Catalytic compound for polymerization of monomers

FIELD: chemical industry; production of catalytic compounds for polymerization of monomers.

SUBSTANCE: the invention is dealt with the field of polymerization of the monomers and with the methods of production of catalytic compounds and compounds, which are applied at polymerization of at least one monomer. The offered methods contain: 1) a treated solid oxide compound produced due to a contact at least of one solid oxide with at least of one compound having an electron-seeking anion; 2)a metallocenes compound of a metal from IVA group; 3) an organoaluminum compound. The technical result: production of a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

EFFECT: the invention allows to produce a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

71 cl, 99 ex, 13 tbl

 

The SCOPE of the INVENTION

This invention relates to the field of catalytic compositions that can be used for polymerization of the monomers of at least one polymer.

Prior art

The production of polymers is an industry with a turnover of several billion dollars. In this industry annually produces millions of tons of polymers. On the development of technologies that provide added value in this industry spent millions of dollars.

One such technology is the technology with a metallocene catalyst. Although metallocene catalysts have been known about since 1960, they have not found industrial application due to the low performance of these catalysts. Around 1975, it was discovered that you can get a metallocene catalyst having high activity, by contacting one part water with two parts of trimethylaluminum with education methylalumoxane subsequent contacting of such methylalumoxane with metal-price connection. However, it soon came to the conclusion that for forming the active metallocene catalyst required large quantities of expensive methylalumoxane. This is a significant impediment to industrial development of metallocene catalysts.

Instead of big Ko is iciest of methylalumoxane were used borate compounds. However, this is impractical because borate compounds are very sensitive to poisons and easily decomposed, and, in addition, can be quite expensive.

It should be noted the importance of having a heterogeneous catalyst. This is because for most modern industrial polymerization processes require heterogeneous catalysts. Moreover, heterogeneous catalysts can provide almost homogeneous polymer particles that have a high bulk density. These types of practically homogeneous particles are desirable because they improve the efficiency of production and transport polymers. Attempts have been made to obtain a heterogeneous metallocene catalysts, however, these catalysts have not been completely satisfactory.

Therefore, to solve these problems, the authors have developed this invention.

The INVENTION

In this invention, a method of obtaining a composition which can be used for polymerization of the monomers of at least one polymer.

The invention also provides such a composition.

This invention additionally provides a method of polymerization of the monomers of at least one polymer using the said composition.

In addition, this invention relates to the product, the content is properly at least one specified polymer, and to the device that contains at least one specified product.

In accordance with one purpose of this invention, a method of obtaining songs. This method comprises (or optionally, mainly consists of, or consists of) contacting the ORGANOMETALLIC compound, the treated solid oxide compound and alyuminiiorganicheskikh connection with obtaining the specified composition in which this composition is practically comprises (or optionally consists of a) ORGANOMETALLIC compound after contact, the treated solid oxide compound after contact and, optionally, aluminum organic compounds after contact.

In accordance with the second purpose of this invention, is provided a composition of matter. This composition consists of almost ORGANOMETALLIC compound after contact, the treated solid oxide compound after contact and, optionally, alyuminiiorganicheskikh connection after contact.

In accordance with the third purpose of this invention, a method of polymerization of the monomers of at least one polymer using the said composition. This method comprises contacting the specified composition with monomers.

Under the fourth purpose of this invention, available product. The specified product contains at least one above-mentioned polymer.

In accordance with the fifth purpose of this invention, is provided a device. This device contains at least two of these products.

These and other objects of the invention will become more obvious to a person skilled in this technical field, after reading this description.

It should be noted that the phrase "mainly composed of" means that the only other elements (such as, for example, stage of the process and other compounds)included in the scope of claims, are those elements that have no harmful effects on the main and the only indication of characteristics of the claimed invention.

In addition, it should be noted that the terms "comprises" means that no other elements (such as, for example, stage of the process and other compounds) are not included in the scope of the claims, with the exception of items that represent impurities generally present in the composition, or items that represent the process steps associated with the method.

DETAILED description of the INVENTION

Used in this invention ORGANOMETALLIC compound (MHI) have the following General formula:

formula one - (X1) (X2) (X3) (X4)M1

In this form the e M 1selected from the group consisting of titanium, zirconium and hafnium. Currently, most preferably, when M1is a cubic Zirconia.

In this formula (X1) independently selected from the group (hereinafter "the group OMC-I"), consisting of cyclopentadienyl, indenolol, fluorenyl, substituted cyclopentadienyl, substituted indenolol, such as, for example, tetrahydroindene, and substituted fluorenyl, such as, for example, octahydronaphthalene.

The substituents in substituted cyclopentadienyl, substituted indenyl and substituted fluorenyl can represent aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and ORGANOMETALLIC groups if these groups do not have a significant and harmful impact on the activity of the composition during polymerization. In addition, the Deputy may be a hydrogen atom.

Suitable examples of aliphatic groups are hydrocarbon radicals, such as, for example, paraffin and olefin. Suitable examples of cyclic groups are cyclopropenone, cycloolefine, cyclooctanone and arene. Additionally can also be used alkylsilane groups in which each alkyl contains from 1 to 12 carbon atoms, alkylhalogenide groups in which each alkyl contains from 1 to 12 atoms angle of the ode, or halides.

Suitable examples of such substituents are methyl, ethyl, propyl, butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl, chlorine atom, bromine or iodine.

In this formula (X3) and (X4) independently selected from the group (hereinafter "the group OMC-II"), consisting of halides, aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and ORGANOMETALLIC groups, as these groups do not have a significant and harmful impact on the activity of the composition during polymerization.

Suitable examples of aliphatic groups are hydrocarbon radicals, such as, for example, paraffin and olefin. Suitable examples of cyclic groups are cyclopropenone, cycloolefine, cyclooctanone and arene. Presently preferably, when (X3) and (X4) selected from the group consisting of halide and hydrocarbon radicals, and these hydrocarbon radicals contain from 1 to 10 carbon atoms. However, most preferably, when (X3) and (X4) is selected from the group consisting of fluorine atom, chlorine and methyl group.

In this formula (X2you can select or group OMC-I or from the group OMS-II.

When (X2choose from gr is PPI OMC-I, it should be noted that (X1) and (X2can be combined with a bridging group, such as, for example, aliphatic bridging group, a cyclic bridging group, a combination of aliphatic and cyclic bridging groups, and ORGANOMETALLIC bridging group, while these bridge groups do not have a significant and harmful impact on the activity of the composition during polymerization.

Suitable examples of aliphatic bridging groups are hydrocarbon radicals, such as, for example, paraffin and olefin. Suitable examples of cyclic bridging groups are cyclopropenone, cycloolefine, cyclooctanone and arene. In addition, it should be noted that silicon and germanium are also a good bridge elements.

For obtaining these compositions are known various methods. See, for example, U.S. patents№№: 4939217, 5210352, 5436305, 5401817, 5631335, 5571880, 5191132, 5480848, 5399636, 5565592, 5347026, 5594078, 5498581, 5496781, 5563284, 5554795, 5420320, 5451649, 5541272, 5705478, 5631203, 5654454, 5705579 and 5668230.

Specific examples of such compositions are the following:

dichloride, bis(cyclopentadienyl)hafnium,

dichloride, bis(cyclopentadienyl)zirconium

dichloride [ethyl (indenyl)2] hafnium,

dichloride [ ethyl (indenyl)2] zirconium

dichloride [ethyl(tetrahydroindene)2] hafnium,

dichloride [this is (tetrahydroindene) 2] zirconium

dichloride, bis(n-butylcyclopentadienyl)hafnium,

dichloride, bis(n-butylcyclopentadienyl}zirconium,

dichloride ((dimethyl)(vindenes)silane)zirconium,

dichloride ((dimethyl)(vindenes)silane)hafnium,

dichloride ((dimethyl)(datatravelermini)silane)zirconium,

dichloride ((dimethyl)(di-(2-methylindenyl)silane)zirconium

and

dichloride, bis(fluorenyl)zirconium.

Alyuminiiorganicheskikh compounds have the following General formula:

formula two - Al(X5)n(X6)3-n

In this formula (X5) represents a hydrocarbon radical containing from 1 to 20 carbon atoms. At the present time is preferable when (X5is alkyl containing from 1 to 10 carbon atoms. However, most preferably, when (X5) selected from the group consisting of methyl, ethyl, propyl, butyl and isobutyl.

In this formula (X6is a halide, hydride or alkoxide. At the present time is preferable when (X6) independently selected from the group consisting of a fluorine atom and chlorine. However, most preferably, when (X6is a chlorine atom.

In this formula, "n" is a number from 1 to 3 inclusive. However, preferably, when n is equal to three.

Examples of such compounds are the following:

trim illumini,

triethylaluminium,

Tripropylamine,

diethylaminoethoxy,

tributylamine,

triisobutylaluminum,

triisobutylaluminum and

diethylaluminium.

Currently preferred is triethylaluminum.

The treated solid oxide compounds are compounds that have a high Lewis acidity. Preferably, when the specified treated solid oxide compound contains oxygen and at least one element selected from the group consisting of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 (revised) of the Periodic table, including the lanthanides and actinides (see the 11th edition of the Handbook Hawley''s Condensed Chemical Dictionary). However, preferably, when this item is selected from the group consisting of Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr. It is important that these treated solid oxide compounds have the ability to accept electrons; although not wishing to be bound by any theory, I believe that the treated solid oxide compound should have a high Lewis acidity compared with the untreated solid oxide compound. However, to accurately measure the Lewis acidity of these treated and untreated solid oxide compounds is difficult, so other methods are used. In the us Aasee time preferably compare the activity of treated and untreated solid oxide compounds in the reaction acid catalyzed.

The treated solid oxide compound can be obtained in various ways, such as, for example, the formation of the gel formation of the joint gel or impregnation of one compound with another roasting.

In General, preferably in contact with at least one solid oxide compound, such as, for example, aluminum oxide, zirconium dioxide, titanium dioxide and mixtures thereof, or in a mixture with other solid oxides, such as, for example, aluminosilicate, at least one compound having electron-withdrawing anion, and optionally at least one compound is a salt of the metal with the formation of the first mixture and then calcined first mixture with the formation of the treated solid oxide compound. In this alternative you can simultaneously contacting and calcined solid oxide compound; a compound having electron-withdrawing anion; and specified optional connection - salt of the metal. In yet another embodiment, the compound is a salt of a metal can at the same time to have electron-withdrawing anion.

Connection - metal salt is any compound that increases the Lewis acidity of the solid oxide under the conditions described in this invention, to obtain a treated solid oxide the connection. Preferably, when the metal in the specified metal salt selected from the group consisting of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 (revised) of the Periodic table, including the lanthanides and actinides (see the 11th edition of the Handbook Hawley''s Condensed Chemical Dictionary). However, preferably, when this item is selected from the group consisting of Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr.

The compound having electron-withdrawing anion, is any compound that increases the Lewis acidity of the solid oxide under the conditions described in this invention, to obtain a treated solid oxide compound. These compounds having electron-withdrawing anion, increase the Lewis acidity of the solid oxide, giving a contribution to the formation of electron-withdrawing anion, such as, for example, sulfate, halide, and triftorbyenzola (triplet). It should be noted that it is possible to use one or more electron-withdrawing anions. Moreover, I believe that salt metal joints increase the activity of the composition during polymerization.

