The catalyst for propylene polymerization, the catalyst system for propylene polymerization and method for producing polypropylene polymerization of propylene

 

(57) Abstract:

Usage: for the polymerization of olefins. The essence of the invention: catalyst for propylene polymerization as titanium compounds contains added to the media tetracritical and titanium tetrachloride in the form of solutions in inert hydrocarbon, followed by washing the obtained solid product with an inert hydrocarbon. As a carrier, the catalyst contains the product serial interaction processed hexamethyldisilazane porous silica with alkoxysilanes, silicon tetrachloride in solution of an inert hydrocarbon and trichlorosilane, followed by the separation and washing of the solid product in the following ratio of the components of the reaction mixture, mmol/g silica: alkoxylated magnesium 1 - 10; silicon tetrachloride 0.5 to 25,0, trichlorosilane 0,075 - 3,750; tetracritical titanium 0,1 - 1,0; titanium tetrachloride 1 - 40. Catalytic system for the polymerization of propylene contains a catalyst comprising as titanium compounds are added sequentially to the media tetracritical and titanium tetrachloride in the form of solutions in inert hydrocarbon, followed by washing the obtained solid product inert ugly hexamethyldisilazane porous silica with alkoxysilanes, the silicon tetrachloride in solution of an inert hydrocarbon and trichlorosilane, followed by the separation and washing of the solid product in the following ratio of the components of the reaction mixture, mmol/g silica: alkoxylated magnesium 1 - 10; silicon tetrachloride 0.5 to 25,0; trichlorosilane 0,075 - 3,750; tetracritical titanium 0,1 - 1,0; titanium tetrachloride 1 - 40. As socializaton system contains trialkylaluminium and dialkylammonium in the following ratio of components, mol.h: trialkylaluminium 80 - 160; dialkyldimethyl 8 - 16; catalyst (in terms of titanium) 1. In the method of producing polypropylene polymerization of propylene using a catalytic system containing a catalyst comprising as titanium compounds are added sequentially to the media tetracritical and titanium tetrachloride in the form of solutions in inert hydrocarbon, followed by washing the obtained solid product with an inert hydrocarbon. As a carrier, the catalyst contains the product serial interaction processed hexamethyldisilazane porous silica with alkoxysilanes, silicon tetrachloride in solution of an inert hydrocarbon and trichlorosilane, followed by the separation and washing ignored magnesium 1 - 10; silicon tetrachloride 0.5 to 25,0; trichlorosilane 0,075 - 3,750; tetracritical titanium 0,1 - 1,0; titanium tetrachloride 1 - 40. As socializaton system contains trialkylaluminium and dialkylammonium in the following ratio of components; mol.h.: trialkylaluminium 80 - 160; dialkyldimethyl 8 - 16; catalyst (in terms of titanium) 1. 3 S. p. f-crystals, 2 tab.

Polymerization of olefins using the catalysts of the Ziegler-Natta finds wide application. These catalysts allow to obtain high yield of polyolefins with the desired properties. However, the conventional catalysts of this type has important disadvantages. In this regard, we constantly search for new and improved catalysts. An important class of catalysts, among which there is a search improvements are polymerization catalysts are commercially very important alpha-olefin, propylene.

Usually in many polymerization of alpha-olefins, particularly propylene, are used catalysts supported on magnesium halides. However, when further processed in molding machines of the polyolefins produced using deposited on a magnesium halide catalyst is korrodirovaniju molding equipment. Atania corrosion causes damage to expensive Moldagulova equipment. In addition, more importantly, the final product obtained by means of such equipment, often characterized by the presence of cracks.

Another disadvantage of the catalysts normally used in the polymerization of olefins, namely propylene polymers, due to the presence of these catalysts internal electron donor. These donors are introduced into the catalyst to obtain vysokoenergeticheskogo polypropylene polymer product.

It is known that stereoregularity strongly affects the properties of the propylene - materials. In addition, the presence of an internal electron donor creates certain difficulties. If you do not choose carefully the number and type of electron-donating compounds, not only stereoregularity of the obtained polymer becomes imperfect, but often decreases and the activity of the catalyst. These effects can occur even when the number and type of electron donor selected correctly, but when the catalyst elektromotoren compound is added in an erroneous sequence.

The use of electron-donor compounds often creates additional problems, for example, leads to unpleasant smells from condoning connection in the desired concentration, added at the right time upon receipt of the catalyst. Therefore, the polymers obtained in the presence of catalysts containing elektromotory connection, often need to be cleaned from the connection or dezodorirovanie to eliminate odor in the final product.

Known catalytic component for the polymerization, obtained by the reaction of a magnesium alkoxide, halogenated hydrocarbons, halogenated silane and titanium compounds [1] it is Noted that this catalyst is useful for obtaining ethylene homopolymers and copolymers comprises a halogenated hydrocarbon. This catalyst not only mainly directed to the polymerization of ethylene polymers, but also, significantly, results in polymers with a high index of fusion. However, despite the fact that the use of this catalyst for the ethylene polymers useful, the possibility of its use for propylene polymers limited. Most of the propylene polymers used in processes that require polymers with a low flow rate of the melt. I.e., molecular weight of polymers produced using the catalyst of this patent is substantially less than the third result is the catalyst for propylene polymerization, representing compounds of titanium on the carrier based on the product of the interaction of porous silica with compounds of magnesium and silicon [2]

In addition, a well-known kataliticheskaya system for propylene polymerization, including socialization and a catalyst comprising a compound of titanium on the carrier based on the product of the interaction of porous silica with compounds of magnesium and silicon, and a method of producing polypropylene polymerization of propylene in the presence of a catalytic system including socialization and a catalyst comprising a compound of titanium on the carrier based on the product of the interaction of porous silica with compounds of magnesium and silicon [2]

The disadvantage of the invention is low stereoregularity of the obtained polymer.

The aim of the invention is to provide opportunities for vysokostoimostnyh olefin Homo-and copolymers.

