RU2505549C2 - Vanadium catalyst system for copolymerisation of ethylene with alpha-olefins (versions) and method of producing ethylene and alpha-olefin copolymer (versions) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: described are vanadium catalyst systems which consist of a vanadium complex, a cocatalyst and a reactivator, where the vanadium compound used is the following vanadium complexes:

.

Also described is a method of producing an ethylene and α-olefin copolymer with a hydrocarbon chain containing 2-12 carbon atoms, using the disclosed vanadium catalyst systems in the medium of a hydrocarbon solvent in a temperature interval from 0 to 80°C and monomer pressure in the range from 0.1 to 1.1 MPa in the presence of a chain-terminating agent.

EFFECT: high activity of the catalyst system, which is maintained for the entire duration of the copolymerisation process, reduced consumption of components of the catalyst system, reduced content of vanadium in the end product and the obtained polymer has statistical distribution of comonomers and a narrow molecular weight distribution.

15 cl, 1 tbl, 27 ex

Description

The invention relates to a catalytic system for the copolymerization of ethylene with α-olefins and a method for producing copolymers of ethylene with α-olefins having a high molecular weight, a narrow molecular weight distribution and a controlled content of α-olefin.

Recently, interest in copolymers of ethylene with higher α-olefins has increased markedly. Dow has developed and implemented an ethylene-octene copolymer technology called Insite®. In this technology, a monocyclopentadienyl derivative of titanium is used as a copolymerization catalyst, and methylaluminoxane (MAO) is used as a cocatalyst. This technology also produces copolymers of ethylene with octene under the brand name Affinity® (octene content up to 20 mass%) and Engage® (octene content above 20 mass%). It is known that the Exxon company produces about 30 grades of ethylenebutene and ethylene hexene copolymers under the name Exact® [S. S. Ivanchev, Catalysis in Industry, 2002, No. 6, pp. 15-26].

In the middle of the 20th century, considerable attention to the process of copolymerization of ethylene and propylene was due to the fact that in their properties, in comparison with all other known elastomers, ethylene and propylene copolymers are close in some properties to natural rubber, and in some they surpass it. In terms of elasticity, the width of the operating temperature range, resistance to oxidizing agents, solvents, thermal aging, and abrasion, ethylene propylene rubbers significantly exceed all known synthetic rubbers [N.M. Seidov New synthetic rubbers based on ethylene and α-olefins, Elm, Baku, 1981].

To obtain copolymers with the best properties, it is necessary to ensure a uniform distribution of monomer units in the macromolecules, a narrow molecular weight distribution and the absence of homopolymers of ethylene and α-olefins [Chirkov NM, Matkovsky P.E. Copolymerization on complex catalysts. Science, 1974].

The first catalytic systems for the copolymerization process were obtained by Natta et al. in the middle of the 20th century. They are the product of the interaction of organoaluminum compounds and vanadium oxytrichloride [Natta G., J. Polymer Sci., 34, 21-48 (1959)]. A significant drawback of these systems is the high final metal content in the resulting polymer, which increases its cost due to additional purification of the copolymerization product before further use.

There is a Ziegler-Natta type catalyst system for the polymerization of ethylene and the copolymerization of ethylene with α-olefins [RF patent 2047355], which is a product of the interaction of the magnesium chloride adduct and aliphatic alcohols in the presence of vanadium halide in combination with chlorine-containing organoaluminum compounds AlR _x Cl _3-x

The main disadvantages of such a catalytic system are its low activity at temperatures below 50 ° C and a high polydispersity of the resulting polymerization product is more than 3.5. In addition, the disadvantages of Ziegler-Natta catalytic systems include their polycentricity, which determines the formation of copolymers with wide molecular weight characteristics and significant fractional and compositional heterogeneity [Chirkov NM, Matkovsky P.E. Copolymerization on complex catalysts, Science, 1974; RF patent 2250237].

The latest trend in the synthesis of copolymers of ethylene and α-olefins is the use of metallocene or postmetallocene catalyst systems, which are transition metal complexes containing one or more organic ligands. The use of such catalysts allows one to achieve high polymer yields, improve its compositional uniformity, and more flexibly control the composition of the final product. In addition, metallocene and postmetallocene catalyst systems have a drawback — a large amount of activator — MAO — is required, approximately 1000 equivalents, which greatly complicates and increases the cost of the process [Angew. Chem. Int. Ed. 1999, 38, 428-447].