The acidity of the solid oxide compound can be further increased by using two or more metal salts and/or compounds having electron-withdrawing anion, two (or more) separate stages of contactyou the deposits. An example of such a method is contacting at least one solid oxide compound with a first compound having electron-withdrawing anion, with the formation of the first mixture and then calcining the first mixture, and then contacting the mixture with a second compound having electron-withdrawing anion, with the formation of the second mixture, and subsequent calcination of the specified second mixture get treated solid oxide compound. It should be noted that these first and second compounds having electron-withdrawing anion, which may be the same, but, preferably, they are different.

Suitable examples of solid oxide compounds include, but are not limited to, the following: Al2O3In2About3, EEO, Bi2O3, CdO, Co3O4, CR3About3, CuO, Fe2O3, GA2About3La2O3, MP2O3Moo3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2V2About3WO3, Y2About3, ZnO, ZrO2and mixtures thereof, such as, for example, aluminosilicate and silica-Zirconia. It should be noted that in the currently preferred solid oxide compounds that contain links aluminum-oxygen.

Preferably, TV is Joe oxide compound was also hot. This annealing may be carried out in the atmosphere environment, preferably in a dry environment at a temperature in the range from about 200 to 900°and in the course of time in the range from about 1 min to 100 hours At present, the preferred temperature of approximately 400 to 800°and time in the range from about 1 h to 10 h

The treated solid oxide compound should have a pore volume greater than about 0.01 ml/g, preferably greater than about 0.1 ml/g, and most preferably greater than about 1 ml/year

The treated solid oxide compound should have a surface area greater than about 1 m2/g, preferably greater than 100 m2/g, and most preferably greater than 200 m2/year

The compositions of this invention can be obtained by joint contact ORGANOMETALLIC compound, the treated solid oxide compound and alyuminiiorganicheskikh connection. This contacting can be performed in various ways, such as, for example, stirring. Moreover, each of these compounds can be fed into the reactor separately or in a joint engagement of different combinations of these compounds to their additional shielding in the reactor,or all three of these compounds can be subjected to the contacting together before their entry into the reactor.

Currently, one method consists in the initial joint contacting the ORGANOMETALLIC compound and the treated solid oxide compound for approximately 1 min to 24 h, preferably from about 1 min to 1 h at a temperature of from about 10 to 200°C, preferably from about 25 to 100°with the formation of the first mixture, and then this first mixture is in contact with alyuminiiorganicheskikh connection and receive the composition. During contact or after contacting this mixture or composition can be calcined. This annealing may be carried out in the atmosphere environment, preferably in a dry environment at a temperature in the range from about 300 to 900°and in the course of time in the range from about 1 min to 100 hours At present, the preferred temperature of approximately from 500 to 700°and time in the range from about 1 h to 10 h At the present time, preferably using dry nitrogen as the atmosphere of the environment.

After contacting the composition is practically consists of (or consists of) ORGANOMETALLIC compound after contact, the treated solid oxide compound after contact and, optionally, alyuminiiorganicheskikh a connection to the clocking. It should be noted that the treated solid oxide compound after contact is a big part of the composition by weight.

Since the exact order of contact is unknown, believe that this terminology best describes the components of the composition.

The composition according to the invention has a higher activity than a composition that uses the same ORGANOMETALLIC compound and the same alyuminiiorganicheskikh connection, but uses the raw aluminum oxide Ketjen, grade b (see comparative Examples 4, 5 and 6), instead of treated solid oxide compound of this invention. This activity is measured under conditions of suspension polymerization using isobutane as diluent at a temperature polymerization 50-150°and the pressure of ethylene to 2.8 and 5.6 MPa. In the reactor there should be no signs of scale walls, coverings, or other types of contamination.

However, it is preferred if the activity exceeds 100 g of polyethylene per 1 g of treated solid oxide compound per hour (hereinafter "se/(GT·h), more preferably greater than 250, even more preferably more than 500, even more preferably more than 1000, and most preferably greater than 2000. This activity is measured in terms of uspension polymerization using isobutane as diluent at a temperature of polymerization of 90° And pressure of ethylene 3,86 MPa. In the reactor there should be no signs of scale walls, coverings, or other types of contamination.

These compositions are often sensitive to hydrogen, and sometimes also include comonomers, and usually give polymers with a low value of the ratio IRWIN/IL (melt index under high load to the melt index).

One important aspect of this invention is that for the formation of the composition does not require the use alumoxane. This also means that the formation of such alumoxane does not require the use of water. This is advantageous because the water can sometimes cause the termination of the polymerization process. In addition, it should be noted that for the formation of the composition does not require the use of borate compounds. In General, this means that the composition is heterogeneous, and which can be used for polymerization of monomers, can be easily obtained at low cost because there is little or no alumoxane connection or borate compounds. In addition, to obtain a composition of the present invention there is no need to add as homaranismo compounds, and magnesium chloride.

The monomers used in this invention are unsaturated hydrocarbons containing about is 2 to 20 carbon atoms. Presently preferably, when the monomers are selected from the group consisting of ethylene, propylene, butene-1, 3-methylbutane-1, pentene-1, 3-methylpentene-1, 4-methylpentene-1, hexene-1, 3-ethylhexane-1, Heptene-1, octene-1, nonene-1, mission-1 and mixtures thereof. However, when the target product is a homopolymer, it is most preferable to use as monomers ethylene or propylene. In addition, when the target product is a copolymer, it is most preferable to use as the monomers ethylene and hexene.

Methods that can be used for polymerization of the monomers in the polymers known from the prior art, such as suspension polymerization, polymerization in the gas phase and polymerization in solution. Suspension polymerization is preferably carried out in a loop reactor.

In addition, more preferable to use isobutane as a diluent for suspension polymerization. Examples of such technological solutions can be found in U.S. patent No. 4424341, 4501885, 4613484, 4737280 and 5597892.

It should be noted that in the conditions of suspension polymerization of these songs very well carry out the polymerization of the individual ethylene or of ethylene with alpha-olefin, or propylene. In particular, this method of composition give polymer particles of good quality is without substantial contamination of the reactor. When this composition is used in a loop reactor under conditions of suspension polymerization, to better control the progress of the polymerization, it is preferable that the particle size of the solid mixed oxide compound was in the range of from about 10 to 1000 μm, preferably from 25 to 500 μm and most preferably from about 50 to 200 microns.

After receipt of the polymers they can be formed into various articles, such as, for example, household containers and utensils, boxes for packing, fuel tanks, pipes, geomembranes and cladding. These products can be molded in a variety of ways. Typically, to provide the desired effects in polymer add various additives and modifiers. It can be assumed that, using the invention described here, these products can be produced with lower cost, while retaining most, if not all, of the unique properties of polymers obtained by metallocene catalysts.

In addition, these products can also be part of a device, such as, for example, a car, reducing its weight, with the attendant advantages of this application.

EXAMPLES

In these examples, additional information provided to a person skilled in this technical field. These examples should not be considered in the plan is limited to the volume I of the claims.

DESCRIPTION of EXPERIMENTS POLYMERIZATION

All the polymerization experiments are carried out in a steel reactor, which has a volume of 2.2 liters of This reactor equipped with a stirrer drive. During polymerization, the installation of the mixer provides a stirring speed of 400 rpm, the reactor is enclosed in a steel jacket, associated with steel refrigerator. Inside the steel jacket is boiling methanol. The boiling point of methanol is adjusted, by varying the pressure of the nitrogen attached to steel refrigerator and steel shirt. This method of regulation has provided the temperature is constant with an accuracy of ±0,5°C.

First, treated or untreated solid oxide compound is loaded into the current of nitrogen to the dry reactor. Secondly, the reactor type ORGANOMETALLIC compound from a syringe. Thirdly, in the reactor add 0.6 liter of isobutane. Fourth, in the process of introducing isobutane add alyuminiiorganicheskikh connection. Fifthly, in the reactor add 0.6 liter of isobutane. Sixthly, in the reactor add ethylene to excess pressure of 3.8 MPa. Seventh, the reactor is heated to 90°C. the pressure support in the polymerization process. During a specified period of time, during polymerization continue stirring the mixture. The catalyst is determined by registering the flow of ethylene into the reactor to maintain constantly what about the pressure. Eighth, after the specified period, stop the flow of ethylene and slowly relieve the pressure from the reactor. Ninth, the reactor is opened to extract granulated powder of the polymer.

In all experiments, the polymerization according to the invention the reactor was clean, there were no any signs of scale from the walls, coverings, or other types of pollution. The polymer powder is removed and weighed. Activity is defined as the weight of 1 hour of polymer in grams, referred to 1 gram of treated or untreated solid oxide compound.

In some cases, the treated solid oxide compound and ORGANOMETALLIC compound first contact in the reactor for 30 min at 90°With 1 liter of isobutane to add alyuminiiorganicheskikh compounds and ethylene in the reactor.

GETTING SOLID OXIDE

Silicon dioxide brand 952 having a pore volume of 1.6 ml/g and a surface area of about 300 square meters per 1 g receive from the company W.R. Grace. This material, approximately 10 g was placed in a quartz tube with a diameter 44,4 mm, the bottom of which has a disk of sintered quartz. When silicon dioxide is placed on the disk, and through him, blow dry air with a linear speed of 45.3-51 normal liters per hour. Then include electric heating this quartz is th tube and increase the temperature at a speed of 400° With an hour to a temperature of 600°C. At this temperature, treated with silicon dioxide in a fluidized bed, in dry air for 3 hours After that silicon dioxide is collected and stored in a dry nitrogen atmosphere.

According to this method, described for silicon dioxide, also get some samples of aluminum oxide. A commercial alumina manufactured by AKZO Co., as the aluminum oxide Ketjen brand In having pore volume of approximately of 1.78 ml/g and a surface area of approximately 340 square meters 1 was Used in the preparation of these samples of aluminum oxide in the temperature range 400°C, 600°and 800°C.

The silicate also receive from the company W.R. Grace (MS 13-110 containing 13% alumina and 87% silica). This sample of aluminum oxide is prepared as described upon receipt of the silicon dioxide. Used in the preparation of this sample aluminosilicate temperature is 600°C.

Titanosilicate get in the joint formation of the gel, as described Datcom in U.S. patent No. 3887494. The titanyl sulphate is dissolved in concentrated sulfuric acid with the formation of the first mixture. After this first mixture is added slowly to the sodium silicate solution under vigorous stirring, obtaining a second mixture. When the pH of the second mixture reaches about six, this second mixture VC is tineretea, forming a homogeneous, almost transparent first product. This first product is then sostarivayut at 80°C and pH 7 for 3 h and subsequent washing 9 times with water and 2 times with 1% solution of ammonium nitrate receive the second product. This second product is a gel, and then subjected to azeotropic drying in ethyl acetate with the formation of the third product. This third product contains 8% titanium. He also has a surface area of 450 square meters per gram and a pore volume of 2.0 ml/year Then titanosilicate prepared as described for the preparation of silicon dioxide.

Used in the preparation of this sample titanosilicate temperature is 600°C.

