least one of both compounds [compound based on an ionizing agent and a compound based on a neutral metallocene] insoluble. As the organic liquid can be used aliphatic hydrocarbon selected among linear alkanes (such as n-butane, n-hexane and n-heptane); branched alkanes such as isobutane, isopentane, isooctane and 2,2-DIMETHYLPROPANE), and cycloalkanes such as cyclopentane and cyclohexane). Also suitable monocyclic aromatic hydrocarbons such as benzene and its derivatives, for example, toluene, polycyclic aromatic hydrocarbons, and each cycle can be substituted for the above heterogeneous environment.

In the method of receiving according to the invention, the neutral metallocene and the ionizing agent are similar to those described above. The phrase "compound based on a neutral metallocene" understand net neutral metallocene or mixed compound comprising a neutral metallocene and at least one other solid, non-neutral metallocene and ionizing all the ionizing agent or a mixed compound, including the ionizing agent and at least one other solid, non-ionizing agent and neutral metallocene and inert towards them. These solids can be polymer type (such as polyolefins) or inorganic type (such as oxides and halides of metals). These corresponding mixed compounds, for example, can be obtained by mechanical mixing in the solid state neutral metallocene or ionizing agent with a solid. Alternatively, they can be obtained by impregnating solids solution of a neutral metallocene, respectively, of the ionizing agent. You can also use a neutral metallocene and the ionizing agent in pure form.

In the method of obtaining a solid precursor according to the invention at least one of the two compound [compound based on a neutral metallocene and the compound based on an ionizing agent] is used in the solid state, usually in powder form. When both compounds are used in the form of powders, these powders preferably have a similar grain size distribution, to the mixture remained homogeneous without Russ is ocena preferably have the same order, characterized by, for example, an average diameter D of 1-100 μm and a standard deviation of 5-25 microns.

In the method of obtaining a solid precursor according to the invention, it may be necessary drying of powders of the compound based on a neutral metallocene and/or a compound based on an ionizing agent prior to their mixing, and this drying can be achieved, for example, by treatment with hydrophilic compounds or by heating at a temperature below the temperature of decomposition of these powders and for a time sufficient to remove all traces of moisture from the powder.

The number of connections on the basis of metallocene and connections based on an ionizing agent used in the proposed method of obtaining a solid precursor according to the invention are typically in a molar ratio of 0.5 to 2; preferably they equimolarly.

In the method of obtaining a solid precursor according to the invention the mixture of compounds on the basis of neutral metallocene with a compound based on an ionizing agent can be accomplished in any appropriate known method, implemented in a heterogeneous environment, for example, equipped with a stirrer mixer, reactionare. Usually when mixing is carried out in the absence of organic liquids effect the desired implementation of a mixture of compounds on the basis of neutral metallocene with a compound based on an ionizing agent by their joint grinding. Preferably operate in a rotating reactor or equipped with a mixer the mixer.

The temperature at which this mixture can be any temperature below the decomposition temperature of the neutral metallocene and connections based on an ionizing agent. The temperature depends on the nature of these substances; usually it is at least equal to the 0oC, preferably 20oC; maximum sleep 100oC, the most common values below 60oC, for example, 50oC, most preferred. When a heterogeneous environment is a suspension comprising an organic liquid, the temperature should be such that at least 80% [preferably at least 90%] one or both of the compounds [compound based on an ionizing agent and a compound based on a neutral metallocene was insoluble in the organic liquid. Mixing can be implemented in dostojnoj temperature iconica according to the invention, the duration, in the course of which the mixture must be sufficient for the maximum homogenization of the mixture. The duration of mixing depends on the mixer. It is usually at least equal to one minute, preferably is 5 hours; for reasons of economy, it is desirable that the duration of the mixture did not exceed 100 hours, particularly 50 hours. Particularly well suitable duration of mixing for about 24 hours.

In the variant proposed in the invention method of producing a solid precursor of a solid compound based on a neutral metallocene and the compound based on an ionizing agent is preferably mixed in an inert atmosphere. The inert atmosphere may be formed by nitrogen, argon, helium or a mixture of two or more of these gases.

A method of obtaining a solid precursor according to the invention has a preferred feature to give stable precursors of catalytic systems and contact the neutral metallophone with ionizing agent is implemented in the absence of alyuminiiorganicheskikh connection, which makes the implementation of this contact is particularly simple. Besides, these grams of polymer, produced per hour per gram of solid predecessor, divided by the partial pressure of olefin, expressed in bars] in the methods of polymerization of olefins.

In a first, particularly preferred form of implementation of the method of obtaining a solid precursor according to the invention, the cream, with a compound based on a neutral metallocene and the compound based on an ionizing agent is mixed media and/or catalyst compound. In this form of implementation, it is preferable to use a number of media [respectively, the catalytic compounds], so that the weight ratio of the carrier [respectively, the catalytic compounds] to the compound based on a neutral metallocene was at least 0.05, preferably 2; preferably it does not exceed 1000, in particular 100, with recommended values close to 10.

In this form of realization of the method of obtaining a solid precursor according to the invention, the mixing should be carried out at a temperature below the temperature of decomposition of the carrier and/or catalyst compound.

In the first variant of this form of implementation, the connection on the basis of neutral metallocene, soeding conditions [equipment, temperature, duration, atmosphere].

