Polymerization catalyst prepared by spraying drying and method for polymerization using this catalyst

FIELD: catalysts, chemical technology.

SUBSTANCE: invention elates to catalytic compositions, methods for preparing such compositions, and to methods for preparing polymers based on thereof. Invention describes a composition of a spraying drying catalyst precursor and a method for preparing a spraying drying catalyst precursor wherein this composition comprises inert filling agent, magnesium, transient metal, solvent and one electron-donor compound. The composition of catalyst precursor doesn't contain practically other electron-donor compounds and the molar ratio of electron-donor compound to magnesium = 1.9 or less, and the composition comprises particles with particles size from about 10 mcm to about 200 mcm. Also, invention describes catalysts prepared from spraying drying catalyst precursors, and methods for polymerization using such catalysts. Invention provides the improved output and catalytic activity of catalyst.

EFFECT: improved properties of catalyst, improved method of polymerization.

29 cl, 4 tbl, 4 dwg, 5 ex

 

The technical field to which the invention relates.

The present invention relates to catalyst compositions, methods of producing such compositions and methods of producing polymers based on them.

Background of invention

Properties of polymers depend on the properties of the catalyst used. For catalyst it is important to regulate the shape, dimensions and distribution of the catalyst particles by size to ensure a good and suitable for industrial application performance. This is especially important in the processes of gas-phase polymerization and polymerization in suspension. For example, to obtain pellets of a copolymer of 1000 μm, the size is generally preferred catalyst particles for use in the polymerization is from about 10 to about 50 microns. The catalyst should possess good mechanical properties to withstand the wear and tear in the polymerization process, and to ensure a good bulk density of the resulting polymer. One of the important aspects in the development of a catalyst of polymerization is, therefore, in providing the catalyst and method of preparation of the catalyst, which allows you to adjust and correct the structure and dimensions of the catalyst particles, and the distribution of particle sizes. The receipt of such a catalyst is in should be a simple process.

Spray drying is one of the methods of obtaining the catalyst particles, which allows you to adjust the size and shape of the resulting catalysts. When spray drying the liquid droplets containing dissolved and/or suspended materials are popped from the flywheel grinder or nozzles. The solvent is evaporated and the solid residue remains. The size and shape of the resulting particles depend on the characteristics of the droplets formed during the spraying process. The structural organization of the particles can be affected, changing the volume and size of droplets. Depending on the conditions of the spray drying process, you can get large, small, or aggregated particles. Depending on conditions, you can also obtain particles that are uniform in composition, or a mixture of the components of the solution. The use of inert fillers in the spray drying can help to regulate the shape and composition of particles.

Numerous catalysts spray drying process for the polymerization of olefins containing magnesium and titanium, and methods of obtaining, using such catalysts described in the literature. However, the content of magnesium in such methods is limited by the solubility of magnesium in a solvent. In General, it is expected that the solubility increases with temperature. However, the solubility of magnesium halides in kotoryj preferred organic solvents, such as tetrahydrofuran (THF), in which dissolve the magnesium-containing components, in fact, decreased from approximately room temperature to the boiling temperature of these solvents. It is believed that the decrease in solubility is due to the formation of polymeric complexes of magnesium halide with the solvent having lower solubility, such as MgCl2(THF)1,5-2. For example, the maximum concentration of ultra-pure magnesium chloride, which can be achieved in THF, is less than about 0.75 mol MgCl2/liter At a temperature of about 60°near the boiling point of THF, the solubility of magnesium chloride is markedly reduced to less than 0.5 mol/L. However, if you use magnesium chloride selling brands, its maximum solubility in THF is reduced to about 0.6 mol MgCl2/L. the solubility of magnesium chloride in the solutions obtained from magnesium chloride sales quality at 60°C is only about 0.35 mol/L.

The low solubility of magnesium in a solvent limits the number and distribution of the halide of magnesium, which can be fed into the catalyst particles spray drying. However, high concentrations of magnesium particles in spray drying to provide catalysts that allow to obtain polymers with more desirable properties, and which have high catalytic activity; therefore, increase the demand and the economic efficiency of the catalysts. Thus, it is desirable that provision catalyst spray drying, which has a high magnesium content.

Summary of the invention

Addressing the needs described above, in one of the preferred variants of the present invention provides the composition of the catalyst precursor, comprising (1) a mixture of the reaction product of a magnesium halide, a solvent, and an electron-donor compound; and (2) an inert filler. The transition metal in the transition metal compound selected from transition metal of groups 3-10 and lanthanides. The composition of the catalyst precursor contains almost no other electron-donor compounds, and the molar ratio of electron donor compound to magnesium is less than or equal to 1.9. The composition of the catalyst precursor also include a spherical or nearly spherical particles having an average particle size of more than about 10 microns.

In addition, in the present invention are included the methods of obtaining compositions of the catalyst precursor. Such methods include (1) providing a mixture of the reaction product of a magnesium halide, a solvent, electron-donor compounds and compounds of the transition metal; (2) contacted the e mixture or reaction product with an inert filler with the formation of the suspension; (3) spray drying the suspension. The compound of the transition metal can be selected from transition metal compounds containing a transition metal of groups 3-10 and lanthanides. In these methods, the composition of the catalyst precursor will be virtually free of other electron donor compounds, and the molar ratio of electron donor composition to magnesium is less than or equal to 1.9. The composition of the catalyst precursor also include a spherical or nearly spherical particles having an average particle size of more than about 10 microns.

In another aspect, this invention involves a catalytic composition, which include the product of (1) a mixture of the reaction product of a magnesium halide, a solvent, an electron-donor compound; the transition metal compound, and an inert filler; and (2) a co-catalyst composition. The catalytic composition contains almost no other electron-donor compounds, and the molar ratio of electron donor compound to magnesium is less than or equal to 1.9, with a catalytic composition comprises spherical or nearly spherical particles having an average particle size of more than about 10 microns.

In another aspect, methods for producing polymers comprising the reaction of at least one polyolefin monomer in the presence of catalytic comp the dispositions, also included in the present invention.

In some preferred embodiments, the composition of the catalyst precursor or catalyst composition comprises particles in which the ratio of magnesium to titanium is greater than about 5:1. In other preferred embodiments, the ratio of magnesium to titanium is from about 6:1 to about 10:1.

In some preferred embodiments, the particles of the composition of the catalyst precursor or catalyst compositions have such a distribution of particle size at which 10% by weight of the particles are of a particle size of less than about 15 microns. In other preferred embodiments, 90% by weight of the particles are of a particle size from less than about 40 to about 70 microns. In some preferred embodiments, the particles are almost spherical and have a wingspan distribution from about 1 to about 2.5. In some particularly preferred embodiments, the particles are not agglomerated and have a distribution of particle size at which 50% by weight of the particles have sizes less than about 20 to about 35 microns. Some preferred catalytic compositions described in the present description, have an average particle size of from about 10 to about 60 μm and the scale of distribution of from about 1.5 to about a 2.0.

In some preferred embodiments, the electron donor is in is a donor of electrons, which includes linear or branched aliphatic or aromatic alcohol containing from one to about 25 carbon atoms. Preferred alcohols include methanol, ethanol, propanol, ISO-propanol, butanol, 2-ethylhexanol, 1-dodecanol, cyclohexanol and tert-butylphenol. In some preferred embodiments, the molar ratio of alcohol to magnesium is less than around 1.75. In other preferred embodiments, the molar ratio of alcohol to magnesium is from about 0.1 to about 1.1. In some preferred embodiments, the molar ratio of alcohol to magnesium is from about 0.1 to about 0.5.

Preferred transition metal compounds suitable for the preferred options of the compositions and methods described in the present description, include compounds of titanium, zirconium, hafnium, vanadium, niobium, tantalum, or combinations thereof. Some compounds of titanium are described by the formula:

Ti(R)aXb,

where R represents R' or COR'where R' represents a C1-C14aliphatic or aromatic hydrocarbon radical, X is chosen from Cl, Br, I, or mixtures thereof, a is 0 or 1, b is from 2 to 4 inclusive, a+b=3 or 4. Examples of titanium compounds include TiCl3, TiCl4, Ti(OS6H5)Cl3, Ti(ASON3)Cl3, Ti(EA6H5)Cl or mixtures thereof.

The solvent is chosen from the group comprising alkyl esters of aliphatic and aromatic carboxylic acids, ethers, and aliphatic ketones. Preferred solvents based on alkyl esters include, but are not limited to, methyl acetate, ethyl acetate, ethylpropane, methylpropionate, ethylbenzoic and combinations thereof.

Preferred ethers include diethyl ether, diisopropyl ether and di-n-butyl ether, ethylisopropylamine ether, methylbutylamine ether, metalalloy ether, ethylenically ether, tetrahydrofuran, 2-methyltetrahydrofuran and combinations thereof. In some preferred embodiments, the tetrahydrofuran is preferred. Typical ketone solvents include acetone, methyl ethyl ketone, cyclohexanone, cyclopentylmethyl, 3-bromo-4-heptanone, 2-chlorocyclopentane, allylmercaptan and combinations thereof. Some preferred variations include two or more such solvents.

The magnesium halides for use in the present description, the compositions include, but are not limited to, MgCl2, MgBr2, MgI2, MgClBr, MgBrI or mixtures thereof. In some preferred embodiments, these halides can be used to prepare compositions of the catalyst precursor and catalyst compositions, to the E. include compositions of the formula:

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

where ROH includes linear or branched alcohol containing from one to about 25 carbon atoms, R is R' or COR', where each R' individually represents an aliphatic hydrocarbon radical containing from one to about 14 carbon atoms, or aromatic hydrocarbon radical containing from one to about 14 carbon atoms; X is individually Cl, Br or I; S is chosen from the group comprising alkyl esters, aliphatic ethers, cyclic ethers, and aliphatic ketones; m is from 0.5 to 56; n is 0, 1 or 2; p ranges from 4 to 116; q is from 2 to 85; d is from 0.1 to 1.9. In some preferred embodiments, g is from 0.1 to less than about 0.5.

In some preferred embodiments, compositions in the present description further include a mixture or reaction product of a Lewis acid with the composition of the catalyst precursor or catalyst composition. Some suitable Lewis acid correspond to the formula RgMX3-gwhere R represents R' or or' or NR'2where R' represents a substituted or unsubstituted aliphatic or aromatic hydrocarbonous group containing from 1 to 14 carbon atoms, X is chosen from gr is PPI, includes Cl, Br, I and mixtures thereof; g is 0-3, and M represents aluminum or boron. Typical Lewis acid include tri-n-hexylamine, triethylamine, chloride diethylamine, trimethylaluminum, chloride dimethylamine, dichloride methylalanine, tri-ISO-butylamine, tri-n-butylamine, chloride, di-ISO-butylamine, dichloride isobutylamine, (C2H5)AlCl2, (C2H5O)AlCl2, (C6H5)AlCl2, (C6H5)AlCl2, (C6H13O)AlCl2, and combinations thereof. Typical boron-containing Lewis acid include BCl3, BBr3B(C2H5)Cl2, B(OC2H5)Cl2In(C2H5)2Cl, (C6H5)Cl2, B(OC6H5)Cl2B(C6H13)Cl2, B(OC6H13)Cl2and B(OC6H5)2Cl, and combinations thereof.

Although you can use any co-catalyst, some suitable co-catalysts correspond to the formula AlX'd(R)cHewhere X' represents Cl or or"', R" and R"' are individually C1-C14substituted hydrocarbon radicals, d is 0-1,5, f is 0 or 1; c+d+e=3. Typical catalysts include Al(CH3)3, Al(C2H5)3, Al(C2H5)2Cl, Al(i-C4H9)3, Al(C2H5)1,5C 1,5, Al(i-C4H9)2H Al(C6H13)3, Al(C8H17)3, Al(C2H5)2H, Al(C2H5)2(OS2H5), and combinations thereof.

Preferred inert fillers in the present description include silicon dioxide, titanium dioxide, zinc oxide, magnesium carbonate, magnesium oxide, carbon, and calcium carbonate. Typically use one type of filler; however, some preferred variants further include a second inert filler. In some preferred embodiments, the particles of the filler or fillers include from about 10 to about 95 wt.% particles of the catalytic composition.

In some particularly preferred embodiments, the compound of the transition metal includes Ti, and the ratio of co-catalyst and Ti is from about 1 to about 400 mol of catalyst per 1 mole of Ti. In other preferred embodiments it may be preferable ratio of co-catalyst to Ti, which is from about 15 to about 60 mol of catalyst per 1 mole of Ti. In some preferred embodiments, the ratio of co-catalyst to Ti is from about 4 to about 10 mol of compound-activator 1 mol Ti.

