Supported catalyst precursor composition (options), supported catalytic composition (options) method of preparation thereof (option), polymer preparation process

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

 

The technical FIELD TO WHICH the INVENTION RELATES.

The present invention relates to supported on a carrier catalyst compositions, methods of preparing such compositions and methods of producing polymers with their use.

BACKGROUND of INVENTION

Properties of polymers depend on the properties of the catalyst used to produce it. As catalysts, in order to guarantee the possibility of successful industrial applications important to the regulation of shapes, sizes and distribution of the catalyst particles by size. This is particularly important in gas-phase and slurry polymerization. For example, if you need a copolymer granules with the size of 1000 μm for use in the polymerization is generally preferable catalyst with a particle size of from about 10 to about 50 microns. When copolymerization of olefins often requires a catalyst with a developed system of pores in its structure. Finally, the catalyst should possess good mechanical properties to withstand the wear and tear during the polymerization process and to guarantee a good volumetric weight of the polymer product. Therefore, one important aspect related to the creation of a polymerization catalyst, is to develop a method of preparation of the catalyst, which allow the us to control and regulate the structure and size of the catalytic particles and the distribution of particle sizes and which nevertheless remains relatively simple way.

However, the implementation of these methods using catalysts containing magnesium and titanium, often requires a long series of stages of synthesis. This stage of the synthesis provided for the preparation of the catalyst with a high content of magnesium, because the higher the concentration of magnesium increase the activity of the catalyst and cause the formation of polymers having more target properties. Creating a catalyst on the material media provides an opportunity to simplify or eliminate many of the stages of synthesis. Unfortunately, even when the catalyst is impregnated with the material of the carrier, the amount of catalyst that can be entered is limited by the solubility of the magnesium component used for the preparation of solvent.

With regard to typical sources of magnesium, such as magnesium halides, their solubility in polar organic solvents with increasing temperature from about room temperature up to the boiling point of these solvents actually decreases. This reduced solubility due to, say, a consequence of the formation having low solubility polymer complexes of magnesium halide, a solvent, such as MgCl2(THF)1,5-2. So, for example, ultrapure solutions of magnesium chloride in tetrahydrofuran (THF) under heating to form solid precipitates with litically composition MgCl 2(THF)1,5and the maximum concentration of MgCl2that can be achieved in such a solution is less than about 0.75 mole of MgCl2/l At about 60°near the boiling point of THF, the solubility significantly reduced to a level below 0.5 mol/L. However, when using magnesium chloride technical grade, its maximum solubility in THF is even lower, presumably due to the presence of impurities such as water, and is equal to about 0.6 mole of MgCl2/L. In these cases, at 60°the solubility is only about 0,35 mol/L. This low solubility sources of magnesium limits the number and distribution of the halide of magnesium, which can be introduced into the particle deposited on the catalyst carrier.

Usually reduced solubility in the solvent is the reason for the lower concentration of the halide of magnesium in the resulting catalyst particles. However, another problem associated with the use of halides of magnesium, is a selective deposition. The magnesium halides tend to easily form sediments on the outer surfaces of the porous catalyst carrier during the drying process, while the component of the transition metal during the drying remains soluble. Thus, the resulting particle is characterized by a rather homogeneous distribution and the concentration of the transition metal. However, the preferential precipitation of magnesium halide leads to the variation of the ratio of magnesium/transition metal in the catalyst particle. In some cases, the ratio between the magnesium and the transition metal on the periphery of the particles can be more than ten times larger than the same ratio in the center of the particle.

Thus, it would be efficient new supported on a carrier catalysts, including inside the catalyst particles of the magnesium halide in a relatively higher concentration. Such higher concentrations must be achieved by the method, which does not create problems in subsequent stages of preparation.

SUMMARY of the INVENTION

Considering the above requirements, in one embodiment, the invention features supported on a carrier of a catalytic composition comprising the product of the interaction: 1) the composition of the catalyst precursor, comprising, in turn, the product of the interaction of (a) magnesium halide, (b) solvent C) electron-donating compound and (d) compounds of the transition metal, in which the transition metal is an element of groups 3-10 or lanthanide; 2) a porous inert carrier, and 3) Socialisticheskaya composition.

Another object of the invention provides methods of cooking is deposited on the al catalytic composition, includes 1) preparation of magnesium-containing solution, the solution includes the product of the interaction of (a) magnesium halide, (b) solvent, and C) electron-donating compounds; 2) contacting the magnesium-containing solution with a transition metal compound, in which the transition metal is an element of groups 3-10 or lanthanide, to obtain the composition of the catalyst precursor; (3) contacting the composition is dissolved catalyst precursor with a porous inert carrier to obtain the final mixture; 4) drying this final mixture with the receipt supported on a carrier composition of the catalyst precursor and 5) activating supported on a carrier composition of the catalyst precursor Socialisticheskaya composition.

There are also methods of polymer synthesis. These methods include the reaction of at least one polyolefin monomer in the presence of supported on a carrier of a catalytic composition comprising the product of the interaction: 1) a magnesium-containing solution, the solution includes the product of the interaction of (a) magnesium halide, (b) solvent C) electron-donating compounds, g) compounds of the transition metal, in which the transition metal is an element of groups 3-10 or lanthanide; 2) a porous inert carrier, and 3) acetamidocinnamic.

The methods and compositions presented in the present description, characterized by a catalytic compositions that are essentially free of other electron-donating compounds and in which the molar ratio between the electron-donating compound and the magnesium is less than or equal to 1.9.

In some preferred embodiments, electron donor is a donor of electrons, which is a linear or branched aliphatic or aromatic alcohol containing between 1 and about 25 carbon atoms. Preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, 1-dodecanol, cyclohexanol and tert-butylphenol. In some embodiments, the value of the molar ratio between alcohol and magnesium is less than around 1.75. In other embodiments, the value of the molar ratio between alcohol and magnesium is in the range from about 0.1 to about 1.1. However, in other embodiments, the value of the molar ratio between alcohol and magnesium is in the range from about 0.1 to about 0.75. In some embodiments, preferred is a molar ratio between alcohol and magnesium is in the range from about 0.1 to about 0.5.

Preferred transition metal compounds are acceptable in embodiments of the compositions and the method is in, presented in the present description, include compounds of titanium, zirconium, hafnium, vanadium, niobium, tantalum, and combinations thereof. Some compounds of titanium correspond to the formula

Ti(R)aXb,

in which R is R' or COR'where R' represents an aliphatic or aromatic hydrocarbon radical with C1With14the value X is chosen from Cl, Br, I and mixtures thereof, and a represents 0 or 1, b is from 2 to 4 inclusive, and the sum a+b is 3 or 4. Examples of titanium compounds include TiCl3, TiCl4, Ti(OS6H5)Cl3, Ti(ASON3)Cl3, Ti(EA6H5)Cl3and mixtures thereof.

The solvent is chosen from the group including aliphatic esters of aliphatic and aromatic carboxylic acids, ethers, and aliphatic ketones. Preferred aliphatic esters as solvents include, though 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 embodiments, the preferred tetrahydrofuran. Examples of the ketone solvents include AC the tone, methyl ethyl ketone, cyclohexanone, cyclopentylmethyl, 3-bromo-4-heptanone, 2-chlorocyclopentane, allylmercaptan and combinations thereof. Some options include two or more such solvents.

The magnesium halides for use in the described compositions include, though not limited to, MgCl2, MgBr2, Mgl2, MgClBr, MgBrI and mixtures thereof. In some embodiments, such halides may be used to prepare compositions of the precursors and catalytic compositions that include a composition of the formula

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

where ROH is a linear or branched alcohol containing within one and about 25 carbon atoms, R is R' or COR', where each R' individually represents an aliphatic hydrocarbon radical containing between 1 and about 14 carbon atoms, or an aromatic hydrocarbon moiety containing between 1 and about 14 carbon atoms; X is individually denotes Cl, Br or I; S is chosen from the group including aliphatic esters, aliphatic ethers, cyclic ethers, and aliphatic ketones; the values of m are in the interval from 0.5 to 56; n denotes 0, 1 or 2; the values of R lie in the interval from 4 to 116; the values of q are in the range from 2 to 85; and mn is ing r are in the range from 0.1 to 1.9. In some preferred embodiments, the values of r are in the range of from 0.1 to less than about 0.5.

In some embodiments, the proposed composition further includes a compound or a product of the interaction of the Lewis acid with the composition of the catalyst precursor or catalyst composition. Some acceptable Lewis acid correspond to the formula RgMX3-gin which R represents R' or or'or NR'2where R' represents substituted or unsubstituted aliphatic or aromatic hydrocarbonous group containing from 1 to 14 carbon atoms, the value X is chosen from the group comprising Cl, Br, I and mixtures thereof; g-values are in the range from 0 to 3, and M denotes an atom of aluminum or boron.

Examples of aluminium-containing Lewis acids include tri-n-hexylamine, triethylamine, diethylaluminium, trimethylaluminum, dimethylammoniumchloride, methylaluminoxane, triisobutylaluminum, tri-n-butylamine, diisobutylaluminium, sibutraminegeneric, (C2H5)AlCl2, (C2H5O)AlCl2, (C6H5)AlCl2, (C6H5O)AlCl2, (C6H13O)AlCl2and their combinations. Examples of boron Lewis acids include BCl3, BBr3In(C2H5)Cl2, B(OC2H5)Cl2(OS2H5)2Cl, (C6H5/sub> )Cl2In(OS6H5)Cl2In(C6H13)Cl2(OS6H13)Cl2(OS6H5)2Cl and combinations thereof.