In the second variant of this form of implementation, the mixing is carried out in several successive stages, with the first stage mix two of the components of the solid precursor [compound based on a neutral metallocene, the compound based on an ionizing agent, the carrier and/or catalyst compound]; and other components add to one or more subsequent stages. When the solid precursor contains three components, it may be preferable mixing the first compound based on a neutral metallocene with the media [or catalytic connection], and then add the compound based on an ionizing agent. In this case, the first stage is preferably carried out at a temperature of 10 to 120oC, usually 20-90oC, for example, at a temperature of about 60oC. the Second stage is most often implemented at a temperature below the temperature of the first stage, for example, at a temperature of 0-60oC, usually 20-50oC.

In the third, particularly preferred variant of this form of implementation, the mixing is carried out in several successive stages, and the connection based on nataliastefany in the absence of a liquid; thus the resulting mixture was then at the second stage is impregnated with a solution of the compound based on an ionizing agent. This second stage is at least 80% [preferably at least 90%] compound based on a neutral metallocene insoluble in the solvent for suspension. In this preferred embodiment, the first stage is preferably carried out at a temperature 10-120oC, typically 40-100oC, for example, at a temperature of approximately 80oC. the Second stage is most often implemented at a temperature below the temperature of the first stage, for example, at a temperature of 0-60oC. Well suited to room temperature.

In the second form of implementation of the method of obtaining a solid precursor according to the invention compound based on a neutral metallocene includes as a solid substance, other than a neutral metallocene and ionizing agent, the carrier and/or solid catalytic compound. The latter correspond to the above-mentioned carrier and the catalytic compound. In this second form of implementation of the connection on the basis of neutral metallocene can be obtained by impregnation of the carrier and/or catalyst compound solution neutral metallic, as toluene.

In the third, a particularly interesting form of implementation of the method of obtaining a solid precursor according to the invention a compound based on an ionizing agent includes as a solid substance, other than ionizing agent and neutral metallocene, carrier and/or catalyst compound. The latter correspond to the above-mentioned carrier and the catalytic compound. In this third form of implementation, the compound based on an ionizing agent preferably is obtained by impregnation of the carrier and/or catalyst compound solution ionizing agent in a hydrocarbon diluent. The hydrocarbon diluent is preferably chosen among the aromatic hydrocarbons, such as toluene, or halogenated aliphatic hydrocarbons, such as methylene chloride and chloroform.

The fourth form of implementation of the method of obtaining a solid precursor according to the invention, use neutral metallocene formula (Cp)a(C'p)bMXX(Rt-Si-R R"R"'), which is produced by introducing into the interaction of silane with the compound of the formula (Cp)a(C'p)bMXXHZ[where the characters from scratch]. This reaction is preferably carried out in an appropriate solvent. The compounds of formula Cp)a(C'p)bMXXHZthat leads to very good results, are especially derivatives of zirconium, titanium and hafnium, Cpand C'pthat are selected from cyclopentadienyls, ingenering and fluoroanilino radicals. Preferably use derivatives of zirconium. Preferably X is chlorine. As examples used in this form of implementation of the silanes can be called allylimidazole, allylmethylamine, 5-(bicycloheptene) -trichlorosilane, 2-bromo-3-trimethylsilyl-1-propene, 3-chloro-profilemeter-vinylsilane, 2-(3-cyclohexenyl)ethylimidazolium, diphenyldichlorosilane, vinyltriethoxysilane, vinyltrichlorosilane, 2-(trimethylsilylmethyl)-1,3-butadiene and 3- (trimethylsilyl)cyclopentene. The preferred silanes are the non-chlorinated alkenylsilanes) such as allyltriethoxysilane, allyltrimethylsilane, 5-(bicycloheptene)triethoxysilane, vinyl (trimetoksi)silane and 2-(3-cyclohexenyl)ethyltrimethoxysilane. Particularly well suited vinyl/trimetoksi/silane. The solvent of the reaction between the silane and the compound of the formula (Cp)a(C'p) oC. the Preferred temperature is room temperature.

In the fifth form of implementation of the method of obtaining a solid precursor according to the invention, use neutral metallocene formula (Cp)a(C'p)bMXXZZ[where the characters CpC'p, M, X, a, b, x and Z have the above meaning and Z is non-zero, and Z is a hydrocarbon radical], which is obtained by reacting the compounds of formula Cp)a(C'p)bMXXHZsuch as the above, with the olefin. This reaction is preferably carried out in an appropriate solvent. Used to this form of implementation of the olefins preferably contain up to 20 C-atoms, preferably up to 12 C atoms and can be selected among monoolefins, such as ethylene and 3-ethyl-1 - butene; unpaired of diolefines, such as 1,5-hexadiene; paired diolefins, such as 1,3-pentadiene; and alicyclic diolefins, such as dicyclopentadienyl. The preferred olefin is ethylene. The solvent of the reaction between the aromatic hydrocarbon, preferably toluene. The temperature at which this reaction is carried out may vary from room temperature up to the boiling point of the used solvent, for example, 20-100oC. the Preferred temperature is room temperature.

The solid precursor according to the invention can be used for polymerization as it was received. However, it may be desirable to subject it to grinding before use in polymerization.