For this purpose, the catalyst for polymerization of propylene, which are compounds of titanium on the carrier based on the product of the interaction of porous silica with compounds of magnesium and silicon, according to the invention as compounds of tiande followed by washing the obtained solid product with an inert hydrocarbon, and as a media product consistent communication processed hexamethyldisilazane porous silica with alkoxysilanes, silicon tetrachloride in solution of an inert hydrocarbon and trichlorosilane, followed by the separation and washing of the solid product in the following ratio of the components of the reaction mixture, mmol/g silica: Alkoxylated magnesium 1-10 silicon Tetrachloride 0.5 to 25,0 Trichlorosilane 0,075-3,750 Tetracritical titanium 0.1 to 1.0 titanium Tetrachloride 1-40

To solve this problem catalytic system for the polymerization of propylene, including socialization and a catalyst comprising a compound of titanium on the carrier based on the product of the interaction of porous silica with a compound of magnesium and silicon, according to the invention contains a catalyst comprising as titanium compounds are added sequentially to the media tetracritical and titanium tetrachloride in the form of solutions in inert hydrocarbon, followed by washing the obtained solid product with an inert hydrocarbon, and as a media product consistent communication processed hexamethyldisilazane porous silica with alkoxysilanes, TEI solid product in the following ratio of the components of the reaction mixture, mmol/g silica:

Alkoxylated magnesium 1-10 silicon Tetrachloride 0.5 to 25,0 Trichlorosilane 0,075-3,750 Tetracritical titanium 0.1 to 1.0 titanium Tetrachloride 1-40, and as socializaton it contains trialkylaluminium and dialkyldimethyl in the following ratio of components, mol.h. Trialkylaluminium 80-160 Dialkylzincs - silane 8-16 Catalyst (in re account on Titan) 1

A method of producing polypropylene polymerization of propylene in the presence of a catalytic system including socialization and a catalyst comprising a compound of titanium on the carrier based on the product of the interaction of porous silica with compounds of magnesium and silicon, according to the invention using a catalytic system containing a catalyst comprising as titanium compounds are added sequentially to the media tetracritical and titanium tetrachloride in the form of solutions in inert hydrocarbon, followed by washing the obtained solid product with an inert hydrocarbon, as a media product consistent communication processed hexamethyldisilazane porous silica with alkoxysilanes, silicon tetrachloride in solution of an inert hydrocarbon and trichlorsilane mixture, mmol/g silica: Alkoxylated magnesium 1-10 silicon Tetrachloride 0.5 to 25,0 Trichlorosilane 0,075-3,750 Tetracritical titanium 0.1 to 1.0 titanium Tetrachloride 1-40 and socializaton it contains trialkylaluminium and dialkyldimethyl in the following ratio of components, mol.h. Trialkylaluminium 80-160 Dialkylammonium 8-16 Catalyst (in re account on Titan) 1

The polymer product of polymerization using the catalyst proposed in this invention, is characterized by a homogeneous distribution of particle sizes, a good spherical morphology and high bulk density. These characteristics improve the performance and ease of processing of the polymer. In addition, the catalyst is highly active, high performance upon receipt of the polymer, as is clear from the mass of polymer produced per unit weight of catalyst per hour.

This catalyst is also safe and easy to prepare. Unlike cooking deposited on a magnesium halide catalysts in this case does not require expensive processing in a ball mill. There is no need for other costly stage of prepolymerisation required setele, the polymer product has a low halogen content, which significantly reduces corrosion problems often encountered during the processing of such polymers obtained using deposited on a magnesium halide catalysts. Moreover, since the catalyst retains a small residual amount of metal, purification of the polymer product from the ash is not required. In addition, when using this catalyst, the polymerization reaction is accelerated due to the exceptional activity of the catalyst, which remains almost constant for a long time. Finally, the use of this catalyst allows to obtain a highly active catalyst and is easy to control the molecular weight of the polymer with the introduction of reasonable quantities of hydrogen.

The catalyst obtained in accordance with the present invention. The catalyst comprises the product obtained by the direct interaction of silica with at least one soluble in the hydrocarbon compound of magnesium and at least two of the modifying compounds. The processing sequence of silicon dioxide is soluble in the hydrocarbon compound of magnesium, the first and second modifying compounds is one the interaction with the second modifying compound and the processing of silicon dioxide modifying compounds must not be interrupted by interaction with soluble in the hydrocarbon compound of magnesium. The first modifying compound is selected from the group consisting of silicon halides, boron halides, aluminum halides and mixtures thereof. The second modifying compound that interacts with the silicon dioxide after the first modifying compound is selected from the group consisting of halogenated silanes of the formula SiHRXS2where X2halogen, R is an integer from 1 to 3 and S is an integer from 1 to 3 with the proviso that the sum of R and S is 4; halides of the formula HX3where X3halogen, and mixtures thereof. Modified silicon dioxide coated with magnesium further communicates with the first titanium containing compound of the structural formula Ti(OR)mXn, where R is a hydrocarbon radical, cresyl or a mixture thereof, X is halogen, m is an integer from 1 to 4; n is 0 or an integer from 1 to 3 provided that the sum of m and n is 4. The product of this interaction process the second titanium containing compound having the structural formula TiXp1(OR1)qwhere X1halogen, R1hydrocarbon radical, R is an integer from 1 to 4 and q is 0 or an integer from 1 to 3 provided that the sum of p and q is 4 and the first and second titanium containing such compounds replicats the mA consists of the above-mentioned catalyst, first socializaton aluminium-containing compounds, and the second socializaton of hydrocarbonylation.

Another aspect of the present invention is the polymerization of olefins. In this process, at least one olefin will polimerizuet in terms of olefin polymerization using the proposed in the present invention the catalytic system, which includes the catalyst of the present invention, the first acetalization aluminium-containing compound, and the second acetalization hydrocarbonylation.

The catalyst of the present invention receive a direct interaction of silica with at least one soluble in the hydrocarbon compound of magnesium and at least two of the modifying compounds.

Preferably, the silicon dioxide used in the catalyst was clean. However, it may contain a small number of other inorganic oxides of the type of oxides of aluminum, titanium, zirconium, magnesium and the like. In General, the silicon carrier must contain at least 90 wt. pure silicon dioxide. More preferably, the mass fraction of pure silicon dioxide was at least 95% Finally, the most predpochtitelney for the formation of the catalyst, had the surface in the range from about 80 to about 300 m2/g, average particle size from about 20 to 200 microns and a pore volume of about 0.6 to 3.0 cm3/,

Preferably, silicon dioxide, used to obtain the catalyst was treated in a manner that contains the hydroxyl group of the surface was replaced by a surface characterized by the structural formula

i-O-i

To achieve this, the replacement of silicon dioxide may be warmed in an inert atmosphere at a temperature of at least 150aboutC. Preferably, this operation included the calcination of the silica at a temperature in the range of 550-650aboutWith in an inert atmosphere, preferably under nitrogen atmosphere.