Some of the ways polymerization described in the present description, provide a polymer containing ethylene in number is the number, which is greater than or equal to about 90% mole., and containing one or more co-monomers in a quantity less than or equal to about 10% mole. Some preferred variants of the methods of polymerization to provide a polymer having a density in the range from 0.88 to to about 0,98 g/cm3.

Brief description of drawings

Figure 1 presents the characteristics of solubility MgCl2in solutions in THF for three preferred variants of the present invention, i.e. the dependence of solubility on alcohol content and temperature of the solution.

Figure 2 presents the solubility profiles of several preferred variants of the present invention depending on temperature, concentration of MgCl2and relationships alcohol: Mg in THF.

Figure 3 shows the reaction system with fluidized bed used in the preferred embodiments of the catalysts of the present invention.

On figa shows a photograph of a scanning electron microscope (SEM), comparative conventional catalyst spray drying.

On FIGU shows a photograph of a scanning electron microscope (SEM), one of the typical preferred options of the catalyst according to the present invention.

Description of the preferred variants of the present invention

Preferred variants of the present from which retene provide the composition of the catalyst precursor, obtained by spray drying, and a method of obtaining the composition of the catalyst precursor obtained by spray drying with an inert filler, magnesium, transition metal, solvent and one electron-donor compound. The composition of the catalyst precursor contains almost no other electron-donor compounds, the molar ratio of electron donor compound to magnesium is less than or equal to 1.9, and it includes a spherical or nearly spherical particles having a particle size of from about 10 to about 200 microns.

In one of the preferred variants of the method of obtaining such compositions catalyst precursor includes forming solid compositions predecessor of inert filler, magnesium, transition metal; a solvent; and one electron-donor compound by forming a suspension solution of magnesium compounds, electron-donor compounds, and compounds of the transition metal in a solvent containing an inert filler. The mixture is subjected to spray drying by breaking into small particles, to obtain particles having a usable distribution of particle sizes. The catalysts can be obtained by contacting the composition of the catalyst precursor with a co-catalyst. The composition of predestin the ka of the catalyst or catalyst composition optionally modify the Lewis acid and/or alkylating agent.

In the following description, all numbers listed in the description, are approximate values, regardless of whether used or not used in connection with them the words "about" or "approximately". They can vary in size up to 1.2, 5%, or sometimes 10-20%. When using the numeric interval with a lower limit, RLand the upper limit of RUany number R that fall in this interval, specifically included in the description. Specifically, the following numbers R within the range are specifically included: R=RL+k·(RU-RL), where k is a variable ranging from 1 to 100%, with increment of 1%, that is, k is 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 defined above, specifically incorporated in the present description.

The expression "nearly spherical" in the present description means that the particles have an average aspect ratio of from about 1.0 to about a 2.0. Aspect ratio is defined in the present description as the ratio of the maximum linear dimension of the particle to the minimum linear dimension of the particle. The characteristic value can be determined from the data of scanning electron microscopy (SEM). Of course, this definition, in accordance with the intent of the m authors, includes spherical particles, which by definition have a characteristic ratio equal to 1.0. In some preferred embodiments, the catalytic composition has an average aspect ratio of about 1.8, and 1.6, and 1.4, or 1.2.

Any reference in the present description by "electron-donor compounds" means compounds that modify the solubility of the halide of magnesium in the electron donor solvent so that the solubility is not falling within any interval of temperatures 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 if such solvents are electron-donor character. Typical electron-donor compounds include alcohols, thiols, weak donor amines and phosphines. In the present description, the term "contains almost no other electron-donor compounds" means that other electron-donor compounds"as defined in the present description, are not present in concentrations higher than the concentrations typically found as impurities in sales agents containing such compounds that are sold for use as solvents. Thus, the compositions containing the solvent region is giving the electron-donor characteristics, and "electron-donor substance" is considered as "practically free of other electron donor compounds". In some preferred embodiments, the "practically free" means less than 1, of 0.1, 0.01, or about 0.001 wt.%.

Usable solvents include any connection on the basis of simple ester, ketone or ether complex. If these solvents possess electron-donor characteristics, any reference in the present description by "solvent" or "solvent" does not include those compounds defined above as "electron-donor compounds". Thus, compositions which contain virtually no other electron donor compounds can include one or more solvents.

In the present description, the term "simple" air " is defined as any compound of the formula R-O-R', where R and R' represent a substituted or unsubstituted gidrolabilna group. In some cases, R and R' are the same. Typical, but not limiting scope of the present invention, symmetrical ethers are diethyl ether, di-isopropyl ether and di-n-butyl ether. Typical unsymmetrical ethers include ethylisopropylamine ether and methylbutanoyl ether. Examples of suitable substituted ethers include, for example, metalalloy ether and ethylenically ether. In e is e some preferred embodiments, R and R' may form a condensed ring, which may be saturated or unsaturated. One example of such compound is tetrahydrofuran. Other suitable substance of such cyclic ester is 2-methyltetrahydrofuran. Here again, the individually listed compounds are given only as examples of the types of compounds which are suitable, however, any connection with the ether functional group R-O-R', suitable for use.

In the present description, the term "ketone" is defined to indicate any of the compounds having the formula R(C=O)R'. R and R' may be individually substituted or unsubstituted hydratability groups as another way described above with respect ethers. Typical ketones are acetone, methyl ethyl ketone, cyclohexanone, cyclopentylmethyl. You can also use halogenated ketones, such as 3-bromo-4-heptanone, or 2-chlorocyclopentane. Other suitable ketones may include other functional groups such as unsaturated groups, as in allylmethylamine. Each of these compounds corresponds to 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 for use esters include any compound of General formula R(C=O)OR'. In such compounds the carbon atom of the carbonyl gruppierte one relationship with the carbon atom, and another bond with the oxygen atom. R and R' are individually selected from substituted or unsubstituted hydrocarbonrich groups, and they may be the same or different. In some preferred embodiments, ester include alkyl esters of aliphatic and aromatic carboxylic acids. Cyclic esters, saturated esters and halogenated esters are also included in this group. Typical, but not limiting scope of the present invention the esters include methyl acetate, ethyl acetate, ethylpropane, methylpropionate and ethylbenzoic. Here again individually listed compounds are given only as examples of the types of compounds suitable for use. Any compound corresponding to the General formula R(C=O)OR', suitable for use in the present invention.

Any suitable solvent can be brought into contact with a source of magnesium by direct mixing of the magnesium halide with the solvent. In some preferred embodiments, the magnesium halide is a chloride of magnesium; however, you can also use magnesium bromide and magnesium iodide. As sources of halides can be used, the magnesium halides, such as MgCl2, MgBr2, MgI2or mixed halides of magnesium, for example, MgClI, MgClBr and MgBrI. In some preferred embodiments, halo is and magnesium is added to the solvent in anhydrous form. In other preferred embodiments, the halide of magnesium added in hydrated form.

Usually the solvent is provide in a large excess with respect to the first coordination environment of magnesium. In some preferred embodiments, the ratio of solvent to magnesium is about 100:1, in other preferred embodiments, the ratio may be even greater. In some preferred embodiments, the solvent is present in such quantities that one mol of magnesium have the following number of moles of solvent from at least about 1.0, at least about 2,0; at least about 5.0 to at least about 10, or at least about 20. In some preferred embodiments, it is possible to use two or more solvents.

Electron-donor compound is added to the mixture of solvent and halide of magnesium in whatever way is appropriate. Preferred electron-donor compound is directly added to the mixture. Alcohol can represent any single chemical compound having the General formula ROH. R can be any substituted or unsubstituted hidrocarburos group. In some preferred embodiments, the alcohol is an aliphatic alcohol containing from about 1 to about 25 carbon atoms. In some before occhialini embodiments, the alcohol is a monodentate alcohol. In the present description, the term "monodentate alcohol" means an alcohol in which R is a Deputy that the substitution does not result in a molecule containing more than one hydroxyl group (OH), which is coordinated with the atom of magnesium in solution. Typical of such alcohols may include methanol, ethanol, propanol, ISO-propanol and butanol. Alcohols containing more than long-chain aliphatic group, such as 2-ethylhexanol, or 1-dodecanol, also form a solution in which the solubility of the halide of magnesium increases with temperature. You can also use alcohols containing more carbon atoms. Alcohol may also be a cyclic alcohol, such as cyclohexanol, or aromatic alcohol such as phenol or tert-butylphenol.

In certain preferred embodiments, the ratio of the used electron-donor compound to magnesium halide is less than or equal to 1.9. In some preferred embodiments, the molar ratio of electron donor compound to magnesium is less than approximately 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 still other preferred embodiments, the molar ratio of electron donor compound to magnesium is about 0.1. In other preferred embodiments, the molar ratio may be higher to 1.9, for example approximately 2,0, approximately 2.1, about 2.2, about 2.5 and about a 3.0. In General, some amount of electron-donor compounds can communicate with other components in the cooking process.

Adding small amounts of one electron-donor compounds, other relative to the solvent, mixtures, solvent-and halide of magnesium, gives a magnesium-containing 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 comparative solubility of the adducts of the magnesium halide/electron donor containing additional electron-donor compounds. I think that adding small amounts of one of the electron donor to the solvent in the presence of a halide of magnesium inhibits the conversion of soluble particles in the polymer adducts. In some preferred embodiments, the soluble particles correspond to the formula

MgXx(ED)ySz,

where x is usually 2, satisfy the oxidation state of magnesium, and less than 4, x+y+z is less than or equal to 6. In some preferred embodiments, y is about 0.5, 0.75, and 1, of 1.5, about 1.75, or 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 increasing temperature up to the boiling point of the solvent. If the solvent is a THF concentration of the halide of magnesium in solution can be up to five times more than in the comparative solutions, in which there is no electron-donor compound, especially if the electron-donor compound is an alcohol.

Figure 1 shows the solubility profile of solutions of magnesium chloride in tetrahydrofuran depending on temperature. As can be seen from figure 1, the composition does not contain alcohol, typically have a solubility of the halide of magnesium, which increases from about 0.5 mol of magnesium per liter up to a maximum value less than about of 0.65 mol of magnesium per liter at about 30°C. Above 30°solubility decreases gradually until it reaches the boiling point of the solvent. On the contrary, the mixture to which is 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, a mixture in which the ratio of ethanol to magnesium is about 0.5, exhibit a solubility of magnesium in 15°S, SOS is alleyway to about 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 increases above 30°C, the solubility remains almost constant until it reaches the boiling point.

Figure 1 also shows the change in 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 about 55°and remains almost constant up to the boiling point of the solvent. Samples that contain two moles of alcohol per mole of magnesium, also demonstrate that the solubility of magnesium increases with increasing temperature up to the boiling point, at which the value is around 1.75 mol of magnesium per liter.

Figure 2 shows the profile of the solubility of several compounds containing various amounts of added alcohol. Each data point in figure 2 was obtained by adding the amount of magnesium chloride, necessary to achieve the required concentration at which the entire magnesium chloride dissolved in THF as an electron donor. Then add a portion of the alcohol to obtain the desired ratio of alcohol: magnesium, and the mixture is then heated to dissolve the composition in THF. Then the solution was slowly cooled, until then, until it started to form a precipitate. The temperature at which they began to precipitate formed, was recorded as the value on the y-axis in figure 2. Thus, figure 2 shows the temperature, which is necessary to obtain solutions of magnesium chloride of different concentrations in the presence of alcohol. For example, some data 210 shows the temperature required to achieve a solution in which the concentration of magnesium chloride is 0.75 M, where the solvent is THF in the presence of different concentrations of ethanol. In mixtures, prepared at the 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, comprising 0.5 to attain a concentration in magnesium 0.75 M at about 15°Since, while the mixture with the ratio of 1.0 reaches 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 mole., the solutions reach the magnesium concentration of approximately 0.75 in, at about 47 and 53°C, respectively. Thus, the number of data 210 shows that mixtures with higher relationship alcohol: magnesium tend to be the fact that they are less Astoria in the solvent.

