RU2230074C1 - Method of preparing catalyst and method of preparing agent reducing hydrod ynamic resistance based on polyhexene prepared using this catalyst - Google Patents

Abstract

FIELD: polymer production. SUBSTANCE: preparation of catalyst comprises preparing magnesium-containing carrier followed by interaction of resulting carrier with titanium tetrachloride and alkylaromatic ether, wherein magnesium-containing carrier is obtained in two stages including reaction of magnesium metal with aromatic halide in presence of an ether to form slurry containing organomagnesium compound and solid phase followed by consecutive interaction of the slurry with silicon alkoxy derivative and then with an electronodonor compound, in particular alcohol or cyclic ether. Catalytic polymerization of 1-hexene is conducted at temperature between 0 to 50(r). Thus obtained polymers may find use in various areas, in particular as agents reducing hydrodynamic resistance, for example when pumping oil through pipeline. EFFECT: simplified catalyst preparation procedure, increased its activity, and increased molecular weight of poly-olefin obtained at elevated polymerization temperature. 4 cl, 2 tbl, 12 ex

Description

The invention relates to methods for producing high molecular weight higher polyalphaolefins, in particular polyhexene, and catalysts for implementing this process. High molecular weight higher polyalphaolefins are used in various fields, in particular, as agents for reducing hydrodynamic resistance during the movement of hydrocarbon liquids, for example, when pumping oil through a pipeline.

A known method of producing agents to reduce the hydrodynamic resistance (GDS) of hydrocarbon liquids by polymerization of higher alpha-olefins using an aluminum thermal catalyst TiCl ₃ · 1 / 3AlCl ₃ and organoaluminum cocatalyst diethylaluminium chloride (DEAH) for 31 hours (US Patent No. 3692676, C 08 F 6/12 , 1972). The yield of the target product is 88%, the decrease in the hydrodynamic resistance of oil is 12% at an agent concentration of 5 ppm (parts per million). The disadvantages of the method are the low value of reducing the hydrodynamic resistance, a long polymerization time and low catalyst activity.

There is also a method of producing agents for reducing the GDS of hydrocarbon liquids by polymerization of higher alpha-olefins with a number of hydrocarbon atoms from 6 to 10 in a hydrocarbon solvent in the presence of a catalyst obtained by reduction of titanium tetrachloride with an organoaluminum compound and an organoaluminum cocatalyst (RF Patent No. 2075485, C 08 F 10 / 14, 1997). This catalyst has a higher activity than the aluminothermic catalyst and allows at a temperature of from -30 to 20 ° C (mainly at 0 ° C) within 5 hours to achieve the conversion of hexene-1 58-70%. By this method, high molecular weight polymers are obtained with an intrinsic viscosity [η] = 1.2-1.7 m ³ / kg, which reduces the hepatane GDS by 30-58% at a polymer concentration of 2 ppm. The disadvantages of this method are the low activity of the catalyst, the need to use low temperatures (0 ° C) during polymerization, and the relatively low molecular weight of the obtained polymer.

A known method of producing higher polyalphaolefins using a catalytic system consisting of supported titanium-magnesium catalyst containing titanium tetrachloride on a support - magnesium chloride and a stereo-regulating electron-donating additive (for example, dibutyl phthalate) and cocatalyst, which is a mixture of aluminum trialkyl containing silicon oxide. Such a catalytic system has a significantly higher activity compared to TiCl ₃ catalysts and is widely used to produce polypropylene and copolymers of propylene with alpha-olefins. A number of methods for preparing supported titanium-magnesium catalysts are described, for example, in the book EPMoore (Jr.), Polypropylene Handbook. Hansen Publishers, 1996.

The closest in technical essence and the achieved result is a method using a catalyst obtained in three stages (RF Patent No. 2152404, C 08 F 4/64, 10.07.2000).

Stage (a). Contacting metallic magnesium with an aromatic halide RX, in which R is an aromatic group containing from 6 to 20 carbon atoms, X is a halogen atom. The result is a suspension that contains a solution of an organomagnesium compound and a solid by-product, consisting mainly of magnesium chloride. A solution of the organomagnesium compound is separated from the solid by-product and used in the next step (b).

Stage (b). The introduction of a silicon compound containing an alkoxy group or an aryloxy group into a solution of an organomagnesium compound at a temperature of from -20 to 20 ° C to form a solid product, which in the next step (c) is contacted with titanium tetrachloride and an alkyl aromatic ether to form a catalyst.