Solid predecessor agreement to the invention is used for polymerization of olefins, in Association with the ORGANOMETALLIC compound.

The invention also relates to a catalytic system for the polymerization of olefins, obtained by bringing into contact of the solid precursor according to the invention, such as defined above, with an ORGANOMETALLIC compound, a derivative of metal, selectable in groups IA, IIA, IIB, IIIA and IV of the periodic system.

In the catalytic system according to the invention ORGANOMETALLIC compound, a derivative of a metal selected from groups IA, IIA, IIB, IIIA and IV of the periodic system may be, for example, selected among the ORGANOMETALLIC compounds of lithium, magnesium, - at least one communication aluminium-carbon and which in certain cases may include oxygen and/or halogen. As examples trialkylaluminium connection) halogenated alkylamine connection and alkylamine compounds comprising at least one CNS group. Alyuminiiorganicheskikh connection preferably meet the General formula AITT'T", in which groups T,T' and T" each denote alkyl, alkenylphenol, aryl or CNS group, in some cases substituted, containing up to 20 C-atoms. We can talk about, for example, trimethyl-, triethyl-, tripropyl, triisopropyl, tributyl, triisobutyl, tridecyl-, trioctyl and tridodecyl-aluminum. Particularly well suitable triethylaluminium and triisobutylaluminum.

Preferred trimethylaluminum. It is especially preferred, as it allows to reduce, even eliminate, the phenomenon of formation of deposits in the polymerization reactor. Usually, the formation of deposits in the reactor, polymerization occurs when using high-yield catalytic system and/or when polymerized in the presence of hydrogen and in some cases one or more comonomers.

Using trimethylaluminum as the ORGANOMETALLIC compound in the catalytic system is ease in enhancing catalytic activity in the reduction of the phenomenon of deposition, even in the presence of hydrogen and/or one or more comonomers. Its impact on reducing the formation of deposits is especially unexpected.

In the catalytic system according to the invention the amount of ORGANOMETALLIC compound may vary within wide grandfathers. It usually corresponds to a molar ratio of ORGANOMETALLIC compound to the neutral metallocene at least equal to 5. However, practically, there is no interest in the fact that this ratio was higher than 5000, and recommended values below 2000. Usually well-fit values close to 100-500, when the catalytic system is intended for the polymerization of olefins.

The catalytic system according to the invention can be used to homopolymerization and copolymerization of olefins with the number of carbon atoms in the molecule up to 20. The olefins preferably contain 2 to 12 C-atoms molecule and selected from among, for example, ethylene, propylene, 1-butene, 1-pentene, 3-methyl - 1-butene, 1-hexene, 3-and 4-methyl-1-pentanol, 1-octene, 3-ethyl-1 - butene, 1-Heptene, 3,4-dimethyl-1-hexene, 4-butyl-1-octene, 5 - ATIP-1-mission and 3,3-dimethyl-1-butene, and vinyl monomers, such as styrene. Catalytic apolymeric of ethylene and propylene with one or more olefinonesaturat the comonomers. The comonomers may be different compounds. They can be monoolefinic, which may include up to 8 C-atoms, such as 1-butene, 1-penten, 3-methyl-1-butene, 1-hexene, 3 - and 4-methyl-1-pentene and 1-octene. One or more diolefins, including 4-18 C-atoms, can also be copolymerizable with ethylene and propylene. Preferably, diolefine choose among aliphatic non-conjugate of diolefines, such as 4-vinyl-cyclohexene and 1.5-hexadiene; alicyclic diolefins containing industrijski bridge, such as Dicyclopentadiene, methylene - and ethylene-norbornene, and aliphatic conjugated diolefins, such as 1,3-butadiene, isoprene and 1,3 - pentadiene.

The catalytic system according to the invention is particularly preferred to obtain homopolymers of ethylene or propylene and copolymers of ethylene and propylene containing at least 90 wt%, preferably at least 95 wt.%, ethylene or propylene. Preferred comonomers of ethylene are propylene, 1-butene, 1-hexene, 1-octene and 1.5-hexadiene and mixtures thereof; and the preferred Seminaire propylene are ethylene, 1,3-butadiene, 1,5-hexadiene and mixtures thereof.

The catalytic system according to the picture is referring to the method of polymerization of at least one olefin, in which use catalytic system according to the invention, such as defined above.

According to the invention it is not necessary to use an aromatic solvent during polymerization.

According to a particularly preferred form of the method of polymerization according to the invention is first mixed olefin with an ORGANOMETALLIC compound of a catalytic system and then to the thus obtained mixture of the solid precursor of the above catalytic system. In this preferred form of the method of polymerization according to the invention the ORGANOMETALLIC compound is usually used in the form of a solution in a hydrocarbon diluent. This hydrocarbon diluent may be selected from among aliphatic hydrocarbons, such as linear alkanes (such as n-butane, n-hexane and n-heptane); branched alkanes (e.g., isobutane, isopentane, isooctane and 2,2-DIMETHYLPROPANE) and cycloalkanes (e.g., cyclopentane and cyclohexane). Preferably operate in isobutane or hexane.

In this preferred form of the method of polymerization according to the invention, since, when solid predshestvennikami compound react with each other, to turn neutral metallocene in the catalytically active substance in the ionized state.

This form of the method of polymerization according to the invention has the advantage that it does not require the presence of an aromatic solvent in the polymerization reactor.