Thus, figure 2 shows that at lower relationship of alcohol to magnesium chloride obtained solutions with a higher concentration of dissolved magnesium. The decrease in solubility with increasing ratio ROH/MgCl2implies that small amounts of added ROH prevent the formation of polymeric adduct MgCl2(THF)2and add more significant amounts of ROH, or more alcohols, shifts the solution to less soluble adducts containing more than ROH. Used ratio ROH/Mg determines the maximum solubility that can be achieved at the desired temperature. The data series 220-260 in figure 2 show that the relationship alcohol: magnesium increased temperature leads to increased levels of soluble magnesium. For example, solutions having a molar ratio alcohol: magnesium, amounting to 0.5, have the concentration of magnesium in solution of approximately 0.75 M, about 15°With, while at about 20°With achievable concentration of magnesium in solution, component 1.0 M 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 also increases for temperatures above 30°C. for Example, solutions having a molar ratio of alcohol is magnesium, component 1 are at a temperature of about 35°the solubility of magnesium chloride of approximately 0.75 M, while at about 41°the solubility increases to about 1 M. the Data are represented by lines 230-260 show that the solubility continues to increase until it approaches the boiling point of THF. Solutions having a higher ratio of alcohol:magnesium, show similar behavior.

The nature of the particles in the solution was found using a variety of methods. The study by NMR showed that the electron donors, coordinated with MgCl2in THF solution, are in rapid equilibrium, individual long-lived particles do not exist. The gas phase above the solution on the basis of THF containing MgCl2and two equivalents of ethanol (EtOH) per Mg, contains significantly less alcohol than the gas phase above the same with a solution of EtOH/THF, containing MgCl2. This suggests that ethanol captured molecules MgCl2located in the solution. Obviously, alcohol group coordinated with the center MgCl2in the solution phase. The maximum solubility at average relationship alcohol: MgCl2suggests that in solution there are some particles, whose concentration depends on the nature of alcohol, specific relationships alcohol: Mg and t is mperature solution.

When forming the catalyst precursor solution of magnesium halide in contact with the source of titanium. Suitable precursors of magnesium described in the related applications Burkhard E. Wagner, and others, under the heading "Enhanced Solubility of Magnesium Halides and Catalysts and Polymerization Processes Employing Same", filed July 15, 2002, is incorporated into this description by reference; "Spray-Dried Polymerization Catalyst and Polymerization Processes Employing Same", filed July 15, 2002, is incorporated into this description by reference; and "Spray-Dried Polymerization Catalyst and Polymerization Processes Employing Same", filed July 15, 2002, is incorporated into this description by reference.

The transition metal compounds that are soluble in the solvent, can be used as a source of the transition metal catalyst. The amount of transition metal compounds or mixtures of compounds of the transition metal used in the preparation of precursors of the catalyst may vary within wide limits, depending on the type of catalyst required. In some preferred embodiments, the molar ratio of magnesium to transition metal compound can be high, up to about 56, preferably from about 20 to about 30. In other preferred embodiments, the molar ratio of magnesium to transition metal compound is low, approximately 0.5. In General, preferred are molar ratio of magnesium is to the compound of the transition metal, constituting from about 3 to about 6, and the transition metal is titanium.

However, in some preferred embodiments, the titanium source may not be highly soluble, and in other cases it may be insoluble in the solvent. In some preferred embodiments, the titanium can be put in the form of compounds having the General formula Ti(OR)aXbwhere R represents a C1-C14aliphatic or aromatic hydrocarbon radical, or COR'where R' represents a C1-C14aliphatic or aromatic hydrocarbon radical, X is chosen from the group comprising Cl, Br, I, or mixtures thereof, a is 0 or 1, b is from 2 to 4 inclusive, a+b=3 or 4. Some examples of suitable titanium compounds include, but are not limited to, TiCl3, TiCl4, Ti(OS6H5)Cl3, Ti(ASON3)Cl3and Ti(EA6H5)Cl3. In some preferred embodiments, it is possible to use one connection titanium, while in others the titanium source may be one or more different containing titanium compounds. Regardless of the source of titanium, it can be added to a mixture solution of a precursor of magnesium in quantities to achieve a molar ratio of magnesium to titanium, comprising from about 0.5 to about 1.0, from the ome 1.0 to about 5.0 and from about 5.0 to about 10.0, or from about 10.0 to about 56.

The titanium source can be added to the reaction mixture at any convenient time. In some preferred embodiments, the titanium added after the magnesium halide and an electron-donor compound were added to the solvent. In some preferred embodiments, the composition of the catalyst precursor has the formula according to the following General equation:

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

where ROH is a linear or branched alcohol containing from one to about 25 carbon atoms, R is R' or COR', where each R' individually represents an aliphatic hydrocarbon radical containing from one to about 14 carbon atoms, or aromatic hydrocarbon radical containing from one to about 14 carbon atoms; X is individually Cl, Br or I. B formula S is a solvent selected from the group comprising alkyl esters of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers, and aliphatic ketones, m is from 0.5 to 56, n is 0, 1 or 2, p ranges from 4 to 116, and q is from 2 to 85, r ranging from 0.1 to 1.9. In some preferred embodiments, r in formulaically 0,25, 0,3, 0,4, 0,5, 0,75, 1,0, 1,25, 1,5 1.75.

Typically, the solution containing the mixture of the reaction product of the composition based on the magnesium halide and the source of titanium is in contact with an inert filler. Suitable fillers are solid, granular compounds or compositions, which are inert to the other components of the catalytic composition, and other active components of the reaction system. Any solid bulk composition, which is inert to the other components of the catalytic system and does not cause harmful effects on the polymerization, can be used as filler in preferred embodiments of the present invention. Such compounds can be organic or inorganic and include, but are not limited to, silica, titanium dioxide, zinc oxide, magnesium carbonate, magnesium oxide, carbon, and calcium carbonate. In some preferred embodiments, the filler is a vaporized hydrophobic silicon dioxide, which gives a relatively high viscosity of the suspension and good hardness particles obtained by spray drying. In other preferred embodiments, it is possible to use two or more filler. In some preferred embodiments, the filler has a particle size of about 0.05 microns to about 1 the km In other preferred embodiments, the average particle size is about 0.1 μm, about 0.2 μm, about 0.3 μm, or about 0.4 μm. One useful fillers is Cabosil®who supplies the company Cabot Corporation. According to the manufacturer, one of Cabosil®is an amorphous silicon dioxide having a maximum content of remnant size of 325 mesh, amounting to 0.02%and a bulk density of about 3.0 lb./cu.ft. You can also use crystalline fillers. In some preferred embodiments, the filler may have a specific surface area comprising from about 100 to about 300 m2/g, for example, approximately 200 m2/g, approximately 225 m2/g, or about 250 m2/g measured by the BET method, as described in article S.Brunauer, .Emmet, E.Teller in the Journal of the American Chemical Society, 60, SS-319 (1939). In other preferred embodiments, the filler may have a specific surface area which is not included in the specified interval.

The filler should be dry and not contain absorbed water. Drying of the filler is carried out by heating it at a temperature below the sintering or melting of the material of the carrier. Usually use a temperature of at least 100°C. you Can use a lower temperature, if acceptable is to increase drying time,or if the carrier has a low melting point or agglomeration. Inorganic materials media is usually dried at a temperature of about 200-800°C. moreover, the filling material can optionally be processed by one or more Lewis acid in an amount of 1-8 wt.%, for example, but not limiting scope of the present invention example, compounds alkylamine or Grignard reagents, in order to accelerate the removal of the absorbed water. This modification of the filler compounds allylamine also provides a catalytic composition having increased activity and improves the morphology of the particles of the polymer end-of polymers of ethylene.

After cooking the dried filler it is combined with the composition of the catalyst precursor or suspension of the composition of the catalyst precursor, to obtain a slurry suitable for spray drying. Suitable suspension include, but are not limited to such suspensions, which include a filler which contains from about 1 to about 95 wt.% the catalytic composition. In some preferred embodiments, the filler comprises about 30, about 40, about 50, or about 60 wt.% the catalytic composition. In the process of spray drying such suspension give the individual catalyst particles, in which the filler is present in an amount of from 10 to about 95 wt.% from the mass of the hour the Itza catalyst. In some preferred embodiments, the filler is about 10-20 wt.% by weight of the catalyst particles obtained by spray drying. In other preferred embodiments, the filler may be about 30, about 40, about 50, or about 60 wt.% by weight of the catalyst particles obtained by spray drying.

Spray drying can be accomplished using any suitable technique. However, the catalysts described in the present description, are not limited to those who receive the spray drying. Typical methods of spray drying are described in patents US 4293673 and 4728705, both of which are included in the present description by reference. In preferred embodiments of the invention, the spray drying is usually carried out by mixing the solution or suspension of the complex of the magnesium and titanium compounds with a suitable filler. After mixing the solution or suspension with a filler, the mixture can be heated and then sprayed with suitable spraying device, with the formation of separate particles of approximately spherical shape. Sputtering is typically called by passing the suspension through a nozzle together with an inert drying gas. To cause the spray, you can use a spray nozzle or a centrifugal disc height is low speed. The volume flow rate of the drying gas is significantly higher than the volumetric rate of the suspension to cause atomization of the suspension and removal of excess electron donor compound and another solvent. The drying gas should be not reactive under the conditions of sputtering. Suitable gases include nitrogen and argon. However, you can use another gas, provided that it is not reactive and performs the desired dehydration catalyst. In General, the drying gas is heated to a temperature below the boiling point of the electron donor, or solvent. In some preferred embodiments, the drying gas is heated to a temperature above the boiling point of the electron-donor compound or solvent. In some preferred embodiments, the drying gas is heated to about 200°to accelerate the removal of excess electron donor. If the volumetric rate of flow of drying gas to maintain a very high level, you can use a temperature below the boiling point of the electron-donor compounds. In some preferred embodiments, the pressure of the spray nozzle is about 1, about 2, about 5, about 10, about 25, or about 50 lb./square inch (Rel.). In other preferred embodiments, the spray pressure of approximately 100, 150, or about 200 pounds is./square inch (Rel.). When the centrifugal dispersion of the diameter distribution of the wheel is usually from about 90 to about 180 mm wheel Speed pick so as to adjust the particle size. Normal speed distribution wheel is from about 8,000 to about 24000 rpm, although to obtain particles of the desired size, you can use a higher or lower speed.

Of course, skilled in the art man will appreciate that the concentration of magnesium in the droplets formed during the spray drying, will be directly related to the amount of magnesium in the resulting spray drying the particle.

In some preferred embodiments, the catalyst precursor obtained from the spray drying process in the form of thin, free flowing powder. In some preferred embodiments, the catalyst precursor can have the characteristics of a mixture of crystalline phases and amorphous phases, or to have the characteristics of a mixture containing crystalline and amorphous components. The average particle size of the composition of the catalyst precursor is generally determined by the amount of filler, and other curing components, which shows that at least in some preferred embodiments, the solubility of the magnesium halide is not prewashed is. Thus, the higher the solubility of the magnesium-containing components described in the present description, allows to obtain catalysts and precursors of catalysts containing larger amounts of magnesium. In turn, a higher amount of magnesium give larger particles with higher relationship of magnesium to titanium. In certain preferred embodiments, the ratio of magnesium to titanium is from about 1.5:1 to about 15:1. In some preferred embodiments, the ratio is about 2:1, about 3:1, about 4:1, about 5:1, about 6:1 or about 10:1. Other preferred variants may have a relationship of magnesium to titanium, outside these limits.

In some preferred embodiments, the catalyst particles spray drying have an average particle size of from about 10 to about 200 microns. In some preferred embodiments, the average particle size is about 20 μm or about 30 μm. In other preferred embodiments, the average diameter of the particles obtained by spray drying, is about 40 μm, 50 μm, 60 μm, 75 μm or 90 μm. The average particle size of the catalyst precursor can be determined using a commercially available laser diffraction, such as particle size analyzer Malvern 2600®.

Particles which, obtained by spray drying, are also characterized by their particle distribution. In the present description the expression "D10", "D50and D90" show the corresponding percentiles of the logarithm of the normal distribution of particle size, determined using particle size analyzer Malvern 2600®when using the solvent hexane. Thus, particles for which D50is 12, have an average particle size of 12 μm. D90average of 18 shows that 90% of the particles have a particle size less than 18 microns, and D10equal to 8, shows that 10% of the particles have a particle size less than 8 microns. In some preferred embodiments, the particles of the spray drying have D10, comprising from about 3 to about 20. In other preferred embodiments, D10can be outside of this interval. In some preferred embodiments, D10is about 4.0, about 5,0, or about to 6.0. In other preferred embodiments, D10may be approximately 6.5, about to 7.0, about 7.5, about 8.0 to, or about 8.5. In some embodiments, the value of D10is about 9.0 to about 10.0 to about 11.0 in, about to 12.0, or about 13. Other particles spray drying can have a value of D10approximately 15.