This catalyst has a narrow particle size distribution and provides polypropylene powder with a small amount of fine fraction, which is an important advantage in the production of polypropylene in modern industrial processes in a liquid monomer and in a gas phase. The catalyst provides a significantly higher yield during the polymerization of higher olefins compared to the catalyst based on TiCl ₃ . The disadvantage of this method of preparation of the catalyst is the presence of a significant amount of solid waste in the first stage of preparation of the catalyst. The need to separate these wastes complicates the preparation of the catalyst.

The invention solves the problem of simplifying the method of producing the catalyst and increasing the activity of the catalyst, as well as the task of increasing the molecular weight of polyhexene obtained at elevated polymerization temperatures.

The problem is solved by using a catalyst, which is prepared in three stages as follows.

Stage (a). Contacting metallic magnesium with aromatic halide RX is similar to the method described in the prototype (RF Patent No. 2152404, C 08 F 4/64, 10.07.2000). This gives a suspension (product I) containing a solution of an organomagnesium compound and a solid phase, and then use this suspension without separating the solution from the solid phase to carry out the next step (b).

Stage (b). At this stage, to the suspension obtained in stage (a) and containing a solution of an organomagnesium compound and a solid phase, a silicon compound containing an alkoxy group is added first, and then an additional electron-donating organic compound (alcohol, cyclic or ether) to form a solid magnesium-containing product carrier II .

The interaction of the magnesium-containing product II with titanium tetrachloride and alkyl aromatic ether to obtain the final catalyst [stage (c)] is carried out similarly to the known solution.

In addition to simplifying the catalyst preparation technology and reducing the amount of waste in stage (a), an additional advantage of the catalyst over the prototype is a higher activity, which is achieved through the use of an electron-donor compound in the second stage of the synthesis of solid magnesium-containing product II.

Step (a) during the preparation of the catalyst according to the invention is carried out by contacting the magnesium metal with an aromatic halide, which is used as chlorobenzene, bromobenzene and iodobenzene, preferably chlorobenzene. A combination of two or more aromatic halides may also be used. Magnesium and aromatic halide are brought into contact with each other in the presence of an inert hydrocarbon solvent and ether. Examples of solvents are aliphatic, alicyclic or aromatic solvents containing 4-10 carbon atoms. Examples of esters are diethyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, diallyl ether, tetrahydrofuran (THF) and anisole.

The reaction temperature in step (a) is usually from 20 to 150 ° C, preferably from 90 to 110 ° C; the interaction time is from 2 to 20 hours, mainly 4-8 hours

After completion of stage (a), a suspension (product II) is obtained consisting of a precipitate, which is mainly magnesium dichloride, and a solution of an organomagnesium compound of the composition Mg ₃ Ph _n Cl _m (n = 3.5-4.5; m = 1.5 -2.5). This product is used for the subsequent step (b).

In step (b), the suspension obtained in step (a) is brought into contact with an alkoxy-containing silicon compound and an electron-donating compound. This is done by adding to the suspension of product I first a silicon compound containing an alkoxy group or an aryloxy group at a temperature of from -20 to 20 ° C, and then subsequent addition of an electron-donating compound at a temperature of from 0 to 20 ° C, holding the reaction medium at a temperature of from 20 to 70 ° C and purification of the obtained solid product (II) by washing with a hydrocarbon solvent.

As a silicon compound containing an alkoxy group or an aryloxy group, a compound of the general formula R is used $\genfrac{}{}{0ex}{}{\text{1}}{\text{n}}$ Si (OR ² ) _4-n , where R ¹ and R ² are a hydrocarbon group containing from 1 to 6 hydrocarbon atoms, n = 0-2. Tetraethoxysilane is preferably used.

ROH alcohols are used as the electron donor compound in stage (b), where: R is a hydrocarbon group containing from 2 to 8 hydrocarbon atoms, cyclic and ethers. Examples of cyclic ethers are furan, tetrahydrofuran and their derivatives. Mostly tetrahydrofuran is used.

The molar ratio between silicon and magnesium in step (b) can vary from 0.2 to 20, preferably from 0.2 to 1. The molar ratio between electron-donating compound and magnesium in step (b) can vary from 0.5 to 5, preferably from 1 to 3.

The product II formed in step (b) is then used to prepare the catalyst in step (c). The preparation of the catalyst is carried out by contacting in stage (c) of product II obtained in stage (b) with titanium tetrachloride and alkyl aromatic ether.