Although you can use any socialization, some acceptable according to the present invention socializaton meet the formula AlX'd(R)cHc;in which X' represents Cl or or"', R" and R"' are individually represent saturated hydrocarbon radicals with C1With14, d denotes a number from 0 to 1.5, e represents 0 or 1, and the sum of C+d+e is 3. Examples of socialization include Al(CH3)3, Al(C2H5)3, Al(C2H5)2Cl, Al(ISO-C4H9)3, Al(C2H5)1,5Cl1,5, Al(ISO-C4H9)2H, Al(C6H13)3, Al(C8H17)3, Al(C2H5)2H Al(C2H5)2(OS2H5) and their combinations.

Although you can use any acceptable carrier, examples of inert carriers include inorganic oxides of transition metals, aluminum, silicon, and combinations thereof. Some inert carriers have a specific surface area greater than or equal to 3 m2/year

Although the size of the particles deposited on the carrier of the catalytic compositions according to the invention a specific value is not limited, preferably supported on a carrier rolled the practical compositions have an average particle size of from about 1 to about 250 microns.

The implementation of some methods of polymerization, represented in the present description provides the polymers containing greater than or up to about 90 mol.% ethylene units and less than or up to about 10 mol.% links one or more comonomers. Preferred polymers have a density in the range from approximately 0.88 to about 0,98 g/cm3.

BRIEF DESCRIPTION of DRAWINGS

Figure 1 illustrates the characteristic solubility for solution of MgCl2three versions of the invention in THF depending on alcohol content and temperature of the solution.

Figure 2 illustrates the profile of solubility in several variants of execution of the invention, depending on temperature, concentration of MgCl2and the ratio of alcohol/Mg in THF.

Figure 3 illustrates the structure of a variant containing the magnesium halide catalyst component.

Figure 4 illustrates the characteristic thermogravimetric analysis (TGA) for options proposed according to the invention the catalytic component.

Figure 5 illustrates the reaction system with a fluidized bed, which can be used in versions of the invention.

Embodiments of the INVENTIONS

Supported on a carrier catalysts according to the present invention include a composition protogonists media; the mixture or the product of the interaction of the halide of magnesium compound, a solvent, electron-donating compounds in addition to the solvent and the transition metal, where the metal is an element of groups 3-10 or lanthanide, and Socialisticheskaya composition. Supported on a carrier of the catalytic composition is virtually free of other electron-donating compounds, and the molar ratio between the electron-donating compound and the magnesium is less than or equal to 1.9.

In the following description, all of the presented numbers are approximate values, regardless of whether you used in connection with them the word "about" or "approximately". They can range up to 1, 2, 5 or sometimes 10 to 20%. Whenever numerical range with a lower limit of Rnand the upper limit of Rinspecifically indicate any number of R covered by this range. Thus, in particular, specify the following numbers R in the range: R=RH+k*(RB-RH), where k denotes a variable in the range from 1 to 100% in 1%increments, i.e. k is 1, 2, 3, 4, 5, ..., 50, 51, 52, ..., 95, 96, 97, 98, 99 or 100%. Moreover, specify any numerical range defined by two of the above numbers R.

Any reference in the present description by "electron-donating compounds" relative who are getting ready for connections which improve the solubility of the halide of magnesium in the electron-donating solvent so that at any temperature up to the boiling point of this electron-donating solvent solubility is not decreased. Used in the present description the term "electron-donating compound" does not cover "solvents", as defined below, even when such solvents have electron-donating character. Examples of electron-donating compounds include alcohols, thiols, as a weak donor amines and phosphines. Used in the present description the term "essentially free of other electron-donor compounds" means that other electron-donating compound", as they are presented in the present description, are not contained in concentrations that generally exceed the levels of impurities in such compounds supplied as food grade solvents. Thus, the composition including a solvent with electron-donor characteristics and the electron-donating compound"are considered to be "essentially free of other electron-donating compounds." In some embodiments, "essentially free" means containing less than 1, 0,1, is 0.01 or 0.001 wt.%.

Used solvents include any simple ether, ketone or ester compound. Although these solvents on adut electron-donating characteristics, any reference in the present description by "solvent" or "solvent" does not encompass those compounds that are above defined as "electron-donating compounds. Thus, compositions which are essentially free of other electron-donating compounds can include one or more solvents.

Under used in the present description the term "simple ether" means 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' have the same values. Examples of symmetrical ethers, although their list is not limited, are diethyl ether, diisopropyl ether and di-n-butyl ether. Examples of unsymmetrical ethers include ethylisopropylamine ether and methylbutanoyl ether. Examples of acceptable substituted ethers include, in particular, metalalloy ether and ethylenically ether. However, in other embodiments, R and R' may form a condensed ring which may be saturated or unsaturated. One example of such a compound is tetrahydrofuran. Other acceptable cyclic simple ether is 2-methyltetrahydrofuran. Specifically, these compounds are also referred to only as examples of compounds of the types that are acceptable, however, if this is referring to any connection containing functional groups of simple ether R-O-R'.

Used in the present description, the term "ketone" as shown refers to any compound corresponding to the formula R(C=O)R'. R and R' may be individually denote a substituted or unsubstituted gidrolabilna groups, and in other respects their values above with reference to the ethers. Examples of ketones are acetone, methyl ethyl ketone, cyclohexanone, cyclopentylmethyl. Can also be suitable halogenated ketones, such as 3-bromo-4-heptanone and 2-chlorocyclopentane. Other suitable ketones may contain other functional groups such as unsaturated groups, as in allylmethylamine. Each of these compounds corresponds to the formula R(C=O)R', in which the carbon atom of the carbonyl group of the molecule forms a connection with two other carbon atoms.

Suitable ester solvents include any compound of General formula R(C=O)OR'. In such compounds the carbon atom of the carbonyl group forms a bond with the carbon atom and another bond with an oxygen atom. The values of R and R' are individually selected from substituted and unsubstituted hydrocarbonrich groups and they may be the same or different. In some embodiments, esters include aliphatic esters of aliphatic and aromatic carboxylic acid is so This series also includes cyclic esters, saturated esters and halogenated esters. Non-limiting examples of esters include methyl acetate, ethyl acetate, ethylpropane, methylpropionate and ethylbenzoic. These individually listed compounds also serve only as examples of the types of compounds that are acceptable. Suitable for any connection that meets functional groups of General formula R(C=O)OR'.

Source of magnesium can be introduced into contact with any acceptable solvent to the direct mixing in the form of a magnesium halide with the solvent. In some embodiments, the magnesium halide is magnesium chloride, however, can be also used magnesium bromide and magnesium iodide. Suitable sources of halides are halides of magnesium, such as MgCl2, MgBr2, Mgl2and mixed magnesium halides, such as MgClI, MgClBr and MgBrI. In some embodiments, the magnesium halide is introduced into the solvent in anhydrous form. In other embodiments, the magnesium halide is introduced into the hydrated form.

Typically, the solvent is used in a large excess relative to the first coordination environment of magnesium. In some embodiments, the ratio between electrondonor and magnesium is approximately 100 to 1, in another embodiment, this ratio may be even more grave is. Nevertheless, in other embodiments, the solvent is contained at a ratio of at least about 1.0, at least about 2.0 to at least approximately 5,0, at least about 10 or at least about 20 moles of electron-donor compound per 1 mol of magnesium. In some embodiments, it is possible to use two or more solvents.

Electron-donating compound is introduced into the mixture of solvent and halide of magnesium using any acceptable means. In a preferred embodiment, electron-donating compound is introduced into this mixture directly. In some embodiments, the electron-donating compound is an alcohol, thiol, as a weak donor amine or as a weak donor phosphine. When the electron donor is an alcohol, it can be any chemical compound that meets the General formula ROH. R may denote any substituted or unsubstituted hydrocarbonous group. In some embodiments, the alcohol is an aliphatic alcohol containing from about 1 to about 25 carbon atoms. In some embodiments, the alcohol is a monodentate alcohol. Used in the present description the term "monodentate alcohol" refers to those compounds in which R can have the following values, in which the result of the substitution is not a molecule with more than one hydro is strong (IT) functional group, which in solution forms an atom of magnesium coordination bond. Examples of such alcohols may include methanol, ethanol, propanol, isopropanol and butanol. Alcohols containing an aliphatic group with a longer chain, such as 2-ethylhexanol and 1-dodecanol, also form a solution in which the solubility of the magnesium halide with the growth temperature increases. Can also be used alcohols with greater number of carbon atoms. In addition, this alcohol can also serve as a cyclic alcohol, such as cyclohexanol, or aromatic alcohol, such as tert-butylphenol.

In some embodiments, the ratio between the electron-donating compound and magnesium added in the solution is less than or equal to about 1.9, less than around 1.75, less than 1.5, or less than 1.0. In other embodiments, the ratio between the electron-donating compound and the magnesium is less than about 0.75, less than about 0.5, or less than about 0.25 in. However, in other embodiments, the value of the molar ratio between the electron donor and magnesium is approximately 0.1. Other options can be characterized by the ratio between the electron donor and magnesium, which exceeds approximately 1.9, in particular such as approximately 2,0, approximately 2.1, about 2.2, about 2.5 and about a 3.0.

Adding small if the EU ETS one electron-donating compound in the mixture, solvent-and halide of magnesium leads to the formation of magniysoderzhaschee composition, solubility with increasing temperature increases and the solubility of which at the boiling temperature of the solvent is relatively higher than the solubility product of the joining of magnesium halide/electron donor, when electron-donating compound is not contained. I believe that the addition of small amounts of one electron donor in a solvent in the presence of a halide of magnesium inhibits the conversion of soluble materials in polymeric addition products. In some embodiments, the soluble materials meet the formula

MgXx(ED)y(S)z,

in which x usually denotes 2, corresponding to the oxidation state of magnesium is less than or equal to 4, and the sum of x+y+z is less than or equal to 6. In other embodiments, y may denote approximately 0,5, 0,75, 1, 1,5, 1,75, approximately 1.9 or less. In some other embodiments, y is about 0.1, of 0.25, 0.3 or 0.4. The solubility of these materials with increasing temperature usually rises. When the solvent is THF, the concentration of the halide of magnesium in the solution can be up to five times higher than in the comparative solutions that do not contain electron-donating compound.

