Catalyst component, catalyst precursor, and magnesium halide-based olefin polymerization catalyst

FIELD: polymer production.

SUBSTANCE: invention relates to magnesium halide-based compositions, processes for preparation thereof and catalysts as well as to polymerization processes. Invention provides a component of magnesium halide-based olefin polymerization catalyst prepared from magnesium halide, solvent appropriate as electron donor, and electron-donor compound represented by linear or branched, substituted or unsubstituted aliphatic or aromatic alcohol having 1 to 25 carbon atoms, wherein magnesium halide is characterized by solubility in the solvent exceeds 0.7 mole/L and does fall under effect of increase in temperature up to boiling temperature. Catalyst precursor includes reaction product of the above-defined catalyst component and a second component including transition metal selected from group consisting of titanium, zirconium, hafnium, vanadium, and a combination thereof. Olefin polymerization catalyst disclosed includes reaction product of catalyst precursor with co-catalyst, namely alkylaluminum compound.

EFFECT: increased contend of magnesium in catalyst, increased solubility of catalyst, and reduced expenses on catalyst preparation in case of small amount of charge.

14 cl, 4 dg, 1 tbl

 

The scope of the invention

The present invention relates to compositions based on magnesium halides, the catalysts prepared on their basis, methods of producing compositions based on magnesium halides and the catalysts and methods of polymerization.

Background of invention

Solutions of MgCl2in various electron-donor solvents, as has been used in industry to obtain polymerization catalysts. Often these solutions use ethers, ketones and esters, to obtain the Mg-Ti precursors of the catalyst, which have found wide application in the catalytic polymerization of olefins. Known precursors obtained by dissolving magnesium chloride and titanium chloride in a solvent, followed by evaporation or distillation of the excess solvent. Tetrahydrofuran (THF), as shown, is a particularly suitable solvent due to its ability to coordinate as MgCl2and TiClxand its relatively low boiling point, which facilitates the Stripping and recovery of the solvent. The resulting dried catalyst precursor is treated with a catalyst, typically a connection alkylamine, with the purpose of obtaining a composition which is active when Polimeri the purpose of olefins.

The use of such precursors of catalysts in industrial polymerization processes based on the solubility of the MgCl2in the solvent. The halides of alkaline earth metals are usually insoluble in hydrocarbon solvents. However, the solubility in certain coordinating electron donor solvents may be high enough for industrial applications. For example, the solubility of MgCl2in tetrahydrofuran (THF) increases from approximately 0.2 mol/l at -25°up to about 0.7 mol/l at 30°C. the Number of predecessor, which you can get at one time is limited by the solubility of MgCl2.

It is interesting, however, that at higher temperatures the solubility of MgCl2in such solvents is reduced. For example, if the boiling point of THF (65° (C) the solubility of MgCl2is only about 0.4 mol/l at atmospheric pressure. This decrease in solubility complicates the process of drying the precursor, since removing the solvent by heating is usually carried out most effectively at a temperature close to the boiling temperature of the solvent. To avoid the reduction of concentration of MgCl2in the solution of the precursor to an undesirable level, the drying process is carried out at low temperatures and pressures. Unfortunately, the destruction of races is varicela under such conditions requires more time and is less effective reducing, thus, the performance of the installation.

Reduced solubility MgCl2at elevated temperatures also causes the formation of hard crusts precipitated MgCl2on the walls of the reactor and tubes, when the limits of dissolution at a given temperature is exceeded.

For these reasons, the catalytic system of the predecessor with improved solubility can be used in polymerization processes. Would also be useful ways to increase solubility and profile changes the solubility of the MgCl2as a function of temperature. Consequently, it would be useful components of the catalyst based on magnesium halides, having a higher solubility, or such solubility, which does not decrease with increasing temperature, and methods of using such components of the catalysts, and the catalysts obtained on the basis of them.

Summary of the invention

In some preferred embodiments, the invention provides a method of increasing the solubility of magnesium halides, including: 1) ensuring electron-donor solvent; contacting the magnesium halide with the electron-donor solvent; and 2) providing an electron-donor compound with the aim of obtaining compositions based on magnesium halide, where the composition is characterized by solubility Gal who genid magnesium in a solvent, which is not reduced with increasing temperature up to the boiling point of the solvent.

In other preferred embodiments, features component of the polymerization catalyst comprising a magnesium halide, an electron-donor solvent and an electron-donor substance, the composition is characterized by a solubility in the electron donor solvent, which does not decrease with increasing temperature up to the boiling point of the solvent.

In some other preferred embodiments, we propose a method of preparation of the catalyst. In such preferred embodiments, the method includes obtaining containing magnesium composition, contacting containing magnesium composition with the compound of the transition metal in order to obtain a catalyst precursor, and contacting the catalyst precursor with a co-catalyst. Containing magnesium composition includes a magnesium halide, electron-donor solvent and electron-donor compound, which is characterized by solubility in electron-donor solvent, which does not decrease with increasing temperature up to the boiling point electron-donor solvent.

Some preferred options offer ways to obtain a polymer that includes the interaction of at least one monomer of olei the s in the presence of a catalyst, comprising the reaction product of the following components: containing magnesium composition containing magnesium halide, electron-donor solvent and electron-donor compounds. Containing magnesium composition is characterized by solubility in electron-donor solvent, which does not decrease with increasing temperature up to the boiling point electron-donor solvent. The catalytic composition also includes a compound of a transition metal, where the transition metal is selected from the group including titanium, zirconium, hafnium, vanadium, niobium, tantalum, and combinations thereof, and the composition of the co-catalyst.

In some of the above-described preferred embodiments, the composition for the most part do not contain electron-donor compounds, and the molar ratio of the electron-donor compound and the halide of magnesium is less than or equal to 1.9. In some preferred embodiments, the ratio of the electron donor compound to magnesium halide is less than about 1,75, while in other preferred embodiments, the ratio of the electron donor compound to magnesium halide varies from about 0.1 to less than about 0.5.

In some ways, the precursor of the catalyst, the catalyst components and catalysts described in the present description, the halide of magnesium PR is dstanley a magnesium chloride, the magnesium bromide, magnesium iodide, or combinations thereof. Electron-donor compound may be linear, branched, substituted or unsubstituted aliphatic or aromatic alcohol containing from one to 25 carbon atoms. Examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, 1-dodecanol, cyclohexanol, and di-tert-butylphenol.

The solvent can be selected from the group including alkalemia esters of aliphatic or aromatic carboxylic acids, aliphatic ethers, cyclic ethers, and aliphatic ketones. In some preferred embodiments of the invention the solvent is selected from the group including alkalemia esters of aliphatic and aromatic carboxylic acids, ethers, and aliphatic ketones. Examples alilovic esters suitable as solvents include methyl acetate, ethyl acetate, ethylpropane, methylpropionate, ethylbenzoic and combinations thereof. Ethers suitable for use as a solvent include, but are not limited to, diethyl ether, diisopropyl ether, di-n-butyl ether, ethylisopropylamine ether, methylbutylamine ether, metalalloy ether, ethylenically ether, tetrahydrofuran, 2-methyl-tetrahydrofuran, and combinations thereof. Suitable ketones include the try acetone, methyl ethyl ketone, cyclohexanone, cyclopentylmethyl, 3-bromo-4-heptanone, 2-chlorocyclopentane, allylmercaptan and combinations thereof. Of course, mixed solvents containing a second electron-donor solvent, which is alkilany ester of aliphatic or aromatic carboxylic acids, aliphatic or cyclic simple ether or aliphatic ketone, can be used in some preferred embodiments. In some preferred embodiments described herein, the solubility of the composition based on the magnesium halide in the solvent is higher than about 0.7 mol/L.

In some examples, the magnesium halide is a chloride of magnesium, the alcohol is an ethanol or isopropanol, molar ratio of alcohol to magnesium is from about 0.1 to about 1.1, the solubility of the halide of magnesium or of compositions based on magnesium halide in the solvent is from about 0.8 to 2.5 mol MgCl2/HP

Some preferred options offer component catalyst comprising a composition of the formula

Mg(ED)rCl2[S]q,

where r is greater than 0 and less than 1.9, q is greater than 0 and less than 4.

Some precursors of the catalysts described in the present description, include compositions containing the reaction product or a mixture of magnesium-containing component, the catalysis of the Torah, having such a solubility in a solvent, which does not decrease with increasing temperature up to the boiling point of the solvent, and the second component containing a transition metal selected from the group comprising titanium, zirconium, hafnium, vanadium, niobium, tantalum, and combinations thereof. Some of the typical such second components include at least one compound of titanium of the formula Ti(OR)andXbwhere R†′is an Ror CORwhere R†′represents one of an aliphatic hydrocarbon radical from C1 to C14 or aromatic hydrocarbon radicals from C6 to C14; each X represents a separately Cl, Br or I; and has a value of 0 or 1; b has a value from 2 to 4 inclusive; and a+b is 3 or 4. In some preferred embodiments, at least one compound of titanium include titanium halide, such as, but not limited to, TiCl4, TiCl3or recovered aluminum TiCl3.

In certain preferred embodiments, the composition of the catalyst precursor comprises a composition of the formula

[Mg(ED)r]mTi(OR)nXp[S]q,

where ED includes linear or branched alcohols containing from one to about 25 carbon atoms; X represents a separately Cl, Br or I; S is ybiraut from the group including alkalemia esters of aliphatic or aromatic carboxylic acids, aliphatic ethers, cyclic ethers, and aliphatic ketones; m varies from 0.5 to 56; n is 0, 1, or 2; p varies from 4 to 116; q varies from 2 to 85 and r varies from 0.1 to 1.9.