High molecular weight polyhexene having the properties of an agent for reducing hydrodynamic resistance is obtained by polymerization of hexene-1 in the presence of a catalyst prepared according to the procedure described above and cocatalyst. Aluminum trialkyls, for example triethyl aluminum or triisobutyl aluminum, are used as cocatalyst. The polymerization process is carried out at a temperature of from 0 to 50 ° C, preferably at 10-30 ° C.

In the polymerization of olefins, an electron-donating compound is usually added to the reaction medium, which increases the stereo-regulating ability of the catalyst. As such a compound, an alkoxy (alkyl) -containing silicon compound of composition R may be used. $\genfrac{}{}{0ex}{}{\text{1}}{\text{n}}$ Si (OR ² ) _4-n , where R ¹ and R ² are a hydrocarbon group containing from 1 to 6 hydrocarbon atoms, n = 1-2.

Prepared by the proposed method, the catalyst is suitable for the polymerization of olefins, such as ethylene, propylene, butylene, hexene, octene, decene, dodecene. This catalyst is particularly suitable for the polymerization of hexene-1.

The polymerization is carried out mainly in the liquid phase in the presence of a hydrocarbon solvent such as hexane, heptane, octane, cyclohexane. benzene, toluene or xylene. The polymerization temperature is from 0 to 50 ° C. An important technological advantage of the catalyst is the possibility of carrying out the polymerization process at an elevated temperature (20-30 ° C) while maintaining a high molecular weight of the polymer.

Using the proposed method, it is possible to obtain high molecular weight polyhexene in a high temperature range from 10 to 30 ° C. In this case, the resulting polymers have an intrinsic viscosity [η] of 1.7-0.7 m ³ / kg and possess the properties of an agent for reducing hydrodynamic resistance ( GDS) during the movement of hydrocarbons. In particular, it provides a 50–20% reduction in GDS at a polymer concentration of 2 ppm.

Hydrodynamic testing of agents is carried out on a capillary turbo-meter in a solution of n-heptane. The length of the capillary and its inner diameter are 0.8 m and 1.1 · 10 ^-3 m, respectively. The concentration of the GDS agent in each test is 2 ppm. The decrease in GDS is determined by the formula:

where τ ₀ is the expiration time of the pure solvent, s;

τ is the expiration time of the polymer solution, s.

The present invention will be further explained using examples that do not limit the invention.

Example 1

Catalyst Preparation

Stage (a). In a three-necked flask equipped with a reflux condenser and a dropping funnel, 26 g of magnesium powder (1.07 mol) are charged. The flask is purged with nitrogen. The magnesium is heated for 1 h at 80 ° C and then a mixture of 173 ml of dibutyl ether and 80 ml of chlorobenzene is added. Then, 0.03 g of iodine and 3 ml of n-butane chloride are successively added to the reaction mixture. After the disappearance of iodine staining, the temperature of the mixture was raised to 97 ° C and 250 ml of chlorobenzene were slowly added over 2.5 hours. The resulting reaction mixture was stirred vigorously for 8 hours at 97 ° C. The result was a suspension (product I) containing an organomagnesium solution compounds (MOS) of the composition Mg ₃ Ph ₄ Cl ₂ and a solid phase containing MgCl ₂ in the ratio Mg ₃ Ph ₄ Cl ₂ / MgCl ₂ = 2: l.

Stage (b). The suspension obtained in stage (a), (100 ml, 0.25 mol of Mg), is loaded into the reactor. The reactor is cooled to 0 ° C. and a mixture of 22 ml of tetraethoxysilane (TES) and 38 ml of heptane is added over 2 hours with stirring.

After that, the reaction mixture was kept at 0 ° C for another 0.5 h and, with vigorous stirring, a mixture of 14.6 ml of ethanol (0.25 mol) and 45.4 ml of heptane was metered in for 1 h. Then, the temperature of the reaction mixture was increased to 70 ° C and kept at this temperature for 2 hours. After this, stirring and heating were stopped and the solid product was allowed to precipitate. The liquid above the precipitate is removed by decantation. The solid is washed with heptane (4 times 250 ml). 25.2 g of solid magnesium-containing product (II) are obtained, suspended in 100 ml of heptane.