Usually particles Raspletin the second drying have a value of D 50constituting from about 10 to about 60, although in some preferred embodiments, the value of D50may be outside the specified interval. In some preferred embodiments, D50approximately 15,0 about 17,0, approximately 20,0, or about 22,0. In other preferred embodiments, the value of D50is about 23, about 24,0, approximately 25,0, or about 26,0. In some preferred embodiments, the value of D50approximately 28,0, about 30,0 about 40,0, or about 50,0.

The particles have a size of D90that is usually from about 20 to about 70. In some preferred embodiments, D90is about 35, about 40, or about 45. In other preferred embodiments, D90approximately 46,0, about 47,0, about 48,0, or about 49,0. In some preferred embodiments, the filler has a value of D90constituting about 50, about 52, about 54, about 56, about 58, or about 60.

The width or narrowness of the distribution of particles can be described using the peak-to-peak distribution. The amplitude distribution is defined as (D90-D10)/(D50). Suitable for use particle spray drying usually also have the breadth of distribution of about 1.0 to about 30. In some preferred embodiments, the scope of the distribution is about 1.2, about 1.3, about 1.4, or about 1.5. In other preferred embodiments, the amplitude distribution of the filler particles is about 1.6, or about 1.8, about 2,0, about 2.2, or about 2.5. In some preferred embodiments, the catalyst particles spray drying have momentum distribution comprising less than about 2.0 to less than about 1.8, or less than about 1.6. In other preferred embodiments, the particles have a momentum distribution that is less than about 1.5, about 1.3, or about 1.1. The desired amplitude distribution changes depending on the application.

In some preferred embodiments, the composition of the catalyst precursor spray drying modify using the Lewis acid. Processing can be done through a dissolution of the compounds (compounds) of the Lewis acid in an inert liquid solvent, and processing of the composition of the catalyst precursor spray drying the resulting solution used with any convenient method of processing, for example, by simple immersion of the printed composition of the catalyst precursor in the solution of the Lewis acid. The solvent for the Lewis acid must be non-polar and capable of dissolving the compound (link is) a Lewis acid but not the composition of the catalyst precursor. Among the solvents that can be used to dissolve the compounds (compounds) a Lewis acid can be called hydrocarbon solvents, including substituted hydrocarbon solvents such as ISO-pentane, hexane, heptane, toluene, xylene, and aliphatic naphtha mineral oil, such as, but not limited to, Kaydol™, Hydrobrite™ 1000, Hydrobrite™ 550, and the like. It is preferable to use such solvents together with the connection (connection) Lewis acid in such amounts that the resulting solution contains from about 1 to about 25 percent by weight of the compounds (compounds) of the Lewis acid. If desired, the composition of the catalyst precursor can be added to the inert liquid solvent to form a slurry before the connection (connection) Lewis acid is dissolved in a solvent. Alternatively, the connection (connection) Lewis acid can be dissolved in an inert liquid solvent before it is added to the suspension. This technique is particularly suitable in the case when using gaseous compound, for example, BCl3. Alternatively, if desired, a Lewis acid can be directly added to the dry composition of the catalyst precursor.

Suitable Lewis acids is Vlada reagents, which can at least partially remove an electron donor without destroying the inorganic components of the composition of the catalyst precursor. In General, suitable connections acid Lewis have the structure RgAlX3-gand RgI3-gwhere R represents R' or or'or NR'2where R' represents a substituted or unsubstituted aliphatic hydrocarbonous group containing from 1 to 14 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbonyl radical containing from 6 to 14 carbon atoms; X is chosen from the group comprising Cl, Br, I and mixtures thereof; g in each case is 0-3.

Typical compounds of the Lewis acid include tri-n-hexylamine, triethylamine, chloride diethylamine, trimethylaluminum, chloride dimethylamine, dichloride methylalanine, triisobutylaluminum, tri-n-butylamine, chloride diisobutylaluminum, dichloride isobutylamine, (C2H5)AlCl2, (C2H5O)AlCl2, (C6H5)AlCl2, (C6H5O)AlCl2, (C6H13O)AlCl2and the corresponding compounds of bromine and iodine.

Suitable connections - boron halides include BCl3, BBr3In(C2H5)Cl2, B(OC2H5)Cl2(OS2H5)2Cl, B(C6H5)Cl2, B(OC6H5)Cl2B(C 6H13)Cl2(OS6H13)Cl2and B(OC6H5)2Cl. You can also use bromine and iodine congeners listed above compounds. The Lewis acid can be used individually or in combination.

Additional details regarding the Lewis acids which are suitable for this purpose can be found in patents US 4354009 and 4379758.

The catalyst precursor is treated with an activating co-catalyst. The catalyst precursor can be treated with the catalyst at any time after carrying out spray drying. In some preferred embodiments, the catalyst precursor is treated with a catalyst after the optional treatment with Lewis acid or alkylating agent. Usually the co-catalyst corresponds to the formula AlX'd(R)cHewhere X' represents Cl or or"'; R" and R"' independently represent a1-C14saturated hydrocarbon radicals; d is 0-1,5; e is 0 or 1; c+d+e=3. Typical catalysts include Al(CH3)3, Al(C2H5)3, Al(C2H5)2Cl, Al(i-C4H9)3, Al(C2H5)1,5Cl1,5, Al(i-C4H9)2H Al(C6H13)3, Al(C8H17)3, Al(C2H5)2H, Al(C2H5 2(OS2H5), or mixtures thereof.

In some preferred embodiments, the catalyst precursor is partially activated outside the polymerization reactor, together with a co-catalyst in a hydrocarbon slurry. This partial activation is not required. After contacting the composition of the catalyst precursor with a co-catalyst, the hydrocarbon solvent is removed by drying, and the catalytic composition can be fed to the polymerization reactor where the activation is completed with additional quantities of any suitable co-catalyst. In the first stage caused the catalyst precursor reacts with a co-catalyst, so as to provide a molar ratio of Al:Ti of about 0,1, 0,5, 1, 2, 5, or 6. In some preferred embodiments, the activation is carried out in a hydrocarbon solvent, followed by drying the resulting mixture, to remove the solvent, at the temperature of at least 20, 30, 40 or 50°C. In some preferred embodiments, the temperature is less than 50, 60, 70 or 80°C. Another alternative method of partial activation is described in the patent US 6187866 in which the procedure of partial activation proceeds in a continuous mode.

In some preferred embodiments, particularly those in which p is electonic of the catalyst is not fully activated, can be added to the polymerization reactor additional co-catalyst, to further activate the catalyst precursor. In some preferred embodiments, the partially activated catalyst or the composition of the catalyst precursor, as well as additional co-catalyst fed into the reactor through separate feed lines. In other preferred embodiments, the suspension is partially activated catalyst and co-catalyst in mineral oil fed into the reactor through one feed line. Alternatively, the slurry composition of the catalyst precursor in mineral oil can be treated with a catalyst, and the resulting suspension can be fed into the reactor. Additional co-catalyst can be sprayed into the reactor in the form of its solution in a hydrocarbon solvent, for example, ISO-pentane, hexane or mineral oil. This solution usually contains about 2-30 wt.% the composition of the co-catalyst. The co-catalyst can also be added to the reactor in solid form when it is absorbed on the carrier. In some preferred embodiments, the medium contains about 10-50 wt.% activator for this purpose. Additional co-catalyst added to the reactor in such amounts, to get in the reactor, the total molar ratio Al/Ti of about 10, about 15, primerno, about 45, about 60, about 100, or about 200 to 1. In other preferred embodiments, the ratio may be about 250, or about 400 to 1. Additional quantities of the compounds of the activator added to the reactor, optionally activate the deposited catalyst. In other preferred embodiments, the catalyst can be activated as described in International patent application WO 01/05845 included in the present description by reference in its entirety.

Preferred variants of the catalysts described above can be used in the polymerization in solution, suspension or in the gas phase. The catalysts described above, can be prepared for use in the suspension polymerization according to any suitable technique. In some preferred embodiments, such catalysts prepared as catalysts used in gas-phase polymerization. The conditions of polymerization in suspension include polymerization2-C20olefins, diolefins, cycloolefins, or mixtures thereof in an aliphatic solvent at a temperature below such that the polymer is easily soluble in the presence of the applied catalyst. Processes in the phase of the suspension, suitable for homopolymerization of ethylene and copolymerization of ethylene with C3-C8alpha-olefins, such as butene-1, hexe is -1, 4-methylpentene-1 and octene-1, can also be accomplished using the preferred options of the catalysts of the present invention. You can obtain thus a high density polyethylene (HDPE), medium-density polyethylene (PASP) and linear low density polyethylene (LLDPE).

In a continuous gas-phase process is partially or fully activated composition of the catalyst precursor is continuously fed into the reactor with separate portions of any additional connections activator required for complete activation of the partially activated composition of the catalyst precursor in the process of continuous polymerization, in order to replace active catalytic centers that have trashdolls in the process of reaction.

The polymerization reaction is usually carried out by contacting ethylene flow in gas-phase process, for example, in the process of boiling layer, described below, and almost in the absence of catalyst poisons such as moisture, oxygen, CO, CO2and acetylene, using a catalytically effective amount of the completely activated composition of the precursor of the catalyst (the catalyst) at a temperature and pressure sufficient to initiate the polymerization reaction. Preferred variants of the catalyst suitable for polymers the tion With 2-C6olefins, including homopolymers and copolymers of ethylene with alpha-olefins, such as butene-1, hexene-1, 4-methylpentene-1. In General, the reaction can be conducted under any conditions suitable for polymerization type Ziegler-Coloring conducted in the conditions of suspension or gas-phase polymerization. Such methods are used in industry to obtain high density polyethylene (HDPE), medium-density polyethylene (PASP), and linear low density polyethylene (LLDPE).

When gas-phase polymerization can be used, the reaction system with the liquefied layer. The reaction system fluidized bed are discussed in detail in the patents US 4302565 and 4379759, which in its entirety is incorporated into this description by reference. However, to be sure, figure 3 shows a typical reactor system with a fluidized bed. The reactor 10 consists of a reaction zone 12 and zone speed reduction 14. The reaction zone 12 includes a layer of growing polymer particles, formed polymer particles and a small amount of catalyst particles, liquefied by blowing through reaction zone a continuous stream capable of polymerization and modifying gaseous components in the form prepared in advance of the stream, and reciklirawe gas. The mass flow rate of gas through the catalyst bed is sufficient to liquefaction layer. For about the values of the minimum gas flow, required to achieve liquefaction, it is acceptable to use the abbreviation Gmf, .Y.Wen and Y.H.Yu, "Mechanics of Fluidization", Chemical Engineering Progress Symposium Series, t, p.100-111 (1966). In some preferred embodiments, the mass flow rate of gas is 1.5, 3, 5, 7, or ten times more Gmf. The catalyst layer is prepared so as to avoid the formation of localized "hot spots" and to separate the catalyst particles were inside and were well distributed throughout the reaction zone. At the time of starting the reaction, the reaction zone typically contains the basis in the form of granular polymer particles, before starting to apply the gas stream. Such particles can be of the same nature with the polymer that can be formed, or it may differ. If the source of the other particles, they are removed together with the target formed by the polymer particles as the first product. Over time, the initial layer is replaced liquefied layer consisting of particles of the target polymer.

Partially or completely activated catalyst used in the liquefied layer, preferably stored until use in the vessel 32 under a layer of gas, which is inert to the stored material, for example, under nitrogen or argon.

Liquefaction is achieved by high speed reciklirawe gas into and through the layer, typically comprising approximately 50 times the RMS of the spine of the fresh gas flow. The liquefied layer is usually dense mass of stable particles in possible irrotational flow, which is generated by the escape of gas through the layer. The pressure drop in the layer is equal to or slightly higher than the mass of the layer divided by the cross-sectional area. Therefore, it depends on the geometry of the reactor.

Fresh gas is fed into the layer at a rate equal to the rate at which the granular polymer product is removed. The composition of the fresh gas determined by the gas analyzer 16, located above the layer. The gas analyzer determines the composition of the gas, which is recycled, and the composition of the fresh gas govern in accordance with these data, with the objective of maintaining almost steady state composition of the gas inside the reaction zone.

To ensure sufficient liquefaction, recyclery gas and, if desired, part of the fresh gas back to the reactor at point 18 below the layer. There are naturally plastic 20 above the point of return, which helps in the liquefied layer.

Part of the gas stream, which is not reacted in the layer is recyclery gas, which is removed from the polymerization zone, preferably by passing into a zone of lower velocity layer 14 above, where picking up particles getting a chance to go back in the liquefied layer. The return of the particles is facilitated by the use the of the cyclone 22, which can be a part of a line of recycling. If desired recyclery gas can then pass through a preliminary heat exchanger 24, aimed at cooling small entrained by a stream of particles, to prevent sticking in the compressor, or through the downstream heat exchanger 26.