Some of the preferred options are offered by the catalyst, which is a product of the interaction of the precursor of the catalyst and co-catalyst. Other preferred variants include modification of the catalyst is a Lewis acid. Some suitable Lewis acid have the formula

,

where R*is an R*1or or*1; where R*1is an aliphatic hydrocarbon having from 1 to 14 carbon atoms, or aromatic hydrocarbon radical containing from 6 to 14 carbon atoms; M represents Al or In; X represents Cl, Br or I; and g varies from 0 to 3. Specific examples of Lewis acids on the basis of chlorides include tri-n-hexylamine, triethylamine, diethylaluminium, ethylaminoethanol, trimethylaluminum, dimethylammoniumchloride, methylaluminoxane, triisobutylaluminum, tri-n-butylamine, diisobutylaluminium, sibutraminegeneric, ethoxy dichloride, aluminum, fenilalanina arid and phenoxodiol aluminum. Some examples bromodomain of Lewis acids include diethylaluminium, ethylaluminum, dimethylaminopropyl, methylamine, dibromide, diisobutylaluminium, isobutyleneisoprene, amoxicillingeneric, phenylalaninamide and peroxyacetylnitrate. The Lewis acid on the basis of iodine include diethylaluminium, ethylaminomethyl, trimethylaluminium, methylamine, diiodide, diisobutylaluminium, Isobutyraldehyde, ethoxyaniline, phenylalaninamide and phenoxyalkanoic.

Other suitable Lewis acid include trichloride boron, tribromide boron, activationid, ethoxypropylamine, diethoxymethane, phenylpropionic, phenoxypropionic, diphenoxybenzophenone, (C6H13)BCl2or (C6H13O)BCl2.

Additional suitable Lewis acid or co-catalysts have the formula

AlX'd(R)cHe

where X' represents Cl or or"'; R" and R"' are individually a substituted hydrocarbon radical from C1 to C14; d is 0 to 1.5; f takes on the values 0 or 1; c+d+e is 3. Some examples of such activators include Al(CH3)3, Al(C2H5)3, Al(C2H5)2Cl, Al(i-C4H9)3, Al(C2H5)1,5Cl1,5, Al(i-Csub> 4H9)2H Al(C6H13)3, Al(C8H17)3, Al(C2H5)2H Al(C2H5)2(OS2H5). In some preferred embodiments, one or more activators are present at a ratio of activator: compound of the transition metal, varying from about 1 to about 400 moles of activator per mole of the compound of the transition metal. In some preferred embodiments, the ratio of activator to the amount of the compound of the transition metal is about 4, about 10, about 15, or about 60 moles of activator per mole of the compound of the transition metal.

Some are described in the present description, methods of polymerization to provide a polymer having a density in the range of from 0.88 to 0.98 g/cm3. Some polymers contain ethylene in amounts equal to or greater than about 90 mole percent, and one or more co-monomers in a quantity equal to or less than about 10 molar percent.

Brief description of drawings

Figure 1 shows the dependence of the solubility of the MgCl2for the three preferred variants of the present invention from the content in the alcoholic solution and the solution temperature.

Figure 2 shows the profile of solubility in several preferred embodiments of the present invention depending on the temperature, to the centration MgCl 2and the ratio of alcohol : Mg in THF.

Figure 3 shows the structure of one example of the catalyst component containing a magnesium halide.

Figure 4 shows the results of thermogravimetric analysis (TGA) for the preferred options proposed in the present invention catalyst component.

Description of the preferred embodiments of the invention

Preferred variants of the present invention offer ways to increase the solubility of the halide of magnesium, which includes getting electron-donor solvent, the contacting of the magnesium halide with the solvent and the provision of electron-donor substances, with the aim of obtaining compositions based on magnesium halide, where the composition is soluble in a solvent which does not decrease with increasing temperature up to the boiling point of the solvent. We offer components of the catalyst having a solubility which is not reduced with increasing temperature. Identified preferred variants of the present invention, which offer the precursor of the catalyst comprising the components of the catalyst. Also identified methods of preparing such compounds as polymerization catalysts and methods of polymerization using such catalysts.

Land with an upper limit of RUany number R from the interval drop-down, explained separately. In particular, the following numbers R within the interval describe separately: R=RL+k*(RU-RL), where k represents a variable, varying from 1 to 100% with increment of 1%, that is, k takes on the values 1, 2, 3, 4, 5, ... 50, 51, 52, ... 95, 96, 97, 98, 99 or 100%. Moreover, any numerical interval defined by two numbers, R, as described above, also describe separately.

Any references in this description to "electron-donor compounds" means compounds that alter the solubility of the halide of magnesium in the electron donor solvent so that the solubility decreases in the temperature range up to the boiling point of the electron donor solvent. In the present description, the term "electron-donor compound" does not include "solvents", as defined below, even when such solvents are electron-donor properties. Some examples of electron donor compounds include alcohols, thiols, subdominio amines and phosphines. In the present description, the term "almost nesadurai other electron-donor compounds" means, what other electron-donor compounds"as defined in the present description, are not present in concentrations higher than levels typically found as impurities in such substances supplied as solvent and with the appropriate degree of purity. So composition comprising a solvent having electron-donor properties, and electron-donor substance is considered" practically free of other electron donor compounds". In some preferred embodiments, the "practically free" means less than 1, 0,1, is 0.01 or 0.001 wt.%.

Suitable solvents include any ethers, ketones or esters. If these solvents possess electron-donor properties, any references in this description to "solvent" or "solvent" does not include compounds indicated as "electron-donor substances". So songs that are "almost do not contain electron-donor compounds can include one or more solvents.

In the present description, the term "simple" air " is defined as any substance formula R-O-R', where R and R' represent a substituted or unsubstituted hydrocarbon group. In some cases, R and R' are the same. As examples, not limiting the invention, the symmetric simple EF the market are diethyl ether, diisopropyl ether, and di-n-butyl ether. Examples of unsymmetrical ethers include ethylisopropylamine ether and methylbutanoyl ether. Examples of suitable substituted esters include, for example, metalalloy ether and ethylenically ether. In other preferred embodiments, R and R' may form a condensed ring which may be saturated or unsaturated. One example of such compound is tetrahydrofuran. Other such suitable cyclic ethers are 2-methyltetrahydrofuran. Again it should be emphasized that specifically enumerated substances is provided only as examples of suitable types of compounds; however, any substance having the functional group R-O-R', may be in their place.

In the present description, the term "ketone" refers to any substance having the formula R(C=O)R'. R and R' can be separately substituted or unsubstituted hydrocarbon group as described above in the description of simple esters. Examples of ketones are acetone, methyl ethyl ketone, cyclohexanone and cyclopentylmethyl. Halogenated ketones, such as 3-bromo-4-heptanone or 2-chlorocyclopentane, can also be used. Other suitable ketones may include other functional groups, including unsaturated, as in allylmethylamine. Each of these substance meet yet the formula R(C=O)R', where the carbon atom of the carbonyl group in the molecule forms a connection with two other carbon atoms.

Suitable esters include any compound of General formula R(C=O)OR'. In such compounds the carbon atom of the carbonyl group forms a bond with the carbon atom and another bond with an oxygen atom. R and R' are individually selected from substituted or unsubstituted hydrocarbon groups, they may be the same or different. In some preferred embodiments, esters include alkalemia esters of aliphatic and aromatic carboxylic acids. Cyclic esters, saturated esters and halogenated esters are also included in this group. Do not limit the present invention examples include methyl acetate, ethyl acetate, ethylpropane, methylpropionate and ethylbenzoic. Again it should be emphasized that specifically enumerated substances is provided only as examples of suitable types of compounds; however, any substance having the functional group R(C=O)OR', can be used instead.

Typically, the solvent is present in large excess with respect to the first coordination environment of magnesium. In some preferred embodiments, the ratio of solvent to magnesium is about 100 to 1; in other preferred embodiments of the wear can be even higher. In other preferred embodiments, the solvent is present in a ratio of at least about 1.0, not less than approximately 2,0, not less than about 5.0 and not less than about 10, or at least about 20 moles of solvent per mole of magnesium. In some preferred embodiments, it is possible to use two or more of solvent.

The contacting of the magnesium halide with any suitable solvent, is carried out directly by mixing the magnesium halide and solvent. In some preferred embodiments, the magnesium halide is a chloride of magnesium; however, you can also use magnesium bromide and magnesium iodide. Suitable sources of halides are halides of magnesium, such as MgBr2, MgCl2, MgI, or mixed magnesium halides, such as MgClI, MgClBr and MgBrI. In some preferred embodiments, the halide of magnesium is added to the solvent in anhydrous form. In other preferred embodiments, the halide of magnesium added to the hydrated form.