Lumotast receive according to U.S. patent No. 4364855 (McDaniel). Nitrate aluminum, 380 g, and 94 g of monoammonium phosphate is dissolved in deionized water to form a first mixture. Then, in this first mixture was added approximately 170 ml of ammonium hydroxide with the formation of the second mixture. When the pH value is about 8 this second mixture gelatinases, forming a first product. This first product is then washed 2 times with water and 1 times n-propyl alcohol, then the product is dried in vacuum at 80°during the night and get the second product. This second product contains phosphorus and aluminum in an atomic ratio of 0.8, it has a pore volume of 2.1 ml/g and the area on which ernesti 250 square meters per gram. Then this lumotast prepared as described for the preparation of silicon dioxide. Used in the preparation of this sample alumophosphate temperature is 600°C.

COMPARATIVE EXAMPLES 1-2

These examples demonstrate that the ORGANOMETALLIC compound after contact with alyuminiiorganicheskikh connection has low activity (or does not) during polymerization.

Experience the polymerization carried out as described previously. First, the reactor type ORGANOMETALLIC compound (2 ml of a solution of 0.5 g of the dichloride bis(n-butylcyclopentadienyl)zirconium in 100 ml of toluene). Secondly, in the reactor add half of isobutane. Thirdly, in the reactor, add 2 ml of 15% (by weight) solution of triethylamine for example 1 or 2 ml of 25% (by weight) solution of ethylaminoethanol (EACH) for example 2. Fourthly, in the reactor, add the remaining half of isobutane.

Then the reactor type ethylene, however, the polymerization reaction does not proceed, the activity is absent. After 1 h contact discharge pressure and the reactor opened.

In both cases, the polymer was not detected. These results are shown in table I.

COMPARATIVE EXAMPLES 3-9

These examples demonstrate that the solid oxide compound after contact with the ORGANOMETALLIC compound and alyuminiiorganicheskikh connection has iscoe activity (or does not) during polymerization.

Each of the previously described solid oxide compounds added to the reactor followed by the addition of ORGANOMETALLIC compounds (2 ml of a solution of 0.5 g of the dichloride bis(n-butylcyclopentadienyl)zirconium in 100 ml of toluene) and then alyuminiiorganicheskikh connection (triethylaluminium). These examples are presented in table I.

The first two examples show that ORGANOMETALLIC compound after contact with alyuminiiorganicheskikh connection has low activity (or does not) during polymerization. In the example where used silicon dioxide, the polymer is almost not formed. In the case of aluminum oxide, which is more acidic than silicon dioxide, polymer is formed more, but the activity is very small. Aluminophosphate, aluminosilicate and titanosilicates carriers provide only low activity. In table I, the activity expressed in the se/(GT·h).

COMPARATIVE EXAMPLE 10

Prepare a solution of 244 g of ammonium sulfate, dissolved in water, the total volume of the solution of 437 ml Then 100 ml of this solution is impregnated with a 33.2 g of silicon dioxide W.R. Grace, grade 952. This wet mixture is dried in a vacuum Cabinet at 110°C for 12 h Material contains 12.7 mmol sulfate 1 g of silicon dioxide. The dried material is ground and sieved 35 mesh and then calcined in air at 400 In accordance with the described methodology. We found that this material has a pore volume 1,22 ml/g and surface area of 223 square meters per gram. Then test a sample of this material, determining its activity in the polymerization of ethylene, as described previously. The formation of polymer is not observed. This experience is presented in table II as example 10.

EXAMPLES 11-12

Impregnate 40/6 g of aluminum oxide Ketjen brand In 122 ml of the above solution of ammonium sulfate. This wet mixture is dried in a vacuum Cabinet at 110°C for 12 h Material contains 12.7 mmol sulfate 1 g ' green ' of aluminum oxide. Then the dried material is ground and sieved 35 mesh and calcined in air at 400°in accordance with the described methodology. We found that this material has a pore volume of about 0.25 ml/g and surface area of 38 square meters per gram. Then test a sample of this material, determining its activity in the polymerization of ethylene, as described previously. Despite the low porosity of the material, yet it acquires 33 g/(g·h) polymer. This experience is presented in table II as example 11.

Then the same material again calcined in air at 750°Since, as described above, and again determine its activity during polymerization. This time the material gives 583 g/(g·h) polymer. This all is and it is noteworthy in connection with a very small surface area. It was found that the polymer has a melt index of 0.15 and a melt index under high load 3,24. This experience is presented in table II as example 12.

EXAMPLES 13 a, b, C

Aluminum oxide Ketjen brand In the first calcined in air at 600°Since, as described earlier. Then 11.1 g of this material is suspended in 30 ml of isopropyl alcohol mixed with 1.73 g of sulfuric acid. This is the equivalent of 1.6 mmol of sulfate per 1 g of calcined alumina. Isopropyl alcohol is then evaporated by heating in a nitrogen atmosphere. Then dry the solid is calcined in air at 550°Since, as described earlier. Then test a sample of this material, determining its activity in the polymerization of ethylene, as described previously. It is formed 1387 g/(g·h) polymer. This experience is presented in table II as example 13A.

Aluminum oxide Ketjen marks obtained by the former method, first calcined in air at 600°With, then 5.9 g of this material is suspended in 15 ml of isopropyl alcohol mixed with 0,453 g of sulfuric acid. This is the equivalent of 1.6 mmol of sulfate per 1 g of calcined alumina. Isopropyl alcohol is then evaporated by heating in a nitrogen atmosphere. Then dry the solid is calcined in air at 550°Since, as described earlier. We found that this material has a pore volume of 0.93 ml/g and surface area of 205 square is meters per gram. Then test a sample of this material, determining its activity in the polymerization of ethylene. It is formed 324 g/(g·h) polymer. This experience is presented in table II as example 13B.

Then this material was again calcined in air at 800°C for 3 h as described above. We found that this material has a pore volume of 1.03 ml/g and surface area of 236 square meters per gram. Its activity is 58 g/(g·h) polymer. This experience is presented in table II as example 13C.

EXAMPLES 14 AND 15 and

Repeat the procedure of example 11, except that the aluminum oxide Ketjen marks impregnated with 11.6 g of ammonium sulfate and then calcined at 550°C. the test Results are shown in table II as example 14A. During this experience, sulfated alumina and metallocene compound pre-contact in the reactor for 32 min at 90°before the introduction of other components to start the experience. Found that the results obtained in this experiment, the polymer has a melt index of 0.21 and a melt index under high load of 3.5, which gives the ratio of the shear 16,7. By the method of gel permeation chromatography found that the polymer has srednevekovoy molecular mass Mw=168000, average numerical molecular mass Mn=67900 and Mw/Mn=2,5. It was found that after annealing the sulfated hydroxy the aluminum has a surface area of 284 square meters per gram, pore volume of 0.67 ml/g and average pore 94 Angstrom.

Above (example 14A) sulfated alumina is then calcined in air at 650°C for 3 h and again experience during polymerization. Again sulfated alumina and metallocene compound pre-contact within 30 min at 90°C. Details of this experiment is shown in table II as example 14C. It was found that this material has a surface area of 305 square meters per gram, a pore volume of 0.9 ml/g and average pore 110 angstroms.

Another example of the sulfated alumina prepared by the same method as in example 14A, except that 26.9 g of aluminum oxide Ketjen brand To impregnate 5,41 g of ammonium sulfate. Calcined sample at 550°C. it was Found that this sample has a surface area of 352 square meters per gram, a pore volume of 0.93 ml/g and average pore 106 angstroms. Details of the polymerization are shown in table II as example 15.

COMPARATIVE EXAMPLE 16,

Prepare a solution of 2.0 g of concentrated sulfuric acid in 200 ml of isopropyl alcohol. Aluminum oxide Ketjen In calcined in air at 600°Since, as described above. Then 6,34 g of this material are suspended in 16 ml of this solution. This is equivalent to 0.26 mmol sulfate 1 g of calcined alumina. Isopropyl alcohol is then evaporated p. and heated in nitrogen atmosphere. Then dry the solid is calcined in air at 550°Since, as described earlier. We found that this material has a pore volume of 0.95 ml/g and surface area of 213 square meters per gram. Then test a sample of this material in the polymerization of ethylene. It is formed of 6 g/(g·h) polymer. This experience is presented in table II as example 16.

EXAMPLE 17

The aluminosilicate receive from the company W.R. Grace (trade name MS 13-110). Its properties and activity have already been described above. The silicate impregnated with sulfuric acid as described above in example 16, to the content of 1.6 mmol of sulfate to 1, the material is Then calcined in air at 600°Since, as described earlier. Then a sample of this material is loaded into the reactor together with the metallocene compound and isobutane and stirred for 32 min at 90°before adding ethylene. This material gives 82 g/(g·h) polymer. This experience is presented in table II as example 17.

EXAMPLE 18

A solution of 0.5 g of byflorida of ammonia in 30 ml of methanol is added to 4.5 g of aluminum oxide Ketjen brand In which calcined in air at 600°Since, as described earlier. While aluminum oxide is hydrated almost to the point of capacity. This is equivalent to 3.9 mmol fluoride per 1 g of calcined alumina. Then the methyl alcohol is evaporated by heating in a nitrogen atmosphere. Then dry solid proquali is up in the air at 500° Since, as described earlier. Then test a sample of this material in the polymerization of ethylene. It is formed 927 g/(g·h) polymer. This experience is presented in table III as example 18.

EXAMPLES 19-21

Described in example 18, the method is repeated, except that the final calcination is carried out at 250°C, 400°and 600°C. Determine the activity of each material during polymerization, and the results are presented in table III as examples 19, 20 and 21.

EXAMPLE 22

Described in example 18, the method is repeated, except that the ' green ' aluminum oxide Ketjen soaked In fluoride content of 5.8 mmol/g After calcination at 500°To determine the activity of this material during polymerization, and the results are presented in table III as example 22.

EXAMPLES 23-24

Aluminum oxide W.R. Grace, the variety of HPV, calcined in air at 600°C for 3 h, the receiving material with a surface area of approximately 500 square meters per gram and a pore volume of about 2.8 ml/year of This material (3,36 g) heated to 600°in the fluidized bed in a stream of nitrogen. Then in a stream of nitrogen injected 5.0 ml of perftorgeksan to the aluminum oxide layer. In the next 15 min perference evaporates at room temperature, is fond of nitrogen and passes through the fluidized bed of alumina, where he responds. is this processing is equivalent to approximately 55 mmol of fluoride per 1 g of aluminum oxide, if you react the whole fluoride (which, of course, is not implemented). Aluminum oxide is black, alleged deposited on carbon. Then determine the activity of this material during polymerization, when the sample is loaded into a reactor with a metallocene compound at 90°C. After 30 min stirring triethylamine and ethylene and find that this sample gives 1266 g/(g·h) polymer. Details are presented in table III as example 23.

Then this material was again calcined in air at 600°C for 3 hours to burn out the residual carbon. Black material again becomes white. Then determine the activity in the polymerization, when the sample material is loaded into the reactor together with the metallocene compound and triethylaluminum, followed by immediate addition of ethylene. This sample gives 2179 g/(g·h) polymer. Details are presented in table III as example 24.