Recyclery gas is compressed in the compressor 25 and then passed through a heat exchanger 26, where the selected reaction heat before returning to the layer. As a result of continuous discharge of the heat of reaction, apparently, there is no significant temperature gradient within the upper part of the layer. A temperature gradient exists in the bottom of the layer, in a layer thickness of about 6-12 inches, gradient occurs between the temperature of the incoming gas and the temperature of the rest of the layer. Thus, it was observed that the layer regulates temperature reciklirawe gas above the lower layer of the reaction zone, which makes it corresponding to the temperature of the rest of the reaction layer, thus it is maintained at almost constant temperature in stationary conditions. Then recyclery gas return to the reactor at its base 18 and the liquefied layer through the distribution plate 20. The compressor 25 can also be placed above the heat exchanger 26.

The liquefied layer contains growing and obrazuyuschie the granular polymer particles, and catalyst particles. Because the polymer particles are hot and active, they should be protected from deposition to prevent the coalescence of two particles. Therefore it is important transmission reciklirawe gas through the bed at a rate sufficient to maintain the layer in the liquefied state at the bottom layer. The distribution plate 20 serves for this purpose and may be a screen plate with slits, perforated plate, a variant of the jet nozzles and the like. The plate elements can all be fixed, or the plate may be movable type is described in patent US 2298792. No matter how it was arranged that she should ignore recyclery gas through the particles at the base of the liquefied layer, to maintain these particles in the liquefied state, and also to serve as a support for the deposited polymer particles when the reactor is not operating. The movable plate elements can be used to discharge any polymer particles captured inside or on the plate.

Hydrogen can be used as an agent of transfer chains in the polymerization reaction. Used the ratio of hydrogen/ethylene can vary from about 0 to about 2.0 moles of hydrogen per mole of ethylene in the gas stream.

Connection patterns ZnRaRbwhere Randand Rbare the same or different With -C14aliphatic or aromatic hydrocarbon radicals, can be used in combination with hydrogen to control molecular weight, or as agents of transfer circuit, for increasing values of the index melting polymers, which are produced in this process. You can use approximately 0-50, preferably about 20-30 moles of zinc compounds (zinc) in the gas stream in the reactor per mole of the compounds of titanium (calculated as titanium) in the reactor. The connection of zinc can be introduced into the reactor preferably in the form of a diluted solution (2-30 wt.%) in a hydrocarbon solvent, or sorbed on solid diluent, for example, silicon dioxide, in the above forms, in amounts of about 10-50 wt.%. These compounds tend to proforest. Zinc compounds can be added separately or together with any additional portions of the connection - activator, which is served in the reactor from the supply device of Fig. not shown, which will lead connection in the hottest part of the recycle gas, for example, adjacent to the feeding device 27 described in the present description.

In the gas stream may be any gas inert to the catalyst and reactants. Connection-activator is preferably added to the reaction the system in the hottest part reciklirawe the gas stream. Adding in-line recycling downstream from the heat exchanger is therefore preferable, as, for example, of the distributor 27 to line 27A.

To be sure that the adhesion of the particles does not occur, it is desirable to use temperatures below the temperature adhesion. For more homopolymers of ethylene, the preferred operating temperature is from 30 to 115°and a temperature from about 80 to 105°preferably be used to obtain products having a density of less than 0.94 g/cm3.

The fluidized bed reactor operates at pressures up to about 1000 lbs./square inch and preferably operates at a pressure of from about 150 to 350 lb./square inch, and work at higher pressures in such ranges conducive to heat transfer, because the increased pressure increases the volumetric heat capacity of the gas.

Partially or fully catalytic composition is injected into the fluidized bed at a rate equal to its consumption at a point 30 which is located above the distribution plate 20. The injection can be continuous or intermittent. Preferably the catalyst is injected at a point above the distribution plate. As described catalysts are highly active, injection fully activated catalyst into the area below the distribution plate may, in order to predict the beginning of the polymerization in this place, and eventually cause plugging of the distribution plate. The introduction of the liquefied layer, on the contrary, helps in the distribution of the catalyst layer and helps prevent the formation of local spots with a high concentration of catalyst, which can lead to the formation of "hot spots".

The gas that is inert to the catalyst, for example, nitrogen or argon, are used for feeding partially or fully restored the composition of the catalyst precursor, and any necessary additional connections-activator in the reaction layer. Alternatively, a mixture of solvents, for example, isopentane, pentane, hexane, or the like, can be used as a carrier for catalysts, in the form of a suspension. In combination with a carrier, you can use the nitrogen.

The rate of formation of polymer in the reaction layer is governed by the feed rate of the catalyst. The rate of formation of the polymer can be increased by simply increasing the feed rate of the catalyst and to reduce the decrease in the feed rate of the catalyst.

Because changes in the feed rate of the catalyst changes the rate of generation of heat of reaction, temperature reciklirawe gas regulating, reducing, or increasing, in order to adapt to changes to the rate of heat generation. what that enables us to maintain a practically constant temperature in the reaction layer. Of course, you have full equipment as the liquefied layer, and cooling system reciklirawe gas necessary equipment to determine any changes in the temperature in the reaction layer, so as to enable the operator to properly adjust the temperature reciklirawe gas.

For a given set of operating conditions the liquefied layer is maintained at almost a constant height by removing part of the layer as product at a rate equal to the rate of formation of bulk polymer product. Because the rate of heat generation is directly related to the formation of the product, measuring the increase of the gas temperature along the height of the reactor (temperature difference between the inlet gas and outlet gas temperature) is crucial for the rate of formation of bulk polymer at a constant gas velocity.

Granular polymer product is preferably continuously removed at the point 34 located on or close to the distribution plate 20, and in suspension with a portion of the gas stream that is blown before the particles will settle, to prevent further polymerization and adhesion when the particles reach the end zone for their collection. You can also use suspendisse gas, as mentioned above, in order to transfer the product from one reactor to another reactor.

Yuchi polymer product preferably, although not required, is removed by sequential operation of a pair of valves periodic steps 36 and 38 that separates the separation zone 40. If the valve 38 is closed, valve 36 is opened to select the locked portion of the gas and the product in the area 40 between it and the valve 36, which is then closed. Valve 38 is then opened to put the product in the external zone of the selection. Valve 38 is then closed, waiting for the next steps in the selection of the product. You can also use the method of offloading the liquefied layer in accordance with the patent US 4621952, in its entirety is incorporated into this description by reference.

Finally, the reactor with the liquefied layer equipped with the appropriate purging system, which allows purging of the reaction layer during start and stop. The reactor does not require the use of tools mixing and/or means for cleaning the walls.

The catalytic system described in the present description, apparently, gives the product in a fluidized bed having an average particle size from roughly 0.005 to about 0.06 inch, sometimes from about 0.02 to around 0.04 inches, and having a residual content of catalyst, which is unusually small.

The flow of the gaseous raw material monomer containing or not containing an inert gaseous diluents, served in a reactor with a volumetric feed rate, the composition of the managing approximately 2-10 pounds/hour/cubic foot of volume of the reaction layer.

In some preferred embodiments, the catalysts obtained in accordance with the present description, have improved performance. Performance is measured by ashing the sample obtained resin and determination of weight percent ash. The ash is essentially composed of the catalyst. Performance calculated as pounds of polymer obtained per pound of total catalyst. The amount of Ti, Mg and Cl in the ashes determine the elemental analysis. In some preferred embodiments, the performance of the catalyst is from about 6000 to about 15000 for suspension polymerization. In other preferred embodiments, the catalysts have value performance above or below this interval. For reactions of gas-phase polymerization of some of the catalysts of this invention have the performance component of from about 2 to about 5 ppm million Ti. Here again, other catalysts may have performance beyond the specified interval.

The molecular weight of the polymer is convenient to measure using measurements of melt flow. One of these indicators is the index of fusion (PI), which is determined in accordance with the method of ASTM D-1238, condition E, measured at 190°and With applied load of 2.16 kg, and lead as grams per 10 minutes. Polymers, Paul is obtained with the use of certain catalysts, described in the present description have the value of PI, which is from about 0.01 to about 10,000. Other polymers can have values of PI beyond these limits. Another method of characterizing polymer - speed measurement of the melt flow, it is measured in accordance with the method of ASTM D-1238, condition F, using ten times more polymer by weight, compared with the index definition of the melting point described above. The flow rate of the melt is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the flow velocity of the melt, although the relationship is not linear. The ratio of the melt flow (ODA) represents the ratio of the flow velocity of the melt index melt. It correlates with the distribution of the obtained polymer molecular weight. Lower ODA mean more narrow distribution of molecular weight. The polymers obtained with the use of some of the catalysts described in the present description, have values ODA comprising from about 20 to about 40.

The average particle sizes of the polymers calculated on the basis of sieve analysis in accordance with ASTM D-1921, Method a, using 500 g of the sample. Calculations based on the mass fractions of polymer remaining on each sieve. Bulk density is determined in accordance with ASTM D-1895, the Method is, by pouring resin into a graduated cylinder to 100 ml up to the 100 ml mark without shaking the cylinder, and determine the mass difference.

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/cm3if it is measured in accordance with method ASTM D-792, which made the drive and condition within one hour at 100°to achieve equilibrium crystallinity. The density measurement performed then in the column density gradient. Others may have a bulk density determined in accordance with ASTM D-1895, a method In which ranges from about 0.2 to about 0.4 g/cm3.

Examples

The following examples are given to illustrate various preferred variants of the invention described in the present description. They should not be perceived as intended to limit the scope of the invention other than that described in the description and the claims. All numerical values are approximate.

The spray drying device

Typical catalysts were prepared using a spray drying device Niro®. Atomizing chamber diameter was 4 feet, a length to diameter was approximately 1.2, and the angle at the base of the cone part of the yawl approximately 45° . The sputtering was performed using a rotating chopper Niro FU-11, equipped belopotosky wheel 120 mm in diameter. The spray drying device worked in a continuous closed loop. Although spray drying device, you can use any gas inert to the components of the components of the catalyst, typically using nitrogen, due to its low cost, and easy availability of high purity nitrogen. The evaporated solvent is removed from the recirculating return gas and cooled by passing through onto the Packed column in which a cold solvent circulates in counter-current. Exhaust return gas then saturate the solvent at the temperature at the outlet. Return the gas is then heated in the heat exchanger and return to the system. Dry solids emit using cyclone and store under inert gas.

Preparation of raw materials

Typical catalysts were prepared in a mixing vessel made of stainless steel with a volume of 40 liters, equipped with a suitable feed opening, turbine stirrer with flat blades, and a purge gas. The components of the catalyst can be loaded into the mixer, not observing the particular boot order. Usually, however, at least part of the solvent is loaded into the mixer in the first place. In one example of the mixer was loaded tetrahydrofuran, and then optional loaded filler, if used. The temperature of the contents of the mixer were brought to the desired value, usually around 35-50°C. Then, while maintaining the contents of the vessel under an inert gas, without following a specific order of addition were loaded into the mixer with the required amount of magnesium chloride and recovered aluminum chloride, titanium (TiCl3AA). Then add the alcohol. The contents of the vessel were continuously stirred. The internal temperature is brought up to the desired value, and the content was stirred for 2-4 hours. However, the mixing times up to 48 hours are not harmful to the product. There is no specific minimum time of mixing, the time should be just sufficient to achieve dissolution.

In another example, the raw material is prepared by adding a solvent to the mixer, and then they added filler. Added a small amount alkylamine, for example, triethylaluminum, in the form of a solution in the electron donor solvent, so that he reacted with moisture, which is inevitably present in combination - filler. Then, while maintaining the contents of the vessel under inert gas, not adhering to the particular order of addition, the mixer was loaded in the required amounts of magnesium chloride and recovered aluminum is a titanium chloride (TiCl 3AA). A small additional amount of the solution alkylamine you can add to make it react with moisture present in MgCl2. The reaction was maintained under these conditions for about 30 minutes - 1 hour. After this period, the added alcohol. The resulting mixture was constantly stirred, the internal temperature is brought up to the required level, and the content was stirred for 2-4 hours.

In the third example, the raw material was prepared by first downloading the solvent in the reaction vessel, then add the filler. Added a small amount alkylamine, for example, triethylaluminum in the form of a solution in the electron donor solvent. Then, while maintaining the contents of the vessel under inert gas, not adhering to the particular order of addition was loaded metallic Mg and TiCl4as described in patent US 5290745 included in the present description by reference. After a period of mixing duration 1-4 hours download advanced MgCl2to increase the overall molar ratio Mg/Ti to the appropriate value. Although this is not required at this point in the reactor was loaded small amount of the solution alkylamine. The reaction continued as described above.