Stage (s). The reactor is purged with nitrogen and a mixture of 150 ml of titanium tetrachloride and 150 ml of chlorobenzene and 12 g of product (III) in 48 ml of heptane is successively loaded into it. The reaction mixture is heated with stirring to 115 ° C, 7.2 ml of dibutyl phthalate is introduced into it and kept at 115 ° C for 1 hour. After this, the stirring is stopped and the solid product is allowed to precipitate.

The supernatant is removed by decantation, after which a mixture of 150 ml of titanium tetrachloride and 150 ml of chlorobenzene is added. The reaction mixture is again heated to 115 ° C and stirred for 30 minutes, after which the solid product is allowed to settle for 30 minutes. This last cycle is repeated again. The resulting solid was washed 5 times using 300 ml of heptane at 60 ° C. A catalyst suspended in heptane was obtained. The titanium content in the catalyst is 1.9 wt.%.

Polymerization

At a temperature of 20 ° C, 150 ml of heptane 5 ml of a solution of triisobutylaluminum (TIBA) in heptane with a concentration of 0.29 mmol / ml (1.45 mmol of TIBA), 1.2 mmol of propyltrimethoxysilane (PTMS) and 62 ml (0.5 mol) of hexene-1, which corresponds to a concentration of hexene-1 in the reactor of 2.5 mol / l and 0.0144 g of catalyst. The polymerization is carried out at a temperature of 20 ° C for 1 h. The polymer is unloaded, 20 ml of isopropanol and 20 ml of a solution of ANOX stabilizer in acetone with a concentration of 1 g / l are added. The polymer is dried to constant weight. The output of polyhexene is 1.0 kg / g cat .; the conversion of hexene-1 is 46%. The characteristic viscosity of the polymer [η], determined in gasoline at 20 ° C, is 1.3 m ³ / kg, the effect of reducing the hydrodynamic resistance (DR) is 39%.

Example 2

The catalyst was prepared as described in Example 1, except that in step (b) 21.9 ml of ethanol (0.375 mol, molar ratio of ethanol: Mg = 1.5) and 38.1 ml of heptane were used.

The polymerization of hexene-1 is carried out analogously to example 1, but using 0.0121 g of catalyst. The yield of polyhexene is 1.1 kg / g cat .; conversion of hexene-1 - 46%. The intrinsic viscosity of polyhexene is 1.6 m ³ / kg and the value DR = 50%.

Example 3

The catalyst was prepared as described in Example 1, except that in step (b) 43.8 ml of ethanol (0.75 mol, molar ratio of ethanol: Mg = 3) and 16.2 ml of heptane were used.

The polymerization of hexene-1 is carried out analogously to example 1. The output of polyhexene is 0.8 kg / g cat. Received polyhexene with a characteristic viscosity of 1.41 m ³ / kg, and the value of DR = 46%.

Example A (comparative)

Catalyst Preparation

Stage (a). In a three-necked flask equipped with a reflux condenser and a dropping funnel, 26 g of magnesium powder (1.07 mol) are charged. The flask is purged with nitrogen. The magnesium is heated for 1 h at 80 ° C and then a mixture of 173 ml of dibutyl ether and 80 ml of chlorobenzene is added. Then, 0.03 g of iodine and 3 ml of n-butane chloride are successively added to the reaction mixture. After the disappearance of iodine staining, the temperature of the mixture was increased to 97 ° C and 250 ml of chlorobenzene were slowly added over 2.5 hours. The resulting reaction mixture was stirred vigorously for another 8 hours at 97 ° C. Then, stirring and heating were stopped and the solid material was allowed to precipitate. within 48 hours. After decanting the solution over the precipitate, a solution (MOS) is isolated having a concentration of 1 g-at Mg / L. This solution is used in the future for stage (b).

Stage (b). A solution of reaction product 1 (100 ml, 1 mol / L) was metered into the reactor. The reactor is cooled to 0 ° C. and a mixture of 11.2 ml of tetraethoxysilane (TES) and 38 ml of dibutyl ether is added over 2 hours with stirring.

After that, the reaction mixture was kept at 0 ° C for another 0.5 h and then the temperature was raised to 60 ° C. Then the reaction mixture was kept at 60 ° C for 1 h, then stirring and heating were stopped and the solid product was allowed to settle for 30 min The liquid above the precipitate is removed by decantation. The solid is washed 4 times using 150 ml of heptane. 13.5 g of a light yellow solid are obtained, suspended in 40 ml of heptane.