Electron-donor substance is added to the mixture of solvent and halide of magnesium in whatever way is appropriate. Preferably, the electron-donor compound are added directly to the mixture. In some preferred embodiments, the electron-donor substance is an alcohol, thiol, lobodomy amine or labotomy fo the fin. The alcohol may be any chemical compound having the General formula ROH. R can be any substituted or unsubstituted hydrocarbon group. In some preferred embodiments, the alcohol is an aliphatic alcohol comprising from about 1 to about 25 carbon atoms. In some preferred embodiments, the alcohol is a monodentate alcohol. In the present description, the term "monodentate alcohol" includes such compounds, in which R can be obtained so that the substitution does not lead to a molecule containing more than one hydroxyl group (OH), which coordinates with the atom of magnesium in solution. Examples of such alcohols may include methanol, ethanol, propanol, isopropanol and butanol. Alcohols containing an aliphatic group with a longer chain, such as 2-ethylhexanol or 1-dodecanol, also form a solution in which the solubility of the halide of magnesium increases with temperature. It is also possible to use alcohols containing more carbon atoms. The alcohols may also be cyclic, such as cyclohexanol, or aromatic alcohols such as phenol.

In certain preferred embodiments, the ratio of the content of the electron donor substance to the halide of magnesium is less than or equal to 1.9. In some preferred embodiments, the molar ratio of the alcohol is to magnesium is less than around 1.75, less than 1.5, less than 1.0, less than 0,75 less than 0.5, less than about 0.4, or less than about 0.25 in. In other preferred embodiments, the molar ratio of electron donor to magnesium is about 0.1. In other preferred embodiments, the molar ratio may be higher to 1.9, for example, about 2.0 to about 2.2 to about 2.5 and about a 3.0.

Adding small amounts of one electron donor compound different from the solvent to the mixture containing the solvent and the halide of magnesium results containing magnesium composition, the solubility of which increases with temperature and the solubility of which at the boiling temperature of the solvent is relatively higher than the solubility of the adducts of magnesium halide/electron donor, in which there is an electron-donor compound. Solubility is also higher than the solubility comparable adducts of magnesium halide/electron donor containing certain types of electron-donor compounds. Suggested that the addition of small quantities of one of the electron donor to the solvent in the presence of halides of magnesium suppresses the conversion of soluble particles in polymer adducts. In some preferred embodiments, the soluble particles have the formula

MgXx(ED)ySz,

where x usually is about equal to 2, which corresponds to the oxidation state of magnesium, less than 4, and x+y+z is less than or equal to 6. In some preferred embodiments, y is about 0,5, 0,75, 1, 1,5, 1,75, 1,9 or less. In some other preferred embodiments, y is about 0.1, of 0.25, 0.3 or 0.4. Such particles typically have a solubility in the solvent, which increases with temperature up to the boiling point of the solvent. If the solvent is THF, the concentration of the halide of magnesium in solution can be up to five times higher than comparable solutions not containing electron-donor compounds, particularly where the electron-donor compound is an alcohol.

Figure 1 shows the solubility profile of solutions of magnesium chloride in tetrahydrofuran and alcohol depending on the temperature. As can be seen from figure 1, the composition does not contain alcohol, as a rule, have a solubility of the halide of magnesium, which increases from about 0.5 moles of magnesium per liter up to a maximum of less than approximately 0,65 moles of magnesium per liter at 30°C. Above 30°solubility decreases gradually until it reaches the boiling point of the solvent. On the contrary, the mixture to which was added the alcohol, such as ethanol, have a solubility of the halide of magnesium, which does not decrease with increasing temperature up to the boiling point of the solvent. For example, the mixtures, in which the ratio of ethanol to magnesium is about 0.5, the solubility of magnesium in 15°With approximately 0.75 mol/L. the solubility of magnesium chloride increases with temperature up to about 30°in which the concentration of magnesium in solution is around 1.75 mol/L. When the temperature rises above 30°solubility remains approximately constant up to the boiling point of the solvent.

Figure 1 also shows the solubility of mixtures in which the ratio of alcohol to magnesium is about 1. At 25°With the concentration of magnesium present in the solution is about 0.5 mol/L. However, the concentration increases to about 2 mol/l by the time when the temperature reaches 55°and remains approximately constant up to the boiling point of the solvent. In samples in which the molar ratio of alcohol to magnesium is two, the solubility of magnesium also increases with increasing boiling point up to the boiling point, at which the value of the solubility is 1.75 moles of magnesium per liter.

Figure 2 shows the profile of the solubility of several compounds containing various amounts of added alcohol. Each point in the data in figure 2 was obtained by adding such amount of magnesium chloride, which is necessary to achieve the desired concentration of the emission, when all the magnesium chloride is dissolved in THF. Then add a certain amount of alcohol in order to obtain the desired ratio of alcohol : the magnesium, and the mixture was heated to dissolve the composition. Then the solution was slowly cooled prior to sedimentation. The temperature at which they began to precipitate formed, was recorded on the y-axis of figure 2. Thus, figure 2 shows the temperature required for the preparation of solutions of magnesium chloride in various concentrations in the presence of alcohol. For example, some data 210 is the temperature required to obtain a solution containing 0.75 M of magnesium chloride, in which the solvent is THF, in the presence of different concentrations of ethanol. In mixtures prepared at a ratio of alcohol to magnesium of 0.25, the concentration of magnesium in solution is approximately 0.75 M only 5°C. the Mixture prepared at the ratio of alcohol to magnesium chloride, 0.5 to attain a concentration of 0.75 M in magnesium at about 15°Since, while the mixture with a ratio of 1.0 to reach a concentration of 0.75 M at about 33°C. If a mixture is prepared so that the ratio of alcohol to magnesium chloride is 1.5 or 2.0 moles, concentration of magnesium in the solution of 0.75 M is achieved at 47 and 53°s, respectively. Thus, the number of data 210 shows that mixtures with higher regard is the group of alcohol : magnesium become less soluble.

Thus, figure 2 shows that the smaller the relationship of alcohol to magnesium chloride to give a solution with a higher concentration of dissolved magnesium. The decrease in solubility with increasing ratio ROH/MgCl2suggests that small amounts of added ROH prevent the formation of polymeric adduct MgCl2(THF)2while the addition of large quantities of ROH or more alcohols promotes the formation in solution of the less soluble adducts containing more than ROH. Used the ratio ROH/Mg determines the maximum solubility, which can be achieved at the desired temperature. The data series 220-260 in figure 2 show that the relationship alcohol : magnesium raising the temperature increases the amount of dissolved magnesium. For example, solutions having a molar ratio alcohol : magnesium, 0.5 to contain the concentration of magnesium to about 0.75 M and about 15°C, while at 20°in solution it is possible to achieve a concentration of 1.0 M magnesium Line 230 shows that approximately 23°With the same solution can dissolve approximately 1.25 mol/l of magnesium chloride. Figure 2 also shows that the solubility of magnesium chloride in such solutions is also raised to a temperature of about 30°C. for Example, solutions in which the molar ratio of alcohol to magnesium is 1, show that at a temperature of primers is 35° Since the solubility of magnesium chloride is about 0.75 M, while at about 41°solubility increases to about 1M. The data curves 230-260 show that the solubility continues to rise as it approaches the boiling point of THF. Solutions having a higher ratio of alcohol:magnesium, show similar behavior.

The nature of the particles present in the solution was found using a variety of methods for the determination. Studies by NMR show that the electron donors, coordinated with MgCl2in THF solution, are in rapid equilibrium, and individual long-lived particles are absent. The gas phase above the THF solution containing MgCl2and 2 equivalents of ethanol (EtOH) on Mg, contains significantly less alcohol than the gas phase above the same with a solution of EtOH/THF, containing MgCl2. This suggests that ethanol is isolated molecule MgCl2in the solution. Apparently, alcohol group coordinated with the center MgCl2in the solution phase. The maximum solubility at average ratio of alcohol : MgCl2means that in the solution there are different particles, the concentration of which depends on the nature of the alcohol, the specific relationship of alcohol and the temperature of the solution.

Figure 3 shows the x-ray structure of the isolated crystal one is about of the catalyst components, allocated in the form of solids. As shown in figure 3, this component comprises a molecule with magnesium in the center. In a preferred embodiment of the invention, the precursor contains two molecules of solvent THF associated with magnesium, as well as two halogen as chlorine and two alcohol ligand. Thus, the component has the formula MgCl2ROH2THF2where ROH represents the isopropyl alcohol. There were also highlighted such compounds, in which the ROH represents ethanol. In this particular example, the structure is usually called a TRANS-octahedral magnesium-centered structure, since the ligands of the same kind are connected through the center of symmetry - atom of magnesium. However, this structure is not required for any of the preferred option component of the catalyst. In other preferred embodiments, the component may include mixtures of one or more individual compounds. In other preferred embodiments, the component may include a mixture of MgCl2ROH1THF3and MgCl2ROH2THF2. Any number of individual compounds can be represented so that the mixture as a whole satisfies the formula MgXx(ED)ySzwhere y is less than or equal to 1.9.

In other preferred embodiments, component-based catalyst, the halogen is Yes magnesium has the formula MgX 2(ED)ySzwhere y+z is less than or equal to 4, y is less than or equal to 1.9. In such preferred embodiments, where y+z is less than 4, a component of the catalyst may be regarded as deficient in relation to the solvent. These compositions may also be called non-stoichiometric compositions. Such compositions can be obtained in solid form from a fully coordinated MgCl2(ROH)2(THF)2or another song composition MgXx(ED)ySzby heating, applying a reduced pressure or a combination of both methods.