The closest analogue to the present invention is a catalytic system for the production of ethylene-α-olefin copolymers described in [Organometallics 2009, 28, 1817-1825, Synthesis, Structural Characterization, and Olefin Polymerization Behavior of Vanadium (III) Complexes Bearing Tridentate Schiff Base Ligands, Ji-Qian Wu, Li Pan, Yan-Guo Li, San-Rong Liu and Yue-Sheng Li], which is a compound of vanadium with a phenoximine ligand, in combination with chlorine-containing organoaluminum compounds and a chlorine-containing organic acid ester. The activity of the catalytic system in the polymerization of ethylene and the copolymerization of ethylene with hexene is investigated. These catalysts are highly active in the polymerization of ethylene (20,600 kg PE / mol _met * h) at a molar ratio of Al / V = 4000. When using such a catalytic system, a polymer with a polydispersity of 2.00 is obtained, which indicates that the catalyst system is single-centered. The time of testing the catalysts in all experiments is 10 minutes. The calculation of catalytic activity is carried out in units of kg of polymer / mol of _metal · h, that is, the polymer yield during catalyst operation for one hour. However, from literature it is known [Ivanchev S.S. Advances in creating new catalysts for the polymerization of ethylene and α-olefins // Advances in Chemistry 76 (7) 2007 669-690], that for homogeneous catalytic systems, the polymerization kinetics is characterized by a high speed at the initial time, with its subsequent decrease.

Thus, in this work, when calculating the catalytic activity for the first 10 minutes, its further decrease is not taken into account, and the obtained value cannot be used to calculate the polymer yield during catalyst operation for 1 hour.

The main disadvantage of this catalytic system is the use of a large amount of cocatalyst (Al / V = 4000). The use of this ratio increases the activity of the catalytic system, but requires thorough washing of the reaction product to achieve the required consumer properties of the final product, namely resistance to aggressive substances and ash content.

There is a method for producing polyethylene and copolymers of ethylene with α-olefins [RF patent 2381236] in suspension in a hydrocarbon solvent using a Ziegler type catalyst system, which is titanium tetrachloride deposited on a magnesium-containing support, in combination with trialkylaluminium cocatalyst. The process is carried out at a temperature of 60-100 ° C and a pressure of 0.2-4.0 MPa in the presence of hydrogen as a molecular weight regulator.

The disadvantage of the above method is the need to use high temperatures and pressures due to the fact that at lower temperatures Ziegler catalysts are inactive in both polymerization and copolymerization processes.

The closest in technical essence to the present invention is a method for producing copolymers of ethylene with α-olefins and copolymers of propylene with α-olefins [RF patent 2250237], in the presence of a homogeneous two-component catalytic system containing dialkyl bridged bisindenyl metallocene complexes of Group IVB metals and aluminum trialkyl at molar the ratio of Al / M = 50-500 in an environment of an organic solvent or liquid monomer at a temperature of 30 ° C. The copolymerization process is carried out at a molar ratio of ethylene / propylene monomers = 0.7 / 1 and a total pressure of 1.1 MPa. The content of α-olefins in the resulting copolymer does not exceed 17 mol%.

The disadvantage of this method of producing copolymers is the need to use high pressure during the process. In addition, the kinetics of polymerization on zirconium catalysts is characterized by a high rate at the initial moment of time, and a distinctive property of zirconium systems is their short lifetime, usually the first 10 minutes [Doklady AN 404, 57 (2005)]. Moreover, the process is accompanied by a high exothermic effect, which leads to difficulties in removing a large amount of heat from the reaction mixture in order to maintain its constant temperature [Ethylene-propylene copolymerization with 2-Arylindene Zirconocenes, R. Kravchenko, RMWaymouth, Macromolecules 31 (1), 1998, 1-6]. In the present invention, the zirconium methyl complexes are expensive and require special methods for the preparation of the active components of the catalytic system. Thus, at the initial moment of time, the process has an unsteady nature, which makes it difficult to precisely control the distribution of monomer units in the polymer chain and to control the entry of the second α-olefin into the copolymerization product.