EXAMPLES 25-26

Aluminum oxide Ketjen brand In calcined in air at 600°C for 3 h as described in example 5. Download 9,29 g of this alumina in dry quartz tube to activate and process it in the fluidized bed in a stream of carbon monoxide at 600°C. Then in a stream of carbon monoxide is injected with 4.5 ml of methyl bromide to the aluminum oxide layer. Over the next 30 min bromine is a simple methyl evaporates when heated by an electric heater, he is fond of gaseous carbon monoxide and passes through the fluidized bed of alumina at a temperature of 600°C. After this treatment, the aluminum oxide is black, alleged deposited on carbon. Then determine the activity of the sample of this material during polymerization and find that it gives 223 g/(g·h) polymer. In the second similar experience found that it gives 181 g/(g·h) polymer. These two experiments are presented in table IV as examples 25 and 26.

EXAMPLE 27

Aluminum oxide Ketjen brand In calcined in air at 600°C for 3 h as described in example 5. Download 9,82 g of this alumina in dry quartz tube to activate and process it in the fluidized bed in a stream of carbon monoxide at 600°C. Then in a stream of carbon monoxide is injected with 1.0 ml of liquid bromine to the aluminum oxide layer; bromine slowly evaporates and passes through the fluidized bed of alumina at a temperature of 600°C. After this treatment, the aluminum oxide remains white. Determine the activity of the sample of this material during polymerization and find that it gives 106 g/(g·h) polymer. This experience is presented in table IV as example 27.

EXAMPLES 28-31

Calcined 10 ml alumina Ketjen brand In air at 600°C for 3 h as described in example 5. After this stadiumrailway reduce the oven temperature to 400° And in a stream of nitrogen injected with 1.0 ml of carbon tetrachloride, which evaporates to the aluminum oxide layer. Carbon tetrachloride is fond of nitrogen and passes through the layer where it reacts with aluminum oxide, hareruya surface. This processing is equivalent to approximately 15.5 mmol chloride 1 g digidratirovannogo of aluminum oxide. After this treatment, the aluminum oxide remains white. Then determine the activity of the sample of this material during polymerization. In addition to ethylene in the reactor also add hexene-1 as a co-monomer. This material gives 939 g/(g·h) copolymer having the following properties: melt index was 0.63, the melt index under high load 10,6, the ratio of shear 16,7, density 0,9400, srednevekovaja molecular mass Mw=126000, srednekislye molecular mass Mn=50200, and the polydispersity (Mw/Mna 2.5. This experience is presented in table V as example 28.

This chlorinated sample of aluminum oxide test again, but without hexene, and the details are presented in table V as example 29. He gives 1019 g/(g·h) a polymer having the following properties: melt index of 0.15, the melt index under high load 2,68, the ratio of shear to 17.9, density 0,9493, srednevekovaja molecular weight 202000, srednekislye molecular weight 62400 and a polydispersity of 3.2.

In a similar experience the e of 7.3 g of aluminum oxide Ketjen marks, already calcined in air at 600°With handle and 0.37 ml of carbon tetrachloride, which is evaporated in a stream of nitrogen at 400°C. This treatment is equivalent to approximately 2.4 mmol of chloride per 1 g of calcined alumina. This material has the activity of 146 g/(g·h) and are presented in table V as example 30.

In another similar experiment, repeat the procedure of example 29, except that 6.2 g of aluminum oxide, calcined at 600°C, treated with 5.0 ml of carbon tetrachloride at 400°that is equivalent to 37.6 mmol of chloride in 1, This material has activity 1174 g/(g·h) polymer shown in table V as example 31.

EXAMPLES 32-35

Calcined three different sample of aluminum oxide Ketjen brand In air at 600°as described in the examples above, and then treated with various amounts of carbon tetrachloride at different temperatures. Table V shows the results of these experiments as examples 32, 33 and 34. In example 33 this treatment is carried out in the gaseous carbon monoxide instead of nitrogen.

The activity of the catalyst of example 33 test again during polymerization, but with the following changes. Instead of downloading all the components in the reactor and the immediate start of the experiment, first download the oxide and metallocene compound with isobutane give them to connect at 90° With over 37 min before adding socializaton and ethylene and the start of the experiment. This experience is presented in table V as example 35.

EXAMPLE 36

Aluminum oxide W.R. Grace, the variety of HPV, calcined in air at 600°C for 3 h, the receiving material with a surface area of approximately 500 square meters per gram and a pore volume of about 2.8 ml/year, Then this aluminum oxide (5,94 g) is treated with 600°in a stream of nitrogen 5.0 ml of carbon tetrachloride. The test results in the polymerization are presented in table V as example 36.

EXAMPLE 37

The aluminosilicate W.R. Grace, grade MS 13-110, calcined in air at 600°C for 3 h as described above in example 8. Then this aluminosilicate (11.2 g) is treated with 600°in a stream of nitrogen and 2.8 ml of carbon tetrachloride. The test results in the polymerization are presented in table V as example 37.

EXAMPLE 38

Aluminum oxide Ketjen marks (of 6.96 g), which is calcined in air at 400°C for 3 h, loaded into a dry tube for activation and heated in a stream of nitrogen to 400°C. Then in a stream of nitrogen introduced to 2.1 ml of silicon tetrachloride to the aluminum oxide layer. As the evaporation of silicon tetrachloride he passes through a layer of aluminum oxide and chlorium surface. Determine the activity of the sample of this material during polymerization, it gives 579 g/(g·h) polymer having a melt index of 0.0 and a melt index under high load 3.58 and the ratio of shear to 17.9. The details of this test during polymerization are presented in table VI as example 38.

EXAMPLE 39

Aluminum oxide Ketjen marks (8,49 g), which is calcined in air at 600°C for 3 h, loaded into a dry tube for activation and heated in a stream of nitrogen up to 300°C. Then in a stream of nitrogen introduced with 2.8 ml of chloride tiomila to the aluminum oxide layer. As the evaporation of chloride tiomila it passes through the layer of aluminum oxide and chlorium surface. Determine the activity of the sample of this material during polymerization, it gives 764 g/(g·h) polymer having a melt index of 0.13 and a melt index under high load 2.48 and the ratio of shear to 18.6. The details of this test during polymerization are presented in table VI as example 39.

EXAMPLE 40

Aluminum oxide Ketjen marks (7,63 g), which is calcined in air at 400°C for 3 h, loaded into a dry tube for activation and is heated in a current of dry air up to 300°C. Then the air flow is injected to 2.55 ml chloride Sulfuryl to the aluminum oxide layer. As the evaporation of chloride Sulfuryl for approximately 45 min at room temperature, it passes through a layer of aluminum oxide and chlorium surface. Determine the activity of the sample of this material during polymerization, it gives 459 g/(g·h) polymer having a melt index of 0.11 and a melt index at high is the recalls of 2.83 and the ratio of the shear 25,6. The details of this test during polymerization are presented in table VI as example 40.

COMPARATIVE EXAMPLES 41-43 AND EXAMPLES 44-45

In the reactor add 2,6955 g of solid aluminum trichloride, along with 2.0 ml of a 15%solution of triethylamine and 2.0 ml of a solution of metallocene compounds used in the previous experiments. Add isobutane and ethylene, as in the previous experiments. However, it was not observed any activity. This experience is summarized in table VI as example 41. Then this experience is repeated with a reduced amount of aluminum trichloride in the reactor, however, and in this case, the activity was not observed. This experience is an example of 42.

Thus, it is aluminum trichloride is not an activator for metallocenes. There is a certain difference between aluminum trichloride and chlorinated aluminum oxide.

In the following example, aluminum trichloride precipitated on the surface of digidratirovannogo of aluminum oxide, in order to increase its surface area. Dissolve 1.4 g of anhydrous aluminum trichloride in 100 ml of dichloromethane. Then this solution was added to 6 g of aluminum oxide Ketjen brand In which calcined in air at 600°With over 3 hours Dichloromethane is evaporated in nitrogen at 60°C. Then, the sample of this material have in the polymerization reaction (example 43), but his asset is ity was low. Then this material is heated in a nitrogen atmosphere at 250°C for 1 h and again experience in the polymerization reaction (example 44); this time found some activity. Then this material is again heated in nitrogen atmosphere at 400°C for 1 h and again experience in the polymerization reaction (example 45) and detect the activity of the material.

COMPARATIVE EXAMPLES 46 and 48 and EXAMPLE 47

In another experiment, the aluminum oxide Ketjen brand In (3.5 g), which is calcined at 600°C, treated with 10 ml of 25%solution of dichloride ethylaluminum (DHEA) at 60°C for 10 min, then washed twice to remove unreacted residue of DHEA. When tested in the polymerization reaction (first without Skatalites, then acetalization) activity was not detected (example 46). Then this material is heated in a nitrogen atmosphere at 200°C for 1 h and again have (example 47); this time found some activity.

In a similar experiment, the aluminum oxide Ketjen marks (or 4.31 g), which is calcined at 400°C, treated with 30 ml of 25% (by weight) solution of dichloride ethylaluminum (DHEA) at 90°C for 30 minutes the Excess of DHEA decanted, and the solid is washed 3 times with dry heptane. Then the solid is dried in nitrogen at 100°and experience in the polymerization reaction (example 48), this material has act shall want to make 29 g/(g· h).

COMPARATIVE EXAMPLE 49

The sample of silicon dioxide Davison 952 (of 2.26 g), which was previously calcined in dry air at 600°C for 3 h, soaked to the state capacity of 3.4 ml of pure (95,7%) triftormetilfullerenov acid. This processing is carried out in a flask under nitrogen atmosphere. Then this material is mixed with 8,96 g of aluminum oxide Ketjen of the brand, which was pre-calcined in dry air at 600°C, for 3 hours resulting solid material contained 79,9% wt. aluminum oxide and 29.1 wt.% silicon dioxide. This processing is carried out in a dry tube for activation in the fluidized bed in a stream of nitrogen. The mixture is heated to 193-230°C for 3 h in nitrogen to ensure evaporation triftormetilfullerenov acid and its interaction with the alumina; the result is a material containing 1 mm triftormetilfullerenov acid in 1 g of aluminum oxide. Then test the activity of this material during polymerization, as described above, except that the pressure of ethylene was set at 3.1 MPa instead of 3.8 MPa in the reactor add 25 ml of 1-hexene. The results are shown in table VII.

EXAMPLE 50

Solid oxide of example 49 is again heated in nitrogen to a temperature of 400°for another 3 hours, to further improve the distribution and interaction of cryptomaterial the OIC acid. Then test the activity of this material during polymerization, as described above, except that the pressure of ethylene was set at 3.1 MPa instead of 3.8 MPa in the reactor add 25 ml of 1-hexene. The results are shown in table VII.

EXAMPLE 51

Solid oxide of example 49 is again heated in nitrogen to a temperature of 600°for another 3 hours, to further improve the distribution triftormetilfullerenov acid. Then test the activity of this material during polymerization, as described above, except that the pressure of ethylene was set at 3.1 MPa instead of 3.8 MPa in the reactor add 25 ml of 1-hexene. The results are shown in table VII.