Figure 1 illustrates the profile of solubility for solution of magnesium chloride in the threaded depending on the temperature in tetrahydrofuran and alcohol. As illustrated in figure 1, a composition that does not contain alcohol, usually characterized by the solubility of the halide of magnesium, which is at about 30°increases from approximately 0.5 mol of magnesium per liter up to a maximum of less than approximately 0,65 mol of magnesium per liter. Above 30°solubility gradually decreases until, until you reach the boiling point of the solvent. In contrast to this mixture, add the alcohol, such as ethanol, are characterized by the solubility of the halide of magnesium, which with increasing temperature up to the boiling point of the solvent is not reduced. For example, a mixture having a ratio between ethanol and magnesium, about 0.5, show that the solubility of magnesium in 15°C is about 0.75 mol/L. the solubility of magnesium chloride increases with increasing temperature up to about 30°when the concentration of magnesium in solution is around 1.75 mol/l as the temperature rises above 30°solubility remains essentially constant up until not reach the boiling point.

Figure 1 also illustrates the characteristic solubility of mixtures having a value of correlation between alcohol and magnesium, which is about 1. At 25°With the concentration of magnesium contained in the solution is about 0.5 mol/L. However, when the temperature is and reaches about 55° With the concentration increases to about 2 moles/l and remains essentially constant up to the boiling point of the solvent. Samples with a ratio of two moles of alcohol per mole of magnesium, also show that depending on the temperature, the solubility of magnesium increases until reaching the boiling point, when this value is around 1.75 mol of magnesium/L.

Figure 2 illustrates the solubility profile of several mixtures containing different amounts of added alcohol. Each point of the data in figure 2 was obtained by adding such amount of magnesium chloride, which was necessary to achieve the target concentration, when the magnesium chloride was dissolved in THF. Next I added some alcohol to achieve the target ratio of alcohol/magnesium and the mixture was heated up until the composition remained dissolved in THF. Then the solution was slowly cooled until then, until it started to form a precipitate. The temperature at which they began to form a precipitate, figure 2 was recorded on the y-axis. Thus, figure 2 shows the temperature necessary for the preparation of solutions of magnesium chloride of different concentrations in the presence of alcohol. For example, the data indicated by the position 210, illustrate the temperature necessary to obtain a solution, which is approximately 0.75 M solution of magnesium chloride, when Rast is orichalum serves as THF, in the presence of different concentrations of ethanol. In mixtures prepared in the ratio between alcohol and magnesium of 0.25, the concentration of magnesium in solution was approximately 0.75 M only 5°C. the mixtures prepared with the ratio between the alcohol and magnesium chloride to 0.5, the concentration of magnesium 0.75 M was reached at about 15°With, while in a mixture with a ratio of 1.0 concentration of 0.75 M was reached at about 33°C. When preparing the mixture with the value of the molar ratio between alcohol and magnesium chloride 1.5, or 2.0, the solutions reached in the concentration of magnesium to about 0.75 M, respectively, about 47 and 53°Stack way, the data indicated by the position 210, show that mixtures with higher ratios of alcohol/magnesium characterized by a low solubility.

Thus, figure 2 shows that at lower ratios between alcohol and magnesium chloride are formed solutions with a higher concentration of dissolved magnesium. The decrease in solubility with increase in the ratio ROH/MgCl2suggests that small amounts of added ROH prevent the formation of polymer product accession MgCl2(THF)2and add more significant amounts of ROH or more alcohols turns the solution into the system with a less soluble product is m joining, containing more than ROH. Used the ratio ROH/Mg determines the maximum solubility, which can be achieved, and the desired temperature. The data indicated in figure 2 positions 220-260 show that for a given ratio of alcohol/magnesium increased temperature leads to increased amounts of magnesium, which is soluble. So, for example, solutions having a molar ratio alcohol/magnesium 0,5, at about 15°characterized by the concentration of magnesium in solution to about 0.75 M, while about 20°can be achieved concentration of magnesium in solution 1.0 M Line 230 shows that the same solution can dissolve approximately 1.25 mol/l of magnesium chloride at about 23°C. Figure 2 also shows that the solubility of magnesium chloride in such solutions at temperatures above 30°also increases. So, for example, solutions having a value of molar ratio between alcohol and magnesium 1 show that at a temperature of about 35°the solubility of magnesium chloride is about 0.75 M, while at about 41°solubility increases to about 1 M Data lines 230-260 show that when approaching the boiling point of THF solubility continues to rise. Similar behavior solutions are characterized by higher ratios of alcohol/mA the deposits.

The nature of these materials in solution has been interpreted using a variety of methods okharakterizovanie. Studies using NMR show that electron donors, forming with MgCl2in THF solution, coordination bond, coming in fast equilibrium, so no individual durable materials does not exist. The gas phase above THF solution containing MgCl2and 2 EQ. ethanol (EtOH) at equivalent Mg, involves significantly less alcohol than the gas phase over the same EtOH/THF solution not containing MgCl2. This suggests that in this solution, the ethanol-associated molecules MgCl2. Obviously, in the mortar phase of the alcohol functional group forms with the center MgCl2coordination bond. The maximum solubility at intermediate ratios of alcohol/MgCl2suggests that in solution are some of the materials, the concentration of which depends on the distinctive properties of alcohol, the specific ratio of alcohol/Mg and the temperature of the solution.

Figure 3 presents the x-ray structure of a single crystal, which exemplifies the catalytic component selected in the form of a solid substance. As can be seen from figure 3, this compound is a molecule with magnesium in the center. In this embodiment, the connection there are two molecules of THF electronoc the burrowing solvent, associated with an atom of magnesium, as well as two halide in the form of chlorine and two molecules of alcohol. Thus, the precursor corresponds to the formula MgCl2(ROH)2(THF)2where ROH represents the isopropyl alcohol. Can also be selected similar compounds, in which ROH is an ethanol. In this particular illustrated embodiment, the structure is usually called a TRANS-octahedral structure with the Central atom of magnesium, since the ligands of the same type associated with an atom of magnesium through the center of symmetry. However, such structure for any variant of the catalytic component is not required. In other embodiments, this component can be a mixture of two or more individual compounds. For example, in one embodiment, the component may include a mixture of MgCl2(ROH)2(THF)2and MgCl2(ROH)1(THF)3.

There is a possibility for any number of individual compounds, provided that the composition of the mixture as a whole corresponds to the formula MgXx(ED)ySzwhere x is less than or equal to 1.9.

In other embodiments, the halide of magnesium as the catalytic component corresponds to the formula

MgX2(ED)ySz,

where the sum of y+z is less than or equal to 4 and the value of y is less than or equal to 1.9. In those embodiments, where the sum of y+z is less than 4, the catalytic component can be considered the AMB as a component of the deficit of the solvent. These compositions may also be called non-stoichiometric compositions. Such compositions can be prepared in solid form from a fully coordinated composition MgCl2(ROH)2(THF)2or another song, MgXx(ED)ySz, heating, creating a low pressure or a combination of these two techniques.

Figure 4 presents the results of the determinations using thermogravimetric analysis (TGA), demonstrating the behavior of MgCl2(ROH)2(THF)2. Data TGA received at a heating rate of 10°C/min during periods when the mass loss was not determined. During periods when the sample was losing weight, sudden temperature changes linearly excluded until such time as no longer celebrated mass loss. As shown in figure 4, the largest part of the solvent and alcohol can be pressed by heating the composition of 50-200°With, and initially lost one of the molecules of THF, and then as ROH and THF (see figure 4). Thus, in some embodiments, the catalytic component may have a rather coordination and unsaturated polymer structure than Monomeric.

Upon receipt of the catalyst precursor magnesium component is introduced into contact with the source of titanium. Acceptable magnesium components described in conjunction considering applications Burkhard E.Wagner and others,"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.

As the source of the transition metal catalyst can be used compounds of transition metals which are soluble in the solvent. The amount of coupling of the transition metal or mixture of transition metal compounds used in the preparation of the precursors of catalysts can be varied widely depending on the type of the target catalyst. In some embodiments, the value of the molar ratio between the magnesium and the compound of the transition metal can be quite high, approximately 56, preferably from about 20 to about 30. In other embodiments, the value of the molar ratio between the magnesium and the compound of the transition metal is quite low, approximately 0.5. Usually the value of the molar ratio between the magnesium and the compound of the transition metal is from about 3 to about 6, where the preferred transition metal is titanium.