Stage (C) of the preparation of the catalyst is carried out analogously to example 1. The polymerization of hexene-1 is carried out analogously to example 1, but using 0.015 g of the catalyst. 7.5 g of polyhexene are obtained. The yield is 0.50 kg / g cat., The characteristic viscosity of the polymer is 1.25 kg / m ³ , the value of DR = 37%.

Example B (comparative)

Stage (a) is carried out analogously to example 1. Stage (b) is carried out as described in example 1, except that ethanol is not used at this stage and after adding tetraethoxysilane and holding at 0 ° C for 0.5 h, the temperature is raised to 70 ° C and further preparation is carried out analogously to example 1.

Stage (C) and the polymerization of hexene-1 is carried out analogously to example 1. The output of polyhexene is 0.55 kg / g cat; the characteristic viscosity of polyhexene is 1.2 m ³ / kg, the value of DR = 29%.

Example 4

Step (a) is carried out as described in Example 1, except that 24.3 g of magnesium (1 mol), 169.5 ml of dibutyl ether (1 mol) and 370 ml of chlorobenzene are used. The result is a suspension containing a solution of the MOC composition Mg ₃ Ph ₄ Cl ₂ and a solid phase containing MgCl ₂ .

Stage (b). The suspension obtained in stage (a) (100 ml, 0.2 mol of Mg) is loaded into the reactor and 40 ml of heptane are added with stirring. The reactor is cooled to −15 ° C. and a mixture of 17.9 ml of tetraethoxysilane (TPP, 0.08 mol) and 42.4 ml of heptane are added with stirring over 1 hour. After that, the reaction mixture was kept at -15 ° C for another 0.5 h and then the temperature was raised to 60 ° C for 1 h. Then, the reaction mixture was kept at 60 ° C for 1 h, cooled to a temperature of 20 ° C. at a temperature with vigorous stirring, a mixture of 3.7 ml of ethyl benzoate (0.026 mol) and 26.3 ml of heptane is dosed for 1 h. It was then incubated for 0.5 h and a mixture of 5.8 ml of ethanol (0.1 mol) and 54.2 ml of heptane was dosed for 2 hours. Then, the temperature was raised for 1 h to 70 ° C and kept at 70 ° C for 2 hours. After this, stirring and heating were stopped and the solid product was allowed to precipitate. The liquid above the precipitate is removed by decantation. The solid is washed 4 times using 250 ml of heptane. A magnesium-containing product (II) is obtained, suspended in 100 ml of heptane.

Stage (C) and the polymerization of 1-hexene is carried out analogously to example 1. The output of polyhexene is 0.65 kg / g cat. The characteristic viscosity of polyhexene 1.3 m ³ / kg, the value of DR = 34%

Example 5

Stage (a) is carried out as described in example 4.

Stage (b) is carried out as described in example 4, except that after cooling the reaction mixture to 20 ° C, a mixture of 7.8 ml of 2-ethylhexanol (2-EG, 0, 05 mol), 8.8 ml of ethanol (0.15 mol) and 73.4 ml of heptane. Then, the temperature was raised for 1 h to 70 ° C and kept at 70 ° C for 2 hours. After this, stirring and heating were stopped and the solid product was allowed to precipitate. The liquid above the precipitate is removed by decantation. The solid is washed 4 times using 250 ml of heptane. A magnesium-containing product II is obtained, suspended in 100 ml of heptane.

Stage (C) and the polymerization of 1-hexene is carried out analogously to example 1. The output of polyhexene is 0.72 kg / g cat. The intrinsic viscosity of polyhexene is 1.4 m ³ / kg, and DR = 49%.

Example 6

Step (a) and step (b) are carried out as described in Example 5, except that in step (b) a mixture of 15.6 ml of 2-ethylhexanol (0.1 mol), 17.5 ml of ethanol (0 , 3 mol) and 56.9 ml of heptane.

Stage (C) and the polymerization of hexene-1 is carried out analogously to example 1. The output of polyhexene is 1.0 kg / g cat. The characteristic viscosity of polyhexene is 1.24 m ³ / kg, the value of DR = 34%.

Example 7

Stage (a) is carried out as described in example 4.

Stage (b) is carried out as described in example 4, except that after cooling the reaction mixture to 20 ° C, a mixture of 5.8 ml of ethanol (0.1 mol) and 24, is dosed with vigorous stirring for 1 h. 2 ml of heptane, incubated for 1 hour, and then a mixture of 8.1 ml of tetrahydrofuran (0.1 mol) and 21.9 ml of heptane was additionally dosed for 1 hour. Then the temperature was raised for 1 h to 60 ° C and kept under stirring for 2 hours. After this, stirring and heating were stopped and the solid product was allowed to precipitate. The liquid above the precipitate is removed by decantation. The solid is washed 4 times using 250 ml of heptane. A magnesium-containing product (II) is obtained, suspended in 100 ml of heptane.