Another processing method of silicon dioxide used in the preparation of the catalyst involves the interaction of silica with exulceration. Useful for this application hexadecylamine is preferable to use hexamethyldisilazane.

The third method of processing silicon dioxide to replace gidroksilsodyerzhascimi surface is the use of both previous methods: treatment exulceration and calcining. Pol processing exulceration was preceded by the calcination. It should also be noted that in this preferred embodiment, the calcination requires only cure at temperatures of at least about 100aboutS, although higher temperature processing is definitely not harm.

As stated previously: silicon dioxide reacts with at least one soluble in the hydrocarbon magnesium-containing compound. Soluble magnesium-containing hydrocarbon compounds that can be used for the preparation of the catalyst of this invention include dihydrocarbamazepine, halides hydrocarbonylation and mixtures thereof. Preferred magnesium compounds are dialkoxy derivatives of magnesium halides Aleksievich derivatives of magnesium and mixtures thereof. The most desirable magnesium compounds in the preparation of the catalyst of the present invention include 2-methylenebismethacrylamide magnesium, pentyloxide magnesium, 2-ethylhexylacrylate magnesium, di-2-ethylhexylamine and mixtures thereof. Of these compounds, particularly preferable to use 2-ethylhexylacrylate magnesium and 2-methylpentylamine magnesium.

The interaction between silica and a soluble compound or connectivity was carried out at a temperature of 50-110aboutC. the Duration of the contact is approximately 30 min to 4 h Preferred contact time 1 to 3.5 hours Even more preferably the contact time is approximately 1.5 to 2.5 hours

In addition to the fact that silicon dioxide is in contact with at least one soluble in the hydrocarbon compound of magnesium, silicon dioxide also is in contact with at least two modifying compounds. The first of these modifying compounds selected from the group consisting of silicon halides having the structural formula SiX44, boron halides having the structural formula BX35, aluminum halides having the structural formula AG36where X3X5and X6are the same or different Halogens, or mixtures of these compounds. Preferably, X4X5and X6were the same or different Halogens and were chlorine or bromine. Thus, it is preferable that the first modifying ingredient was silicon tetrachloride, tetrabromide silicon, trichloride boron, tribromide boron, trichloride aluminum, tribromide aluminum or mixtures thereof. Even more preferably, X4X5the reed silicon, trichloride boron, trichloride aluminum or mixtures thereof. Of these compounds the most desirable is silicon tetrachloride.

The second modifying compound which is in contact with the silicon dioxide directly after contact with the first modifying compound is selected from the group consisting of halogenated silanes having the structural formula SiHrXS2where X2halogen, r is an integer from 1 to 3 and S is an integer from 1 to 3 provided that the sum of r and s is 4, and halogenated having the structural formula NH3where X3halogen, and mixtures thereof.

Preferably, the second modifying compound having one of the two above structural formula, was characterized by identical or different Halogens X2and X3and to halides were chlorine or bromine. In a preferred embodiment, in which the second modifying compound is a silane, preferably, r was equal to 1 or 2 and S is equal to 2 and 3. Even more preferably, the second modifying compounds X2and X3was the chlorine in the case of silane compound r was equal to 1 and S is equal to 3.

Preferred second by modifying the mixtures thereof. Of those, more preferred are trichlorosilane, chlorodrol and mixtures. Using trichlorosilane as a second modifying compound is most preferable.

It is preferable to use for the preparation of the catalyst the concentration of the first and second modifying compounds, so that the molar ratio of the first modifying compound to the second was in the range of from about 50:50 with 99:1. More preferably, this molar ratio modifying the first connection to the second was in the range of from about 60:40 to about 95:5, respectively. Even more preferably, this molar ratio was in the range of from about 70: 40 to about 92:8. And even more preferably, this molar ratio was in the range of from about 80:20 to about 90:10.

Preferably, between the processing of silicon dioxide first and second modifying compounds was a long period of time and this treatment was consistent, i.e., it is preferable that the first and second modifying compounds interacted with the silicon dioxide consistently is I, processed or not processed pre-soluble hydrocarbon compound of magnesium, it is preferable to carry out at a temperature in the range of approximately 10aboutWith up to approximately 60aboutC. More preferably, the temperature during contact between the silicon dioxide and modifier compounds was in the range of from about 20aboutWith up to approximately 55aboutC. Even more preferably to this interaction was carried out at a temperature in the range from approximately 25aboutWith up to approximately the 50aboutC. Most preferably, this interaction is carried out at a temperature in the range of from about 30aboutWith up to approximately 45aboutC. Preferably, the duration of exposure was from about 10 minutes to about 2 hours, More preferably, the time period during which occurs the contact was in the range of from 20 minutes to 1.5 hours Even more preferably, the length of time for which there is an interaction between silicon dioxide and modifier compounds was in the range of from about 30 min to about 1 o'clock number from 1 to 3 and S is an integer from 1 to 3 provided that the sum of r and S is 4, and Gal is timeline, to the second modifying compound having one of the two above structural formula, was characterized by identical or different Halogens X2and X3and to halides were chlorine or bromine. In a preferred embodiment, in which the second modifying compound is a silane, preferably, r was equal to 1 or 2 and S is equal to 2 and 3. Even more preferably, the second modifying compounds X2and X3was the chlorine in the case of silane compound r was equal to 1 and S is equal to 3.

Preferred second modifying compounds are trichlorosilane, tribromsalan, dichlorsilane, dibromsalan, florodora, Pomodoro and mixtures thereof. Of those, more preferred are trichlorosilane, chlorodrol and mixtures. Using trichlorosilane as a second modifying compound is most preferable.

It is preferable to use for the preparation of the catalyst the concentration of the first and second modifying compounds, so that the molar ratio of the first modifying compound to the second was in the range of from about 50:50 to about 99:1. More preferably, this molar otnositelno 95:5, respectively. Even more preferably, this molar ratio was in the range of from about 70:40 to about 92:8. And even more preferably, this molar ratio was in the range of from about 80:20 to about 90:10.