In one embodiment, this special form of the method of polymerization according to the invention by copolymerization with at least two olefins both olefin is injected simultaneously or separately into the polymerization reactor before adding the solid precursor of a catalytic system.

In the polymerization method according to the invention the polymerization can be performed in solution, in suspension or in the gas phase, and it can be performed continuously or periodically, for example, by polymerization in suspension in a first reactor, and then the polymerization in the gas phase in the second reactor or operating in the gas phase in both reactors connected in series. Alternatively, you can also implement the polymerization of a few, arranged in a row, the reactor, and the temperature and/or pressure in the first reactor differ from that prevailing in other reacted or diethylzinc.

In the case of suspension polymerization, it is carried out in a hydrocarbon diluent at a temperature such that at least 80% [preferably at least 95%] of the resulting (co)polymer was insoluble in the diluent. The hydrocarbon diluent may be selected from among aliphatic, cycloaliphatic and aromatic liquid hydrocarbons. Preferred diluents are linear alkanes such as n-butane, n-hexane, n-heptane, or branched alkanes such as isobutane, isopentane, isooctane and 2,2-DIMETHYLPROPANE, or cycloalkanes such as cyclopentane and cyclohexane or mixtures thereof. The temperature is usually at least equal to the 20oC, preferably at least 50oC; it is usually a maximum of equal to 200oC, most preferably 100oC. the Partial pressure of olefin most often at least equal to atmospheric pressure, preferably 0.4 MPa, for example, 0.6 MPa; this pressure is usually most equal to 5 MPa, preferably 2 MPa, for example, 1.5 MPa.

In the case of polymerization in solution, it can be implemented in a hydrocarbon diluent, such as the above. The operating temperature depends on the hydrocarbon diluent and to whom) at least 95%] of the polymer was dissolved in it. In addition, the temperature should be low enough to prevent thermal decomposition of the polymer and/or catalyst system. Usually, the optimum temperature is 100-200oC. the Partial pressure of olefin most often at least equal to atmospheric pressure, is preferably 0.4 MPa, for example, 0.6 MPa; this pressure is usually most equal to 5 MPa, preferably 2 MPa, for example, 1.5 MPa. At the same time, the polymerization can be carried out using the olefin as a hydrocarbon diluent. In this embodiment, it is possible to use olefin, liquid under normal conditions of pressure and temperature, or to operate under pressure sufficient to normally gaseous olefin was Sigala.

When the polymerization is carried out in the gas phase, it can be implemented in the fluidized bed. For this purpose, the gas stream comprising the olefin, and enter it into contact with a catalytic system in the fluidized bed. From this point, the volumetric rate of gas flow should be sufficient to maintain the polymer in a fluidized state and depends on the rate of polymer formation and the rate at which spent catalic the equipment partial pressure varies from atmospheric to about 7 MPa. Usually, well suitable pressure of 0.2 to 5 MPa. The choice of temperature is not critical; it is usually 30-200oC. In some cases, you can use the dilution gas, which must be inert to the polymer.

The method of polymerization according to the invention particularly preferred to obtain homopolymers of ethylene and propylene and copolymers of ethylene and/or propylene.

The examples below serve to illustrate the invention. In these examples, get a solid precursor according to the invention, using the proposed in the invention method, and then used for polymerization stelena.

The value used in these examples, symbols, units, expressing these values, and ways of measuring these values is explained below.

HLMI = flow index of the polymer was molten at 190oC, measured under a load of 21.6 kg and expressed in g/10 min according to the standard ACTM D 1238.

= catalytic activity, expressed as the number of grams of polymer obtained per hour and per gram used solid predecessor, divided by the partial pressure of venison, expressed in bars.

PSA = apparent specific weight of the floor is indecency vessel with a capacity of 50 cm3fill the powder of the analyzed polymer, avoiding compaction, through the funnel, the lower edge of which is located 20 mm above the upper edge of the vessel. The vessel is then filled with powder, weighed, subtract the tare and the result (expressed in grams) divided by 50,

MZ= average molecular weight of the polymer, defined by the ratio:

Mz= WiM2i/WiMi,

where "Wi" indicates the weight of the polymer with a molecular mass Mi. The value of MZmeasured by spatial exclusion chromatography implemented in 1,2,4-trichlorobenzene at 135oC chromatograph company BOTEPC type 150oC.

FO = the oligomeric fraction of the polymer, expressed in grams of oligomers per kilogram of polymer and determined by extraction

within 2 hours of hexane at a temperature of its boiling;

<M> = the content of the transition metal M in the polymer, expressed in M. E. weight and measured by diffraction of X-rays.

MVS = standard volume weight of the polymer, expressed in kg/m3and measured according to the standard of ASTM D 1928.

SS = specific surface of the solid precursor, expressed in m2/g and measured according to the norm of the m using measuring porosity company CARLO ERBA Co., and expressed in cm3/,

MW/Mn= the ratio between srednevekovoi molecular weight (MWand srednetsenovoj molecular weight (Mn), measured by spatial exclusion chromatography implemented in 1,2,4 - trichlorobenzene at 135oC chromatograph firm WOUTERSE type 150 C.