EXAMPLE 52

Dissolve 0.5 g of byflorida of ammonia in 30 ml of methanol and this solution is then precipitated onto the sample of aluminum oxide Ketjen brand In (4.5 g), which is calcined in air at 600°C for 3 hours Under this treatment, the solid is saturated almost to capacity. Then the methanol is evaporated in a stream of nitrogen on a hot tile, and the material is transferred into a tube for activation, where it is heated in nitrogen to 500°and incubated for 2 hours Then 1,89 g of this material is treated at a temperature of 500°With the nitrogen to 0.5 ml of carbon tetrachloride, which is injected into the gas stream. Then test the activity of this material during polymerization with metal the price connection and socialization - 2.0 ml of triethylamine. The material gives 3132 g/(g·h) polymer. Details are given in table VIII.

EXAMPLE 53-54

In a dry tube for activation download 6,18 g of aluminum oxide W.R. Grace, the variety of HPV, which is calcined in air at 600°C for 3 h and has a surface area of about 500 square meters per gram and a pore volume of about 2.8 ml/g, and heated to 600°in a stream of nitrogen. Then in a stream of nitrogen introduced to 0.24 ml perftorgeksan, above the heater. Liquid perference evaporates and passes through the layer of aluminum oxide, Porirua surface. Then in a stream of nitrogen introduced to 1.55 ml of carbon tetrachloride, which passes through the layer of aluminum oxide at 600°C. the Tube is cooled to 25°and the resulting fluorinated-chlorinated aluminum oxide is stored in a nitrogen atmosphere. Then determine the activity of a small sample of this material during polymerization with metallocene compound and triethylaluminum. The activity of this sample is very high - 4390 g/(g·h) (example 53).

Then this material again experience, with the modification that it is in contact under stirring in isobutane with metallocene compound at 90°C for 30 minutes before adding other components. This technique provides activity 6298 g/(g·h) (example 54).

EXAMPLE 55

The Degussa aluminum oxide C, obtained by the hydrolysis of PLA is EIW, calcined in air for 3 h at 600°C. Then to 2.74 grams of this calcined alumina is heated in air up to 600°With the current of air, which is injected with 4.1 ml of perftorgeksan, above the heater. As the evaporation of liquid perference entrained air in the aluminium oxide layer. Then switch the flow of gas from the air into nitrogen and injected with 1.0 ml of carbon tetrachloride. After complete evaporation of the carbon tetrachloride, the solid is cooled to room temperature and stored in a dried nitrogen. Determine the activity of a small sample of this material during polymerization with metallocene compound and socialization, as described above. It is established that the activity of this material is equal 1383 g/(g·h). Details are given in table VIII.

EXAMPLES 56, 60-61, 63-64 and COMPARATIVE EXAMPLES 57-59, 62, 65-66

Chlorinated alumina prepared by the method of example 33. In each experiment a sample of the oxide is loaded into the reactor and the nitrogen atmosphere, then add 2 ml of a solution of 0.5 g of the dichloride bis(n-butylcyclopentadienyl)zirconium in 100 ml of toluene and 0.6 l of liquid isobutane, then 1 mmol of socializaton (usually in the form of a solution in hexane), followed by another portion of 0.6 l of liquid isobutane and finally add ethylene, after the temperature of the reactor reaches 90°C. the Results of these experiments are given in tables is IX, as examples 56-62.

A similar comparison of socialization carried out using aluminium oxide, which has been fluorinated, instead of chlorination, according to the method of preparation used in example 21. The results of these experiments are shown in table IX as examples 63-66.

EXAMPLES 67-71

In each of the following experience was charged to the reactor fluorinated-chlorinated alumina used in example 50, then add 2 ml of a solution of 0.5 g of the selected metallocene compound in 100 ml of toluene and 0.6 l of liquid isobutane, and then 2 ml of 1-molar solution of triethylaluminum as socializaton followed by another portion of 0.6 liter of isobutane and finally add the ethylene. These experiments are performed at 90°With, as all previous experiments. Details are given in table X.

COMPARATIVE EXAMPLE 72

Aluminum oxide Ketjen brand In calcined in the fluidized bed in a stream of dry air at 600°C for 3 h, as described in the previous examples, and store the dried nitrogen. Then 9.3 g of this material was again heated in the fluidized bed in a stream of nitrogen to 600°C. At this temperature in a stream of nitrogen introduced with 2.3 ml of carbon tetrachloride to the aluminum oxide layer. Carbon tetrachloride evaporates within a few minutes and passes through the aluminium oxide layer where it reacts with the formation of chlorinated surface. Then this material is stored in a dried nitrogen and subsequently determine the activity of this material during polymerization. The results are presented in table XI.

COMPARATIVE EXAMPLE 73

Aluminum oxide Ketjen brand In suspended in isopropyl alcohol, to which is added sulfuric acid in an amount equivalent to 2.5% by weight of aluminum oxide. Then the alcohol is evaporated in vacuum at a temperature of approximately 100°With during the night. Then a sample of this material is calcined in a dehumidified air at 600°C for 3 h as described above. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XI.

EXAMPLE 74

The sample source of aluminum oxide Ketjen marks (24,68 g) is impregnated with a solution of 4.2 g of dihydrate of copper chloride in 55 ml of deionized water. The sample was then dried in a vacuum at a temperature of approximately 100°during the night, sieved 35 mesh (40 resp./29 m is) and calcined in a layer in a stream of dry air at 600° Since, in the fluidized bed in a stream of dry air for 3 h, in order to turn most of chloride in the mixed oxide. Then 16,53 g of this material was again calcined in the fluidized bed in a stream of nitrogen at 600°brought in 4.3 ml of carbon tetrachloride, as described above, in order to re-gloriavale surface. Then this material is stored in a dried nitrogen and subsequently determine the activity of this material during polymerization. This material gives 164 g/(g·h) polyethylene having a melt index (IR) of 0.17 and a melt index under high load (IRWN) 4.02 and attitude IRWIN/IL 23,6. The results are presented in table XI.

EXAMPLE 75

Impregnated with a solution of 5.0 g of the pentahydrate of copper sulfate in 50 ml of deionized water, 20 g of a source of aluminum oxide Ketjen brand C. the Sample is dried in vacuum at 100°during the night, sieved through a sieve of 100 mesh (197 resp. 50 mm) and calcined at 600°in the fluidized bed in a stream of dry air for 3 hours Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XI.

EXAMPLE 76

Sample 13,35 g of material, which is described above in example 13, again calcined in nitrogen at 600°C. In a stream of nitrogen above the layer of sample injected 3.4 ml of carbon tetrachloride, which ispar what is and passes through the layer of the sample, where it reacts. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XI.

EXAMPLE 77

Sample 9.0 g of aluminum oxide Ketjen brand In pre-calcined in air flow at 600°C for 3 h, and then impregnated with a solution of 4.77 g of anhydrous trichloride gallium dissolved in 24 ml of carbon tetrachloride. The solvent is evaporated in a stream of nitrogen on a hot tile. The sample was then 12,74 g of this material was again calcined in air at a temperature of 600°C for 3 h to transform a large part of gallium chloride in a mixed oxide. Then the gas flow of the air is replaced by nitrogen, and the top of the sample injected 3.4 ml of carbon tetrachloride, which evaporates and passes through the aluminium oxide layer where it reacts to re-gloriavale surface. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XII.

EXAMPLES 78 AND 79

A sample of aluminum oxide Ketjen marks (50.0 g) is impregnated with a solution of 25 ml of liquid tin tetrachloride in 50 ml of heptane. The sample is heated and emits gaseous hydrogen chloride, indicating some interaction with structural moisture. The sample was then dried in vacuum at pace is the atur 100° With during the night, sieved through a sieve with 69 resp. 50 mm, Then some of this material again calcined in a stream of dry air at 600°C for 3 h, in order to make some tin chloride in the mixed oxide. Then 4.9 g of this material is calcined in a stream of nitrogen at 600°that is injected 1 ml of carbon tetrachloride, in order to re-gloriavale surface. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. In one experiment this material gives 202 g of polyethylene having a melt index of 0.16, the melt index under high load 3.27 and attitude IRWIN/IL 20,7, srednevekovaja molecular mass Mw=174,000 sq, srednekislye molecular mass Mn=57500 and the ratio of Mw/Mn3,1. The results are presented in table XII.

EXAMPLE 80

Impregnated with a solution of 6.0 g of silver nitrate in 60 ml of deionized water sample 30.0 g of aluminum oxide Ketjen brand C. the sample was Then dried in a vacuum at a temperature of 100°during the night and sieved 69 resp. 50 mm, Then part (12,6 g) of this material is calcined in a stream of dry air at 600°C for 3 h in order to convert the silver particles in the mixed oxide. Then the gas flow of the air is replaced by nitrogen and injected 1.9 ml of carbon tetrachloride to gloriavale surface is here at 600° C. Then the material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XII.

EXAMPLE 81

Impregnated with a solution of 9.0 g of pentaoxide niobium in 40 ml of isopropyl alcohol sample of 20.0 g of aluminum oxide Ketjen brand C. the sample was Then dried in a vacuum at a temperature of 100°during the night and sieved 69 resp. 50 mm, Then part (for 10.68 g) of this material is calcined in a stream of dry air at 600°C for 3 h, in order to make the particles of niobium in the mixed oxide. Then the gas flow of the air is replaced by nitrogen and injected 1.6 ml of carbon tetrachloride to gloriavale surface at 600°C. Then the material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XII.

EXAMPLE 82

To 20 g of a 50%solution dinitrate manganese in the water, add 35 ml of deionized water. Then impregnated with this solution the sample (20,0 g) of aluminum oxide Ketjen brand C. the sample was Then dried in a vacuum at a temperature of 100°during the night and sieved 69 resp. 50 mm, Then part (being 9.61 g) of this material is calcined in a stream of dry air at 600°C for 4 h, in order to make the particles of manganese in the mixed oxide. Then the gas flow of the air is replaced by nitrogen and the lead of 2.3 ml of carbon tetrachloride, to gloriavale surface at 600°C. Then the material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XII.

EXAMPLE 83

Impregnated with a solution of 20.0 g of metavolume of ammonia in 100 ml deionized water 50.0 g sample of aluminum oxide Ketjen brand C. the sample was Then dried in a vacuum at a temperature of 100°during the night and sieved 69 resp./50 mm, Then part (15,43 g) of this material is calcined in a stream of dry air at 600°C for 3 h, in order to make the tungsten particles in the mixed oxide. Then the gas flow of the air is replaced by nitrogen and injected 2.35 ml of carbon tetrachloride to gloriavale surface at 600°C. Then the material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XII.

EXAMPLE 84 Impregnated with a solution of 25.0 g of uranyl trinitrate lanthanum in 100 ml of deionized water 50.0 g sample of aluminum oxide Ketjen brand C. the sample was Then dried in a vacuum at a temperature of 100°during the night and sieved 69 resp./50 mm, Then part (9,38 g) of this material is calcined in a stream of dry air at 600°C for 3 h, in order to make the particles of lanthanum in the mixed oxide. Then the gas flow of the air is replaced by the OST and injected 2.4 ml of carbon tetrachloride, to gloriavale surface at 600°C. Then the material is stored in a dried nitrogen and subsequently determine its activity during polymerization, thus receive the 94.5 g of polyethylene having a melt index of 0.14, the melt index under high load 2,43 and attitude IRWIN/IL 17,6. The results are presented in table XII.