Preferably, between the processing of silicon dioxide first and second modifying compounds was a long period of time and this treatment was consistent, i.e., it is preferable that the first and second modifying compounds interacted with the silicon dioxide is consistently the second modifying compound immediately after the first modifying compound. Contact with the silicon dioxide-treated or not pre-processed soluble in the hydrocarbon compound of magnesium, it is preferable to carry out at a temperature in the range of from about 10aboutWith up to approximately 60aboutC. More preferably, the temperature during contact between the silicon dioxide and modifier compounds was in the range of from about 20aboutWith up to approximately 55aboutC. Even more preferably, this interaction was carried out at a temperature in the range from approx and a temperature in the range of from about 30aboutWith up to approximately 45aboutC. Preferably, the duration of exposure was from about 10 minutes to about 2 hours, More preferably, the time period during which occurs the contact was in the range of from 20 minutes to 1.5 hours Even more preferably, the length of time for which there is an interaction between silicon dioxide and modifier compounds was in the range of from about 30 min to about 1 h

Although the order of interaction between the silica and the magnesium compound and between silicon dioxide and modifier compounds is random, it is necessary to stress again that the first modifying compound is in contact with silicon dioxide prior to contact with the second modifying compound. It is worth noting, however, that, although the sequence of interaction of silica with magnesium and modifying connections are random, it is preferable that the silicon dioxide is first contacted with the magnesium compound with subsequent contact with the first and then with the second modifying compounds.

In the preferred embodiment the product of the interaction between silica from soluble Lanchester solvent to remove soluble organics residues. Although the organic solvent can be any solvent which does not dissolve the solid product, it is preferable that the solvent was a hydrocarbon, aliphatic or aromatic. Of these the most preferred hydrocarbons are alkanes with the number of carbon atoms from 5 to 15. One of them even more preferably hexane or heptane. Heptane is the most suitable solvent.

At the stage of washing the product is immersed in a solvent and stirred at room temperature. The solvent is then separated by decantation, siteniravam or similar. The procedure can be repeated. This stage leaching is preferable to repeat two to four times.

Obtained after exposure to soluble in the hydrocarbon magnesium compound and two modifying compounds washed or not washed silica further process the first titanium containing compound having the structural formula Ti(OR)mXnwhere R CRISIL, a hydrocarbon radical or mixtures thereof, X is halogen; m is an integer from 1 to 4; n is 0 or an integer from 1 to 3 provided that the sum of m and n is equal to 4.

In the preferred embodiment the first titantron or bromine, m is an integer from 2 to 4 and n is an integer from 0 to 2. Thus, it is preferable that the first such compound was dihydrocarbamazepine titanium, dihydrocarbamazepine titanium, trihydrochloride titanium, trihydrochloride titanium or tetrahydroquinoxaline.

In a particularly preferred embodiment, the first titanium containing compound is a simple ester of titanium, free from halide, i.e., the first such connection must be above structural formula, in which m is 4 and n is 0. Particularly preferred esters of titanium, proposed for use in obtaining the catalyst of the present invention include tetracritical titanium, tertbutoxide titanium, tetraconazole titanium, Tetra-2-ethylhexyl titanium, tetraisostearate titanium, Tetra-N-propylate titanium, tetraisopropyl titanium and the like.

The first such compound to improve contact with the composition on the silicon dioxide preferably should be in the form of a solution in an inert organic solvent, which has no effect on the composition based on silicon dioxide and in which the first such on the basis of silicon dioxide done at room temperature.

The final stage of preparation of the catalyst of the present invention includes the interaction of silicon dioxide, previously treated magnesium-containing compound, modifying compounds, immediately after the first titanium containing compound with a second titanium containing compound having the structural formula TiXp1(OR1)qwhere X1halogen, R1hydrocarbon radius, R an integer from 1 to 4 and q is 0 or an integer from 1 to 3 provided that the sum of p and q is 4. The second titanium containing compound is limited by the requirement that it is not identical to the first such connection.

In the preferred embodiment, the second titanium containing compound described above structural formula in which X1is chlorine or bromine, R is an alkyl, p is an integer from 2 to 4 and q is 0, 1 or 2. Compounds included in this preferred embodiment, desirable for use in obtaining the catalyst of the present invention include titanium tetrachloride, tetrabromide titanium, metoxichlore titanium, methoxycarbonyl titanium, amoksitsillin titanium, ethoxycarbonyl titanium, dimethoxyethane titanium, dimethoxy - titanium bromide,asteriidae connection was determined by the formula, R, equal to 4, and q equal to 0.

I.e., the titanium compound is titanium tetrachloride or tetrabromide titanium. Of these two compounds, the titanium tetrachloride is particularly desirable to use as the second titanium containing compounds.

The first and second titanium containing compound and a composition of silicon dioxide, with which they communicate, interact at a temperature in the range from about 60aboutWith up to about 130aboutC. it is Preferable that these components interact at a temperature in the range from approximately 75aboutWith up to approximately 120aboutC. More preferably, the temperature of the interaction was in the range of from about 85aboutWith up to approximately 115aboutC. Most preferably, the temperature was in the range of approximately 90aboutWith up to about 105aboutC.

The length of time that contact at an elevated temperature from about 15 minutes to about 3 hours is Preferable that this duration was from about 30 minutes to about 2 hours, More preferably, the contact time between the composition of silicon dioxide and the first and second titanium containing compounds were present in diapprove product of the interaction of the composition of the silicon dioxide with the first and second titanium containing compounds. Rinsing this product includes the same process that was described above in the discussion of the washing composition of silicon dioxide before processing the first and second titanium containing compounds. Thus, it is preferable to use a hydrocarbon solvent of the same type as the preferred solvents in the first washing. Preferably, however, in the preferred embodiment to increase the number of wash cycles after treatment with titanium compounds. Thus, while the first washing stage comprises from two to four wash cycles is preferable that the second optional washing procedure consisted of about six to eight wash cycles.

It should be noted that all stages of processing upon receipt of the catalyst of this invention, i.e., the contacts of silicon dioxide with soluble in the hydrocarbon compound of magnesium, modifying connections and the first and second titanium containing compounds include the interaction between solids, silicon dioxide and liquid. This follows from the fact that each of the compounds, which is processed silicon dioxide is liquid or soluble in an inert hydrocarbon Rast is there another procedure of solid-phase mixing. Therefore, this expensive and difficult operation, normal when receiving previously proposed catalysts of polymerization, is excluded. Specialists in this field it is known that the solvent can be left in the reaction mass or can be separated by decantation, filtration, evaporation, or similar methods.