Example 1 (according to the invention)

In this example, get a solid precursor formed halogenated neutral metallocene, ionizing agent and inorganic media. Then use it to obtain homopolymer ethylene.

A. preparation of solid precursor

(a). - Preparation of media

Prepare media by mixing powder of silicon dioxide [having an average diameter D=112 μm and standard deviation = 33 μm], a pre-activated for 16 hours at 600oC in dry air, with a powder of a magnesium dichloride in such quantities that their mixture contained 9.8 wt.% magnesium. This mixture is heated in a rotary furnace for 16 hours at 400oby blowing nitrogen.

(b) Obtaining a binary mixture of carrier - neutral halogenated metallocene

Prepare a mixture of 3.9 g instructed in paragraph(a) Ei rotation for 10 hours at 50oC in nitrogen atmosphere. The mixture was kept in a vessel equipped with a magnetic stirrer for 5 hours at 85oC in nitrogen atmosphere.

(C) Obtaining a triple mixture of carrier-metallocen-ionizing agent

1.2 g obtained in paragraph(b) of powder mixed with 366 mg powder triphenylcarbenium-tetrakis(pentafluorophenyl)borate, in a vessel equipped with a magnetic stirrer for 20 hours at room temperature in a nitrogen atmosphere. The thus obtained precursor contains (in weight%): Cl=14,3; Zr=1,7; Mg= 4.7 and has a specific surface area SS=167 and pore volume VP=1,07.

B. Polymerization of ethylene

In the autoclave with a capacity of 3 l equipped with a stirrer, enter 1 l of isobutane and 1 mmol of triethylaluminum. The temperature is brought to 50oC. Then there is injected ethylene up to a pressure of 1 MPa. The temperature and pressure of ethylene maintain constant throughout the polymerization process. Then there administered 100 mg obtained in the solid precursor. After 30 minutes, the autoclave Tegaserod and cool. Obtain 123 g of polyethylene having the following characteristics: HLMI=0,12; PSA=124; MVS=939,9; FO=0,8, <Zr>=16.5, and MZ=2313000; MW/Mn= 7,4, the Catalytic system has activity = 246.

Example 2 (according to the invention)

A. preparation of solid precursor

(a). Obtaining catalytic compounds

Deatiled magnesium is administered in cooperation with tetrabutyltin titanium in amounts such that the molar ratio of magnesium to titanium was equal to 2. Then, the thus obtained reaction product hairout by introducing it into contact with a solution of ethylaminoethanol. Get a solid connection that contains (wt.%): Ti=17,0; Cl=36,2; Al=1,9; Mg=4,5.

(b). Getting a triple mixture metallocen-media-catalytic compound.

In a vessel equipped with a mixer, mix for 12 hours at 60oC and under nitrogen atmosphere, 511 mg obtained in paragraph(a) catalytic compounds with 3 g obtained in example 1, paragraph(b), of the product.

(in). Obtaining a four-part mixture metallocen-media-catalytic compound-ionizing agent.

Prepare a mixture of 3 g of the powder obtained in paragraph(b) of ternary mixture of 807 mg powder triphenyl-carbene-tetrakis-(pentafluorophenyl)-borate, and the thus obtained product is maintained with stirring for 48 hours at room temperature and in atmostroy surface SS=92 and pore volume = 0,55.

B. Polymerization of ethylene

In the autoclave with a capacity of 3 l equipped with a stirrer, enter 1 l of isobutane and 1 mmol of triethylaluminum. The temperature is brought to 50, then there is injected ethylene up to a pressure of 1 MPa. The temperature and pressure of ethylene maintain constant throughout the polymerization process. Then there enter 101 mg obtained in the solid precursor. After 30 minutes, the autoclave Tegaserod and cool. Obtain 142 g of polymer having the following characteristics: HLMI= 0,04; PSA= 162; MVS=938, FO=0,8;<Zr>=10,5; <Ti>=15,6; MZ=14 955 000; MW/Mn= 18,2. The catalytic system has activity =282.

Example 3 (according to the invention)

In this example, get a solid precursor formed halogenated neutral metallocene, ionizing agent and the catalytic compound. Then it is used to produce a copolymer of ethylene.

A. preparation of solid precursor

(a) Obtaining a binary mixture metallocen-catalytic connection

1.2 g of the Powder obtained in example 2, paragraph a(a), compounds mixed with 590 g of powder dicyclopentadienyl-dichloro-Zirconia in a vessel equipped with a mixer for 4 hours at 85oC and under nitrogen atmosphere.

(b). COI is s-tetrakis(pentafluorophenyl)borate added to the obtained in p. (a) powder in such amounts that the molar ratio of neutral metallocene to ionizing agent was equal to 1. These two powder equipped with a stirrer vessel is stirred for 16 hours at room temperature in a nitrogen atmosphere. The thus obtained solid precursor contains (wt.%): Cl=13,7; Zr=4,9, Ti=5,7;

B. Copolymerization of ethylene with butene

In the autoclave with a capacity of 3 l equipped with a stirrer, enter 1 l of isobutane and 1 mmol of triethylaluminum. The temperature was raised to 50oC. Then there is injected ethylene up to a pressure of 1 MPa and 3 g of liquid butene. The temperature and pressure of ethylene maintain constant throughout the polymerization process. Then there enter 49 mg obtained in the solid precursor. After 60 minutes, the autoclave Tegaserod and cool. Receive 309 g of polymer, which has the following characteristics: HLMI=0,11, PSA=243; MVS=931,5; FO=0,5; <Zr>=5; MZ= 1 700 000; MW/Mn=32,0. The catalytic system has activity = 631.