EXAMPLE 85

Impregnated with a solution 7,29 g of uranyl trichloride neodymium in 35 ml of deionized water sample 23,53 g of aluminum oxide Ketjen brand C. the sample was Then dried in a vacuum at a temperature of 100°during the night, sieved 197 resp./50 mm, Then part of this material is calcined in a stream of dry air at 600°C for 3 h, in order to make the particles of neodymium in the mixed oxide. Then 10.2 g of this material was again heated in a stream of nitrogen to 600°and injected With 2.5 ml of carbon tetrachloride to gloriavale surface at 600°C. Then the material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XII.

COMPARATIVE EXAMPLE 86

Sample 2.9 g of aluminum oxide Ketjen brand In pre-calcined in a stream of dry air at 600°C for 3 h, moisturize 7.5 ml of dichloromethane. Then added to 2.9 ml of 1-molar solution pentachloride antimony in dichloromethane, to obtain a suspension. The ZAT the solvent is evaporated in a stream of nitrogen on a hot tile. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XII.

EXAMPLE 87

Calcined in a stream of dry air at 600°C for 3 h sample 1.55 g of the material from example 23, in order to make some particles of antimony mixed oxide. Then the gas flow of the air is replaced by nitrogen and injected with 0.4 ml of carbon tetrachloride, to re-gloriavale surface at 600°C. Then the material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XII.

COMPARATIVE EXAMPLE 88

Aluminum oxide Ketjen brand In calcined in a stream of dry air at 600°C for 3 hours Then 10,42 g of this material was again calcined in a stream of nitrogen at 600°C. In the flow of injected 2,6 ml of carbon tetrachloride to gloriavale surface. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. Obtain 280 g of polyethylene having a density 0,9410, the melt index of 0.61, the melt index under high load 9,87 and attitude IRWIN/IL of 16.2. The results are presented in table XIII.

COMPARATIVE EXAMPLE 89

Sample 4.5 g of aluminum oxide Ketjen brand In pre-calcined in a stream of dry air at 600°in accordance With the s 3 h, suspended in a solution of 0.5 g of byflorida of ammonia in 30 ml of methanol. Then the solvent is evaporated in a stream of nitrogen on a hot tile. The obtained solid is then calcined for 2 hours in a stream of nitrogen at 500°C. Then the material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XIII.

EXAMPLE 90

Prepare a solution of 2.0 g of zinc dichloride in 40 ml of deionized water. To dissolve all the zinc you need to add a few drops of nitric acid. Then this solution is impregnated with a sample of 10 g of alumina Ketjen mark C. are Thus obtained alumina containing 20% damage of zinc chloride. The sample was then dried in a vacuum at a temperature of 100°during the night and sieved 197 resp./50 mm, Then part of this material is calcined in a stream of dry air at 600°C for 3 h, in order to make the particles of zinc mixed oxide. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XIII.

EXAMPLE 91

Prepare a solution of 1.9 g of zinc chloride in 35 ml of deionized water. To dissolve all the zinc you need to add a few drops of nitric acid. Then this solution impregnated sample 18,35 g of aluminum oxide Ketjen brand Century. Still the way have the aluminum oxide, containing 10% damage of zinc chloride. The sample was then dried in a vacuum at a temperature of 100°during the night and sieved 197 resp./50 mm, Then part of this material is calcined in a stream of dry air at 600°C for 3 h, in order to make the particles of zinc mixed oxide. Then 11,37 g of this material was again calcined in a stream of nitrogen at 600°and in the stream at this temperature enter to 2.85 ml of carbon tetrachloride to gloriavale surface. It was found that this material has a pore volume of 0.90 ml/g and surface area of 248 square meters per gram. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. This material was obtained 158 g of polyethylene having a density 0,9406. The results are presented in table XIII.

EXAMPLE 92

Prepare a solution 34,65 g of zinc chloride in 435 ml of deionized water and 2.5 ml of nitric acid; then this solution impregnated sample 170,35 g of aluminum oxide Ketjen mark C. are Thus obtained alumina containing 20% damage of zinc chloride. The sample was then dried in a vacuum at a temperature of 100°during the night and sieved 158 resp./50 mm, Then part of this material is calcined in a stream of dry air at 600°C for 3 h, in order to make the particles of zinc mixed oxide. Then 25,96 g this is about material again calcined in a stream of nitrogen at 600° With and in flow at this temperature is injected 2.4 ml of carbon tetrachloride to gloriavale surface. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XIII.

EXAMPLE 93

Prepare a solution 13,03 g of zinc chloride in 100 ml of deionized water and a few drops of nitric acid; then impregnated with this solution 64,84 g of aluminum oxide Ketjen mark C. are Thus obtained alumina containing 20% damage of zinc chloride. The sample was then dried in a vacuum at a temperature of 100°during the night and sieved 197 resp./50 mm, Then part of this material is calcined in a stream of dry air at 600°C for 3 h, in order to make the particles of zinc mixed oxide. Then 35,94 g of this material was again calcined in a stream of nitrogen at 600°and at this temperature the flow of injected 5.5 ml of carbon tetrachloride to gloriavale surface. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XIII.

EXAMPLE 94

Prepare a solution of 7.3 g of zinc chloride in 43 ml of deionized water with a few drops of nitric acid, and this solution impregnated sample 17,24 g of aluminum oxide Ketjen brand Century. Thus receive the alumina, containing 40% damage of zinc chloride. The sample was then dried in a vacuum at a temperature of 80°during the night and sieved 197 resp./50 mm, Then part of this material is calcined in a stream of dry air at 600°C for 3 h, in order to make the particles of zinc mixed oxide. Then 12,47 g of this material was again heated in a stream of nitrogen to 600°and in the stream at this temperature, injected with 3.1 ml of carbon tetrachloride to gloriavale surface. It was found that this material has a pore volume of 0.89 ml/g and surface area of 217 square meters per gram. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. This material was obtained 157,8 g of polyethylene having a melt index 0,69 and the melt index under high load 11.4%, against IRWIN/IL of 16.5. The results are presented in table XIII.

COMPARATIVE EXAMPLE 95

Prepare a solution of 4.0 g of zinc chloride in 50 ml of deionized water with a few drops of nitric acid; and the solution is impregnated with a sample of 20.0 g of silicon dioxide W.R. Grace, grade 952. Thus obtained silicon dioxide containing 20% damage of zinc chloride. The sample was then dried in a vacuum at a temperature of 100°during the night and sieved 197 resp./50 mm, Then part of this material is calcined in a stream of dry who the ear at 600° C for 3 h, in order to make the particles of zinc mixed oxide. Then 19,08 g of this material was again calcined in a stream of nitrogen at 600°and in the stream at this temperature is injected 4.8 ml of carbon tetrachloride to gloriavale surface. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. The results are presented in table XIII.

EXAMPLE 96

Part of the material obtained in example 28, calcined in a stream of dry air at 600°C for 3 h, in order to make the particles of zinc mixed oxide. Then, 4.4 g of this material was again heated in a stream of air up to 600°and in the stream at this temperature enter to 2.9 ml of perftorgeksan to fluoridate the surface. Then this material is stored in a dried nitrogen and subsequently determine its activity during polymerization. This material was obtained 124,5 g of polyethylene having a melt index of 0.99 and a melt index under high load of 16.5, attitude IRWIN/IL 16.5 and density 0,9408. The results are presented in table XIII.

EXAMPLE 97

3.0 g portion of the material obtained in example 34, calcined in a stream of dry nitrogen at 600°and in the flow of injected 0.75 ml of carbon tetrachloride is still at 600°to gloriavale surface. Then this material is stored in a dried nitrogen and subsequently determine e what about the activity during polymerization. This material was obtained and 68.5 g of polyethylene having a melt index of 0.54 and a melt index under high load 9,2, attitude IRWIN/IL 17.0% and the density 0,9401. The results are presented in table XIII.

1. The method for the catalytic composition for the polymerization of monomers, which comprises contacting at least one organometal compound, at least one treated solid oxide compound and at least one alyuminiiorganicheskikh connection with the formation of this composition, in which the ORGANOMETALLIC compound has the following General formula:

(X1) (X2) (X3) (X4) M1,

in which M1represents titanium, zirconium or hafnium,

(X1) independently represents a radical group OMC-I, which is a cyclopentadienyl, indenolol, fluorenyl, substituted cyclopentadienyl, substituted indenial or substituted by fluorenyl and in which each Deputy with a substituted cyclopentadienyl, substituted indenyl or substituted fluorenyl represents an aliphatic group, cyclic group, a combination of aliphatic and cyclic groups, an ORGANOMETALLIC group is either a hydrogen atom;

(X3) and (X4) independently represent a radical of the group OMC-II, which represents a halide, an aliphatic group, cyclic group, a combination of aliphatic and cyclic groups, or ORGANOMETALLIC group;

(X2is a radical group OMC-I, or a radical of the group OMC-II;

in which alyuminiiorganicheskikh compound has the following General formula:

Al(X5)n(X6)3-n,

in which (X5) represents a hydrocarbon radical containing from 1 to 20 carbon atoms,

(X6is a halide, hydride, or alkoxide;

"n" is an integer from 1 to 3 inclusive, and

in which the treated solid oxide compound is produced by contacting at least one solid oxide compound with at least one compound having electron-withdrawing anion;

in which at least one solid oxide compound calicivirus before, during or after contact with the compound having electron-withdrawing anion;

in which the activity of the composition above 250 g of polyethylene per 1 g of treated solid oxide compound per hour and

with virtually no alumoxane and organoborate.

2. The method according to claim 1, on the expectation by basically contacting the ORGANOMETALLIC compounds, the treated solid oxide compound and alyuminiiorganicheskikh connection with the formation of the composition.

3. The method according to claim 1, comprising mainly contacting the ORGANOMETALLIC compound and the treated solid oxide compound with the formation of the composition.

4. The method according to claim 1, wherein contacting at least one solid oxide compound with at least one compound having electron-withdrawing anion, is carried out in the presence of at least one compound metal salt.

5. The method according to claim 1, wherein receiving the treated solid oxide compound further includes calcining the product of contacting at least one solid oxide compound and at least one compound having electron-withdrawing anion.

6. The method according to claim 1, wherein the treated solid oxide compound is produced by simultaneously contacting and calcination, at least one solid oxide compound with at least one compound having electron-withdrawing anion.

7. The method according to claim 1, wherein the solid oxide compound is in contact with two or more compounds having electron-withdrawing anion, two or more separate stages of contact.

8. The method according to claim 1, in which compositeimage to polimerizuet ethylene in the polymer with activity, more than 100 (se/(GT·h)); and in which the treated solid oxide compound containing oxygen and at least one element from the group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the Periodic table, including the lanthanides and actinides.