Figure 4 shows the results of thermogravimetric analysis (TGA) for MgCl2(ROH)2(THF)2. TGA was carried out at a heating rate of 10°C/min in those areas, when weight loss was not observed. In those areas, when the sample was losing weight, the temperature is maintained constant up until the change in mass was stopped. Figure 4 shows that a large part of the solvent and the alcohol can be removed by heating the composition of 50-200°and first, it removes one molecule of THF, then as ROH and THF. So you can get a variety of porous containing MgCl2compositions suitable for the formation of porous components of the catalysts. Thus, in some preferred embodiments, the component of the catalyst may have a coordination-not assistnow and polymer, and not Monomeric structure.

In another aspect applies the method of preparation of the catalyst components described above. The methods of preparation of catalyst components include the introduction of the solvent, the contacting of the magnesium halide with the solvent and adding an electron-donor compound, with the purpose of the education component of the polymerization catalyst. In some preferred embodiments, the molar ratio of electron donor to magnesium is less than or equal to 1.9. In other preferred embodiments, particularly when the electron-donor compound is an alcohol, the ratio of alcohol to magnesium may be higher 1,9, such as about 2.0 to about 2.1 to about 2.2 to about 2.5, or about a 3.0. In some preferred embodiments, the method may also include the selection of a component of the polymerization catalyst. Preferred variants of the method can also include removing part of the solvent or alcohol of the selected component of the polymerization catalyst. In certain preferred embodiments, the solvent or alcohol can be carried out by application of heat, vacuum, or combinations thereof.

The contacting of the magnesium halide with the solvent is usually carried out by physical mixing or solid magnesium halide with an electron-donor compound or their solutions. To Tachibana may include stirring or other mechanical mixing. In some preferred embodiments, the mixing is accelerated by the application of ultrasonic frequency to the resulting mixture. The magnesium halide may be any of the compounds based on magnesium halide listed above, and can be prepared in the form of solids or suspensions.

Adding electron-donor compounds in some preferred embodiments is carried out by direct addition. In other embodiments, the electron donor is added in the form of a solution. Alcohols suitable for use as electron-donor compounds include any alcohols having the formula ROH, as defined above. The total amount of the alcohol that is added to the solution, determined on the basis of the number of magnesium. In some preferred embodiments, the molar ratio of alcohol to magnesium varies from values above zero to values less than or equal to 1.9. In other preferred embodiments, the ratio may be higher to 1.9. In still other preferred embodiments, the ratio varies from around 0.1 to around 1.75. In other preferred embodiments, the ratio is approximately of 0.25, 0.3, 0.4, or from about 0.5 to 1.

The formation of the catalyst precursor polymerization, after the components are connected, can be accomplished in any way. In some preferred embodiments, the components merge the Ute at a temperature component from about 0 to about 200°C. In other embodiments of the invention they may come into contact at a temperature of from 0 to approximately 160°C. Preferably, the temperature should be below the boiling point of the solvent. In some preferred embodiments, the solvent, the magnesium halide and the alcohol can be left for the reaction of from about 5 minutes to about 3 days. In other preferred embodiments, from 30 minutes to 5 hours is sufficient to achieve a desired concentration of magnesium in solution.

In some preferred embodiments, the low alcohol concentration allow the formation of solutions containing previously unattainable concentration of magnesium halides. Increased concentration of dissolved halide of magnesium allows the preparation of more preferred polymerization catalysts, as more magnesium halide may be introduced into the catalyst composition.

Suitable precursors of the catalysts are formed by the reaction of a component of the catalyst compound of the transition metal. Suitable transition metal compounds include transition metal compounds III-VI groups. In some preferred embodiments, the transition metal is titanium, zirconium or hafnium. In other preferred embodiments, the metal isone vanadium, niobium, or tantalum. In certain preferred embodiments may also be appropriate for other transition metals, such as transition metals of a larger sequence number and the lanthanides.

The compound of the transition metal can be used in a variety of compositions. In some preferred embodiments, use of titanium compounds having the General formula where the titanium is in the formal oxidation state of +4. From compounds of titanium (IV) catalyst components you can use the halides of titanium and galogenangidridy having the formula Ti(OR)aX4-awherein R individually represents a substituted or unsubstituted hydrocarbon group having from 1 to about 25 carbon atoms, such as methoxy, ethoxy, butoxy, hexose, phenoxy, desoxy, naphthoxy or dodecane group, X is any halide, and can vary from 0 to 4. Optionally, you can use a mixture of titanium compounds.

In certain preferred embodiments, the compound of the transition metal is selected from titanium compounds, halides or galogenarenov containing from 1 to 8 carbon atoms in alcoholate group. Examples of such compounds include TiCl4, TiBr4, TiI4, Ti(och3)Cl3, Ti(OS2H5)Cl3, Ti(OS4H9)Cl3, Ti(OC6H )Cl3, Ti(OS6H13)Br3, Ti(OC8H17)Cl3, Ti(och3)2)Br2, Ti(OC2H5)2Cl2, Ti(OC6H13)2Cl2, Ti(OC8H17)2Br2, Ti(och3)3Br, Ti(OS2H5)3Cl, Ti(OS4H9)3Cl, Ti(OS6H13)3Br, and Ti(OC8H17)3Cl.

In other preferred embodiments, the compound of titanium is a restored titanium halide. Suitable restored the halides of titanium correspond to the formula TiClxwhere x varies from greater than 0 to less than 4. In some preferred embodiments, the recovered compound of titanium is a TiCl3, TiBr3or TiI3.

The amount of transition metal compounds or mixtures of compounds of the transition metal used in the preparation of the catalyst precursor can vary within wide limits depending on the type of catalyst. In some preferred embodiments, the molar ratio of magnesium to transition metal compound may be about 56, preferably from about 20 to about 30. In other preferred embodiments, the molar ratio of magnesium to transition metal compound is low, around 0.5. In General, the molar ratio of magnesium to the connection of the transient is the first metal is preferably from about 3 to about 6, moreover, the transition metal is titanium.

In some preferred embodiments, the catalyst precursor receive physical mixing of the component based on the magnesium halide and the component based on the transition metal. One such method is the spherical grinding. In some preferred embodiments, the solution component based on the magnesium halide is combined with the compound of the transition metal. In other preferred embodiments, the two components connected by physical mixing (not limited to ball milling). In some preferred embodiments, the connection component on the basis of the magnesium halide and the component based on the transition metal forms a reaction product, which may contain a variety of particles, including component-based magnesium halide and the compound of the transition metal. The reaction of the component based on the magnesium halide with the compound of the transition metal can be carried out at any suitable temperature. In some preferred embodiments, the temperature may vary from about -70 to about 100°C. In other preferred embodiments, the temperature may range from about -50 to about 50°C. After the reaction start temperature can be raised and the reaction is carried out at a temperature of from 25 to 150°during the PE the iodine lasting from 30 minutes to about 5 hours. Of course, it is necessary to avoid temperatures at which the decomposition of any component.

In certain preferred embodiments, the catalyst precursor comprises a composition of the formula

[Mg(ROH)r]mTi(OR)nXp[S]q,

where ROH includes monofunctional, linear or branched alcohol having from 1 to about 25 carbon atoms, R is R' or COR', where each R' individually represents an aliphatic hydrocarbon radical containing from 1 to about 14 carbon atoms, or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms, X is individually Cl, Br or I; S is chosen from the group consisting of alilovic esters or aliphatic or aromatic carboxylic acids, aliphatic ethers, cyclic ethers, and aliphatic ketones; m varies from 0.5 to 56; n is 0, 1 or 2; p varies from 4 to 116; q varies from 2 to 85; r varies from 0.1 to 1.9.

In some preferred embodiments, the catalyst precursor may be treated with a Lewis acid. In General, suitable connections based Lewis acids have the structure RgAlX3-gand RgBX3-gwhere R represents R', OR' or NR'2where R' represents an aliphatic hydrocarbon group containing from 1 is about 14 carbon atoms, or aromatic hydrocarbon group containing from 1 to 14 carbon atoms, or aromatic hydrocarbon radical containing from 6 to 14 carbon atoms; X is chosen from the group consisting of Cl, Br, I and mixtures thereof, a g in each case is 0-3.

Suitable connections on the basis of Lewis acids include, but are not limited to, tri-n-hexylamine, triethylamine, diethylaluminium, trimethylaluminum, dimethylammoniumchloride, methylaluminoxane, triisobutylaluminum, tri-n-butylamine, diisobutylaluminium, sibutraminecard, (C2H5)AlCl2, (C2H5O)AlCl2, (C6H5)AlCl2, (C6H5O)AlCl2, (C6H13O)AlCl2and the corresponding compounds of bromine and iodine.

Suitable connections on the basis of the halides of bromine include, but are not limited to, BCl3, BBr3In(C2H5)Cl2(OS2H5)Cl2(OS2H5)2Cl, (C6H5)Cl2(OS6H5)Cl2B(C6H13)Cl2, B(OC6H13)Cl2and(OS6H5)2Cl. You can also use bromine and iodine analogues of the above compounds. The Lewis acid can be used alone or in combination with the above compounds.

Additional Podrobnosti what about the Lewis acids, suitable for this purpose can be found in patents US 4354009 and 4379758, which are fully included in the present description as a reference.