Spray drying

After preparation of raw materials for spray drying, the suspension was filtered through the ito with holes the size of 20 mesh (US), with the aim to homogenize the suspension, and then pumped into the rotating shredder. The inlet temperature was regulated so as to regulate the temperature at the outlet of the drying device, which, in turn, regulates the amount of residual solvent remaining in the dried solids. The feed rate was adjusted to achieve the desired rate of formation solids. The flow rate cycleroute gas was set to be sure that the solids which are formed in the drying chamber is transferred to a cyclone for collecting the solid product. Speed shredder (rpm) was chosen so as to adjust the particle size of the solid products. The temperature at the outlet of the condenser is used to remove solvent from the drying gas was maintained at a level of from about -20°C to about +20°to regulate the amount of residual solvent remaining in the drying gas.

The use of precursors of catalysts spray drying

Suspension/solution predecessor

The number used for cooking, are listed in table 1. All surgeries were performed under nitrogen using anhydrous reagents. In the mixing vessel made of stainless steel, 40 liters was added to the desired loading of tetrahydrofuran (THF), and then specify the second loading of the filler (Cabosil TS-610, production Cabot Corporation). The suspension was stirred at room temperature for 30 minutes Then added a small amount of triethylaluminum (10%solution in THF)to remove residual moisture from the filler and solvent. The suspension was stirred for 15 min, was added the required amount of solid MgCl2and TiCl3-AA. Then add the required amount of absolute ethanol, or before, or after the addition of metal salts. The internal temperature was raised to 60°S, and the suspension was stirred for 5 hours at an internal temperature of 60-70°C.

Table 1
The suspensions spray drying
Solution preparation
ExampleTHF, kgCabosil, kg10% Et3Al, gEt3Al, molMgCl2gMgCl2, molTiCl3-AA, gTiCl3-AA moleEtOH, gEtOH, molRated EtOH/MgNominal [Mgl 2], moslin.
A*181,143630,39189,633271,640000,5
In36,2of 2.514500,39180518,96673,3675016,310,5
27,1of 2.514500,39277629,16673,36120126,111
D281,77700,67312432,81053and 5.30154233,511
* comparative example

The data in table 1 show that solutions with high concentrations of MgCl2it is easy to cook and drain the spray drying at a relatively higher content of active ingredients than was possible previously. On the contrary, attempts were made spray drying 1 Mosley suspension MgCl2with respect MgCl2/TiCl3equal to 6:1, in the absence of the alcohol modifier. Not all MgCl2was in solution at room temperature, and heating the suspension up to 65°and attempt to spray drying caused clogging of pipes dissolved and precipitated in the process of drying the solid residue.

Carrying out spray drying

The resulting suspension A-D containing dissolved MgCl2and TiCl3, then was dried using spray drying, drying conditions were changed using the spray drying device of a closed loop with a diameter of 8 feet, equipped with a rotating chopper. The speed of the rotating chopper regulated in the range of 50-95% of set speed, to obtain particles in a wide range of particle sizes. 100%speed shredder corresponds to 24000 rpm Scrubbing the Department of spray drying device maintained at a temperature of approximately -4°C.

Gaseous nitrogen was introduced into the spray drying device at the inlet temperature in the range of 130-160°and it was circulated at a rate of about 200-300 kg/h Suspension Cabosil/THF containing dissolved MgCl2and TiCl3was applied to the device spray drying at a temperature of about 65°at a rate sufficient to achieve a gas temperature at the outlet of about 90-115°C. the Pressure in the chamber of the spray drying device which was slightly above atmospheric.

The particles obtained by spray drying, had D10D50and D90defined on the particle size analyzer Malvern 2600. Analytical and morphological results are given in table 2.

Table 2
Determination of the parameters of the precursors of catalysts spray drying.
ExampleInstallation shredder, %Ti, mmol/gMg, mmol/gMg/Ti% THF% EtOHD90D50D10The scope of the distribution
A*800,442,746,2526,649,3426,5210,561,5
In800,562,664,7519,3446,5822,16of 6.961,8
850,413,639325,158,70of 29.9812,821,5
D950,63,626 366,247,6523,838,281,7
D'950,63,626366,248,5923,068,241,7
* comparative; inlet temperature 150°except D', where the inlet temperature was 160°C.

The data in table 2 show that the dried particles with good morphological properties at higher concentrations, can be obtained under normal conditions of spray drying. If the concentration of MgCl2in the feeding solution is increased, it is possible to obtain particles with a significantly higher relations of Mg/Ti when loading 0.4-0.5 mmol Ti/g predecessor. Such catalysts can be used where a high degree of modification MgCl2and homogeneous Ti environment. If the concentration of MgCl2and TiCl3in the feeding solution is increased, it is possible to obtain particles with a constant ratio Mg/Ti, but significantly higher Ti content than the control catalyst. Such catalysts can be used in those cases when it is required to carry out the polymerization under conditions of low partial pressures of ethylene, when the low activity per titanium Bud is t otherwise lead to unexpectedly low particle size of the resin.

Table 2 also shows what can be achieved with particle morphology, particle size and distribution of particles of certain precursors of catalysts, approximately equivalent to the same characteristics of traditional predecessors, except that the control sample may contain slightly lower amount of fines. However, from figure 4, which shows obtained by scanning electron microscopy (SEM) pictures of particles, it is seen that the fine particles in comparative traditional predecessor figa present in much more agglomerated than the typical particle of the catalyst according to this invention, shown in figv. So, figa shows that a lower fines content in the comparative catalyst precursor obtained due to the undesirable formation of agglomerated particles. On the contrary, the precursors of catalysts according to this invention show less agglomeration and better traction, as seen by the presence of predominantly uniformly spherical particles figure 4 Century. Usually at least a majority of the particles are not agglomerated.

Polymerization of ethylene in a slurry reactor

The precursors of catalysts from table 2 were used in the tests polymerization of ethylene, the results of which bring the us in table 3. Each test polymerization in laboratory scale were performed as described below, except in those cases specifically provided otherwise. To 500 ml of hexane was added 40-60 micromol of triethylaluminum (C2H5)3Al in micromoles of titanium in the catalyst, and then the reactor was added 5-7 mmol of titanium in the form of a suspension catalyst precursor in mineral oil. The reactor suspension polymerization of 1 l opressively to fifty (40) lb./square inch (Rel.) with hydrogen, and then brought up to a total pressure of two hundred (200) lbs./square inch (Rel.) using ethylene. The polymerization was carried out at a temperature of 85°C for thirty minutes.

Table 3
Experiments by suspension polymerization.
ExampleMg/TiROH/MgTi download, mmol/gActivityandPerformancebPI DG/minABBulk density, g/cm3
A*600,4414,4005,8001,6320,38
In510,5614,4007,000 1,7320,37
910,4123,0009,5000,9350,33
D610,611,8007,2000,9420,29
D'610,619,20011,6001,4300,26
*: comparative example; and in g PE/(mol of titanium-h-100 lb./square inch With2); b: in g PE/(g catalyst-h-100 lb./square inch With2)

From table 3 it is seen that the performance-based catalyst activated precursors in suspension polymerization, calculated in g PE/g of catalyst, higher than the performance of the control of precursor (A). The increase of the ratio Mg/Ti leads to an increase in productivity per Titan. With an equal ratio of Mg/Ti and higher contents as MgCl2and TiCl3, achieves higher performance on the particle for catalysts in examples B-D' in table 3 than in the presence of a control catalyst of experiment 1.

The method of polymerization of ethylene in a fluidized bed reactor

Predecessors of catalysis of the Directors of table 2 were used in the tests polymerization of ethylene, the results are shown in table 4.

As can be seen from table 4, the properties of the resin, such as index, melting point, density, molecular weight distribution resin and the apparent density of the resin obtained with the use of the catalyst In the present invention, similar to the curing properties of the control catalyst obtained on an industrial scale on the sales device spray drying. Although the catalyst of the present invention is slightly less productive than the control, so we would expect a smaller particle size and increased fines content, they instead show a slightly increased particle size and a half smaller fines content, as compared with that obtained using the control catalyst. Analysis of the resin by the method of the SEM shows that the resin of the present invention consist of fused spheres, while the resin obtained with the use of previously known in the art catalyst contains individual particles and a significant amount of de-agglomerating detail.

Performance frequent./million Ti
Table 4
The HDPE polymerization in a fluidized bed
ExampleMg/TiROH/MgThe content of Ti, mmol/gThe density of the resin, g/cm3PI DG/minABBulk density, Lb/ft3The average particle size, inchDetail resin, %
A*600,4720,96458,626,727,10,0272,28
910,412,40,96468,125,427,10,0371,1
D'610,63,70,96407,82627,20,341,33

The polymerization conditions: polymerization temperature 102°C, the pressure of ethylene 170 lb./square inch, 0,4 H2/S2. The co-catalyst - triethylaluminium to the ratio of Al/Ti of about 50-60.

As shown above, the preferred variants of the invention provide a catalyst, method of producing the catalyst and a method of producing the polymer. The catalyst obtained in accordance with the preferred variants of the invention may have one or more of the following advantages. Some are described in this is the description of the catalyst does not dissolve in the polymerization process, that gives you the opportunity to get a more complete polymer particle. Thus, the catalysts provide polymers which have a lower content of undesirable fine particles. The catalyst is also improved performance per particle compared to catalysts that use conventional particle spray drying. Improved performance means that the catalysts provide a more cost effective alternative to existing magnesium-titanium catalyst spray drying. These advantages are provided in part by the wider spacing achievable compositions and more homogeneous distribution of magnesium in the particle. Other advantages and properties clear to persons skilled in the art.

Although the invention is described using a limited number of preferred options, these particular preferred options are not intended to limit the scope of the invention other way than described and set forth in this description. There are modifications and variations of the described preferred options. 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. Sledovatel is but catalysts that do not meet the eligibility criteria under one set of reaction conditions can, however, be used in preferred embodiments of the invention with a different set of reaction conditions. Although some preferred versions described with reference to separate the catalyst, it is in no way preclude the use of two, three, four, five or more catalysts in the same reactor with the same or another capacity for the molecular weight and/or the introduction of a co-monomer. In some preferred embodiments, the catalyst may also include additives or other modifiers. In other preferred embodiments, the catalyst does not include, or practically does not contain any compounds that are not listed in the present description. Moreover, there are derivatives of variation and modification. It should be recognized that the method described in the present description, can be used to obtain polymers that include one or more additional co-monomers. The introduction of additional co-monomers can lead to improved properties that are not attainable for homopolymers or copolymers. If the method is described as including one or more stages, it should be understood that these stages can be used in any order or sequence unless ineet stage can be joined or split. Finally, any number that is included in the present description, should be understood as meaning an approximate value, whether used or not used in the description of this the number of the word "approximately" and "about". Last but not less important that the claimed catalysts are not limited to the methods described in the present description. They can be prepared in any suitable way. The attached claims are intended to cover all such variations and modifications as falling within the scope of the present invention.