9. The method according to claim 1, wherein the catalytic composition has an activity greater than 500 se/(GT·h).

10. The method according to claim 1, wherein the catalytic composition has an activity greater than 1000 se/(GT·h).

11. The method according to claim 1, wherein the catalytic composition has an activity greater than 2000 se/(GT·h).

12. The method according to claim 1, in which the ORGANOMETALLIC compound is a dichloride, bis(cyclopentadienyl)-hafnium, dichloride, bis(cyclopentadienyl)zirconium dichloride [ethyl(indenyl)2]hafnium, dichloride [ethyl(indenyl)2]zirconium dichloride [ethyl(tetrahydroindene)2]hafnium, dichloride [ethyl(tetrahydroindene)2]zirconium dichloride, bis(n-butyl cyclopentadienyl)hafnium, dichloride, bis(n-butylcyclopentadienyl)-zirconium dichloride ((dimethyl)(vindenes)silane)zirconium dichloride ((dimethyl)(vindenes)silane)hafnium, dichloride ((dimethyl)(datatravelermini)silane)zirconium dichloride ((dimethyl)(di(2-methylindenyl))silane)zirconium, or dichloride, bis(fluorenyl)zirconium; in which alyuminiiorganicheskikh connection is a trimethylaluminum, triethylaluminum, Tripropylamine, ditillo initated, tributylamine, triisobutyl-aluminiumhydride, triisobutylaluminum or diethylaluminium and in which the solid oxide compound is an Al2O3In2About3, EEO, Bi2O3, CdO, Co3O4, CR2O3, CuO, Fe2O3, Ga2O3, La2About3, MP2O3Moo3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2V2O5WO3, Y2About3, ZnO, ZrO2or a mixture of any two or more solid oxide compounds, in which the treated solid oxide treated with fluoride or chloride, or both.

13. The method according to claim 1, wherein the compound having electron-withdrawing anion, selected from sulfates, halides or triftormetilfullerenov.

14. The method according to claim 1, wherein the calcination is carried out for a time from about 1 hour to about 10 hours at a temperature in the range from about 400 to about 800°C.

15. The method according to claim 1, wherein the treated solid oxide compound is produced by way, including

1) contacting the solid oxide compound with at least one compound having electron-withdrawing anion, with the formation of the first mixture and

2) calcining the first mixture with the formation of the treated solid oxide compound.

16. Ways who according to claim 1, in which the treated solid oxide compound is produced by way, including

1) contacting at least one solid oxide compound with a first compound having electron-withdrawing anion, with the formation of the first mixture and

2) calcining the first mixture with the formation of the calcined first mixture;

3) contacting the calcined first mixture with a second compound having electron-withdrawing anion, with the formation of the second mixture and

4) calcining the second mixture with the formation of the treated solid oxide compound.

17. The method according to claim 1, wherein the composition is produced by way, including

1) contacting the ORGANOMETALLIC compound with the treated solid oxide compound in a period of time from about 1 minute to about 1 hour at a temperature in the range from about 25 to about 100°with the formation of the first mixture,

2) contacting the first mixture with alyuminiiorganicheskikh connection with obtaining the composition.

18. The method for the catalytic composition for the polymerization of monomers, which comprises contacting at least one organometal compound, at least one treated solid oxide compound and at least one alyuminiiorganicheskikh connection with the education of the composition, in which the ORGANOMETALLIC compound has the following General formula:

(X1) (X2) (X3) (X4) M1,

in which M1represents titanium, zirconium or hafnium,

(X1) independently represents a radical group OMC-I, which is a cyclopentadienyl, indenolol, fluorenyl, substituted cyclopentadienyl, substituted indenial or substituted by fluorenyl and in which each Deputy with a substituted cyclopentadienyl, substituted indenyl or substituted fluorenyl represents an aliphatic group, cyclic group, a combination of aliphatic and cyclic groups, an ORGANOMETALLIC group, or a hydrogen atom;

(X3) and (X4) independently represent a radical of the group OMC-II, which represents a halide, an aliphatic group, cyclic group, a combination of aliphatic and cyclic groups, or ORGANOMETALLIC group;

(X2is a radical group OMC-I or radical group OMC-II;

in which alyuminiiorganicheskikh compound has the following General formula:

Al(X5)n(X6)3-n,

in which (X5) represents a hydrocarbon radical containing from 1 to 20 carbon atoms,

(X6is a halide, Geri is or alkoxide;

"n" is an integer from 1 to 3 inclusive, and

in which the treated solid oxide compound is produced by contacting at least one solid oxide compound with at least one compound having electron-withdrawing anion;

in which at least one solid oxide compound calicivirus before, during or after contact with the compound having electron-withdrawing anion; and

with virtually no alumoxane and organoborate.

19. The method according to p, mainly comprising contacting the organometal compound, the treated solid oxide compound and alyuminiiorganicheskikh connection with the formation of the composition.

20. The method according to p, mainly comprising contacting the ORGANOMETALLIC compound and the treated solid oxide compound with the formation of the composition.

21. The method according to p, in which the contacting at least one solid oxide compound with at least one compound having electron-withdrawing anion, is carried out in the presence of at least one compound metal salt.

22. The method according to p, in which receiving the treated solid oxide compound further includes calcining the product contact, IU the greater extent, one solid oxide compound and at least one compound having electron-withdrawing anion.

23. The method according to p, in which the treated solid oxide compound is produced by simultaneously contacting and calcination, at least one solid oxide compound with at least one compound having electron-withdrawing anion.

24. The method according to p, in which the solid oxide compound is in contact with two or more compounds having electron-withdrawing anion, two or more separate stages of contact.

25. The method according to p, in which the composition may polimerizuet ethylene in the polymer with activity greater than 100 (se/(GT·h)); and in which the treated solid oxide compound containing oxygen and at least one element from the group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the Periodic table, including the lanthanides and actinides.

26. The method according to p, in which the catalytic composition has an activity higher than 250 se/(GT·h).

27. The method according to p, in which the catalytic composition has an activity greater than 500 se/(GT·h).

28. The method according to p, in which the catalytic composition has an activity greater than 1000 se/(GT·h).

29. The method according to p, in which the catalytic composition has an activity greater than 2000 se/(GT·h).

30. The method according to p, corometrics connection represents dichloride, bis(cyclopentadienyl)-hafnium, dichloride, bis(cyclopentadienyl)zirconium dichloride [ethyl(indenyl)2]hafnium, dichloride [ethyl(indenyl)2]zirconium dichloride [ethyl(tetrahydroindene)2]hafnium, dichloride [ethyl(tetrahydroindene)2]zirconium dichloride, bis (n-butyl cyclopentadienyl)hafnium, dichloride, bis(n-butylcyclopentadienyl)-zirconium dichloride ((dimethyl)(vindenes)silane)zirconium dichloride ((dimethyl)(vindenes)silane)hafnium, dichloride ((dimethyl) (datatravelermini)silane) zirconium dichloride ((dimethyl)(di(2-methylindenyl))silane)zirconium or dichloride, bis(fluorenyl)zirconium;

in which alyuminiiorganicheskikh connection is a trimethylaluminum, triethylaluminum, Tripropylamine, diethylaminoethoxy, tributylamine, triisobutyl-aluminiumhydride, triisobutylaluminum or diethylaluminium; and

in which the solid oxide compound is an Al2O3In2O3, BeO, Bi2O3, CdO, Co3O4, CR2O3, CuO, Fe2O3, GA2O3, La2O3, MP2O3Moo3, NiO, R2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2V2O5WO3, Y2O3, ZnO, ZrO2or a mixture of any two or more solid oxide compounds, in which the treated solid oxide treated CFT the reed, or chloride, or both.

31. The method according to p, in which the compound having electron-withdrawing anion, selected from sulfates, halides or triftormetilfullerenov.

32. The method according to p, in which the calcination is carried out for a time from about 1 hour to about 10 hours at a temperature in the range from about 400 to about 800°C.

33. The method according to p, in which the treated solid oxide compound is produced by way, including

1) contacting the solid oxide compound with at least one compound having electron-withdrawing anion, with the formation of the first mixture and

2) calcining the first mixture with the formation of the treated solid oxide compound.

34. The method according to p, in which the treated solid oxide compound is produced by way, including

1) contacting at least one solid oxide compound with a first compound having electron-withdrawing anion, with the formation of the first mixture and

2) calcining the first mixture with the formation of the calcined first mixture;

3) contacting the calcined first mixture with a second compound having electron-withdrawing anion, with the formation of the second mixture and

4) calcining the second mixture with the formation of the treated solid oxide compounds the Oia.

35. The method according to p, in which a composition obtained by the method, including

1) contacting the ORGANOMETALLIC compound with the treated solid oxide compound in a period of time from about 1 minute to about 1 hour at a temperature in the range from about 25 to about 100°with the formation of the first mixture,

2) contacting the first mixture with alyuminiiorganicheskikh connection with obtaining the composition.

36. The method for the catalytic composition for the polymerization of monomers, which comprises contacting at least one organometal compound, at least one treated solid oxide compound and at least one alyuminiiorganicheskikh connection with the formation of the composition, in which the ORGANOMETALLIC compound has the following General formula:

(X1) (X2) (X3) (X4) M1,

in which M1represents titanium, zirconium or hafnium,

(X1) independently represents a radical group OMC-I, which is a cyclopentadienyl, indenolol, fluorenyl, substituted cyclopentadienyl, substituted indenial or substituted by fluorenyl and in which each Deputy with a substituted cyclopentadienyl, substituted indenyl or substituted fluorenyl represents an aliphatic GRU is PU, cyclic group, a combination of aliphatic and cyclic groups, an ORGANOMETALLIC group, or a hydrogen atom;

(X3) and (X4) independently represent a radical of the group OMC-II, which represents a halide, an aliphatic group, cyclic group, a combination of aliphatic and cyclic groups, or ORGANOMETALLIC group;

(X2is a radical group OMC-I or radical group OMC-II,

in which alyuminiiorganicheskikh compound has the following General formula:

Al(X5)n(X6)3-n,

in which (X5) represents a hydrocarbon radical containing from 1 to 20 carbon atoms,

(X6is a halide, hydride, or alkoxide;

"n" is an integer from 1 to 3 inclusive; and

in which the treated solid oxide compound comprises calcined product contacting at least one solid oxide compound with at least one compound having electron-withdrawing anion.

37. The method according to p, mainly comprising contacting the organometal compound, the treated solid oxide compound and alyuminiiorganicheskikh connection with the formation of the composition.

38. The method according to p, comprising mainly of kontaktierung the ORGANOMETALLIC compound and the treated solid oxide compound with the formation of the composition.

39. The method according to p, in which the treated solid oxide compound is produced by simultaneously contacting and calcination, at least one solid oxide compound with at least one compound having electron-withdrawing anion.

40. The method according to p, in which the composition may polimerizuet ethylene in the polymer with activity greater than 100 (se/(GT·h)); and in which the treated solid oxide compound containing oxygen and at least one element from the group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the Periodic table, including the lanthanides and actinides.