In some preferred embodiments, the catalyst may be treated with a catalyst. You can use one or more alkyl aluminum compounds. In some preferred embodiments, the catalyst is partially activated. In such preferred embodiments, it should use a sufficient amount of activator to obtain a catalyst in which the molar ratio of activator compounds to Ti is 10:1, 8:1 or 4:1. This reaction partial activation can be carried out in suspension in a hydrocarbon solvent, and then to drying the resulting mixture, to remove the solvent, at temperatures from about 20 to about 80°C. In some preferred embodiments, the partial activation can be carried out at an approximate temperature range 20-70°C. alternatively, the suspension of catalyst in mineral oil can be processed by the connection of the trigger, and the resulting suspension can be fed into the reactor. Another alternate method of partial activation is described in the patent US 6187866, fully incorporated into the present description by reference, in which a partial activation is carried out in a continuous way. The resulting product provided is employed, or a granular solid composition, or suspension in mineral oil, which is easy to apply to the polymerization reactor where the activation is completed when interacting with the additional compound is an activator, which can be either the same or another connection.

Activation of the modified catalyst is usually carried out in the polymerization reactor, although in some preferred embodiments, the activation can be performed outside of the polymerization reactor. When activation is carried out in the polymerization reactor, the connection-activator and the catalyst was fed into the reactor through a separate supply line. To dispersing additional substance-activator in a reactor, you can also use other gaseous or liquid material fed to the reactor. You can use such substances as ethylene, nitrogen, and co-monomers in the stream. This solution may contain approximately 2, 5, 15, 20, 25 or 30 weight percent of the substance-activator.

In other preferred embodiments, the catalyst is then activated by treatment with activator, and it can be added in the presence or in the absence of solvent. Additional substance-activator add to nonactivated or partially activated catalyst in such amounts to provide a total molar ratio Al/Ti is from about 10 to about 400. In some preferred the variation ratio of Al/Ti in the activated catalyst varies from about 15 to about 60 or from about 30 to about 100, or from about 70 to about 200.

Substance-activators can be used separately or in combination with each other, they include compounds such as Al(CH3)3, Al(C2H5)3, Al(C2H5)2Cl, Al(i-C4H9)3, Al2(C2H5)3Cl3, Al(i-C4H9)2H, Al(C6H13)3, Al(C8H17)3, Al(C2H5)2H and Al(C2H5)2(OC2H5).

Components based on magnesium halides, the precursors of catalysts, or catalysts described in this invention have a characteristic distribution of particle sizes. In the present description, the terms "D10", "D50and D90" show relative percentiles of the logarithm of the normal distribution of particle size, determined using particle size analyzer Malvern 2600®using heptane to obtain a suspension. So particles with D50equal to 12 μm, have an average particle size of 12 μm. D90equal to 18 microns, shows that 90% of the particles have a size less than 18 microns, a D10equal to 8 μm, shows that 10% of the particles have a size less than 8 microns. Distribution of particle size is given as the length of the peak of the distribution on the x-axis. This length is defined as (D90-D10)/(D50 ).

In some preferred embodiments, the particles have an average particle size ranging from about 30 microns to about 5 microns. In some preferred embodiments, the average particle size may be about 7 μm, about 8 μm, about 9 μm, or about 10 μm. In other preferred embodiments, the average particle size is about 11 μm, about 12 μm, or about 13 μm. In still other preferred embodiments, the average particle size may be about 15 μm, about 18 μm, about 20 μm or about 25 microns. In some preferred embodiments, the average particle size may be reduced in the measurement process on the particle analyzer. Some preferred options predecessors, included in the present description, have a distribution of particle sizes from about 1.5 to about 4.0. In some preferred embodiments, the distribution may be above or below these values. Some particles will have a distribution of about 1.6, about 1.8 or roughly 2.0. Other preferred embodiments have a distribution of about 2.2, about 2.4, about 2.6, about 2.8, or about a 3.0. In other preferred embodiments, the particles have a peak size distribution about 3.1, about 3.2, about 3.3, about 3.4, about 3.5, or about 3.75 to.

Still others prefer the performance communications options offer a method of producing polymer using the above catalyst. In such preferred embodiments, at least one olefin monomer will polimerizuet in the presence of a catalyst which comprises a magnesium halide, a solvent, alcohol and titanium, where the catalyst contains almost no other alcohols and where the molar ratio of alcohol to magnesium is less than or equal to 1.9. The amount of catalyst varies depending on the selected method of polymerization, the reactor size, the selected monomer and other factors known to professionals in this field, which can be determined on the basis of the examples below.

The polymerization should be carried out at temperatures sufficiently high to achieve an acceptable rate of polymerization and sufficient in order to avoid excessively long stay starting materials in the reactor, but not so high that they lead to too viscous polymers. Usually temperatures vary from about 0 to about 120°From or from about 20 to about 110°C. In some preferred embodiments, the polymerization reaction is carried out at temperatures varying from 50 to 110°C.

The polymerization of alpha-olefins is carried out at a monomer pressure of about atmospheric or above. Typically, the pressure of the monomer varies from about 20 to about 600 psi (psi).

The contact time of the catalyst with the raw materials of the commonly varies from about several minutes to several hours in the periodic processes. The time of polymerization from about 1 to about 4 hours is typical for reactions of autoclave type. In the processes in liquid fluidized layer curing time can be adjusted as desired. For flow processes in liquid-fluidized bed is usually sufficient to apply the curing time from several minutes to several hours. The contact time in the gas phase is usually the same as in liquid-phase processes in a liquid fluidized bed.

Solvents suitable for use in processes in liquid fluidized bed polymerization include alkanes and cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane and methylcyclohexane; alkylaromatic compounds, such as toluene, xylene, ethylbenzene, isopropylbenzene, atilola, n-propylbenzoyl, diethylbenzene and mono - and dialkylated; and halogenated and hydrogenated aromatics such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, tetrahydronaphthalene and decahydronaphthalene; liquid paraffins of high molecular weight or mixtures thereof; and other well-known diluents. It is often desirable to purify the reaction composition for polymerization before use, for example, by distillation, passing through the molecular sieve; contacts with connections, such as connections alkylamine, is capable of removing trace quantity is of impurities; or in other suitable ways. Examples of polymerization processes in which it is possible to use the catalyst in accordance with a preferred variant of the present invention, are described in patents US 3957448; 3965083; 3971768; 3972611; 4129701; 4101289; 3652527 and 4003712.

The polymerization is conducted under conditions which exclude the presence of oxygen, water and other compounds that act as catalyst poisons. In some preferred embodiments, the polymerization can be carried out in the presence of additives which regulate the molecular weight of the polymer. Usually used for this purpose hydrogen in any suitable form.

After completion of the polymerization, or when it is desirable to terminate the polymerization or deactivate the catalyst, the catalyst can be treated with water, alcohol, acetone or other suitable desactivation to the catalyst in any suitable way.

The molecular weight of the polymers normally indicate, using the measurements of transition in a fluid state. One of these indicators is the melt index (IR)was obtained according to ASTM D-1238, condition E, measured at 190°applied to a sample of 2.16 kilograms (kg), measured in grams per 10 minutes. The polymers obtained with the use of some of the catalysts described herein, have values of IL from about 0.01 to about 10,000 g/10 min With the speed of melt flow is another way characteristics of the polymers, it is measured according to ASTM D-1238, condition F, using 10 times more hitch, compared with used to determine the melt index in the test described above. The flow rate of the melt is always proportional to the molecular weight of the polymer. So, the higher the molecular weight, the lower the flow velocity of the melt, although the relationship is not linear. Flow index (FRI) is the ratio of the flow rate of the melt to the melt index. This figure correlates with the distribution of the polymer product molecular weight. Lower PT shows that the distribution of molecular masses more narrow. The polymers obtained with the use of some catalysts that are included in the present description, have PT in the range of from about 20 to about 40.

The polymers can also be characterized by their density. The polymers in the present description can have a density from about 0.85 to about 0,98 g/cm measured in accordance with method ASTM D-792, which prepare the tablet and adapt for one hour at 100°to achieve equilibrium crystallinity. Then measure the density in the column density gradient.

In some preferred embodiments, the polymer yield is quite high relative to the amount used of the catalyst, so that suitable products can be is about to get without separation of catalyst residues. The polymer products obtained in the presence of the invented catalysts can be formed in various suitable items by extrusion, molding under pressure and other common methods.

Examples

The following examples are meant to illustrate various preferred options given in the present description of the invention. They should not be construed as limiting the scope of the present invention in other ways than as described and set forth in this description. All numerical values are approximate.

Measurement of solubility

In each of the six 100-ml vessels with side outlet, equipped with magnetic stirring, was added 5,09 g (25 mmol) of solid [MgCl2*1.5 THF] in an atmosphere of N2. In each vessel were added different amounts of THF required to obtain the desired concentration of the solution in magnesium (from 0.5 to 2.0 mol/l), and the suspension was stirred for 5 minutes. Then added 12.5 mmol (1,45 ml) of ethanol to obtain the ratio ethanol:magnesium, amounting to 0.5. The mixture was heated on an oil bath at 60°C and kept at this temperature for 2 hours to dissolve under the MgCl2. Then the samples were allowed to cool to room temperature. Besieged connection again suspended and slowly stirred the. Recorded the temperature at which the composition is in the process of heating was dissolved. The solutions or suspensions were allowed to cool to room temperature and added to the next portion of the ethanol. Then the process was repeated with a higher ratio of ethanol:magnesium. These experiments similarly conducted with other alcohols.