1. The composition of the catalyst precursor, which includes

a) a mixture of the reaction product of the following substances:

1) to the halide of magnesium;

2) solvent;

3) an electron-donor compound, where the electron-donor compound is an alcohol; and

4) compounds of the transition metal, where the transition metal is selected from groups 3-10 and lanthanides; and

b) an inert filler;

where a) and b) form a catalyst precursor, and where the specified precursor catalyst was prepared by spray drying, where the catalytic composition contains almost no other electron-donor compounds, the molar ratio of electron donor compound to magnesium is less than or equal to 1.9, and the composition predestin the ICA catalyst comprises particles, having an average particle size of more than about 10 microns, and where the specified magnesium halide has a solubility in a specific solvent in the range from 0.75 to 2.0 moles/liter

2. The method of obtaining the composition of the catalyst precursor, which includes

a) obtaining a mixture or reaction product of:

1) to the halide of magnesium;

2) solvent;

3) an electron-donor compound, where the electron-donor compound is an alcohol;

4) compounds of the transition metal, where the transition metal is selected from groups 3-10 and lanthanides;

b) contacting the mixture or reaction product with an inert filler to obtain a suspension; and

C) spray drying the slurry;

where the composition of the catalyst precursor contains almost no other electron-donor compounds, the molar ratio of electron donor compound to magnesium is less than or equal to the value to 1.9, and the composition of the catalyst precursor comprises particles having an average particle size of more than about 10 microns, and where the specified magnesium halide has a solubility in a specific solvent in the range from 0.75 to 2.0 moles/liter

3. Catalytic composition comprising the reaction product of

a) a mixture or reaction product of:

1) to the halide of magnesium;

2) solvent;

3) ele the throne-donor compound, where the electron-donor compound is an alcohol;

4) compounds of the transition metal, where the transition metal is selected from groups 3-10 and lanthanides; and

5) inert filler, and

6) the composition of socializaton,

where the catalyst composition contains almost no other electron-donor compounds, the molar ratio of electron donor compound to magnesium is less than or equal to the value to 1.9, and the composition of the catalyst precursor comprises particles having an average particle size of more than about 10 microns, and where the specified magnesium halide has a solubility in a specific solvent in the range from 0.75 to 2.0 moles/liter

4. A method of obtaining a polymer comprising the reaction of at least one polyolefin monomer in the presence of a catalytic composition comprising a mixture or reaction product

a) magnesium halide;

b) solvent;

C) an electron-donor compound;

g) compounds of the transition metal, where the transition metal is selected from groups 3-10 and lanthanides;

d) an inert filler, and

e) the composition of socializaton,

where the catalyst composition contains almost no other electron-donor compounds, the molar ratio of electron donor compound to magnesium is less than or equal to the value to 1.9,and the composition of the catalyst precursor includes a spherical or nearly spherical particles, having a particle size of from about 10 to about 200 microns and where the specified magnesium halide has a solubility in a specific solvent in the range from 0.75 to 2.0 moles/liter

5. The composition of the catalyst precursor according to claim 1, where the transition metal is titanium, where the composition of the catalyst precursor comprises particles having a molar ratio of magnesium to titanium, from about 1.0 to about 5,0.

6. The composition of the catalyst precursor according to claim 1, where the transition metal is titanium, where the composition of the catalyst precursor comprises particles having a molar ratio of magnesium to titanium, from about 5.0 to about 10.

7. The composition of the catalyst precursor according to claim 1, where the composition of the catalyst precursor comprises particles having a range of distribution from about 1 to about 2.5.

8. The composition of the catalyst precursor according to claim 1 where the inert filler comprises from about 10 to about 95 wt.% the composition of the catalyst precursor.

9. The composition of the catalyst precursor according to claim 1, where the molar ratio of alcohol to magnesium is less than about 1,75.

10. The composition of the catalyst precursor according to claim 1, where the molar ratio of alcohol to magnesium is from about 0.1 to about 1.1.

11. The composition of the catalyst precursor according to claim 1, where the molar ratio of alcohol to MAGN what Yu is from about 0.1 to about 0.5.

12. The composition of the catalyst precursor according to claim 1, where the compound of the transition metal includes titanium, zirconium, hafnium, vanadium, niobium, tantalum or combinations thereof.

13. The composition of the catalyst precursor according to claim 1, where the transition metal compound corresponds to the formula

Ti(R)aXb,

where R represents R' or COR'where R' represents a C1-C14aliphatic or aromatic hydrocarbon radical, X is chosen from Cl, Br, I, or mixtures thereof, and is 0 or 1, b is from 2 to 4 inclusive, a+b=3 or 4.

14. The composition of the catalyst precursor according to claim 1, where the compound of the transition metal is a TiCl3, TiCl4, Ti(OS6H5)Cl3, Ti(ASON3)Cl3, Ti(EA6H5)Cl3or mixtures thereof.

15. The composition of the catalyst precursor according to claim 1, where the electron donor includes a linear or branched aliphatic or aromatic alcohol containing from one to about 25 carbon atoms.

16. The composition of the catalyst precursor according to item 15, where the alcohol is chosen from the group comprising methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, 1-dodecanol, cyclohexanol and tert-butylphenol.

17. The composition of the catalyst precursor according to claim 1, where the solvent is chosen from the group comprising alkyl esters of al is factual and aromatic carboxylic acids, ethers, and aliphatic ketones.

18. The composition of the catalyst precursor according to claim 1 where the halide of magnesium includes MgCl2, MgBr2, MgI2, MgClBr, MgBrI or mixtures thereof.

19. The composition of the catalyst precursor according to claim 1 where the catalytic composition comprises a composition of the formula

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

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

20. The composition of the catalyst precursor according to claim 19, where r is from 0.1 to less than about 0.5.

21. The composition of the catalyst precursor according to claim 1, additionally comprising a mixture or reaction product of a Lewis acid with the composition of the catalyst precursor.

22. The composition of the precursor rolled atora on item 21, where the Lewis acid has the formula RgMX3-gwhere R represents R'or OR'or NR'2where R' represents a substituted or unsubstituted aliphatic or aromatic hydrocarbonous group containing 1-14 carbon atoms, X is chosen from the group comprising Cl, Br, I, and mixtures thereof; g is 0-3, M represents aluminum or boron.

23. The composition of the catalyst precursor according to item 21, where the Lewis acid is chosen from the group comprising tri-n-hexylamine, triethylamine, chloride diethylamine, trimethylaluminum, chloride dimethylamine, dichloride methylalanine, triisobutylaluminum, tri-n-butylamine, chloride diisobutylaluminum, dichloride isobutylamine, (C2H5)AlCl2, (C2H5)AlCl2, (C6H5)AlCl2, (C6H5O)AlCl2, (C6H13O)AlCl2and combinations thereof.

24. The composition of the catalyst precursor according to item 21, where the Lewis acid is chosen from the group comprising BCl3, BBr3In(C2H5)Cl2, B(OC2H5)2Cl2,B(OC2H5)2Cl2,In(C6H5)Cl2,In(OS6H5)Cl2,In(OS6H13)Cl2(OS6H13)Cl2and(OS6H5)2Cl and combinations thereof.

25. The composition of the catalyst precursor according to claim 1, the de inert filler selected from the group including silicon dioxide, titanium dioxide, zinc oxide, magnesium carbonate, magnesium oxide, carbon, and calcium carbonate.

26. The composition of the catalyst precursor on A.25, where the composition has an average particle size of from about 10 to about 60 μm and the range of distribution of from about 1.5 to about a 2.0.

27. The composition of the catalyst precursor according to claim 1, further comprising a second inert filler selected from the group including silicon dioxide, titanium dioxide, zinc oxide, magnesium carbonate, magnesium oxide, carbon, and calcium carbonate.

28. Catalytic composition comprising the reaction product of

a) magnesium halide;

b) a solvent comprising tetrahydrofuran (THF);

C) an electron-donor compound, where the electron-donor compound comprises an alcohol;

g) compounds of the transition metal, where the transition metal is selected from groups 3-10 and lanthanides; and

d) an inert filler,

where the concentration of the indicated halide of magnesium in the resulting solution a specified halide of magnesium specified alcohol specified THF and the transition metal 5 times higher compared with a solution that does not contain alcohol.

29. A method of obtaining a polymer comprising homopolymerization or the copolymerization of ethylene with C3-C8α-olefins, where is shown homopolymerization or copolymerization is carried out in the presence of one of the predecessors of the catalyst according to claim 2, or catalytic composition according to claim 3, where the specified catalyst precursor further includes socialization.



 

Same patents:

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to a method for preparing supported titanium -manganese catalyst for synthesis of super-high molecular weight polyethylene via suspension ethylene polymerization process in hydrocarbon solvent. Titanium-containing catalyst supported by magnesium-containing carrier is prepared by reaction of organomagnesium compound Mg(C6H5)2•nMgCl2•mR2O, where n=0.37-0.7, m=2, R20 represents ether wherein R is i-amyl or n-butyl, with a silicon compound, namely product obtained by reaction of compound R'kSiCl4-k (R' is methyl or phenyl and k=0-1) with silicon tetraethoxide Si(OEt)4 at molar ratio R'kSiCl4-k/Si(OEt)4 = 6 to 40. Ethylene polymerization process in presence of above-defined catalyst in combination with co-catalyst is also described, wherein obtained super-high molecular weight polyethylene has loose density ≥ 0.39 g/cc.

EFFECT: increased molecular weight and loose density of polyethylene.

4 cl, 1 tbl, 8 ex

FIELD: polymerization catalyst and polymer production.

SUBSTANCE: invention relates to preparation of high-activity catalyst deposited on solid support and designed for suspension polymerization of ethylene and copolymerization of ethylene with α-olefins, in particular, for production of ultrahigh-molecular weight polyethylene. Catalyst according to invention comprises organoaluminum compound (40-200 wt parts) and solid component (1 wt part) containing 12-15% catalytically active titanium compounds and 85-88% magnesium dichloride support prepared by interaction of magnesium metal, ethanol, aluminum, silicon, and titanium compounds, said solid component being represented by particles containing titanium, magnesium, chlorine, aluminum, and silicon at atomic ratio between 1.0:6:16:0.07:0,02 and 1:7:18:0.06:0.01, respectively. Described are also preparation of solid catalyst component, and (co)polymerization of ethylene at temperature between 0 and 100°C and pressure between 0.1 and 5.0 MPa. Catalyst according to invention allows obtaining polyethylene with elevated molecular weight under high polymer yield conditions, which minimizes time required for preparation of homogenous spinning solutions in the gel formation process and minimizes degree of degradation of dissolved polymer properties.

EFFECT: increased molecular weight and yield of polyethylene .

8 cl, 1 dwg, 3 tbl, 26 ex

FIELD: organic chemistry, polymers, in particular method for olefin polymerization.

SUBSTANCE: invention relates to method for CH2=CHR olefin polymerization wherein R represents hydrogen or C1-C12-hydrocarbon group to produce polymer with increased bulk density; catalytic component and catalyst useful in said method. Catalytic component contains at least two fraction (A) and (B), wherein both contain Mg, Ti and halogen as essential elements. Said catalytic component contains 1-60 mass % of (B) fraction whish has less mean diameter than (A) component by 75 % or less. Catalyst of olefin polymerization is obtained by interaction of abovementioned catalytic component organometal compounds of metals from 1-3 groups of Periodical system, optionally in presence of electron-attractive compound. Method for olefin polymerization is carried out in presence of catalytic component (A), containing Mg, Ti and halogen as essential elements and catalytic component (B), also containing Mg, Ti and halogen as essential elements which makes it possible to produce polymer with less mean particle size than mean particle size of polymer obtained with catalytic component (A) at the same polymerization conditions.

EFFECT: method of high productivity; polymer of high bulk density.

25 cl, 6 ex, 1 tbl

FIELD: polymerization processes and catalysts.

SUBSTANCE: invention relates to preparing supported titanium-magnesium catalyst for production of polyethylene and superhigh-molecular weight polyethylene via suspension polymerization of ethylene in hydrocarbon solvent. Invention provides a method for preparing supported ethylene polymerization catalyst containing titanium compound on magnesium-containing support, which is prepared by interaction of dissolved organomagnesium compound having following composition: MgPh2·nMgCl2·mR2O, wherein R represents butyl or isoamyl, n=0.37-0.7, and m=1-2, with compounds inducing conversion of organomagnesium compound into solid magnesium-containing support. As such compounds, there is used a composition including product of reaction of alkylsilane R'kSi4-k, wherein R is alkyl or phenyl and k=1, 2, with silicon tetraalkoxide Si(OEt)4 at molar ratio 2-4, respectively, and a dialkylaromatic ether. Catalyst is characterized by high activity at temperatures ≤60°C and particle size within a range 5.5 to 3.0 μm. Catalyst allows a polymer powder with average particle size ≤150 μm, narrow particle size distribution, and high loose density (≥250 g/L) to be obtained.

EFFECT: enhanced low-temperature catalyst activity and selectivity.

3 cl, 1 tbl, 15 ex

FIELD: polymer production.

SUBSTANCE: superhigh-molecular weight polyethylene is obtained in suspension conditions at temperature between 40 and less than 70°C in hydrocarbon solvent medium using supported catalyst. The latter is prepared through interaction of compound Mg(C6H5)2n*MgCl2*mR2O (R2O is ether, R = i-Am, n-Bu) with silicon compound, which is a product prepared by reaction of compound R1kSiCl4-k with silicon tetraethoxide Si(OR)4 (R1 represents methyl or phenyl and k=0.1) at molar ratio R1kSiCl4-k/Si(OR)4 = 2-4 at 15-45°C and Si/Mg = 1-2.5. Loose weight of obtained polymer is higher than 0.35 g/cc.

EFFECT: increased yield of superhigh-molecular weight polyethylene with improved morphology.