41. The method according to p, in which the catalytic composition has an activity higher than 250 se/(GT·h).

42. The method according to p, in which the catalytic composition has an activity greater than 500 se/(GT·h).

43. The method according to p, in which the catalytic composition has an activity greater than 1000 se/(GT·h).

44. The method according to p, in which the catalytic composition has an activity greater than 2000 se/(GT·h).

45. The method according to p, in which the ORGANOMETALLIC compound is a dichloride, bis(cyclopentadienyl)hafnium, dichloride, bis(cyclopentadienyl)zirconium dichloride [ethyl(indenyl)2]hafnium, dichloride [ethyl(indenyl)2]zirconium dichloride [ethyl(tetrahydroindene)2]hafnium, dichloride [ethyl(tetrahydroindene)2]zirconium dichloride, bis(n-butyl cyclopentadienyl)hafnium, dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride ((dimethyl)(vindenes)silane)zirconium dichloride ((dimethyl)(vindenes)silane)hafnium, dichloride ((dimethyl)(datatravelermini)silane)zirconium dichloride ((dimethyl)(di(2-methylindenyl))silane)zirconium or dichloride, bis(fluorenyl)zirconium;

in which alyuminiiorganicheskikh connection is a trimethylaluminum, triethylaluminum, Tripropylamine, diethylaminoethoxy, tributylamine, triisobutyl-aluminiumhydride, triisobutylaluminum or diethylaluminium; and

in which the solid oxide compound is an Al2About3In2About3, EEO, Bi2O3, CdO, Co3O4, CR2O3, CuO, Fe2About3, Ga2O3, La2About3, MP2About3Moo3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2V2O5WO3, Y2About3, ZnO, ZrO2or a mixture of any two or more solid oxide compounds, in which the treated solid oxide treated with fluoride or chloride, or both.

46. The method according to p, in which the compound having electron-withdrawing anion, selected from sulfates, halides or triftormetilfullerenov.

47. The method according to p, in which a composition obtained by the method, including

1) contact is the formation of ORGANOMETALLIC compounds from the treated solid oxide compound in a period of time from about 1 minute to about 1 hour at a temperature in the range from about 25 to about 100° With the formation of the first mixture,

2) contacting the first mixture with alyuminiiorganicheskikh connection with obtaining the composition.

48. The method for the catalytic composition for the polymerization of monomers, which comprises contacting at least one organometal compound, at least one treated solid oxide compound and at least one alyuminiiorganicheskikh connection with the formation of the composition, in which the ORGANOMETALLIC compound has the following General formula:

(X1) (X2) (X3) (X4) M1,

in which M1represents titanium, zirconium or hafnium,

(X1) independently represents a radical group OMC-I, which is a cyclopentadienyl, indenolol, fluorenyl, substituted cyclopentadienyl, substituted indenial or substituted by fluorenyl and in which each Deputy with a substituted cyclopentadienyl, substituted indenyl or substituted fluorenyl represents an aliphatic group, cyclic group, a combination of the aforementioned aliphatic and cyclic groups, an ORGANOMETALLIC group, or a hydrogen atom;

(X3) and (X4) independently represent a radical of the group OMS-II, which represents a halide, an aliphatic group, C is Klionsky group, a combination of aliphatic and cyclic groups, or ORGANOMETALLIC group;

(X2is a radical group OMC-I or radical group OMC-II;

in which alyuminiiorganicheskikh compound has the following General formula:

Al(X5)n(X6)3-n,

in which (X5) represents a hydrocarbon radical containing from 1 to 20 carbon atoms,

(X6is a halide, hydride, or alkoxide;

"n" is an integer from 1 to 3 inclusive; and

in which the treated solid oxide compound comprises at least one electron-withdrawing solid oxide compound with high acidity as acid Lewis.

49. The method according to p, mainly comprising contacting the organometal compound, the treated solid oxide compound and alyuminiiorganicheskikh connection with the formation of the composition.

50. The method according to p, mainly comprising contacting the ORGANOMETALLIC compound and the treated solid oxide compound with the formation of the composition.

51. The method according to p, in which the composition may polimerizuet ethylene in the polymer with activity greater than 100 (se/(GT·h)); and in which the treated solid oxide compounds contain oxygen and, at IU is e, one element from the group 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the periodic table, including the lanthanides and actinides.

52. The method according to p, in which the catalytic composition has an activity higher than 250 se/(GT·h).

53. The method according to p, in which the catalytic composition has an activity greater than 500 se/(GT·h).

54. The method according to p, in which the catalytic composition has an activity greater than 1000 se/(GT·h).

55. The method according to p, in which the catalytic composition has an activity greater than 2000 se/(GT·h).

56. The method according to p, in which the ORGANOMETALLIC compound is a dichloride, bis(cyclopentadienyl)hafnium, dichloride, bis(cyclopentadienyl)zirconium dichloride [ethyl(indenyl)2]hafnium, dichloride [ethyl(indenyl)2]zirconium dichloride [ethyl(tetrahydroindene)2]hafnium, dichloride [ethyl(tetrahydroindene)2]zirconium dichloride, bis(n-butyl cyclopentadienyl)hafnium, dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride ((dimethyl)(vindenes)silane)zirconium dichloride ((dimethyl)(vindenes)silane)hafnium, dichloride ((dimethyl)(datatravelermini)silane)zirconium dichloride ((dimethyl)(di (2-methylindenyl))silane)zirconium or dichloride, bis(fluorenyl)zirconium;

in which alyuminiiorganicheskikh connection is a trimethylaluminum, triethylaluminum, Tripropylamine, diethylaminoethoxy,tributylamine, triisobutylaluminum, triisobutylaluminum or diethylaluminium; and

in which the solid oxide compound is an Al2O3In2About3, BeO, Bi2O3, CdO, Co3O4, CR2About3, CuO, Fe2O3, Ga2About3La2O3, MP2O3Moo3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2V2O5WO3, Y2About3, ZnO, ZrO2or a mixture of any two or more solid oxide compounds, in which the treated solid oxide treated with fluoride or chloride, or both.

57. The method according to p, in which a composition obtained by the method, including

1) contacting the ORGANOMETALLIC compound with the treated solid oxide compound in a period of time from about 1 minute to about 1 hour at a temperature in the range from about 25 to about 100°with the formation of the first mixture,

2) contacting the first mixture with alyuminiiorganicheskikh connection with obtaining the composition.

58. The method for the catalytic composition, including

1) calcining the alumina for about 3 hours at about 600°obtaining calcined alumina;

2) contacting the calcined alumina with carbon tetrachloride is getting chlorinated aluminum oxide;

3) the connection of chlorinated alumina with dichloride bis(n-butylcyclopentadienyl)of zirconium in the course of time from about 1 minute to about 1 hour at a temperature in the range from about 25 to about 100°with the formation of the mixture; and

4) mix the mixture with triethylaluminium with obtaining a composition.

59. The catalytic composition obtained according to the method according to any one of claims 1 to 58.

60. The method of polymerization of a monomer which comprises contacting at least one monomer in the polymerization conditions with a catalytic composition according p with the formation of the polymer.

61. The method according to p carried out in conditions of suspension polymerization.

62. The method according to p, in which the above polymerization is carried out in a loop reactor.

63. The method according to p or 62 in which the above polymerization is carried out in the presence of a diluent containing isobutane.

64. The method according to p, in which the polymer is formed into a product.

65. The method according to p in which the specified molded product is part of the device.

66. The method according to claim 2 to 8, 19-24, 37-39, 49 or 50, in which the composition may polimerizuet ethylene in the polymer with activity greater than 100 (se/(GT·h)); and in which the treated solid oxide compound containing oxygen and at least one element from the group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the Periodic table is s, including the lanthanides and actinides.

67. The method according to claim 2 to 8, 19-25, 37-40 or 49-51, in which the catalytic composition has an activity higher than 250 se/(GT·h).

68. The method according to claim 2 to 8, 19-26, 37-41 or 49-52, in which the catalytic composition has an activity greater than 500 se/(GT·h).

69. The method according to claim 2 to 9, 19-27, 37-42 or 49-53, in which the catalytic composition has an activity greater than 1000 se/(GT·h).

70. The method according to claim 2 to 10, 19-28, 37-43 or 49-54, in which the catalytic composition has an activity greater than 2000 se/(GT·h).

71. The method according to subparagraph 5, 6, 22, 23 or 39, in which the calcination is carried out for a time from about 1 hour to about 10 hours at a temperature in the range from about 400 to about 800°C.



 

Same patents:

FIELD: polymer production.

SUBSTANCE: invention provides homogenous catalytic system for synthesis of copolymers and terpolymers of olefinic monomers, which system contains dialkyl bridge-type bis(indenyl)metallocene complexes with group IVB metals and trialkylaluminum at Al-to-metal ratio between 50 and 500. Catalytic system enables carrying out polymerization process at rates significantly exceeding ethylene or propylene homopolymerization rate.

EFFECT: significantly accelerated copolymerization process and achieved fractional and compositional homogeneity of ethylene/α-olefin and propylene/α-olefin copolymers.

1 tbl, 16 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalyst is prepared by mixing hydrocarbon solutions of titanium tetrachloride, triisobutylaluminum-diphenyl oxide complex, and 1,3-pentadiene at Al/Ti molar ratio from 0.9:1 to 1.2:1 and at temperature form -70 to +20°C, after which mixture of paraffin, aromatic, and naphthene hydrocarbons is added, in particular industrial or transformer oil in amount 0.05 to 2% on the weight of catalyst suspension.

EFFECT: increased catalytic activity and reduced dosage of catalyst in polymerization process, which allows production of rubber with reduced titanium compound level without increasing intensity of washing away titanium compounds.

2 cl, 1 tbl, 11 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

The invention relates to methods of producing high molecular weight polymers-olefins, soluble in hydrocarbon liquids, and can be used to increase throughput of oil pipelines and product pipelines

The invention relates to bridged metallocene compounds of formula (I) consisting of indenyl-cyclopentadienyls groups

where R1and R2- H, linear, branched, cycloaliphatic or aromatic hydrocarbon group, C1-C20any pair R3, R4, R5, R6adjacent to each other, connected with the formation of a saturated or unsaturated cyclic structure of C4-C20including communication cyclopentadienyls ring; M is zirconium; X1and X2the anion associated with the metal M, or they are connected to each other by obrazovanie C4-C7cycle

The invention relates to a method for producing a catalytic composition, which is used for polymerization of at least one monomer to obtain a polymer, where the specified catalytic composition is produced by interaction of ORGANOMETALLIC compound, of at least one alumoorganic compounds and fluorinated solid oxide compound that is selected from a silicon oxide - aluminum oxide

The invention relates to a method for producing a catalytic composition, which is used for polymerization of at least one monomer to obtain a polymer, where the specified catalytic composition is produced by interaction of ORGANOMETALLIC compound, of at least one alumoorganic compounds and fluorinated solid oxide compound that is selected from a silicon oxide - titanium oxide or silicon oxide - oxide-zirconium, and boron compounds and alumoxane essentially no

The invention relates to the field of chemical technology

The invention relates to a method for producing a catalytic composition, which is used for polymerization of at least one monomer to obtain a polymer, where the specified catalytic composition is produced by interaction of ORGANOMETALLIC compound, of at least one alumoorganic compounds and fluorinated solid oxide compound that is selected from a silicon oxide - aluminum oxide

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FIELD: olefin polymerization.

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EFFECT: polymers with wide bimodal molecular mass distribution.

14 cl, 3 ex

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