However, in other embodiments, the titanium can be introduced through a connection that meets the General formula Ti(OR)aXb1With14or COR'where R' represents an aliphatic or aromatic hydrocarbon radical with C1With14the value X is chosen from the group comprising Cl, Br, I and mixtures thereof, and means 0 or 1, b is from 2 to 4 inclusive, and the sum a+b is 3 or 4. Examples of some acceptable titanium compounds include, though not limited to, TiCl3, TiCl4, Ti(OS6H5)Cl3, Ti(ASON3)Cl3and Ti(EA6H5)Cl3. In some embodiments can use a single connection titanium, while other sources of titanium can be in one or several of such compounds. Regardless of the source of titanium can be added to the mixture solution of the precursor of magnesium in an amount necessary to achieve the values of the molar ratio between the magnesium and titanium from about 0.5 to about 1.0, from about 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 other embodiments, the titanium injected after addition of the solvent of the magnesium halide and electron-donating compounds. In some embodiments, the composition of the catalyst precursor according to the corresponds to the following General formula:

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

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

The composition of the precursor catalyst is introduced into contact with a porous inert carrier with the receipt supported on a carrier or introduced by impregnation of the composition of the catalyst precursor. The solution containing the mixture or the product of the interaction of the composition of the magnesium halide and the source of titanium, as a rule, enter into contact with the material of the carrier. PR is acceptable carriers are solid powdered compounds or compositions, which are inert in respect of other components of the catalytic composition and other active components of the reaction system. In some embodiments, the carrier is an inorganic compound, such as, though not limited to, oxides of transition metals, silicon and aluminum, and molecular sieves, as well as organic compounds such as porous polymers. Acceptable combinations of compounds of the media. The media can be used in the form of dry powders, the average particle size which ranges from about 1 to about 250 microns, and preferably from about 10 to about 100 μm, for gas-phase applications and from about 1 to about 100 microns for suspension applications. Particles of these compounds also are porous and have a specific surface area of from about 3 to about 500 m2/g, specific pore volume from about 0.4 to about 4 cm3/g and an average pore diameter of more than about 100 Å. In some embodiments, the inert carrier has a specific surface area of about 300 m2/, These carriers must be dry, i.e. free from absorbed water. The drying medium is held by the extract at a temperature below the sintering temperature or melting of the material of the carrier. As a rule, the process is carried out at a temperature of at IU the e 100° C. you Can use a lower temperature, when acceptable drying for a long period of time or when the medium is characterized by low temperature melting or sintering. Inorganic materials carriers usually dried at a temperature of from about 200 to 800°Strome addition, the material of the device can, optionally, be treated with the use of from about 1 to 8 wt.% one or more of the preceding aluminiumtechnik compounds. By this modification of the carrier aluminiumtechnik connections preparing the catalytic composition with increased activity, and improve the morphology of the polymer particles obtained ethylene polymers.

After administration of the composition of the catalyst precursor in contact with the material of the carrier, the excess solvent may be removed. You can use any acceptable method. Typically, the excess solvent is removed by heating, creating a low pressure or a combination of both methods. In some embodiments, supported on a carrier, the catalyst precursor thus receive in the form of fine engineering of powder. In some embodiments, supported on a carrier, the catalyst precursor can have the characteristics of or be a mixture of crystalline phases and amorphous phases or possess characteristics or present shall be a mixture of crystalline and amorphous components. The average size of the particles deposited on the carrier composition of the catalyst precursor is usually determined by the particle size of the carrier, and this indicates that at least in some embodiments, the solubility of the halide of magnesium has not been exceeded and that the composition of the catalyst precursor is introduced by impregnation into the pores of the material medium.

Typically, the value of the ratio between the composition of the catalyst precursor and the material of the carrier is from about 0.1 to 1, and preferably from about 0.1 to 0.5. Additional discussion impregnation of solid carriers precursors of catalysts can be found in US patent No. 4302565, which fully included in the present description by reference. The relationship between the composition of the precursor and the material of the carrier should be chosen in such a way as to prepare supported on a carrier composition of the catalyst precursor with the concentration of magnesium more about 0.75 mmole/g of catalyst. In other embodiments, the concentration of magnesium may be about 1.0, about 1.5, about 2.0 or about 2.5 mmole/g of catalyst. In other embodiments, the concentration of magnesium may be approximately equal to 3.0, about 3.2, about 3.4, 3.6 or about 3.8 mmole/g In other embodiments, the magnesium concentration can be higher.

In some embodiments, caused the output to the media the catalyst precursor modify using at least one Lewis acid or composition with Lewis acid. Processing can be performed by dissolving the compounds (compounds) as a Lewis acid in an inert liquid solvent and treatment with the prepared solution applied to the carrier compositions of this predecessor in any convenient way, for example, by simple immersion supported on a carrier composition of the precursor in the solution of the Lewis acid. The solvent for the Lewis acid must be non-polar and capable of dissolving the connection (connection) as the Lewis acid, but not the composition of the precursor. Among the solvents that can be used to dissolve the compounds (compounds) as the Lewis acid, there are hydrocarbon solvents, including substituted hydrocarbon solvent such as isopentane, hexane, heptane, toluene, xylene, gasoline, ligroin fraction and aliphatic mineral oils, such as, though not limited to, products Kaydol™, Hydrobrite™ 1000, Hydrobrite™ 550 etc. In a preferred version of such solvents are used together with the compound (compounds) as a Lewis acid in such quantities that the resulting the solution contains from about 1 to about 25 wt.% this connection (connections) as the Lewis acid.

Optionally supported on a carrier composition of the catalyst precursor can be added in and arty solvent to obtain slurry to dissolve in the solvent compounds (compounds) as the Lewis acid. Alternatively the connection (connection) as the Lewis acid may be dissolved in an inert solvent prior to its combination with supported on a carrier composition of the catalyst precursor. This technology is especially appropriate when using a gas, such as BCl3. Alternatively, if necessary, a Lewis acid may be added directly to the dry composition predecessor.

Usually a suitable connection as Lewis acids have the structures RgAlX3-gand RgBX3-gwhere R represents R' or or'or NR'2, a R' represents 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, a g in each case denotes 0-3.

Acceptable compounds as Lewis acids include tri-n-hexylamine, triethylamine, diethylaluminium, trimethylaluminum, dimethylammoniumchloride, methylaluminoxane, triisobutylaluminum, tri-n-butylamine, diisobutylaluminium, sibutraminegeneric, (C2H5)AlCl2, (C2H5O)AlCl2, (C6H5)AlCl2, (C6H5O)AlCl2, (C H13O)AlCl2and the corresponding compounds of bromine and iodine. Acceptable organohalide compounds include BCl3, BBr3B(C2H5)Cl2, B(OC2H5)Cl2(OS2H5)2Cl, (C6H5)Cl2(OS6H5)Cl2In(C6H13)Cl2(OS6H13)Cl2and(OS6H5)2Cl. Can also be used bromine - and iododerma connection, related to the above. The Lewis acid can be used individually or in combinations thereof.

Additional details regarding the Lewis acids which are suitable for this purpose can be found in US patents No. 4354009 and 4379758, which are not fully included in the present description.

The catalyst precursor or supported on a carrier, the catalyst precursor is treated with an activator of socialization. As a rule, socializaton meet the formula AlX'd(R)withHewhere X' represents Cl or or"'. R" and R"' are individually represent saturated hydrocarbon radicals with C1With14; d denotes a number from 0 to 1.5; e represents 0 or 1, and the sum of C+d+e is 3. Examples of socialization include Al(CH3)3, Al(C2H5)3, Al(C2H5)2Cl, Al(ISO-C4H9)3, Al(C2H5) 1,5Cl1,5, Al(ISO-C4H9)2H, Al(C6H13)3, Al(C8H17)3, Al(C2H5)2H, Al(C2H5)2(OS2H5and mixtures thereof.

In some embodiments, supported on a carrier, the catalyst precursor is partially activated outside the polymerization reactor socialization in a hydrocarbon slurry. This partial activation is optional. After contacting the composition applied to the carrier of the catalyst precursor with socialization drying to remove the hydrocarbon solvent and the catalytic composition can be directed to the polymerization reactor where the activation is completed with additional quantities of any acceptable socializaton. In the first stage carry out the reaction applied to the carrier of the catalyst precursor with acetalization with achievement of the values of molar ratio Al/Ti is approximately of 0.1, 0.5, 1, 2, 5, or 6. In some embodiments, the activation is carried out in a hydrocarbon solvent, followed by drying the resulting mixture to remove solvent at a temperature of at least 20, 30, 40 or 50°C. In some embodiments, the temperature is less than 50, 60, 70 or 80°Sdrugoi, an alternative method of partial activation are described in the patent US 6187866, according to which the process of partial asset the AI carry out continuous path.

In some embodiments, predominantly those in which the catalyst is not fully activate, to further activate the catalyst in a polymerization reactor, you can add additional activator compound. In some embodiments, the partially activated catalyst or the composition applied to the carrier of the catalyst precursor and additional socialization sent to the reactor along the lines of a separate filing. In other embodiments, the suspension in mineral oil partially activated deposited on the catalyst carrier and socializaton fed into the reactor through a single supply line. According to another variant of an activator compound can be treated suspension in mineral oil composition precursor, and the resulting suspension can be directed into the reactor. For more socialization can be sprayed into the reactor in the form of its solution in a hydrocarbon solvent such as isopentane, hexane and mineral oil. This solution usually contains from about 2 to 30 wt.% Socialisticheskaya composition. Socialization can also be added to the reactor in solid form absorbed by the media. For this purpose, in some embodiments, the carrier must contain from about 10 to about 50 wt.% the activator. For more socialization added to the reactor in an amount such that the d is to fight in the reactor, the total molar ratio Al/Ti is about 10, about 15, about 25, about 45, about 60, about 100 or about 200 to 1. In other embodiments, this ratio may be equal to about 250, or about 400 to 1. Additional quantity of an activator compound added to the reactor, optionally activate deposited on the catalyst carrier.

The above-described variants of the catalysts can be used in solution, suspension or gas-phase polymerization processes. The above supported on a carrier catalysts can be prepared for use in the suspension polymerization in accordance with any appropriate methods. In some embodiments, such catalysts receive similar to those used in gas-phase polymerization processes. Conditions of suspension polymerization include polymerization2-C20the olefin, diolefin, cycloolefin or mixtures thereof in an aliphatic solvent at a temperature below that at which the polymer is readily soluble in the presence deposited on the catalyst carrier. Options proposed according to the invention catalysts can also carry out processes in the suspension phase, suitable for homopolymerization of ethylene and copolymerization of ethylene with α-olefins with3C8such as, for example, 1-butene, 1-hexene, 4-methyl-1-penten and 1-octene. Can be half the received high-density polyethylene (HDPE), medium-density polyethylene (PASP) and linear low density polyethylene (LLDPE).