Example 4 (According to the invention)

In this example, use solid precursor of example 3 to obtain homopolymer ethylene.

Polymerization of ethylene

In the autoclave with a capacity of 3 l equipped with a stirrer, enter 1 l of isobutane and the Temperature and pressure of ethylene maintain constant throughout the polymerization process. Then there is injected 57 mg of solid precursor of example 3. After 60 minutes, the autoclave Tegaserod and cool. Get 324 g of polyethylene having the following characteristics: HLMI= <0,1; MVS= 938; FO=0,2; MZ= 3783000; MW/Mn=60. The catalytic system has activity = =568.

Example 5 (according to the invention)

In this example, get a solid predecessor, educated neutral halogenated metallocene, ionizing agent and inorganic media. Then it is used to produce a copolymer of ethylene.

A. preparation of solid precursor

(a) Obtaining a binary mixture of carrier-metallocene

Prepare a mixture of 1.2 g obtained in example 1, paragraph a(a), media 143,4 mg powder dicyclopentadienyl-dichloro-Zirconia, in a vessel equipped with a stirrer leave to rotate for 4 hours at room temperature and under nitrogen atmosphere.

(b). Getting a triple mixture of carrier-metallocen-ionizing agent

To the obtained in paragraph(a) powder add 465,2 mg powder triphenylcarbenium-tetrakis/pentafluorophenyl/borate, and the two powder are mixed in a vessel equipped with a mixer for 16 hours at room temperature and under nitrogen atmosphere. So obrazem VP= 1,12.

B. Polymerization of ethylene

In the autoclave with a capacity of 3 l equipped with a stirrer, enter 1 l of isobutane and 1 mmol of triethylaluminum. The temperature is brought to 50oC. Then there is injected ethylene up to a pressure of 1 MPa. The temperature and pressure of ethylene maintain constant throughout the polymerization process. Then there is administered 80 mg obtained in the solid. After 60 minutes, the autoclave Tegaserod and cool. Get 192 g of polymer having the following characteristics: HLMI=0,1; PSA= 144; MVS= 940,0; FO=0,7; <Zr>=8,5; MZ=1 216 000; MW/Mn=4,7. The catalytic system has activity = 147.

Example 6 (according to the invention)

In this example, get a solid precursor formed halogenated neutral metallocene, ionizing agent and inorganic media. Then use it to obtain homopolymer ethylene.

A. preparation of solid precursor

(a) Preparation of a carrier

Repeat the operation example 1,And ().

(b). Obtaining a binary mixture of carrier-ionizing agent

3.8 g obtained in paragraph(a) carrier impregnated with a solution containing 1,4191 g triphenyl-carbene-tetrakis (Penta-forfinal)- borate in 40 ml of toluene, while Maxi is I powder.

(in). Getting a triple mixture of carrier-ionizing agent-neutral halogenated metallocene

Obtained in paragraph (b) powder mixed with 482,8 mg powder dicyclopentadienyl-dichloro-Zirconia, which is pre-crushed in a rotary mixer at room temperature for 70 hours. The thus obtained solid mixture was then crushed at room temperature for 4 hours in equipped with a magnetic mechancal vessel.

B. Polymerization of ethylene.

In the autoclave with a capacity of 3 l equipped with a stirrer, enter 1 l of isobutane and 1 mmol of triethylaluminum. The temperature is brought to 50oC. Then there is injected ethylene up to a pressure of 1 MPa. The temperature and pressure of ethylene maintain constant throughout the polymerization process. Then there is injected 83 mg obtained in the solid precursor. After 60 minutes, the autoclave Tegaserod and cool. Obtain 130 g of polyethylene having the following characteristics: PSA=243. The catalytic system has activity = 156.

Example 7 (according to the invention)

In this example, use solid precursor of example 6, after storage for 6 days at room temperature and under nitrogen atmosphere, to obtain homapal the isobutane and 1 mmol of triethylaluminum. The temperature is brought to 50oC. Then, there is injected ethylene up to a pressure of 1 MPa. The temperature and pressure of ethylene maintain constant throughout the polymerization. Then there is injected 84 mg of solid precursor of example 6, which were stored, after its preparation, for 6 days at room temperature and under nitrogen atmosphere. After 64 minutes, the autoclave Tegaserod and cool. Get 167 g of polyethylene. The catalytic system has activity = 186.

The results of examples 6 and 7 emphasize the stability of the precursor according to the invention.

Example 8 (according to the invention)

In this example, get a solid predecessor, educated neutral halogenated metallocene, ionizing agent and inorganic media. Then use it to obtain homopolymer ethylene.

A. preparation of solid precursor

(a). Preparation of media

In a rotary kiln, for 16 hours at 400oC and under nitrogen atmosphere, mix of 9.8 g of a powder of silicon dioxide [having an average diameter D=112 μm and standard deviation ==33 µm] pre-activated for 6 hours at 600oC in nitrogen atmosphere, 1.2 g powder metallocen.