The study MgCl2(EtOH)1(THF)x

8,14 g hard MgCl2(THF)1.5(40 mmol Mg) suspended in nitrogen atmosphere with 20 cm3THF in the flask Slence with a magnetic stirrer, at 22°With water bath. Was obtained legkoperevarivaemye suspension. To this suspension was added to 2.3 cm3 (40 mmol) of absolute ethanol in order to obtain the ratio of alcohol: magnesium is 1:1. Suspension zahustovali, however, suspended solids dissolved. By heating the suspension to 60°With all solid precipitates were dissolved, forming a solution of MgCl2with a concentration of 2 mol/l, with the ratio of alcohol:magnesium is 1:1. The solution was slowly cooled. At 45°the solution became turbid, but the sediment was not observed. The flask and contents were allowed to cool to ambient temperature without stirring, and then the crystals were allowed to grow for 2.5 days. Got a solid white precipitate under the solution. The suspension was filtered through a medium filter and quickly about ivali 3 times in units of 10 cm 3chilled on ice THF, receiving material consisting of fine needles and pellets. The obtained solid material was dried overnight under nitrogen at room temperature. Output: 1,55, Analysis: 9.2% Of Mg, 25.2% of THF, 26,75% ethanol. FW (formula weight) 231,8. PV by thermogravimetric analysis (weight loss to net MgCl2): 220. General composition: MgCl2(EtOH)1.53(THF)0.92.

The selected material is a mixture of solvated MgCl2/THF materials. Thermogravimetric analysis of high-resolution revealed 6 major peaks of weight loss in the temperature range of 50-250°With which, apparently, are combinations of TGA MgCl2/THF and connections MgCl2(EtOH)1.53(THF)0.92. Similarly, the x-ray spectrum of the powder material contained peaks MgCl2(THF)2, MgCl2(THF)1.5and MgCl2(EtOH)2(THF)2. Clean material with a ratio ROH/MgCl2comprising 1:1, in General, were not deposited from a solution; rather, it was the mixture of solid products, in which the overall ratio ROH/MgCl2exceeded the stoichiometric ratio of 1:1.

Getting MgCl2(ROH)2(THF)2

In a three-neck flask of 500 ml, equipped with a paddle stirrer and thermometer, were placed 45 g (225 mmol) of [MgCl2*1.5 THF] in nitrogen atmosphere and suspended with 130 ml of THF at 27°With water ban is. Then added for 10 minutes 225 mmol (13,2 ml) of ethanol. The suspension was changed from crystalline to non-transparent thick liquid, and the temperature was increased by 10°C. by heating the suspension to 60°With all solids were dissolved. The solution at this point, according to the calculation, contained 1.75 moles of magnesium at a ratio of ethanol:magnesium is 1:1. During the addition of another portion of ethanol (225 mmol, 13,2 ml) started to precipitate a thick white precipitate. At this point, the ratio of ethanol:magnesium was 2:1. The mixture was cooled to 25°C and stirred for 30 minutes. The first precipitate was filtered on a coarse filter and dried in a stream of nitrogen at room temperature. There were 36 g of the product. The product was identified using the weighting analysis. Analysis: Formula weight (TGA): Rasch. 331,2, detecting. 344,9; Mg: Rasch. 7,34, detecting. 7,89%; THF: Rasch. 43,48, detecting. 46,3%; ethanol: Rasch. 27,78, detecting. 23,8%.

Thermal ageing MgCl2(EtOH)2(THF)2

Portion not solids was heated at 70°under a weak stream of nitrogen. Analysis of the metal and ligands in the dry composition gave a General composition containing 30,1% THF, 30,8% ethanol. Further drying of the sample led to the composition of 20.5% THF, 16.0% of ethanol. TGA showed a molecular mass corresponding to the mass loss of the connection.

MgCl2(IPA)2(THF)2

The connection is ready is whether similar to the above connection, contains ethanol, using as alcohol isopropanol instead of ethanol. The product was identified using TGA weight analysis. Analysis: Formula weight (TGA): Rasch. 359,2, detecting. 362,7; Mg: Rasch. 6,77, detecting. 5,5%; Cl: Rasch. to 19.74, detecting. 20,0%; THF: Rasch. 40,99, detecting. 39,8%.

The reaction MgCl2with dodecanol and 2-amoxicillon

Solubility MgCl2in THF was promoted to the interval of 1-2 mol/l with the use of these alcohols at 60°C. However, the cooling does not lead to crystalline compounds. Evaporation of THF gave an oily sediments that contain both THF and alcohol, coupled with MgCl2.

The reaction MgCl2with 1,4-cyclohexanediol

When processing a 0.4 molar solution of MgCl2in THF diola at 60°immediately after addition of the first drops of diol formed a white precipitate. The precipitate contained the ratio of alcohol to magnesium is higher than the ratio of alcohol:magnesium in solution. If mol of magnesium was added to 0.25 mole of diol formed precipitate, which is the approximate ratio of diol:magnesium was 0.5. The deposition continued as adding additional quantities of diol. When adding a total amount of 0.5 moles of diol per mole of magnesium (or when the ratio of diol:magnesium 1:1), was formed is enriched in the connection of approximate composition MgCl2(1,4-cyclohexanediol)1(THF)2 . Rasch.: Mg: 6,84%, Cl 19,95%, THF 40,5%; detecting. Mg: to 6.19%, Cl 20,0%, THF 39.3 per cent.

The reaction MgCl2with 1,10-decandiol

When processing a 0.4 molar solution of MgCl2in THF diola at 60°immediately after addition of the first drops of diol formed a white precipitate. The precipitate contained only very small amounts of THF.

Properties of the solution of 5:1 MgCl2TiCl3EtOH/THF

In sorokalitrovye mixing vessel made of stainless steel was placed 10,2 l THF, 10,7 moles absolute ethanol (492 g 625 ml) and a 4.86 moles MgCl2(463 g) in a nitrogen atmosphere. The suspension was heated to 55°and was stirred overnight. Then added to 0.85 moles (168,9 g) TiCl3AA, the mixture was stirred for 4 hours. Got a solution consisting of 5:1 MgCl2/TiCl3and related ethanol: MgCl2equal to 2.2:1. Upon cooling to room temperature, deposited white crystals, which consisted of adduct MgCl2/THF/EtOH, very little contaminated titanium. Complete evaporation of the solution gave a powdery solid, which consisted of separate white and green-black particles and individual solvated compounds MgCl2and TiCl3. Complex formation of MgCl2and TiCl3occurred.

Ball grinding catalyst precursor 5:1 MgCl2(EtOH)2(THF)2/TiCl3

To speed up interaction is a journey of components, individual solids MgCl2(EtOH)2(THF)2(31.0 g, 93,6 mmol) and the recovered aluminum TiCl3(3,724 g, 18,72 mmol) were mixed at a ratio of Mg/Ti equal to 5:1, in a ball mill in a porcelain vessel within 24 hours. There was obtained a solid pink substance that broke the light under the microscope. The distribution of particle sizes obtained by the ball milling of the particles did not change significantly after 5 minutes of mixing in a particle size analyzer. The average size was 27 μm, if the width of the peak of the distribution is 1.6. The obtained powdery composition of Mg/Ti was suspended in mineral oil for further polymerization (of 0.025 mmol of titanium/g of suspension).

The polymerization of ethylene in the reactor in a liquid fluidized bed

Every experience by polymerization in laboratory scale was carried out as follows. To 500 ml of hexane in suspension polymerization autoclave of 1:1 was added 1.25 mmol of triethylaluminum ((C2H5)3Al) under nitrogen, then the suspension of catalyst precursor in mineral oil containing 0,0075 mmol of titanium. The relative pressure in the reactor was raised to 40 psig (pounds per square inch) using hydrogen, then raised to a total pressure of 200 psig (pounds per square inch) using ethylene. The polymerization carried out and at a temperature of 85° With in half an hour.

Table 1.

Data on the polymerization of high density polyethylene using a catalyst of the Ziegler ball grinding.
Sample No.mmol TiOutput, gActivity***It degrees/minThe speed of transition in a fluid state
Control*0,007584,5145001,928
1**0,007578,1134001,628
*the predecessor of 5:1 MgCl2(THF)1.5/TiCl3< / br>
**the predecessor of 5:1 MgCl2(THF)2(EtOH)2/TiCl3< / br>
***in g polyethylene/mol of titanium per hour per 100 psi of ethylene.

So the data in table 1 show that the components of the catalyst containing magnesium halide, suitable for the formation of the active catalyst particles. Moreover, the data show that the advantage of the high solubility of some components on the basis of the halide of magnesium does not adversely affect the properties of the resulting catalysts in polymerization processes.