During the continuous gas-phase composition process partially or fully activated precursors are continuously sent to the reactor with separate portions of any additional activator compound needed to complete the activation of the composition is partially activated precursor during continuous polymerization process to replace the active catalytic sites, which had worked during such a reaction.

The polymerization reaction generally is carried out in gas-phase process such as a process in the fluidized bed, as described below, and substantially in the absence of catalyst poisons such as moisture, oxygen, CO, CO2and acetylene, the introduction of a flow of ethylene into contact with a catalytically effective amount of the completely activated composition predecessor (catalyst), temperature and pressure sufficient to initiate the polymerization reaction. Options supported on a carrier of a catalyst suitable for polymerization With2-C6olefins, including homopolymers and copolymers of ethylene with α-olefins such as 1-butene, 1-hexene and 4-methyl-1-penten. Typically, this reaction can be performed under any conditions, priemel is activated for polymerization processes of the type Ziegler-Natta, held in suspension or gas-phase conditions. Such processes are carried out industrially to obtain high density polyethylene (HDPE), medium-density polyethylene (PASP) and linear low density polyethylene (LLDPE).

During the gas-phase polymerization can be used, the reaction system fluidized bed. The reaction system fluidized bed are discussed in detail in US patents No. 4302565 and 4379759, which are not fully included in the present description as a reference. However, for convenience, figure 5 illustrates a reactor system with a fluidized bed, which can be used in versions of the invention. The reactor 10 consists of a reaction zone 12 and zone 14 speed reduction. The reaction zone 12 includes a layer of growing polymer particles, forming a mass of the polymer particles, and a small amount of catalytic particles, pseudoacademic continuous flow capable of polymerization and modifying gaseous components in the form of fresh raw materials and recycle gas through the reaction zone. The mass flow rate of gas through the layer is sufficient for fluidization. In the accepted form as the abbreviation to denote the minimum mass gas flow required to achieve fluidization, use Gmf[see C.Y.Wen and Y.H.Yu, "Mechanics of Fluidization," Chemical Engineering Progress Symposium Series, vol 62, SS-111 (1966)]. In some embodiments, the mass flow rate of gas is 1.5, 3, 5, 7 or 10 times Gmf. The layer is prepared in such a way as to avoid the formation of localized "hot spots" and to capture and distribution of powdery catalyst throughout the reaction zone. At the initial stage in the reaction zone usually upload the basis of the powdered polymer particles prior to initiating the formation of a gas stream. Such particles by nature can be identical to the obtained polymer, or it may differ. When they differ, they are taken with a target formed polymer particles as the first product. Ultimately, the initial layer is displaced fluidized bed of particles of the target polymer.

Partially or fully activated compound, the precursor (catalyst)used in the fluidized bed, in the preferred embodiment, is stored for consumption in the reservoir 32 in the atmosphere gas, which is inert in relation to the stored material, such as nitrogen or argon.

Fluidization is achieved by using high-speed recycle gas moving in the direction of the layer and the via layer, typically about 50 times greater than the feed rate of fresh gas. A fluidized bed is generally the the current views of the dense mass of viable particles in possible irrotational flow, generated due to leakage of gas through the layer. The pressure drop on the way through the layer is equal to or slightly greater than the mass of the layer divided by the cross-sectional area. It, thus, depends on the configuration of the reactor.

Fresh gas is normally sent to the layer with the velocity equal to the speed at which disperses the powdered polymer product. The composition of the fresh gas is determined by gasanalysatorer 16, located above the layer. The detector determines the composition is returned to the process gas, and the composition of the fresh gas respectively regulate in order to keep almost constant the composition of the gases within the reaction zone.

To ensure appropriate fluidization recycle gas and, when necessary, part of the fresh gas back to the reactor at point 18 below the layer. To facilitate fluidization layer above the point of return provided by the gas distribution plate 20.

Part of the gas stream which does not react in the layer is recycle gas which is removed from the polymerization zone, preferably by passing zone 14 speed reduction above the layer where the flowing particles get the opportunity to fall back into the layer. The return of the particles can be facilitated by cyclone 22, which may be part of the recirculation line. Then, if necessary, R is cycle gas can pass through the preliminary heat exchanger 24, designed and built to provide cooling of small-borne particles for adhesion in the subsequent process line heat exchanger 26.

Recycle gas is compressed in the compressor 25 and then passed through a heat exchanger 26, where he has taken the heat of reaction before returning it to the layer. Due to the constant heat of reaction in the upper part of the layer does not occur, apparently, no noticeable temperature gradient. In the gap of from about 6 to 12 inches at the base layer, there is a temperature gradient between the temperature of the incoming gas and the temperature in the rest of the layer. Thus, it is obvious that the layer functions as a regulator of the temperature of the recycle gas above this layer in the base of the zone layer, ensuring that its temperature to the temperature of the rest of the layer, thus supporting essentially constant temperature in a stationary mode. Then recycle stream is returned to the reactor in the base 18 and through the distribution plate 20 in a fluidized bed. In the process line before the heat exchanger 26 can also be posted by the compressor 25.

Fluidized bed contains a growing and formed particles of powdered polymer and catalyst particles. Since the polymer particles are hot and possibly active, you predator who take their sedimentation, as if to provide the possibility of the existence in the state of rest mass, then the whole contained in the active catalyst may result in the continuation of the reaction, which will cause it to melt. Recycle gas diffuses through the layers at a rate sufficient to maintain fluidization in the base layer. This is the purpose of a distribution plate 20, which can mesh with slit plate, perforated plate, type plates with bubble caps, etc. are All elements of this plate may be fixed or you can use a plate movable type is described in US no 2298792. Whatever the design, it must ensure the diffusion of recycle gas through the mass of particles in the base layer for holding a fluid state, and to serve as a support for resting the layer of resin particles when the reactor is not operating. The movable plate elements can be used to delete all captured or is it on the stove polymer particles.

As the regulator of the degree of polymerization during the polymerization reaction, hydrogen can be used. The resulting ratio of hydrogen/ethylene ranges from about 0 to about 2,0 mol of hydrogen per 1 mol of ethylene in the gas stream.

As a means of controlling the molecular weight or regulator article the penalties polymerization to increase the value of the melt index of the polymers, which are formed, in combination with hydrogen, you can use the connection patterns ZnRaRbwhere Raand Rbthat are the same or different, represent aliphatic or aromatic hydrocarbon radicals with C1With14. In the gas flow in the reactor per 1 mol of compound of titanium (in terms of Ti) is used, apparently, from about 0 to 50, and preferably from about 20 to about 30, moles of Zn compounds (in terms of Zn). In a preferred embodiment, the compound of zinc is introduced into the reactor, apparently, in the form of a dilute solution (from 2 to 30 wt.%) in hydrocarbon solvent or absorbed in solid diluent, such as silicon dioxide, as described above in an amount of from about 10 to 50 wt.%. These compositions are characterized by expression of proforest. The connection of zinc can be added alone or with any additional portions of an activator compounds that are intended for introduction into the reactor from a feeder (not shown), which would ensure the supply of this compound in the hottest part of the system recycle gas, such as adjacent to the feeder 27 presented in the present description.

In the gas stream can also contain any gas that is inert towards the catalyst and reagents. In a preferred embodiment, the activator compound is administered in d is Klenow system in the hottest part of the recycle gas stream. Add in the recirculation line after the heat exchanger is thus preferred, as from the distribution device 27 through line 27A.

To prevent sintering of the required working temperature below the sintering temperature. To obtain ethylene homopolymers preferred operating temperature is from about 30 to 115°and to obtain products having a density of from about 0,961 to 0,968 g/cm3in the preferred embodiment, support temperature of from about 90 to 105°C.

A reactor with a fluidized bed operates under pressures up to about 1000 psig, and in the preferred embodiment, operates under a pressure of from about 150 to 350 psi, and the process under higher pressures in this range promotes heat transfer, because the increased pressure increases the gas heat capacity per unit volume.

Partially or fully activated composition predecessor Inuktitut in the layer with a speed corresponding to the velocity of its flow at the point 30, which is above the distribution plate 20. In a preferred embodiment, the catalyst Inuktitut at a point which is above the distribution plate. As described catalysts are highly active, injection completely activated catalyst in sonnige distribution plate may be initiated at the beginning of polymerization and eventually cause plugging of the distribution plate. Instead, the injection into live layer facilitates the distribution of the catalyst throughout the layer and prevents the formation of local points of high concentration of catalyst, which can lead to the formation of "hot spots".

To migrate into the layer of the composition is partially or fully restored predecessor and any additional activator compound, in which there is a need, you can use gas, which is inert in relation to the catalyst, such as nitrogen and argon. Another option as a carrier for catalysts contained in the suspension form, you can apply a mixture of solvents, such as isopentane, pentane, hexane, etc. In combination with the carrier can be also used nitrogen.

Performance layer regulate the speed of injection of the catalyst. Performance can be improved by a simple increase in the speed of injection of the catalyst and to reduce the decrease in the rate of injection of the catalyst.

Because of the rate of injection of the catalyst changes the rate of formation heat of reaction, the temperature of the recycle gas regulate it by raising or lowering, in order to match the change in the rate of formation of heat. It maintains a fairly constant temperature layer. To determine any temperature change is of the layer you want, of course, full instrumentation as fluidized bed, and cooling systems recycle gas, giving, thus, the operator with the ability to implement appropriate regulation of the temperature of the recycle gas.