Cooked in a rotary mixer a mixture of 2.6 g obtained in paragraph(a) media 306,2 mg powder dicyclopentadienyl-dichlorsilane and 40 ml of toluene. Then the toluene is removed by distillation under reduced pressure at a temperature of 70-80oC for 2 hours. After that, the mixer is left to rotate for 5 hours at a temperature of 70-80oC, and the rotation continued for 66 hours at room temperature and for 3 hours at a temperature of 70-80oC, and the mixture is maintained under nitrogen atmosphere.

(in). Getting a triple mixture of carrier-metallocen-ionizing agent

Obtained in paragraph (b), the solid is impregnated with a solution of 966 mg triphenyl-carbene-tetrakis(pentafluorophenyl)borate in 60 ml tawada at room temperature. Then the toluene is removed by distillation under reduced pressure at 30oC, and get a solid precursor, which is mixed in a rotary mixer for 17 hours at room temperature.

B. Polymerization of ethylene

In the autoclave with a capacity of 3 l equipped with a stirrer, enter 1 l of isobutane and 1 mmol of triethylaluminum. The temperature is brought to 50oC. Then there is added ethylene up to a pressure of 1 MPa. The temperature and pressure of ethylene support is destinia. After 120 minutes, the autoclave Tegaserod and cool. Get 213 g of polyethylene having the following characteristics: PSA=281. The catalytic system has activity = 137.

Example 9 the description which follows, represents a comparative example. It serves to show the importance of introducing ionizing agent in a solid precursor of a catalytic system before polymerization.

Take 9 (given as comparison)

A. preparation of solid catalyst precursor

Repeat operations(a) and (b) of example 1, except for the operation(b).

B. Polymerization of ethylene

In the autoclave with a capacity of 3 l equipped with a stirrer, enter 1 l of isobutane and 1 mmol of triethylaluminum. The temperature is brought to 70oC. Then there is injected ethylene up to a pressure of 0.6 MPa. Then there is injected 87 mg obtained in the solid precursor. The temperature and pressure of ethylene support constant for 10 minutes. Then, the temperature was lowered to 50oC and the partial pressure of ethylene is increased to 1 MPa. Then there Inuktitut 0.002 mol triphenylcarbenium-tetrakis(pentafluorophenyl) borate [the ionizing agent]. The temperature and the partial pressure of ethylene support posto is 14 g of the polymer, has the following characteristics: HLMI= 0,07; PSA=82, MVS=938,3, FO=0,8; <Zr>=13,5; MZM=1 199 000; MW/Mn=4,6.

Comparing the results of example 9 with the results of example 1 shows achieved according to the invention, the progress in regard to the average molecular weight and apparent specific gravity of the polymer.

Example 10 (according to the invention)

In this example, get a solid predecessor, educated neutral halogenated metallocene, ionizing agent and inorganic media. Then use it to obtain homopolymer ethylene.

A. preparation of solid precursor

(a). Preparation of media

In a rotary kiln, for 16 hours at 400oC and under nitrogen atmosphere, mix of 9.8 g of a powder of silicon dioxide [having an average diameter D=112 μm and standard deviation =33 μm], a pre-activated for 6 hours at 600oC in nitrogen atmosphere, 1.2 g of powder of anhydrous magnesium dichloride.

(b). Obtaining a binary mixture of carrier-neutral halogenated metallocene

Cooked in a rotary mixer a mixture of 2.0 g obtained in paragraph(a) media 239,7 mg powder dicyclopentadienyl-dichloro-Zirconia and 20 ml of toluene. Smesitel leave to rotate for another 10 minutes at a temperature of 70oC. Get a solid substance and immediately perform the following stage (b).

(in). Getting a triple mixture of carrier-metallocen-ionizing agent

Obtained in paragraph(b), the solid is impregnated with a solution of 750 mg of triphenyl-carbene-tetrakis(pentafluorophenyl)borate in 20 ml of toluene at room temperature. Then the toluene is removed by distillation under reduced pressure at room temperature, and get a solid predecessor.

B. Polymerization of ethylene

In the autoclave with a capacity of 3 l equipped with a stirrer, enter 1 mmol of trimethylaluminum and 1 l of isobutane. The temperature is brought to 50oC. Then there is injected hydrogen under a partial pressure of 0.17 MPa and then ethylene up to a pressure of 1 MPa. The temperature and pressure of ethylene and hydrogen maintain constant throughout the polymerization. Then there is injected 66 mg obtained in the solid precursor. After 60 minutes, the autoclave Tegaserod and cool. Get 197 g of polyethylene. No trace of the formation of deposits inside the polymerization reactor was found. The catalytic system has activity = 299.

1. The solid precursor of a catalytic system for the polymerization of olefins, obtained with one halogen atom, and at least one ionizing agent, characterized in that the corresponding metallocene treated with ionizing agent in a heterogeneous environment.