As is shown above, preferred variants of the present invention provide a method of increasing the solubility of magnesium halides in solution. Preferred options also provide new precursors of catalysts and methods of obtaining such predecessors. Other options provide catalysts, methods of making catalysts, and a method of producing the polymer. Preferred embodiments of the present invention can have one or more of the following advantages. First, increase the solubility of the magnesium halides allows you to prepare such catalysts and precursors of catalysts lesser extent of contamination and to avoid clogging of the reactor due to the deposition of the inside of magnesium compounds. Higher solubility of magnesium in solution also allows one to obtain catalysts and precursors of catalysts with higher magnesium content than previously possible. Therefore, in the reaction vessel may contain more catalyst that reduces the costs associated with the preparation of the catalyst with a small download size. When used in the polymerization with these catalysts show an acceptably high value activity. Thus, the catalysts provide effective against cost alternative to existing magnesium titans is m catalysts. Moreover, some catalysts have activity comparable to the activity of currently used catalysts. So some of the catalysts described here can be used in existing industrial processes without costly changes to the current process parameters. Components based on magnesium halides described in the present description, can also be used to obtain the supported catalysts of polymerization, as described in co-filed application Burkhard E.Wagner, and others, entitled "Applied polymerization catalysts", filed July 15, 2002, entered into the present description by reference. Precursors and catalysts can also be used to obtain catalysts spray drying, as described in the application "polymerization Catalysts spray drying and curing processes with their use," filed July 15, 2002, entered into the present description by reference; and the application of "polymerization Catalysts spray drying and curing processes with their use," filed July 15, 2002, entered into the present description by reference. These advantages are provided, in particular, the wider the interval of available compositions and more homogeneous distribution of magnesium in the particle. Other advantages and properties of the obvious for verifizierung in this area people.

While the invention has been described using a limited number of preferred options, these individual preferred options are not meant to restrict the scope of the invention other than those described and set forth in this description. Moreover, there are variations and modifications are described. For example, various other additives that are not listed in the present description, can also be used to further improve one or more properties of the composition of the catalyst and catalyst precursor, as well as polymers obtained according to the present description. It is clear that the parameters of the methods of polymerization can vary, for example, temperature, pressure, concentration of monomer, concentration of polymer, the partial pressure of hydrogen, and so forth. Therefore, the catalysts that do not meet the criteria under one set of reaction conditions can, in spite of this, to use in preferred embodiments of implementing the present invention with a different set of reaction conditions. While all of the preferred options is described with reference to separate the catalyst, it is in no way prohibits the use of two, three, four, five or more catalysts in the same reactor with the same or other performance of the La molecular weight and/or for the introduction of a co-monomer. In some preferred embodiments, the catalyst may also contain other additives or modifiers not listed specifically. In other preferred embodiments, the catalyst contains no, or substantially does not contain any compounds that are not listed in the present description. It should be recognized that the method described in the present description, can be used to obtain polymers that also contain one or more additional co-monomers. The introduction of additional co-monomers can lead to improved properties that are unattainable by the use of homopolymers or copolymers. While the method is described as including one or more stages, it should be understood that these stages can be applied in any order or sequence unless otherwise specified. These stages can be combined or implemented separately. Finally, any numerical value given in the present description should be considered as approximate, regardless of whether it was or was not used the word "about" or "approximately" when describing a given number. Last but not least, the compositions according to the invention is not limited to the methods described in the present description. They can be obtained using any suitable method. The applied formula image is etenia is intended to cover all such changes and modifications as falling within the scope of the invention.

1. Component of the catalyst for polymerization of olefins, based on the magnesium halide obtained from the

(a) to the halide of magnesium,

b) a solvent suitable as a donor of electrons,

C) an electron-donor compound, represents a linear or branched, substituted or unsubstituted, aliphatic or aromatic alcohol having from 1 to 25 carbon atoms,

where the magnesium halide is characterized by a solubility in the solvent, which is not reduced under the influence of temperature up to the boiling point of the solvent, and the solubility of the magnesium halide in the solvent is higher than 0.7 mol/L.

2. Component of the catalyst according to claim 1, where

1) a halide of magnesium is a magnesium chloride, magnesium bromide, magnesium iodide, or combinations thereof.

2) an electron-donor compound is a linear or branched, substituted or unsubstituted aliphatic or aromatic alcohol having from 1 to 25 carbon atoms,

3) a solvent selected from the group consisting of alilovic esters of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers and aliphatic ketones,

4) the molar ratio of alcohol to magnesium halide edit who is from 0.1 to less than 1.0 and

5) the solubility of the magnesium halide in the solvent is in the range from 0.8 to 2.5 mol of the halide of magnesium per liter of solvent.

3. Component of the catalyst according to claim 1, which is a product of the interaction of the formula

Mg(ROH)rCl2[R]q,

where ROH is an alcohol, R" is chosen from the group comprising alkalemia esters of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers and aliphatic ketones; r is above 0 and below 1.9, and q is greater than 0 and less than 4.

4. The precursor of the catalyst for polymerization of olefins, comprising the product of the interaction component of the catalyst described in claim 1, and a second component comprising a transition metal selected from the group comprising transition metals of group IV, and combinations thereof.

5. The catalyst precursor according to claim 4, where the transition metal group IV selected from the group comprising titanium, zirconium and hafnium.

6. The catalyst precursor according to claim 4, which is a product of the interaction of the formula

[Mg(ROH)r]mTi(OR')nXp[W]q,

where ROH includes linear or branched alcohol containing from 1 to 25 carbon atoms, R' represents R' or COR"', where each R' individually represents a radical of aliphatic hydrocarbon, the content is of ASI from 1 to 14 carbon atoms, or aromatic hydrocarbon radical containing from 1 to 14 carbon atoms; X represents a separately Cl, Br, or I, W is chosen from the group comprising alkalemia esters of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers, and aliphatic ketones, m varies from 0.5 to 0.56; n is 0,1 or 2; p is changed from 4 to 116; and r varies from 0.1 to 1.9.

7. The catalyst for polymerization of olefins, comprising the product of the interaction of the catalyst precursor described in claim 4, and socializaton representing an alkyl compound of aluminum.

8. Component of the catalyst according to claim 1, which is a product of the interaction of the formula

MgCl2(CON)2THF2.

9. Component of the catalyst according to claim 1, where the electron-donor compound is a substituted or unsubstituted, aliphatic or aromatic alcohol containing from 1 to 25 carbon atoms.

10. Component of the catalyst according to claim 2, where the alcohol is chosen from the group comprising methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, 1-dodecanol, cyclohexanol and di-tert-butylphenol.

11. Component of the catalyst of claim 10, where the solvent is chosen from the group comprising alkalemia esters of aliphatic or aromatic carboxylic acids, ethers, and alifaticheskii the ketones.

12. Component of the catalyst of claim 10, where alkalemia esters chosen from the group comprising methyl acetate, ethyl acetate, ethylpropane, methylpropionate, ethylbenzoic and combinations thereof.

13. Component of the catalyst of claim 10, where the ethers are selected from the group comprising diethyl ether, diisopropyl ether and di-n-butyl ether, ethylisopropylamine ether, metalalloy ether, ethylenically ether, tetrahydrofuran, 2-methyltetrahydrofuran and combinations thereof.

14. Component of the catalyst of claim 10, where the ketones are selected from the group comprising acetone, methyl ethyl ketone, cyclohexanone, cyclopentylmethyl, 3-bromo-4-heptanone, 2-chlorocyclopentane, allylmercaptan and combinations thereof.

15. The catalyst precursor according to claim 4, where the product of the interaction component of the catalyst additionally comprises a second solvent selected from the group consisting of alkalemia esters of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers, and aliphatic ketones.



 

Same patents:

FIELD: polymer production.

SUBSTANCE: invention relates to supported catalytic compositions, methods for preparing such compositions, and polymer preparation processes using these compositions. In particular, invention provides supported catalytic composition including interaction product of: (i) catalyst precursor composition comprising product of reaction of magnesium halide, an ether, electronodonor compound, in particular linear or branched aliphatic C1-C25-alcohol, and transition metal compound, in particular compound of group IV element; (ii) porous inert carrier; and (iii) cocatalytic composition; wherein supported catalytic composition contains less than 1% electronodonor compounds other than those including linear or branched aliphatic or aromatic alcohol having from 1 to 25 carbon atoms and wherein molar ratio of electronodonor compound to magnesium is less than or equal to 1.9. Described are also method of preparing supported catalytic composition, method of preparing polymer comprising reaction of at least one olefin monomer in presence of above-mentioned supported catalytic composition. Described are also supported catalyst precursor composition, supported catalytic composition, method of preparing supported catalytic composition, and method of preparing polymer comprising reaction of at least one olefin monomer in presence of supported catalytic composition, and supported catalyst precursor composition.

EFFECT: increased catalytic activity and enabled preparation of polymer for films at lower partial pressure of ethylene.

15 cl, 5 dwg, 3 tbl, 7 ex

FIELD: chemical industry; petrochemical industry; methods of production of the composition of the solid procatalytic agent for utilization in the catalytic compositions for polymerization.

SUBSTANCE: the invention is pertaining to the method of production of: the composition of the solid procatalytic agent for usage in the Ziegler-Natta type catalytic composition for polymerization; to the procatalytic agents for usage in the formation of the similar catalytic compositions; to the methods of their production and to the methods of their application for production of the olefinic polymer. The invention presents the method of production of the composition of the solid procatalytic agent for usage in the composition of the Ziegler-Natta procatalytic agent for polymerization of the olefins providing for: contacting the predecessor composition containing the magnesium compound with the compound being the titanium halogenide and the internal donor of electrons; separation of the solid procatalytic agent from the reactionary medium; the extraction of the composition of the solid procatalytic agent by its contacting one or several times with the liquid dilutant. The invention also presents the method (a version)providing for the phase of the solid procatalytic agent drying before the extraction of the composition. The invention also presents the description of the composition of the solid procatalytic agent for the usage in the Ziegler-Natta type catalytic composition for polymerization of olefins. The technical result of the invention is production of the catalytic compositions used in the production of the polymeric compounds of α-olefins, having the reduced contents of the xylene-soluble fractions and the heightened rigidity. The catalytic agents have the higher productivity and produce the polymers of α-olefins having the higher volumetric possibility to use the reduced levels of hydrogen for achievement of the equivalent molecular mass of the polymer, need the reduced quantities of the agents of regulation of selectivity and produce the polymers having the reduced contents of oligomers.