Further comments on the above stages of preparation of the catalyst include observation that the morphology of the polymer obtained using this catalyst, similar to the morphology of the media; the absence of any halogen in the media contributes to the fact that the halogen content in the resulting polymer is low; that relatively low concentrations of titanium and magnesium on the media of silicon dioxide also contribute to maintaining the concentrations of magnesium and titanium in the polymer to the corresponding low levels that the preparation of the catalyst of the present invention is carried out at moderate temperatures, preferably in the range of from about 0aboutWith up to 100aboutAnd although this catalyst does not require electron-donating compound for good isotacticity, if desired, you can use one or more of such compounds.

First acetalization catalytic systems containing aluminum compound. Preferably, the aluminium-containing compound was trialkylaluminium, alkylhalogenide aluminum or mixtures thereof. More preferably, acetalization was trialkylaluminium. From trialkylaluminium compounds are particularly desirable triethylamine and tri-n-Propylamine.

The second acetalization catalytic system it is desirable to have at least one silane compound. Preferably, celanova connection was hydrocarbonylation. Predpochtitelnye hydrocarbonylation include hydrocarbonylation, dehydrocorydaline and trihydrateclavulanate. Of them the most desirable are dihydrocarbamazepine and trihydrosicariolane.

The hydrocarbon component of the silane in the second socializaton should preferably be a phenyl, alkarim or a linear, cyclic or branched alkyl WITH1-C10. The preferred alkoxygroup are group content of from one to six carbon atoms.

In replaces the polymerization of at least one olefine in the conditions of the polymerization of olefins in the presence of a catalytic system of the present invention, i.e., in the presence of the catalyst of the present invention, the first socializaton and second socializaton.

In a particularly preferred embodiment of this aspect of the present invention is polymerized by the olefin is propylene. In this preferred embodiment, the polymerization occurs at a temperature in the range of approximately 35aboutC to about 100aboutC. More preferably, the temperature for this reaction was in the range of from about 50aboutWith up to approximately 80aboutC. the pressure in the polymerization of propylene should be from about 21 ut to about 42 at; preferably between about 28 and at 25 at. In the preferred embodiment, the polymerization of propylene takes place in the presence of nitrogen gas.

The following examples are given to illustrate possible applications of the present invention. Because these examples are given for illustrative purposes only, the invention is not limited to these examples.

P R I m e R 1. The preparation of the catalyst.

In chetyrehosnuju flask 250 ml, blown free from oxygen and water, gaseous nitrogen, was placed a silicon dioxide (5 g). Silica (Davison) (trade mark) 948) prec under 100aboutC.

The flask was cooled. Upon reaching room temperature was added dissolved in heptane (22 ml) 2-methylpentylamine magnesium (17,4 g, 15 mmol). The flask was heated to 60aboutWith by passing nitrogen and kept at this temperature for 30 minutes Processing was performed under stirring. Then the temperature was raised to 80aboutC and kept at this temperature and stirring for another 30 minutes Then with continuous stirring the temperature was raised to the level of 100-110aboutC and maintained for about 1.5 hours during which time the bulk of the solvent of heptane was distilled. The flask was then cooled to room temperature. The product of this interaction was a more solid substance with the consistency of flour.

To this solid product in the flask 250 ml) was added silicon tetrachloride (of 3.78 g, 22 mmol) in solution in heptane (10 ml). Immediately after this was added trichlorosilane (0.6 g, 4.4 mmol). The solution was immediately utverjdala, the flask was heated for 40 min at 40aboutC and stirring. At the end of this period, the stirring and heating was interrupted.

The solid product of this interaction was allowed to settle and the excess liquid is) was added to the solid product with stirring. After a few minutes the stirring was stopped and the solid product was allowed to settle. Heptane was separated using a siphon. To the washed thus the product in the flask was added tetracritical titanium (1.2 ml, of 1.05 g, 2.2 mmol) in equal volume of heptane (1.2 ml). The solution tetraradiate titanium was added at room temperature. After that the flask was introduced titanium tetrachloride (17.3 g, 87 mmol) also at room temperature. The flask contents were heated to a temperature of 90-100aboutC and kept for 1 h then the solid product was washed with heptane according to the procedure similar to that described above for the first stage of leaching, except that the amount of heptane was increased to 80-90 ml and the number of wash cycles was increased to seven, in contrast to three cycles at an earlier stage.

Thus obtained product was a yellowish-pink solid. Its chemical composition is shown in table. 1.

P R I m m e R 2. The preparation of the catalyst.

The preparation of the catalyst of example 1 was repeated except that the product obtained after the addition of silicon tetrachloride and trichlorosilane, was heated for 30 min at 26aboutC, followed by heating for 30 m is to emphasize the duty to regulate, that in addition to the above changes in procedures, preparation of example 2 is identical to the preparation in example 1.

The chemical composition of the catalyst of this example are given in table. 1.

With R a n t I l n m s p R I m e R 1. The preparation of the catalyst.

Preparing the catalyst in example 1, except that implement the additional interaction with the first and second modifying compounds. I.e., after treatment with silicon tetrachloride and trichlorosilane product of this interaction were washed three times in heptane (70 ml). Before this product was kept for 40 min at room temperature followed by heating to 40aboutWith over 40 minutes After washing, the product was again treated with silicon tetrachloride and trichlorosilane in the same quantities as when you first interaction with these modifying compounds. The product of this second treatment was kept at room temperature for 40 min followed by heating for 40 min at 40aboutC. thereafter, the product was again washed three times in heptane as after the first treatment these modifying compounds.

The chemical composition obtained in this way Catalytica is="ptx2">

Prepared catalyst as in example 1, except that excluded the stage of processing of silicon dioxide modifying compounds, silicon tetrachloride and trichlorosilane and subsequent thermal processing. Instead of these procedures to the product of the interaction of 2-methylenechloride magnesium with silicon dioxide added silicon tetrachloride (3 ml, 4.4 g, 26 mmol) followed by adding about 10 ml of heptane. After this interaction the contents of the flask was stirred at room temperature for 30 min followed by heating to 60aboutC for 30 minutes Further procedure was carried out similarly as described in example 1.

The chemical composition of the obtained catalytic product are given in table. 1.

With R a n t I l n m s p R I m e R 3. The preparation of the catalyst.

Repeated the procedure for preparation of the comparative example 2 without processing stage of the product of the interaction of the composition of silicon dioxide with silicon tetrachloride. Whereas in comparative example 2, the product in the flask was stirred for 30 min at room temperature followed by heating for 30 min at 60aboutWith, the preparation of the catalyst in Dani comparative example was carried out in full accordance with the procedure of example 1 and comparative example 2.