In this series of working conditions of the fluidized bed is maintained at an almost constant height by removing part of the layer as a product with a speed corresponding to the rate of formation of powdery polymer product. Since the rate of heat production is directly related to the formation of the product, the definition of raise the temperature of the gas passing through the reactor (temperature difference between the incoming gas and the temperature of the released gas) allows you to set the rate of formation of powdery polymer at a constant gas velocity.

In a preferred embodiment, the powdered polymer product continuously removed at the point 34 at or near the distribution plate 20 and in suspension with a portion of the gas stream, which assign to the particles to prevent further polymerization and sintering when the particles reach their end zone collection. This suspendisse gas can also be used, as mentioned above, for transporting product from one reactor to another reactor.

In preferred options the ante powdered polymer product is removed by successive actuation of the pair operating in the synchronized mode, the valves 36 and 38, determining an area of 40 division. When the valve 38 is closed, valve 36 is opened to release the portion of gas and product in the area 40 between it and the valve 36, which is then closed. Further, the valve 38 is opened to supply the product to the external discharge area. Then the valve 38 is closed and is in the standby mode, the following allocations of the product. Can also be used a method of discharging fluidized bed in accordance with US patent No. 4621952 included in full in the present description by reference.

Finally, a reactor with a fluidized bed equipped with appropriate ventilation system to ventilate the layer during start and stop. The operation of such a reactor does not require the use of tools mixing and/or cleaning of walls describelayer.

Supported on a carrier of the catalytic system presented in the present description, allows, apparently, to get the product fluidized bed with an average particle size in the range of roughly 0.005 to about 0.06 inches, sometimes from about 0.02 to about 0.04 inch, and the residual content of the catalyst, which is unusually low. In the case of the typical conditions of polymerization of the residual catalyst in the polymer is in the range from about 0.1 to about 10 ppm of titanium.

Input flow hazoor the SNA monomer together with or without an inert gaseous diluents served in the reactor at a volumetric productivity of the catalyst is from about 2 to 10 pounds/hour/cubic ft volume of the layer.

The molecular weight of the polymer is convenient to specify, based on the data to determine the viscosity of the melt. One such result of the determination is that the melt index (IL), installed in accordance with ASTM D-1238, condition E, determined at 190°and the attached load of 2.16 kg (kilogram), expressed in grams per 10 minutes Polymers obtained with the use of some catalysts presented in the present description, have values of IR in the range of from about 0.01 to about 10,000 g/10 min to determine the rate of spreading of the melt is another method of okharakterizovanie polymers, it is determined in accordance with ASTM D-1238, condition F, using 10-fold weight relative to the one used in the definition of the above-mentioned melt index. The spreading rate of the melt is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower spreading rate of the melt, although this relationship is nonlinear. The ratio of the viscosities of the melts (SVR) is the ratio of the speed of spreading of the melt and the melt index. It correlates with the molecular weight distribution of the obtained polymer. Lower values SVR indicate a more narrow molecular weight distribution. The polymers obtained using the m certain catalysts, presented in the present description, have values of SVR in the range of from about 20 to about 40.

The polymers can also be okharakterizovany their density. The polymers of the present invention may have a density of from about 0.85 to about 0,98 g/cm3as is determined in accordance with ASTM D-792, according to which made the plate and condition at 100°C for one hour, before reaching equilibrium crystallinity. Next, in the column with a gradient density density is determined.

EXAMPLES

The following examples are given to illustrate various embodiments of the invention presented in this description. It should not be taken as limiting the scope of invention, which is defined in accordance with how it is described and claimed in the present description. All numeric values are approximate.

Preparation of comparative predecessor Mg/Ti 3:1 (0.25 mmole Ti/d)

Clad in glass 4-liter stirred vessel equipped with a helical blade stirrer and an external heating jacket, a nitrogen atmosphere was loaded 2913 g (3.28 l) of dry tetrahydrofuran (THF). Then added 87 g (of 0.91 mol) of powdered anhydrous MgCl2after which 61 g (0,31 mole) recovered aluminum trichloride titanium (TiCl3-And who). Suspension of chalk-white, turned into a watery green. The extract at a temperature of shirts 70-75°C for five hours in a nitrogen atmosphere caused the dissolution of all solids. Formed a bluish-green solution.

The product of Grace Davison Sylopol 955 was passivatable dehydration at 600°followed by treatment of the suspension of triethylaluminum in isopentane concentration of 5.5 wt.%. Silicon dioxide was dried by evaporation. 530 g of the above passivated silicon dioxide in nitrogen atmosphere was introduced into a 4 liter stirred vessel and added 1750 pre-prepared solution of MgCl2/TiCl3in THF, after which other 337 g of dry THF with obtaining low bluish-purple suspension. This suspension was heated to the temperature of the external shirts 70-75°and was stirred for two hours under reduced pressure (vacuum: 5 inches) to remove solvent/suspending agent. From the vessel unloaded 619 g of dry engineering soaked in 3:1 predecessor. The results of the analysis: 1,23% Al, 1,77% Mg, 1,18% Ti, 12,2% THF (0.72 mmole Mg/g, 0.25 mmole Ti/g).

Attempt to obtain unmodified precursor of Mg/Ti 5:1 (0.25 mmole Ti/d)

The above experiment was repeated, except that he used a solution of 88.3 g (0,93 mole) MgCl2and 39 g (0,19 mole) of TiCl3-AA in 1950 THF. No updat the additional electron donor was added. MgCl2it was established that at room temperature almost all dissolved (0,47 mmole MgCl2/g THF), but at 50°formed pale as chalk, white suspension. After adding 490 g of passivated silicon dioxide suspension was stirred at 55°C for one hour. The temperature of the jacket was increased to 90°and created a 5-inch vacuum. The suspension was dried for 2 h at 15 psi in a nitrogen atmosphere. Formed solid mass predecessor, which was rotated with a speed of rotation of the spiral agitator, around which it formed the unconformity. This solid mass predecessor freely from the vessel is not leaking and included a large flat lumps, which followed the form of the walls of the vessel and agitator blades.

Preparation of modified ethanol predecessor Mg/Ti 5:1 (0.25 mmole Ti/d)

Used the same equipment as described above. 4022 g of dry THF and 184 g (1,93 mole) of powdered anhydrous MgCl2at 65°With was stirred for 5 hours nominal suspension concentration was 0.48 mmole Mg/g of THF. Formed a milky-white suspension containing nerastvorim MgCl2. Then added 90 g of ethanol fortress 200 (1,95 mole, ROH/Mg 1:1). Formed a clear solution, which during the night was allowed to cool to room temperature.

4-whether the normal mixer was loaded 1500 g (720 mmol Mg) solution, modified ethanol MgCl2(˜0.6 M), then 39 g (to 0.19 mol) of recovered aluminum TiCl3(TiCl3-AA), after which additional 440 g (211 mmol) of a solution of MgCl2. The green solution was heated to 50°and examined for the presence of sediment. All components remain in solution. Then added 487 g of passivated silicon dioxide Grace Davison Sylopol 955 and the suspension was stirred at 55°C for one hour. The temperature of the jacket was increased to 90°and created a 5-inch vacuum. The suspension was dried for 2 h in 15" nitrogen atmosphere. Unloaded 597 g engineering catalyst precursor. The solid precipitate on the walls was absent, and on the spiral stirrer there was only a minimal amount of sediment. Data analysis: 0,26 mmole Ti/g, 1,19 mmole Mg/g, 11,35% THF, 2,63% ethanol. The distribution of particle size (Malvern instrument 2600) was almost unchanged in comparison with the particle sizes of the source of silicon dioxide (no agglomeration).

Preparation of other modified predecessors

For the preparation of other modified ethanol precursors used in the future, used the same methods as described above, except that appropriately regulated quantities of alcohol, MgCl2and TiCl3-AA. Received predecessors Mg/Ti 3:1, 0.25 mmole Ti/g when sootnoshenie the ROH/Mg of 0.5:1 and 1:1, predecessor Mg/Ti 3:1, 0,49 mmole Ti/g ratio ROH/Mg 1:1. In all cases received engineering, whether predecessors.

The preparation of the reconstituted predecessors (0,45 DEAH/THF, 0,2 Tngal/THF)

460 g supported on a carrier catalyst precursor with a high value of Mg/Ti (nominally 0.25 mmole Ti/g, 1.25 mmole Mg/g, 11,35% THF), prepared according to the above, in a nitrogen atmosphere at room temperature was transferred into a 4-liter mixer. Then downloaded 1900 ml of isopentane with obtaining low suspension. Then downloaded 837 ml (325 mmol, 0.45 mmole/mmol THF) 10%diethylacetanilide (DEAH) in isopentane. Low yellowish-brown suspension was stirred for 30 min and added 423 ml (145 mmol, of 0.20 mmole/mmol THF) 20%tri-n-hexylamine (Tnhal) in isopentane. Dark brown suspension was stirred for 30 min, and then dried at a temperature of shirts 70°by purging with nitrogen under a pressure of 5 psi for two hours. Allocated 500 g engineering yellowish-brown catalyst. Data analysis: 0.55 mmole Al/g to 0.20 mmole Ti/g of 0.87 mmole Mg/g, 3.2 mmole chloride/year

Using the appropriate quantities of reducing agents similarly restored the other supported on a carrier precursors of catalysts with achievement sootnosheniyah/THF 0.45 and Tnhal/THF 0,20. All represented engineering is a dark brown powder.

The polymerization of ethylene in a slurry reactor

Each experiment polymerization in laboratory scale was carried out as follows. In 500 ml of hexane in a 1-liter autoclave for suspension polymerization in a nitrogen atmosphere was introduced 1.25 mmole of triethylaluminum ((C2H5)3Al), after which was added a suspension of catalyst precursor in mineral oil, containing, as indicated, from 0,0075 to 0,030 mmole of Ti. To maintain control over the process of polymerization catalysts with higher activity was tested in a smaller downloadable quantities and, where possible, other catalysts were tested at loading of the catalyst in the same amount. Using gaseous hydrogen in the reactor created a gauge pressure of 40 psi, then the pressure is further increased ethylene to a total pressure of 200 psig. The polymerization was carried out at a temperature of 85°within half an hour. The results of these processes of the suspension polymerization are presented in table I together with the results of comparative example 1.