2. The solid precursor under item 1, characterized in that the neutral metallocene has the formula

(Cp)a(C'p)bMXxZz,

in which Cpand C'peach represent an unsaturated hydrocarbon moiety coordinated to the Central atom M, and group Cpand C'pcan be linked by covalent bridge;

M denotes a transition metal chosen among the elements of group IVB of the Periodic system;

a, b, x and z denote integers such that (a + b + x + z) = m; x > 0, z 0, and a and/or b 0;

m represents a valence of the transition metal M;

x denotes halogen;

z denotes a hydrocarbon radical which may contain oxygen or strong radical of the formula

(Rt-Si-R R"R"'),

where R denotes alkyl, alkenylphenol, aryl, CNS or cycloalkyl group, possibly substituted, containing up to 20 C-atoms;

R', R" and R"' are the same or different and represent each a halogen or alkyl, alkenylphenol, aryl, CNS or cycle the

3. The solid precursor under item 1 or 2, characterized in that the transition metal is zirconium.

4. The solid precursor according to any one of paragraphs.1 to 3, wherein the ionizing agent is selected from triphenylcarbenium(pentafluorophenyl)borate and three(pentafluorophenyl)boron.

5. The solid precursor according to any one of paragraphs.1 to 4, characterized in that the ionizing agent contains a cation type carbene.

6. The solid precursor under item 5, wherein the ionizing agent is triphenyl-carbene-tetrakis(pentafluorophenyl)borate.

7. The solid precursor according to any one of paragraphs.1 - 6, characterized in that the molar ratio between neutral metallocene and ionizing agent is 0.5 - 2.

8. The solid precursor according to any one of paragraphs.1 to 7, characterized in that it further contains inorganic or polymeric media.

9. The solid precursor under item 8, wherein the carrier is selected from silicon dioxide, aluminum oxide, magnesium dichloride, aluminum phosphate, or mixtures thereof.

10. The solid precursor under item 8 or 9, characterized in that the weight ratio between the carrier and neutral metallocene is 0.1 - 1000.with granules, defined average diameter D = 1 to 500 microns with a standard deviation = 5 - 50 μm, and the halogen content is 1 to 50 wt.% and the content of the transition metal is 0.1 - 30 wt.%.

12. Solid predecessor, PP.1 - 11, characterized in that it has an index of stability above 0.95, and moreover, this measure of stability is the ratio of the weight in grams of polyethylene obtained by polymerization of ethylene for 1 h at a partial pressure of 1 bar and using a catalytic system comprising, in a weight ratio of 0.1 - 10, ORGANOMETALLIC compound and the above solid precursor, which after mixing neutral halogenated metallocene with an ionizing agent was maintained for 48 h at room temperature in a nitrogen atmosphere, and the weight in grams of polyethylene, obtained by the polymerization of ethylene for 1 h at a partial pressure of 1 bar in the presence of the same catalyst system, but in which the predecessor was not subjected to exposure.

13. A method of obtaining a solid precursor according to PP.1 - 12, according to which at least one compound based on an ionizing agent is mixed with at least one connection on oneweek, they use neutral metallocene in halogenated state, and the transition metal is associated with at least one halogen atom, and carry out the mixing in a heterogeneous environment.

14. The method according to p. 13, characterized in that the mixing is carried out at a temperature of 0 - 100oC.

15. The method according to p. 13 or 14, characterized in that the mixture additionally impose the media.

16. The method according to p. 15, wherein the first, cook the mixture of the carrier with the compound based on a neutral metallocene and the resulting mixture was added the compound based on an ionizing agent.

17. The method according to p. 16, characterized in that the addition of a compound based on an ionizing agent is carried out by impregnation of the mixture of the carrier with the compound based on a neutral metallocene obtained without a liquid, a solution of the compound based on an ionizing agent, and at least 80% of the compound based on a neutral metallocene insoluble in the specified solution.

18. The method according to p. 16 and 17, characterized in that the mixing of the carrier with the compound based on a neutral metallocene carried out at a temperature of 10 to 120oWith, and adding a connection on the basis of the ionizing agent is mesh impose additional catalytically active connection.

20. The method according to any of paragraphs.13 to 19, characterized in that the compound based on an ionizing agent is obtained by impregnation of the carrier precursor and/or a catalytically active compound solution ionizing agent.

21. The method according to any of paragraphs.13 to 20, characterized in that the compound based on a neutral metallocene obtained by impregnation of the carrier and/or catalyst compound solution neutral metallocene.

22. The method according to any of paragraphs.19 to 21, characterized in that the catalytically active compound contains 10 to 30 wt.% transition metal, selectable in groups IIIB, IVB, VB and VIB of the Periodic system, 20 to 50 wt.% halogen, 0.5 to 20 wt.% magnesium and 0.5 - 20 wt.% aluminum.

23. Catalytic system for polymerization of olefins, characterized in that it comprises a solid precursor according to PP.1 - 12 and alyuminiiorganicheskikh compound of formula AlTT'T", where T, T' and T" each denote alkyl, alkenylphenol, aryl or CNS group, in some cases substituted, containing up to 20 C-atoms, and the solid precursor containing halogenated metallocene and the ionizing agent is received before processing alyuminiiorganicheskikh connection.

24. CAA and triisobutylaluminum.

25. The catalytic system under item 23 or 24, characterized in that alyuminiiorganicheskikh compound is trimethylaluminum.

26. The method of polymerization of at least one olefin, in which the use of a catalytic system, wherein use of the catalytic system on the PP.23 - 25.

27. The method according to p. 26, wherein the first olefin is mixed with alyuminiiorganicheskikh connection and then add the solid precursor.

28. The method according to p. 26 or 27, characterized in that the olefin is ethylene and/or propylene.

 

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