The chemical composition of the catalyst obtained in this comparative example are shown in table. 1.

With R a n t I l n m s p R I m e R 4. The preparation of the catalyst.

Exactly reproduced the preparation of the catalyst of example 1, except stage of the interaction with two modifiermask compounds, silicon tetrachloride and trichlorosilane. Instead this stage in this comparative example, the silicon dioxide after interaction with 2-methylenechloride magnesium was treated with only the second modifying compound, trichlorosilane (3 ml, 4.0 g, 29 mmol). Further, the catalyst of this comparative example was treated in the same way as in example 1. Thus, the product of the interaction with silicon tetrachloride was heated at 40 ° C for 40 min under stirring. Subsequent phases, starting with washing this product with heptane, produced in accordance with the procedure of example 1.

The chemical composition of the catalyst of this comparative example are shown in table. 1.

P R I m e R s 3 and 4 and C o m p a R a n t I l n s e p R I m e R s 5-8. Polymerization of propylene.

The catalysts prepared according to examples 1 and 2 and comparative examples 1-4 was used for polymerization of propylene separately downloaded 0.02 g sample of each of the catalysts of examples 1 and 2 and comparative examples 5-8. In addition, introduced triethylaluminium (TEAL) and isobutylmethylxanthine (IBIP) in such concentrations that the ratio of TEAL:IBIP:the catalyst was equal to 80:8:1. Each polymerization reaction was carried out at the pressure of 32.2 and at a temperature of 70aboutC. In each of these reactions in the reactor was introduced 200 ml of hydrogen gas. The polymerization reaction was carried out for 1 h under stirring.

Propylene products of polymerization reactions were weighed and analyzed. The results of polymerization are shown in table. 2.

P R I m e R s 5 and 6. Polymerization of propylene.

Additional samples of the catalysts of examples 1 and 2 were used in additional experiments on the polymerization of propylene. The polymerization reaction in these examples was carried out similarly to examples 3 and 4 using the catalysts of examples 1 and 2, respectively, except for the amount used of the catalyst and the number of used hydrogen. In examples 5 and 6, the mass of catalyst was equal to 0.01 g, which corresponds to half the mass of the samples of examples 1 and 2. Since the mass of triethylaluminum (TEAL) and isobutylmethylxanthine (IBIP) remained the same, the molar ratio of TEAL:IBIP: catalyst tx2">

The results of the polymerization experiments are shown in table. 2.

P R I m e R 7. In chetyrehosnuju flask with a capacity of 250 ml, flushed with gaseous nitrogen free from oxygen and water, put silicon dioxide (trade mark Davison 948) in an amount of 0.5 g, which was previously handled by hexamethyldisilazane. The flask content was heated with stirring for 1 h at 100aboutC.

The flask was cooled. After cooling to room temperature was added 5 mmol (5.8 g) 2-methylenechloride magnesium in heptane solution (7.3 ml). The flask was then heated to 60aboutWhen flushing with nitrogen and maintained at this temperature for 30 minutes Processing was performed while stirring. Then the temperature was raised to 80aboutC and maintained at this level while stirring for 30 minutes Then at continuous stirring the temperature was raised and maintained between 100 and 110aboutWith about 30 minutes During this time a large number of heptane solvent was distilled. The reaction product was a white solid mokhoobraznye consistency.

This solid substance in the flask 250 ml of added silicon tetrachloride (0,72 g of 4.25 mmol, of 0.48 ml) in heptane solvent (10 ml). Once p is Wali at 40aboutC for 40 min with stirring. At the end of this period, the stirring and heating was stopped.

The solid product of this contact was settled, and the remaining above the liquid usacialis siphon. The solid product was filtered three times with heptane. In each cycle of the washing was added 70 ml of heptane with stirring. After a few minutes the stirring was stopped and the solid matter was allowed to settle. Heptane solvent was then otshatyvalsya siphon.

To the washed thus the product in the flask was added tetracritical titanium (0,91 g, the 1.04 ml, 0.5 mmol) in equal volume of heptane (1,04 ml). The solution tetraradiate titanium was added at room temperature. After that the flask was introduced titanium tetrachloride (5 mmol, of 0.55 ml, 0,946 g). This addition was also conducted at room temperature. The flask contents were then heated for 1 h to 90-100aboutC. At the end of this period the solid product was washed with heptane according to the procedure of first flush except that the amount of heptane for each wash cycle was increased to 80-90 ml and the number of wash cycles was increased to seven, instead of three cycles earlier stage.

The product from this process was analyzed and its elemental composition of ocas 400 g/h with the heptane insoluble substances, moreover, the percentage was about 96 and bulk density of the polymer 1.24 g/cm3.

P R I m e R 8. In chetyrehosnuju flask with a capacity of 250 ml, flushed with gaseous nitrogen free from oxygen and water, put silicon dioxide (trade mark Davison 948) in an amount of 5 g, which was pre-treated hexamethyldisilazane. The flask and its contents were heated with stirring for 1 h at 100aboutC.

The flask is allowed to cool. Upon reaching room temperature to content added 2-methylenechloride magnesium (50 mmol, 5 g) in heptane solution (73 ml). After the flask was heated to 60aboutWhen flushing with nitrogen and maintained at this temperature for 30 minutes the reaction was conducted with stirring. The temperature was then raised to 80aboutC and maintained at this temperature with stirring for another 30 minutes After that, with constant stirring, the temperature was raised and maintained at the level of 100-110aboutWith about 30 minutes During this period a large part of the heptane solvent was removed. The product of this reaction was a white solid mokhoobraznye consistency.

To this solid product in the flask with a capacity of 250 ml was added silicon tetrachloride (63.5 g, 0,435 ml) is R immediately hardened, while the flask was heated for 40 min at 40aboutWith stirring. At the end of this period, the stirring and heating was discontinued.

The solid product of this reaction was settled and remaining on him, the liquid was sucked away by the siphon. The solid product was filtered three times with heptane. In each cycle of washing heptane (70 ml) was then filled with up to threshold with stirring. After a few minutes the stirring was stopped and the solid product was allowed to settle. Heptane solvent was then otshatyvalsya siphon.

To the washed thus the product in the flask was added tetracritical titanium (2,39 g, 5.4 ml, 5 mmol) in equal volume of heptane. The solution tetraradiate titanium was added at room temperature. Once added into a flask were introduced the titanium tetrachloride (200 mmol, 22,2 ml, 38,2 g) at room temperature. The flask contents were then heated to 90-100aboutC for 1 h By the end of this period the solid product was washed with heptane according to the procedure of first flush, except that the amount of heptane each cycle was increased to 80-90 ml and the number of wash cycles was increased to seven, instead of three cycles earlier stage.