Table I
ExperimentMg/TiROH/Mg mmol/g TiTi (µmol)ActivityaPerformancebIL, DG/minSVRVolume weight, g/cm3
1*300,2529618015500,5310,336
230,50,2829670019000,8260,325
3310,2831700019501270,354
4310,4239500021000,629of 0.332
550,50,2326870020001250,36
6510,2630910024001,428of 0.337
*comparative example; and in g PE/(mmol of titanium·h·100 psi2); b: in g PE/(g of catalyst�B7; h·100 psi2)

Table I shows that deposited on the carrier catalysts of examples 2-3 and 5-6 have a higher activity in terms of Ti and calculated per 1 g of the catalyst than the catalyst of comparative example A. furthermore, supported on a carrier catalysts of examples 2 through 6 does not cause a significant drop in the volumetric weight of the resin, despite the improved performance of the catalyst.

The reaction of suspension polymerization was also performed using the reconstructed supported on a carrier of catalysts. These recovered supported on a carrier catalysts have higher activity than the comparative catalyst, without a significant drop in the volumetric weight.

Table II
ExperimentMg/TiROH/Mgmmol/GTTi (µmol)ActivityaPerformancebIL, DG/ minSVRVolume weight, g/cm3
7*300,202930006000,7280,398
830,5 0,23940009001,3280,383
9310,3333330011000,7270,41
1050,50,198,2535010001,1260,373
11510,207,7515010001,2280.388
*comparative example; and in g PE/(mmol of titanium·h·100 psi2); b: in g PE/(g of catalyst·h·100 psi2)

The data of table II demonstrate the relationship between partial activation in the mixer and subsequent catalytic activity of the control catalyst and the volumetric weight of the resin. As a result of partial activation using DEAH/Tngal catalytic activity of the control catalyst, when compared with the results achieved by using the appropriate control predecessor, was decreased. However, this correlation extends to the partially activated precursor to the present is the invention. The catalysts also exhibit higher activity per g·the catalyst than in the comparative example 7. Moreover, the increase in the content as MgCl2and TiCl3(at constant Mg/Ti) can be prepared catalyst with high activity on the particle and provides a good volume weight of resin.

The polymerization of ethylene in the reactor with a fluidized bed

In separate experiments in the reactor with a fluidized bed of partially activated precursor table II used in the processes of gas-phase polymerization in the fluidized bed. Used 8-inch gas-phase reactor with a fluidized bed and a reaction volume of 50 l, which was suitable for the polymerization of olefins with a speed from 5 to 7 lb/h under a pressure of 300 psig. Used 5 pounds starting resin layer, the nature of nominally identical to the resin, which must be obtained. On a separate supply line has introduced triethylaluminium with achievement in the reactor, the ratio of Al/Ti of 40:1. The reaction temperature was 88°With; to regulate the density and molecular weight of the polymer in the reactor in amounts shown in table III, was also guided by the 1-hexene and hydrogen.

td align="center" namest="c0" nameend="c9"> *comparative example; ND: no data;(a) too active for the process conditions; (b) insufficiently active for the process conditions
Table III
ExampleM/ Ti ROH/MgThe partial pressure2(psi)With6/S2H2/S2The residence time, hPerformance, pounds PE/lb TiIL, DG/minDensity g/cm3
12*30950,150,224at 225,0000,60,918
1330,5950,170,223,47100001,80,917
1450,5950,150,22LP(a)>1500000NDND
1550,5850,150,32,910000002,50,917
1650,5850,160,683,1320000200,918
17*30850,160,68ND(b)<100000NDND

The data of table III show that these catalysts are quite capable of obtaining polymers, for which the previously known catalyst was found to be insufficient to maintain adequate performance or caused the formation of the resin particles is too small due to the low catalytic activity. For example, the comparative catalysts of examples 12 and 17 are the performance values at 225,000 and <100000 pounds of polyethylene/lb Ti. On the other hand, each of the catalysts of examples 13 to 16 has a catalytic performance 320000 pounds of polyethylene/lb Ti or higher. Indeed, while the comparative catalysts are not active catalyst of example 14 is too active for the generated partial pressure of ethylene. These data also show that such catalysts are capable of obespechit for the production of polymer grade films at a lower partial pressure of ethylene than in the case of previously known catalyst.

Although the invention is described using a limited number of options, these particular options are not intended to limit the volume and the gain, which is determined by the description and the accompanying description of the invention. There are modifications and variations of the described variants. So, for example, to further improve one or more properties of the compositions of the catalysts and precursors of catalysts and obtained with the use of polymers can also be used in a variety of other additives that are not listed in the present description. Obviously, you can vary the parameters of the polymerization processes, such as temperature, pressure, monomer concentration, the concentration of polymer, the partial pressure of hydrogen, etc. Therefore, the catalysts that do not meet the criteria of selecting one of a number of reaction conditions, can be however used in versions of the invention with a different number of reaction conditions. Although all the variants described with reference to only the catalyst, it is by no means the case does not constitute obstacles for the simultaneous application of two, three, four, five or more catalysts in the same reactor with the same or another option in regard to molecular weight and/or the introduction of co monomer. In some embodiments, supported on a carrier catalysts can also include additives or other modifiers. In other embodiments, printed on novtel the catalysts do not include or practically free of any not listed in this description connections. Moreover, in this regard, possible variations and modifications. It must be borne in mind that the method presented in the present description, you can apply for polymers, which also include links to one or more additional comonomers. Introduction links additional comonomers may result in improved properties that are not available to homopolymers or copolymers. Although the methods are described as including one or more stages, it is necessary to recognize that in all cases, unless otherwise noted, these stages may be performed in any order or sequence. These stages can be merged or split. Finally, any specified in the present description should be considered as being approximate, regardless of whether you used when writing this number, the word "about" or "approximately". And last, but not least, the possibility of making the claimed supported on a carrier of catalysts is not limited to the methods provided in the present description. They can be prepared by any suitable method. The accompanying claims are intended to cover all such variations and modifications as not departing from the scope of the invention.

1. Supported on a carrier of a catalytic composition comprising the product of the entries batch is I:

a) composition of the catalyst precursor, comprising the interaction product

I) halide of magnesium;

II) simple ether;

III) electron-donating compounds, representing a linear or branched aliphatic alcohol containing between 1 and 25 carbon atoms; and

IV) compounds of the transition metal, in which the transition metal is an element of the 4th group;

b) a porous inert carrier;

in) Socialisticheskaya compositions;

where supported on a carrier of the catalytic composition comprises less than 1 wt.% electron-donor compounds, other than those that involve linear or branched aliphatic or aromatic alcohol containing between 1 and 25 carbon atoms, and where the value of the molar ratio between the electron-donating compound and the magnesium is less than or equal to 1.9.

2. Cooking method applied to the carrier of the catalytic composition, including:

a) preparation of magnesium-containing solution, comprising the interaction product

I) halide of magnesium;

II) simple ether; and

III) electron-donating compounds, representing a linear or branched aliphatic alcohol containing between 1 and 25 carbon atoms;

b) kontaktira is the use of magnesium-containing solution with a transition metal compound, which the transition metal is an element of the 4th group, to obtain the composition of the precursor of the catalyst, where the catalyst composition comprises less than 1 wt.% electron-donor compounds, other than those that involve linear or branched aliphatic or aromatic alcohol containing between 1 and 25 carbon atoms, and where the value of the molar ratio between the electron-donating compound and the magnesium in the catalyst composition is less than or equal to 1.9;

C) contacting the composition is dissolved catalyst precursor with a porous inert carrier to obtain the final mixture;

g) drying the resulting mixture to obtain supported on a carrier composition of the catalyst precursor and

d) activation is supported on a carrier composition of the catalyst precursor Socialisticheskaya composition.

3. A method of obtaining a polymer comprising the reaction of at least one olefinic monomer in the presence of supported on a carrier of a catalytic composition comprising the product of the interaction:

(a) a magnesium-containing solution, comprising the interaction product:

I) halide of magnesium,

II) simple ether;

III) electron-donating compounds, representing a linear or razwell the config aliphatic alcohol, containing between 1 and 25 carbon atoms; and

IV) compounds of the transition metal, in which the transition metal is an element of the 4th group;

b) a porous inert carrier and

in) Socialisticheskaya song,

where magnesium-containing solution, the transition metal compound and an inert carrier to form the composition of the catalyst precursor and supported on a carrier of the catalytic composition comprises less than 1 wt.% electron-donor compounds, other than those that involve linear or branched aliphatic or aromatic alcohol containing between 1 and 25 carbon atoms, and where the value of the molar ratio between the electron-donating compound and the magnesium is less than or equal to 1.9.

4. Supported on a carrier composition of the catalyst precursor, comprising the interaction product:

a) composition of the catalyst precursor, comprising the interaction product

I) halide of magnesium;

II) simple ether;

III) electron-donating compounds, representing a linear or branched aliphatic alcohol containing between 1 and 25 carbon atoms; and

IV) compounds of the transition metal, in which the transition metal is an element of the 4th group; and

b) a porous inert is osites;

where supported on a carrier of the catalytic composition comprises less than 1 wt.% electron-donor compounds, other than those that involve linear or branched aliphatic or aromatic alcohol containing between 1 and 25 carbon atoms, and where the value of the molar ratio between the electron-donating compound and the magnesium is less than or equal to 1.9.