1 tbl, 13 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalytic component according to invention contains magnesium, titanium, halogen, and electron donor, wherein the latter contains at least one compound, notably polyol ester I having general formula R1CO-O-CR3R4-A-CR5R6-O-CO-R2 (I), wherein groups R1 and R2, the same or different, represent substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms; groups R3-R5, the same or different, are selected from group consisting of hydrogen, halogen, and above-defined hydrocarbon residue, said groups R3-R6 optionally containing one or several heteroatoms substituting carbon and/or hydrogen atom, wherein said heteroatoms are selected from group consisting of oxygen and halogen atoms, or two or more groups R3-R6 being connected with each other to form saturated or unsaturated monocyclic ring; and A represents bivalent linking group between two hydrocarbon radicals having from 1 to 10 atoms, said linking group being selected from group consisting of aliphatic, alicyclic, and aromatic bivalent radicals and can bear linear or branched C1-C20-substituents, provided that two or more substituents of said linking group and above-defined R3-R6 groups can be interconnected to form saturated or unsaturated monocyclic ring. Invention further discloses catalyst containing above-defined solid catalytic component and its employment in polymerization of CH2=CHR hydrocarbons, wherein R represents hydrogen or C1-C6-alkyl group.

EFFECT: enabled preparation of polymers characterized by high stereoregularity and increased polymerization yield.

34 cl, 6 tbl, 110 ex

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

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: polymerization catalysts.

SUBSTANCE: invention relates to a method for preparing supported titanium -manganese catalyst for synthesis of super-high molecular weight polyethylene via suspension ethylene polymerization process in hydrocarbon solvent. Titanium-containing catalyst supported by magnesium-containing carrier is prepared by reaction of organomagnesium compound Mg(C6H5)2•nMgCl2•mR2O, where n=0.37-0.7, m=2, R20 represents ether wherein R is i-amyl or n-butyl, with a silicon compound, namely product obtained by reaction of compound R'kSiCl4-k (R' is methyl or phenyl and k=0-1) with silicon tetraethoxide Si(OEt)4 at molar ratio R'kSiCl4-k/Si(OEt)4 = 6 to 40. Ethylene polymerization process in presence of above-defined catalyst in combination with co-catalyst is also described, wherein obtained super-high molecular weight polyethylene has loose density ≥ 0.39 g/cc.

EFFECT: increased molecular weight and loose density of polyethylene.

4 cl, 1 tbl, 8 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to a method for preparing supported titanium -manganese catalyst for synthesis of super-high molecular weight polyethylene via suspension ethylene polymerization process in hydrocarbon solvent. Titanium-containing catalyst supported by magnesium-containing carrier is prepared by reaction of organomagnesium compound Mg(C6H5)2•nMgCl2•mR2O, where n=0.37-0.7, m=2, R20 represents ether wherein R is i-amyl or n-butyl, with a silicon compound, namely product obtained by reaction of compound R'kSiCl4-k (R' is methyl or phenyl and k=0-1) with silicon tetraethoxide Si(OEt)4 at molar ratio R'kSiCl4-k/Si(OEt)4 = 6 to 40. Ethylene polymerization process in presence of above-defined catalyst in combination with co-catalyst is also described, wherein obtained super-high molecular weight polyethylene has loose density ≥ 0.39 g/cc.

EFFECT: increased molecular weight and loose density of polyethylene.

4 cl, 1 tbl, 8 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to a method for preparing supported titanium -manganese catalyst for synthesis of super-high molecular weight polyethylene via suspension ethylene polymerization process in hydrocarbon solvent. Titanium-containing catalyst supported by magnesium-containing carrier is prepared by reaction of organomagnesium compound Mg(C6H5)2•nMgCl2•mR2O, where n=0.37-0.7, m=2, R20 represents ether wherein R is i-amyl or n-butyl, with a silicon compound, namely product obtained by reaction of compound R'kSiCl4-k (R' is methyl or phenyl and k=0-1) with silicon tetraethoxide Si(OEt)4 at molar ratio R'kSiCl4-k/Si(OEt)4 = 6 to 40. Ethylene polymerization process in presence of above-defined catalyst in combination with co-catalyst is also described, wherein obtained super-high molecular weight polyethylene has loose density ≥ 0.39 g/cc.

EFFECT: increased molecular weight and loose density of polyethylene.

4 cl, 1 tbl, 8 ex

FIELD: polymerization processes and catalysts.

SUBSTANCE: invention relates to catalytic system for (co)polymerization of lactide and glycolide and to (co)polymerization process using indicated system. Catalytic system is composed of (a) trifluoromethanesulfonate of general formula (1), (b) (co)polymerization additive of general formula (2), wherein molar ratio of additive to catalyst ranges from 0.05:1 to 5:1. (Co)polymerization process of lactide and glycolide is also described as well as application of thus obtained lactide and glycolide polymer or copolymer.

EFFECT: enabled controlling chain length, nature of end units of the chain of resulting (co)polymers.

10 cl, 8 ex

FIELD: polymerization processes and catalysts.

SUBSTANCE: invention discloses catalyst for obtaining high-molecular weight isoolefin copolymers with small content of gel, which catalyst contains metal halide, in particular, zirconium halide and/or hafnium halide, and, additionally, organic acid halide, wherein molar ratio of said organic acid halide to zirconium and/or hafnium ranges from 0.5 to 50.

EFFECT: simplified technology.

2 cl, 3 ex

FIELD: polymer production.

SUBSTANCE: invention relates to 1-butene copolymers containing up to 40 mol % ethylene or propylene derivatives. Copolymer of 1-butene with ethylene or propylene is described, which copolymer contains up to 40 mol % of ethylene and/or propylene units derivatives and manifests following properties: (a) product of copolymerization constants r1·r2 ≤ 2; (b) content of 1-butene units in the form of stereoregular pentads (mmmm) > 98%; and (c) lack of 4,1-inclusions of 1-butene units. Described are also: polymer compositions for manufacturing films, which contains above-indicated polymer; industrial product obtained from this copolymer; and a method for preparing such copolymer comprising 1-butene/ethylene (and/or propylene) copolymerization in presence of stereoregular catalyst containing (A) solid catalytic component including Ti compound and electron-donor compound selected from MgCl2-supported phthalates; (B) alkylaluminum compound; and (C) outer electron-donor compound of formula Ra5Rb6Si(OR7)c, wherein a and b are integers from 0 to 2, c is integer from 1 to 3, and sum (a+b+c)= 4, R5, R6, and R7 represent alkyl, cycloalkyl, or aryl radicals with 1-18 carbon atoms, optionally containing heteroatoms.

EFFECT: achieved specific balance between stereoregularity and distribution of comonomer, lack of 4,1-inclusions, and increased stretching strength.

26 cl, 8 tbl, 14 ex

FIELD: polymer production.

SUBSTANCE: invention relates to 1-butene copolymers containing up to 40 mol % ethylene or propylene derivatives. Copolymer of 1-butene with ethylene or propylene is described, which copolymer contains up to 40 mol % of ethylene and/or propylene units derivatives and manifests following properties: (a) product of copolymerization constants r1·r2 ≤ 2; (b) content of 1-butene units in the form of stereoregular pentads (mmmm) > 98%; and (c) lack of 4,1-inclusions of 1-butene units. Described are also: polymer compositions for manufacturing films, which contains above-indicated polymer; industrial product obtained from this copolymer; and a method for preparing such copolymer comprising 1-butene/ethylene (and/or propylene) copolymerization in presence of stereoregular catalyst containing (A) solid catalytic component including Ti compound and electron-donor compound selected from MgCl2-supported phthalates; (B) alkylaluminum compound; and (C) outer electron-donor compound of formula Ra5Rb6Si(OR7)c, wherein a and b are integers from 0 to 2, c is integer from 1 to 3, and sum (a+b+c)= 4, R5, R6, and R7 represent alkyl, cycloalkyl, or aryl radicals with 1-18 carbon atoms, optionally containing heteroatoms.

EFFECT: achieved specific balance between stereoregularity and distribution of comonomer, lack of 4,1-inclusions, and increased stretching strength.

26 cl, 8 tbl, 14 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to methods for polymerization of ethylene-unsaturated monomers in the presence of free radical initiating agents. Method involves the following steps: peroxidation step wherein an aqueous mixture is prepared and this mixture contains diacylperoxide of the formula (I): by interaction of one or some acid halogen anhydrides of the formula (II): with (i) MOOH/M2O2 wherein M represents any metal or ammonium-containing group that interacts with H2O2 to form MOOH/M2O2 without decomposition of one or some peroxides taking part in the process; M is chosen from group consisting of ammonium, sodium, potassium, magnesium, calcium and lithium, and/or (ii) one or some peracids of the formula (III): , or with their M salts in aqueous phase. Acid halogen anhydride or mixture of acid halogen anhydrides contact with water only containing MOOH/M2O2 and/or one or some peracids or peracid salts, preferably M2O2 or peracid salt M. Values of radicals in formulae (I), (II) and (III) are given in the invention description. One or some solvents for acid halogen anhydride, one or some salts, one or some colloidal and/or surface-active substances can be added before, in process or after the peroxidation step. Also, the process can comprise one or some steps for purification of an aqueous mixture, one or some steps of homogenization of an aqueous mixture. Then the process involves a step for transfer of product from precede steps that comprises diacylperoxide of the formula (I) into polymerization reactor, and thermal decomposition of this diacylperoxide to form organic free radicals in the presence of one or some ethylene-unsaturated monomers with polymerization of indicated monomers in indicated polymerization reactor. Invention provides synthesis and using peroxides in process for short time period that solved problems associated with peroxides.

EFFECT: improved method of polymerization.

13 cl, 3 ex

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention proposes a catalyst of the following structural formula (I): wherein R1 is chosen from methyl, n-butyl, isobutyl and tert.-butyl; R2 and R2' are chosen from hydrogen atom, propyl and isopropyl, respectively; R3 is chosen from hydrogen atom and methyl; M represents Ti. The proposed catalyst is used for polymerization reaction of ethylene or co-polymerization reaction of ethylene with hexane of high molecular mass and the high rate of removal of co-monomer. Also, invention claims a method for synthesis of indicated catalyst that involves the following steps: (1) interaction of Schiff's reagent ligand of the formula (II) given in the invention description with alkaline metal alkyl derivative in organic medium for preparing alkaline metals salt ligand of Schiff's reagent; (2) interaction of alkaline metal salt of Schiff's reagent ligand with metal cyclopentadienyl chloride of the formula: CpMCl3 in organic medium, removal of solvent, washing out a residue with organic solvent, filtration of a prepared compound and re-crystallization of filtrate.

EFFECT: improved method of synthesis and preparing.

7 cl, 2 tbl, 23 ex

FIELD: polymer production and catalysts.

SUBSTANCE: proposed method comprises contacting monomers with deposited bimetallic catalytic composition over a period of time long enough to obtain bimodal polyolefin composition, which includes high-molecular weight polyolefin component and low-molecular weight polyolefin component, wherein deposited bimetallic catalyst includes first catalyst component, which is preferably non-metallocene, and second catalyst component, which includes metallocene catalytically active substance containing at least one fluoride or fluorine-containing leaving group, wherein bimetallic catalyst is supported by improved silica dehydrated at temperature above 800°C.

EFFECT: increased activity and productivity of catalyst.

16 cl, 2 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to photoinitiating agents of phenylglyoxylic acid order used in polymerizing compositions to be subjected for hardening. Invention describes a photoinitiating agent of the formula (I): wherein Y means (C3-C12)-alkylene, butenylene, butinylene or (C4-C12)-alkylene that are broken by groups -O- or -NR2- and not following in sequence; R1 means a reactive group of the following order: -OH, -SH, -HR3R4, -(CO)-OH, -(CO)-NH2, -SO3H, -C(R5)=CR6R7, oxiranyl, -O-(CO)-NH-R8-NCO and -O-(CO)-R-(CO)-X; R2 means hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R3 and R4 mean hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R, R and R mean hydrogen atom or methyl; R8 means linear or branched (C4-C12)-alkylene or phenylene; R9 means linear or branched (C1-C16)-alkylene, -CH=CH-, -CH=CH-CH2-, C6-cycloalkylene, phenylene or naphthylene; X, X1 and X2 mean -OH, Cl, -OCH3 or -OC2H5. Also, invention describes a method for synthesis of a photoinitiating agent, polymerizing composition and substrate covered by its. Proposed photoinitiating agent possesses the effective introducing capacity and absence of migration in thermal treatments.

EFFECT: improved and valuable properties of agent.

13 cl, 1 tbl, 16 ex

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