EFFECT: the invention ensures production of the catalytic compositions for production of the polymeric compounds of α-olefins with the reduced share of the xylene-soluble fractions, heightened rigidity, higher productivity, producing the polymers of α-olefins with the reduced share of oligomers.

9 cl, 11 tbl, 90 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to catalytic systems used in polymerization of alpha-olefins, methods for preparing catalytic systems for polymerization of alpha-olefins and methods for polymerization (and copolymerization) of alpha-olefins. Invention describes the catalytic system for polymerization of olefins comprising solid titanium component of catalyst, organoaluminum compound comprising at least one bond aluminum-carbon and organosilicon compound comprising at least one (cycloalkyl)-methyl group used as an external donor of electrons. Also, invention describes the catalytic system for polymerization of olefins comprising solid titanium component of the catalyst prepared by contacting titanium compound with magnesium compound and comprising from about 0.01 to about 500 moles of titanium compound per one mole of magnesium compound, organoaluminum compound comprising at least one bond aluminum-carbon wherein the mole ratio of aluminum to titanium in the catalytic system is in the range from about 5 to about 1000, and organosilicon compound comprising at least one (cycloalkyl)-methyl group and used a external donor of electrons wherein the mole ratio of organoaluminum compound and organosilicon compound in the catalytic system is in the range from about 2 to about 90. Also, invention describes methods for preparing catalyst used in polymerization of olefins and comprising interaction of Grignard reactive comprising (cycloalkyl)-methyl group with ortho-silicate to form organosilicon compound comprising a (cycloalkyl)-methyl link, mixing organosilicon compound with organoaluminum compound comprising at least one bond aluminum-carbon and solid titanium component of the catalyst to form the catalyst, and a method for polymerization of olefins. Invention provides preparing propylene block-copolymer showing good fluidity in the melt, capacity for molding, hardness, impact viscosity and impact strength in combination with high effectiveness of the catalyst and good technological effectiveness of the preparing process.

EFFECT: improved and valuable properties of catalysts.

17 cl, 10 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to the catalyst component used in polymerization of olefins comprising Mg, Ti, halogen and at least two electron-donor compounds wherein indicated catalyst component and at least one of electron-donor compounds repenting in the amount in the range from 20 to 50 mole% with respect to the complete amount of donors are chosen from succinic acid esters that are not extractable by above 25 mole% and at least one additional electron-donor compound that is extractable by above 35 mole%. Indicated components of catalyst provides preparing polymers possessing good insolubility level in xylene, high content level of stereoblocks and broad MWD value that is suitable for preparing polymers used in the region using bi-oriented polypropylene films. Also, invention relates to catalyst used in polymerization of olefins, methods for preparing propylene polymers and propylene polymer.

EFFECT: improved preparing method, valuable properties of catalyst.

24 cl, 3 tbl, 17 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to components of catalyst used in synthesis of ethylene (co)polymers by using methods of (co)polymerization in the gaseous phase, in suspension or in mass. The prepolymerized catalyst for polymerization of ethylene being optionally in mixtures with olefins of the formula: -CH2=CHR wherein R represents (C1-C12)-alkyl group comprises a non-stereospecific solid component of catalyst comprising Ti, Mg and halogen. A solid component of catalyst is prepolymerized with α-olefin of the formula: -CH2=CHR1 wherein R1 represents (C1-C8)-alkyl group in the presence of alkylaluminum compound in the mole ratio Al/Ti from 0.001 to 50 in such degree that the amount of α-olefin prepolymer is up to 100 g/g of solid component of catalyst. Also, invention describes a method for (co)polymerization of ethylene that is carried out in the presence of the prepolymerized catalyst and alkylaluminum compound. Invention provides preparing polymers of high bulk density and high activity, and decreasing formation of small particles also.

EFFECT: improved and valuable properties of catalyst.

18 cl, 8 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely phenyltrichloromethane PhCCl3. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 4 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely XkSiCl4-k, wherein X is OR' or R', in which R can be C1-C4-alkyl or phenyl, and k=1-2. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 13 ex

The invention relates to methods for macromolecular higher poly-alpha-olefins, in particular polyacene, and catalysts for carrying out the method

FIELD: rubber industry.

SUBSTANCE: invention relates to a process of manufacturing butadiene rubber, which is product of stereospecific solution polymerization of butadiene or butadiene with isoprene in presence of rare-earth element-based complex catalyst. In one embodiment of the process, blend composed of butadiene or butadiene/isoprene, hydrocarbon solvent and catalytic complex is charged into polymerizer, said catalytic complex being formed by interaction of rare-earth element, diene hydrocarbon, organoaluminum compound, and haloorganic compound. To that end, prior to be charged into polymerizer, blend is supplemented by more organoaluminum compound being mixed with the latter under turbulence conditions, whereupon catalytic complex is added to turbulently moving stream. Turbulence conditions are created with the aid of convergent-divergent-type mixer or Rashig rings, or pump. In another embodiment, organoaluminum compound is additionally added to blend, after which the blend is mixed with organoaluminum compound and catalytic complex preliminarily formed under turbulence conditions, after which mixture is charged into polymerizer under turbulent stream movement conditions, these conditions being created as described above. It is also possible that blend is preliminarily mixed with organoaluminum compound, after which catalytic complex is added, all operations being also performed under turbulence conditions.

EFFECT: reduced consumption of catalytic complex when butadiene rubber is manufactured with required Mooney viscosity index.

3 cl, 3 dwg, 5 ex

FIELD: organic chemistry, polymers, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of polymers by method of "living" radical polymerization and to "living" polymers synthesized by this method. Invention describes a mixture of initiating agent of "living" radical polymerization represented by the formula (1): , and compound represented by the formula (2): (R1Te)2 used for polymerization of vinyl monomers taken in the ratio from 0.1 to 100 moles of compound of the formula (2) per one mole of initiating agent of the formula (1) wherein R1 means (C1-C8)-alkyl, aryl or aromatic heterocyclic group; each among R2 and R3 means hydrogen atom or (C1-C8)-alkyl group; R4 means aryl, substituted aryl, hydroxycarbonyl group or cyano-group wherein R has value given above. Also, invention describes a method for synthesis of "living" polymer by method of "living" radical polymerization wherein vinyl monomer is polymerized by using a mixture of initiating agent of "living" radical polymerization represented by the formula (1) and compound represented by the formula (2). Invention describes polymer synthesized by polymerization of vinyl monomer by using initiating agent mixture given above. Also, invention describes methods of synthesis of diblock-copolymer and triblock-copolymer and these diblock-copolymers and triblock-copolymers are described. Invention provides a method for synthesis of polymers comprising "living" chain allowing carrying out the precise control of molecular masses and molecular-mass pattern. Polymers synthesized by the proposed method allow easy conversion of their terminal groups to other functional groups useful for preparing macromonomers that can be used as places for pouring off and useful as agents providing compatibility and as materials for producing block-polymers.

EFFECT: improved method of synthesis, valuable properties of polymers.

15 cl, 3 tbl, 42 ex

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 methods for producing socialization for the polymerization of butadiene, occurring in the presence of cobalt containing catalysts, and may find application in the IC industry in the production of CIS-1,4-polybutadiene

The invention relates to new colophony to zirconocenes (TP), namely the ANSA-zirconocenes with cyclogeranyl bridge, functionalized directly on the bridge, which can be used as catalysts in the chemical industry for production of polyolefins (PO)

The invention relates to new ANSA-zirconocenes, namely zirconocenes with unsaturated 2,5-dihydro-1H-silydianin bridge, which can be used as catalysts in the chemical industry for production of polyolefins

The invention relates to the field of technology of macromolecular compounds, namely a process for the production of stereoregular Polivanov under the influence of the catalytic systems of the Ziegler-Natta

FIELD: polymer production.

SUBSTANCE: invention relates to polyolefin production technology, notably to synthesis of ethylene copolymers on modified chromium oxide catalyst under low pressure conditions is gas-phase fluidized-bed reactor. More particularly, low-pressure polyethylene production via continuous gas-phase ethylene/α-olefin copolymerization process is disclosed, said process being carried out in a reactor with fluidizing grate using catalyst containing chromium oxide, modifying oxide, fluorine, and silica as carrier. Reaction mixture composed of ethylene, α-olefin, hydrogen, and nitrogen and compositionally adjusted when being circulated by adding appropriate amounts of indicated constituents, provided that nitrogen content lies allays within a range of 30-50% based on the total volume of reaction mixture, is fed into reactor below fluidizing grate. Additional amounts of nitrogen are continuously introduced into reactor as a separate stream above fluidizing grate at the catalyst supply level. Chromium oxide contained in catalyst is chromium reduction product with chromium in the form of Cr2+ and modifying oxide is aluminum oxide prepared from alkoxyalumoxane. Silica carrier is modified with fluorine in the preliminary drying step.

EFFECT: increased yield of polyethylene based on unit mass of catalyst and reduced consumption of catalyst without loss in product quality.

1 dg, 3 tbl, 10 ex

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