5. The composition according to claim 4, in which the transition metal compound corresponds to the formula:

Ti(R)aXb,

in which R is R' or COR'where R' represents an aliphatic or aromatic hydrocarbon radical with C1With14the value X is chosen from Cl, Br, I and mixtures thereof, and a represents 0 or 1, b is from 2 to 4 inclusive, and the sum a+b is 3 or 4.

6. The composition according to claim 4, in which the electron-donating compound selected from the group comprising methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, 1-dodecanol.

7. The composition according to claim 4, in which the ethers are selected from the group comprising diethyl ether, diisopropyl ether and di-n-butyl ether, ethylisopropylamine ether, methylbutylamine ether, metalalloy ether, ethylenically ether, tetrahydrofuran, 2-methyltetrahydrofuran and their combinations.

8. The composition according to claim 4, in which is supported on a carrier of the catalytic composition includes compositions is s formula

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

where ROH is a linear or branched alcohol containing between 1 and 25 carbon atoms, R is R' or COR', where each R' individually represents an aliphatic hydrocarbon radical containing in the range of one to 14 carbon atoms, X individually represents Cl, Br or I, S is a compound selected from the group comprising aliphatic ethers, cyclic ethers, the m values are in the range from 0.5 to 56, n denotes 0, 1 or 2, the values of R lie in the interval from 4 to 116 the values of q are in the range from 2 to 85, and the values of g are in the range from 0.1 to 1.9.

9. The composition according to claim 4, additionally comprising the product of the interaction of the Lewis acid with the composition.

10. The composition according to claim 4 in which the inert carrier has a specific surface area greater than or equal to 3 m2/year

11. The composition according to claim 4, where this composition has an average particle size of from 1 to 250 microns.

12. Supported on a carrier of a catalytic composition prepared from:

a) composition of the catalyst precursor prepared from:

I) halide of magnesium;

II) simple ether;

III) electron-donating compounds, representing a linear or rasvet the military aliphatic alcohol, containing between 1 and 25 carbon atoms; and

IV) compounds of the transition metal, in which the transition metal is an element of the 4th group; and

b) a porous inert carrier and

in) Socialisticheskaya compositions;

where supported on a carrier of the catalytic composition comprises less than 1 wt.% electron-donor compounds, other than those that involve linear or branched aliphatic or aromatic alcohol containing between 1 and 25 carbon atoms, and where the value of the molar ratio between the electron-donating compound and the magnesium is less than or equal to 1.9.

13. Method of cooking is supported on a carrier of a catalytic composition consisting in

a) preparation of magnesium-containing solution consisting of

I) halide of magnesium;

II) simple ether; and

III) electron-donating compounds, representing a linear or branched aliphatic alcohol containing between 1 and 25 carbon atoms;

b) contacting the magnesium-containing solution with a transition metal compound, in which the transition metal is an element of the 4th group, to obtain the composition of the precursor of the catalyst, where the catalyst composition comprises less than 1 wt.% electron-donor compounds, other than the those which include linear or branched aliphatic or aromatic alcohol containing between 1 and 25 carbon atoms, and where the value of the ratio between the electron-donating compound and the magnesium in the catalyst composition is less than or equal to 1.9;

C) contacting the composition is dissolved catalyst precursor with a porous inert carrier to obtain the final mixture;

g) drying the resulting mixture to obtain supported on a carrier composition of the catalyst precursor and

d) activation supported on a carrier composition of the catalyst precursor Socialisticheskaya composition.

14. A method of obtaining a polymer comprising the reaction of at least one olefinic monomer in the presence of supported on a carrier of the catalytic composition, and this catalytic composition prepared from the product of the interaction:

(a) a magnesium-containing solution, comprising the interaction product:

I) halide of magnesium;

II) simple ether;

III) electron-donating compounds, representing a linear or branched aliphatic alcohol containing between 1 and 25 carbon atoms; and

IV) compounds of the transition metal, in which the transition metal is an element of the 4th group;

b) a porous inert carrier and

in) Socialisticheskaya song,

where magnesium-containing solution, the transition metal compound and an inert carrier to form the composition of the catalyst precursor and supported on a carrier of the catalytic composition comprises less than 1 wt.% electron-donor compounds, other than those that involve linear or branched aliphatic or aromatic alcohol containing between 1 and 25 carbon atoms, and where the value of the molar ratio between the electron-donating compound and the magnesium is less than or equal to 1.9.

15. Supported on a carrier composition of the catalyst precursor prepared from the product of the interaction:

a) composition of the catalyst precursor prepared from

I) halide of magnesium;

II) simple ether;

III) electron-donating compounds, representing a linear or branched aliphatic alcohol containing between 1 and 25 carbon atoms; and

IV) compounds of the transition metal, in which the transition metal is an element of the 4th group; and

b) a porous inert carrier;

where supported on a carrier of the catalytic composition comprises less than 1 wt.% electron-donor compounds, other than those that involve linear is whether branched aliphatic or aromatic alcohol, containing between 1 and 25 carbon atoms, and where the value of the molar ratio between the electron-donating compound and the magnesium is less than or equal to 1.9.



 

Same patents:

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

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

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

9 cl, 11 tbl, 90 ex

FIELD: chemical technology, catalysts.

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

EFFECT: improved and valuable properties of catalysts.

17 cl, 10 ex

FIELD: chemical technology, catalysts.

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

EFFECT: improved preparing method, valuable properties of catalyst.

24 cl, 3 tbl, 17 ex

FIELD: chemical technology, catalysts.

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

EFFECT: improved and valuable properties of catalyst.

18 cl, 8 ex

FIELD: polymerization catalysts.

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

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

3 cl, 1 tbl, 4 ex

FIELD: polymerization catalysts.

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

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

3 cl, 1 tbl, 13 ex

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

The invention relates to the components of the catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and at least one 1,3-W, which forms complexes with anhydrous magnesium dichloride in an amount of less than 60 mmol per 100 g of MgCl2and without substitution reactions with TiCl4or reacting in the amount less than 50 mol%, and at least one ester of mono - or polycarboxylic acid, and 1,3-diesters selected from compounds of the formula (II)

where the group RIIIidentical or different, represent hydrogen or C1-C18hydrocarbon group; groups of RIVidentical or different, have the same meaning as RIIIexcept that they cannot be hydrogen; each of the groups RIII- RIVmay contain heteroatoms selected from Halogens, N, O, S and Si, and the radicals RVidentical or different, are selected from the group consisting of hydrogen; Halogens, preferably C1 or F; C1-C20alkyl radicals with a straight or branched chain; C3-C20cycloalkyl,6e radicals Rvcan be connected to each other to form a condensed cyclic structures, saturated or unsaturated, optionally substituted, RVIradicals selected from the group consisting of halogen, preferably C1 or F; C1-C20alkyl radicals, linear or branched; C3-C20cycloalkyl, C6-C20aryl, C7-C20alkalinic and C7-C20Uralkalij radicals; the radicals RVand RVIoptionally contain one or more heteroatoms as substitutes for carbon or hydrogen atoms, or both

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a catalytic system comprising metallocene compound of the formula: wherein CpI and CpII represent carboanions with the cyclopentanedienyl-containing structure wherein from to all hydrogen atoms can be substituted; D means a donor atom possessing at least one electron pair; A means an acceptor atom that in its state it has electronic hole and D and A are bound by the reversible coordination bond and wherein a donor group receives a positive (partial) charge and an acceptor group - a negative (partial) charge; M means a transient metal of III, IV, V or VI subgroup of Mendeleyev's periodic law; x means anionic equivalent or η-complex compound of transient metals of the formula: (IIIa) or, respectively, (IIIb) wherein η means the charged or electrically neutral system that can be condensed with unsaturated or saturated rings; D means a donor atom or A with a transient metal M chosen from this group is carried out either directly or through a spacer and D and A are bound by a coordination bond as given above; X means anionic equivalent; n value depends on charge of M metals, and η means a number 0, 1, 2, 3, 4. Donor-acceptor structure promotes to stability of catalyst being up to high temperatures, i. e. without significant decrease of the catalyst activity and provides preparing polyethylenes with enhanced molecular mass and increased boiling point value. Also, invention relates to a method for preparing alpha-olefins.

EFFECT: valuable properties of catalyst, improved polymerization method.

7 cl, 10 ex

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

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

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

71 cl, 99 ex, 13 tbl

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

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

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

The invention relates to a continuous method of gas-phase fluidized to obtain homopolymerization and copolymerizate ethylene with density d from 0.89 to 0.97 g/cm3

The invention relates to catalysts for (co)polymerization of ethylene containing chromium trioxide deposited on a solid inorganic oxide carrier of nature, i.e

The invention relates to a method for ultracytochemical polyethylene and method of activating the catalyst carrier

The invention relates to a new the ethylene copolymer and the method of its production

FIELD: polymers.

SUBSTANCE: claimed method includes polymerization of one or more water soluble monomers in aqueous salt solution in presence of polymer dispersant, wherein polymer dispersant represents copolymer of monomer (M) mixture containing at least one cationic monomer and at least one monomer, such as tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate or monomer of general formula I wherein R1 is hydrogen or methyl; R2 is hydrogen or C1-C2-alkyl; R3 is hydrogen, C1-C4-alkyl, phenyl or benzyl; n = 1-4; x = 1-50, and monomer (M) mixture essentially having no water insoluble monomers; and/or polymer dispersant may be obtained by monomer (M) mixture polymerization in reaction mixture essentially having no organic solvents. Also disclosed are aqueous polymer dispersion and application thereof as retention agent in paper production, as thickening agent or agent for soil amelioration. Method for paper production from aqueous suspension includes addition of abovementioned polymer dispersion.

EFFECT: polymer dispersion of high stability, high active substance content, low cationic charge, and good retention characteristics.

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