The product of this process was analyzed and elemental composition of the armed catalyst SiO2(ROMqCl) SiCl4(SiCl3) Ti(OR)4TiCl4, 1/1/.5/0,75/.1/1.

In chetyrehosnuju flask with a capacity of 250 ml, purged with gaseous nitrogen without the presence of oxygen and water, put silicon dioxide (5.0 g). Silicon dioxide (Davison (trade name) 948) pre-processed by HEXAMETHYL diseasenon. The flask and its contents were heated with stirring for 1 h at 100aboutC.

Then the flask was cooled. Upon reaching ambient temperature in the flask was added chloride 2-methylpentylamine (5 mmol, 5.5 ml 9M solution in heptane). After the flask was heated to 60aboutWhen purging with nitrogen and held at this temperature for 30 minutes Processing was performed under stirring. Then the temperature was raised to 80aboutC and kept at this temperature with stirring for an additional 30 minutes After that, with continuous stirring the temperature was raised and maintained between 100 and 110aboutC for about 30 minutes during this period a large part of heptane was distilled. The product of this interaction was a white solid having the consistency of flour type.

This solid substance in the flask was added tetr the CL3). The solution immediately hardened, despite the fact that the flask was heated for 40 min at 40aboutWith under stirring. At the end of this period, the stirring and heating was stopped.

The solid product of this interaction was deposited, and the pooled liquid poured the water trap. The solid product was washed 2 times in heptane. In each cycle of washing the solid substance under stirring was added heptane (70 ml). After a few minutes the stirring was stopped and allowed the deposition of solids. The heptane was then poured the water trap.

To the thus washed product in the flask was added tetracritical titanium in the form of about 50. solution in heptane. The solution tetraradiate titanium was added at ambient temperature. After that the flask was introduced titanium tetrachloride (5 mmol, 55 ml, 946 g) at ambient temperature. Then the flask and its contents were heated at 90-100aboutC for 1 h In the conclusion of this period the solid product was washed with heptane in accordance with the procedure of the first stage of leaching, except that the amount of heptane in each washing cycle was increased to 80-90 ml, and the number of washing cycles was increased to seven, instead of three cycles at an earlier stage.

P R I m e R 10. Catalytic characterization of heavily loaded catalyst SiO2(ROMgCl), S, Cl4(SiCl3) Ti(OR)4/TiCl4, 1/10/26/3.75/1/40.

In chetyrehosnuju flask with a capacity of 250 ml, purged with gaseous nitrogen without the presence of oxygen and water, put silicon dioxide (5.0 g). Silicon dioxide (Davison (trade name) 948) pre-processed by HEXAMETHYL diseasenon. The flask and its contents were heated with stirring for 1 h at 100aboutC.

Then the flask was cooled. Upon reaching ambient temperature in the flask was added chloride 2-methylpentylamine (76.9 mmol, 9M solution in heptane). After the flask was heated to 60aboutWhen purging with nitrogen and held at this temperature for 30 minutes Processing was performed under stirring. Then the temperature was raised to 80aboutC and kept at this temperature with stirring for an additional 30 minutes After that, with continuous stirring the temperature was raised and maintained at 100-110aboutC for about 30 minutes during this period a large part of heptane was distilled. The product is>This solid substance in the flask was added silicon tetrachloride (14.7 ml pure SiCl4). Immediately after this was added trichlorosilane (1.89 ml pure Hcl3). The solution immediately hardened, despite the fact that the flask was heated for 40 min at 40aboutWith under stirring. At the end of this period, the stirring and heating was stopped. The solid product was washed 3 times in heptane. In each cycle of washing the solid substance was added heptane (70 ml) with stirring. After a few minutes the stirring was stopped and allowed the deposition of solids. The heptane was then poured the water trap.

To the thus washed product in the flask was added tetracritical titanium (2,77 ml) at 50 rpm. solution in heptane. The solution tetraradiate titanium was added at ambient temperature. Then add in the flask was introduced tetrachloride (21,7 ml) at ambient temperature. Then the flask and its contents were heated at 90-100aboutC for 1 h In the end of this period the solid product was washed with heptane in accordance with the procedure of the first stage of leaching, except that the amount of heptane in each washing cycle was increased to 80-90 ml, and the number of washing cycles was increased to seven, McAlister was about 14,000 g/g h, and substances insoluble in heptane, was approximately 97% bulk density was equal to about 24 lb/cu. ft.

1. The catalyst for polymerization of propylene, which are compounds of titanium on the carrier based on the product of the interaction of porous silica with compounds of magnesium and silicon, characterized in that compounds of titanium from contains added to the media tetracritical and titanium tetrachloride in the form of solutions in inert hydrocarbon, followed by washing the obtained solid product with an inert hydrocarbon, and as a carrier - product sequential interaction processed hexamethyldisilazane porous silica with alkoxysilanes, silicon tetrachloride in solution of an inert hydrocarbon and trichlorosilane, followed by the separation and washing of the solid product in the following ratio component of the reaction mixture, mmol/g silica:< / BR>
Alkoxylated magnesium - 1 - 10

Silicon tetrachloride and 0.5 - 25,0

Trichlorosilane is 0.075 - 3,750

Tetracritical titanium - 0,1 - 1,0

The titanium tetrachloride - 1 - 40

2. Catalytic system for the polymerization of propylene, including socialization and catalyst, predstavleniyam magnesium and silicon, characterized in that it contains a catalyst comprising as titanium compounds are added sequentially to the media tetracritical and titanium tetrachloride in the form of solutions in inert hydrocarbon, followed by washing the obtained solid product with an inert hydrocarbon, and as a carrier - product sequential interaction processed hexamethyldisilazane porous silica with alkoxysilanes, silicon tetrachloride in solution of an inert hydrocarbon and trichlorosilane, followed by the separation and washing of the solid product in the following ratio of the components of the reaction mixture, mmol/g silica:

Alkoxylated magnesium - 1 - 10

Silicon tetrachloride and 0.5 - 25,0

Trichlorosilane is 0.075 - 3,750

Tetracritical titanium - 0,1 - 1,0

The titanium tetrachloride - 1 - 40

and as socializaton it contains trialkylaluminium and dialkylammonium in the following ratio of components, mol.h.:

Trialkylaluminium - 80 - 160

Dialkyldimethyl - 8 - 16

The catalyst (in terms of titanium) - 1

3. A method of producing polypropylene polymerization of propylene in the presence of a catalytic system including socialization and catalyst, mnia with compounds of magnesium and silicon, characterized in that the use of a catalytic system containing a catalyst comprising as titanium compounds are added sequentially to the media tetracritical and titanium tetrachloride in the form of solutions in inert hydrocarbon, followed by washing the obtained solid product with an inert hydrocarbon, and as a carrier - product sequential interaction processed hexamethyldisilazane porous silica with alkoxysilanes, silicon tetrachloride in solution of an inert hydrocarbon and trichlorosilane, followed by the separation and washing of the solid product in the following ratio of the components of the reaction mixture, mmol/g silica:

Alkoxylated magnesium - 1 - 10

Silicon tetrachloride and 0.5 - 25,0

Trichlorosilane is 0.075 - 3,750

Tetracritical titanium - 0,1 - 1,0

The titanium tetrachloride - 1 - 40

and as socializaton it contains trialkylaluminium and dialkylammonium in the following ratio of components, mol.h.:

Trialkylaluminium - 80 - 160

Dialkyldimethyl - 8 - 16

The catalyst (in terms of titanium) - 1

 

Same patents:

The invention relates to catalysts for (co)polymerization of olefins and method () polymerizatio olefins

The invention relates to catalysts suitable for the stereospecific polymerization of propylene, the way to obtain this solid substance and method of polymerization of propylene in the presence of this solid

The invention relates to a catalyst containing product ways, including:

a) processing an inert inorganic substrate to remove surface hydroxyl groups;

b) interactions treated in a similar manner to the substrate with a soluble hydrocarbon compound magnesium;

C) interaction of the product of stage b) with a modifying compound selected from the halides of silicon, boron, aluminum, alkylsilane and hexadecylamine, or mixtures thereof;

g) the interaction of the product of stage b) with a compound of vanadium structural formula V(O)S X'4-Swhere X1halogen and S is 0 or 1; the first compound of titanium with the structural formula Ti(OR2)nX2mwhere R2hydrocarbon radical, X2halogen, n is the target number from 1 to 4, and m is 1 or 0, or an integer from 1 to 3 provided that the sum of n and m is 4; a second compound of titanium with the structural formula TIX3p(OR3)qwhere R3hydrocarbon radical, X3halogen, R is an integer from 1 to 4 and q is 0 or an integer from 1 to 3 provided that the sum of p and q is 4, and these first and second titanium compounds are not identical

The invention relates to components of catalysts for the polymerization of olefins, the catalysts obtained them, and their use in polymerization of olefins such as ethylene, propylene and mixtures thereof
The invention relates to the production of polyethylene of low and medium density, containing in the chain a small number of parts of butene-1

The invention relates to methods for CIS-butadiene rubber SKD and can be used in the synthetic rubber industry, and the product is used in tire, rubber, cable and other industries

The invention relates to catalysts for (co)polymerization of olefins and method () polymerizatio olefins

The invention relates to a catalyst containing product ways, including:

a) processing an inert inorganic substrate to remove surface hydroxyl groups;

b) interactions treated in a similar manner to the substrate with a soluble hydrocarbon compound magnesium;

C) interaction of the product of stage b) with a modifying compound selected from the halides of silicon, boron, aluminum, alkylsilane and hexadecylamine, or mixtures thereof;

g) the interaction of the product of stage b) with a compound of vanadium structural formula V(O)S X'4-Swhere X1halogen and S is 0 or 1; the first compound of titanium with the structural formula Ti(OR2)nX2mwhere R2hydrocarbon radical, X2halogen, n is the target number from 1 to 4, and m is 1 or 0, or an integer from 1 to 3 provided that the sum of n and m is 4; a second compound of titanium with the structural formula TIX3p(OR3)qwhere R3hydrocarbon radical, X3halogen, R is an integer from 1 to 4 and q is 0 or an integer from 1 to 3 provided that the sum of p and q is 4, and these first and second titanium compounds are not identical

The invention relates to a solid catalyst type Ziegler-Natta suitable for polymerization or copolymerization of olefins, and to a method for producing this catalyst

FIELD: polymerization catalysts.

SUBSTANCE: invention describes metallocene catalytic component of catalytic system for production of polyolefin with isotactic or syndiotactic/isotactic block structure with length of monomer unit up to C10, said component having general formula R"(CpR1R2R3)(Cp'R1R2')MQ2, where Cp represents cyclopentadienyl ring substituted by at least one substituent; Cp' is substituted fluorenyl ring; R" structural bridge imparting steric rigidity; R1 optional substituent in cyclopentadienyl ring located at a distance to bridge and including a bulky group XR*3 wherein X is selected from group IVA elements and R*, the same or different, are hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms; R2 optional substituent in cyclopentadienyl ring, nearest to bridge and not vicinal to remote substituent, which substituent has formula YR# wherein Y is selected from group IVA elements and R#, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R3 optional substituent in cyclopentadienyl ring, nearest to bridge and being hydrogen or having formula ZR$ wherein Z is selected from group IVA elements and Rs, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R1' and R2' are independent substituents in fluorenyl ring, one of them having formula AR3’’’ wherein A is selected from group IVA elements and each of R’’’ represents independently hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms and the other being hydrogen or second group AR3’’’; M is transition metal from group IVB or vanadium and each Q is either hydrocarbon radical with 1-20 carbon atoms or halogen.

EFFECT: enabled preparation isotactic or syndiotactic/isotactic block polymer with length of monomer unit up to C10.

30 cl, 13 dwg, 2 tbl, 10 ex

FIELD: metalloorganic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to class of metallocene compounds of the general formula (I) wherein Y means fragment of the formula (II) wherein A means sulfur or selenium atom; B means carbon atom; D means carbon atom; R1, R2, R3, R4 and R5 mean hydrogen atom or hydrocarbon groups; Z is taken among fragment of the formula (II) and fragment of the formula (III) wherein R6, R7, R8 and R9 mean hydrogen atom or hydrocarbon groups; L means bivalent bridge group; M means zirconium atom; X means halogen atom; p = 2. Above described metallocenes are useful especially for polymerization of propylene.

EFFECT: improved preparing method, valuable properties of metallocenes.

15 cl, 5 tbl, 18 ex

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