Stage (C) is carried out as described in example 1. The polymerization of 1-hexene is carried out analogously to example 1. The output of polyhexene is 0.74 kg / g cat. The characteristic viscosity of polyhexene is 1.30 m ³ / kg, the value of DR = 39%.

Example 8

The preparation of the catalyst is carried out as described in example 2.

The polymerization of hexene-1 is carried out as described in example 1, except that instead of propyltrimethoxysilane, propylcyclopentyl dimethoxysilane is used as part of the cocatalyst. The yield of polyhexene is 0.9 kg / g cat. The characteristic viscosity of polyhexene is 1.62 m ³ / kg, the value of DR = 48%.

Example 9

The preparation of the catalyst is carried out as described in example 2. The polymerization of hexene-1 is carried out under the conditions of example 2, except that the polymerization time is 2 hours. The polyhexene yield is 1.4 kg / g cat, hexene conversion is 1-53%. The intrinsic viscosity of polyhexene [η] = 1.41 m ³ / kg; the value of DR = 46%.

Example 10

The catalyst prepared in Example 1 was used. The hexene-1 was polymerized under the conditions of Example 9, but triethylaluminum (TEA) was used as a cocatalyst. The yield of polyhexene under these conditions is 1.1 kg / g cat .: the conversion of hexene-1 reaches 30%. The characteristic viscosity of the polymer is 0.95 m ³ / kg, the value of DR = 27%.

Example 11

Use the catalyst prepared in example 1. The polymerization of hexene-1 is carried out under the conditions of example 10, but at a polymerization temperature of 30 ° C and a weight of the catalyst of 0.0086 g. The polymer yield is 3.1 kg / g cat., Conversion - 67%. The obtained polyhexene has a characteristic viscosity of 0.60 m ³ / kg, the value of DR = 7.

Example 12

Use the catalyst prepared according to example 1. The polymerization of hexene-1 is carried out under the conditions of example 10, but at a polymerization temperature of 11 ° C. The polymer yield is 0.9 kg / g cat. The obtained polyhexene has a characteristic viscosity of 0.97 m ³ / kg, the value of DR = 26%.

As can be seen from the examples and tables 1, 2, the present invention allows to simplify the method of preparation of the catalyst, while the resulting catalyst has a higher activity compared to known catalysts. The use of a catalyst according to the proposed method in the polymerization of hexene-1 leads to an increase in the molecular weight of the obtained polyhexene and an increase in the polymerization temperature. In this case, the obtained polyhexene provides a reduction in hydrodynamic resistance by 50-20% at a polymer concentration of 2 ppm compared with known agents.

Claims (5)

1. A method of preparing a catalyst to obtain a high molecular weight polyhexene having the properties of an agent for reducing hydrodynamic resistance, comprising the step of producing a magnesium-containing support, subsequent interaction of the support with titanium tetrachloride and an alkyl aromatic ether, characterized in that the magnesium-containing support is obtained in two stages, where the reaction is carried out in the first stage magnesium metal with aromatic halide in the presence of ether to form a suspension, with containing a solution of an organomagnesium compound and a solid phase, and in the second stage, the resulting suspension is sequentially reacted with an alkoxy silicon compound and then with an electron-donating compound, which use alcohols, ethers and cyclic ethers. 2. The method according to claim 1, characterized in that the ROH alcohol is used as the electron donor compound in the second stage, where R is a hydrocarbon group containing 2-8 hydrocarbon atoms, cyclic and ethers. 3. The method according to any one of claims 1 and 2, characterized in that the molar ratio between the electron-donating compound and magnesium is 1-3. 4. A method of producing high molecular weight polyhexene having the properties of a hydrodynamic drag reducing agent by polymerizing hexene-1 in the presence of a catalytic system comprising a solid component containing titanium tetrachloride, a magnesium-containing support and an electron-donating compound and a cocatalyst consisting of aluminum trialkyl and an electron-donating compound, characterized in that they use the catalyst obtained according to any one of claims 1 to 3. 5. The method according to claim 4, characterized in that the polymerization process is carried out at a temperature of 0-50 ° C.

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