The objective of the invention is the creation of new effective catalytic systems for the copolymerization of ethylene with α-olefins, as well as a method for the copolymerization of ethylene with α-olefins.

Achievable technical result is expressed in an increase in the activity of the catalytic system, which is maintained during the whole time of the copolymerization process at a low Al / V ratio <100, and a decrease in the consumption of components of the catalytic system. Also, the technical result is expressed in a decrease in the vanadium content in the final product and in that the resulting polymer has a statistical distribution of comonomers and a narrow molecular weight distribution.

The task and technical result are achieved through the use of a homogeneous vanadium catalyst system consisting of a complex compound of vanadium, cocatalyst and a reactivator, where a vanadium complex of the formula is used as a compound of vanadium:

or a vanadium complex of the formula:

or a vanadium complex of the formula:

The concentration of vanadium in the solution is from 0.001 to 0.01 g / l of solvent.

Any aluminum organic compounds with the general formula are used as the cocatalyst necessary to convert the vanadium complex into the active form in the oxidation state of 3+:

AlR _x Hal _y ,

where R is an alkyl radical of C ₁ -C ₉ ; Hal is a halogen from among Cl, Br or I; x is from 1 to 3, y = 3.

The cocatalyst is used with a ratio of vanadium / cocatalyst from 1: 1 to 1: 100.

In the copolymerization process, the active form of the vanadium compound is restored to the form inactive for the copolymerization process. Therefore, during the process, a reactant is added, which is necessary to convert the vanadium compound from an inactive form (oxidation state of vanadium 2+) to active (oxidation state of vanadium 3+).

As a reactivator, any organochlorine compounds of the general formula can be used:

где R - алкильный радикал C₁-С₉.

where R is an alkyl radical of C ₁ -C ₉ .

The reactant is used with a ratio of vanadium / reactant from 1: 1 to 1:20.

The copolymerization reaction is carried out in the medium of any hydrocarbon solvent (hexane, heptane, toluene, a mixture of isomers of pentanes, hexanes, heptanes, nefras) in the temperature range from 0 to 80 ° C and the pressure of the monomers in the range from 0.1 to 1.1 MPa. The polymerization process can be carried out both with a constant supply of monomers for a predetermined period of time in the range from 0 to 180 minutes, and with their single introduction at a given molar ratio of components. The molecular weight of the copolymers can be controlled by introducing a molecular weight regulator, which can be hydrogen, diethylzinc, diisobutylaluminum hydride, etc.

Also, the task and the technical result are achieved if the copolymerization is carried out in the medium of any hydrocarbon solvent (hexane, heptane, toluene, a mixture of pentanes, hexanes, heptanes, nephras isomers) in the temperature range from 0 to 80 ° С and the monomer pressure in the range from 0, 1 to 1.1 MPa in the presence of a molecular weight regulator and a vanadium catalyst system consisting of a complex compound of vanadium and cocatalyst, where a compound of the general formula is used as a complex compound of vanadium:

where Alk is CH3, C2H5, C3H7, C4H9;

The concentration of vanadium in the solution is from 0.001 to 0.01 g / l of solvent.

The use of this compound allows the copolymerization process to be carried out without additional addition of a reactant, since it simultaneously acts as both a vanadium catalytic complex and a reactant.

Also, the task and technical result can be achieved if the copolymerization is carried out in the environment of any hydrocarbon solvent (hexane, heptane, toluene, a mixture of pentanes, hexanes, heptanes, nephras isomers) in the temperature range from 0 to 80 ° C and the monomer pressure in the range from 0.1 to 1.1 MPa in the presence of a molecular weight regulator and a vanadium catalyst system consisting of a complex compound of vanadium, cocatalyst and a reactivator.

In this case, as a complex compound of vanadium, a compound of the formula is used:

or a compound of the formula:

or a compound of the general formula:

Z ₁ , Z ₂ heteroatom, may be selected from O, S, Se, N, P, As, preferably O, S, N, P;

In a heteroatom, may be selected from O, S, Se, preferably O, S;

X is halogen, may be selected from F, Cl, Br, I, preferably Cl, Br;

или ароматического с С6-С24, предпочтительнее

или гетероароматического соединения с С1-С10 с одним или тремя гетероатомами, выбранными из О, S, N, PA containing the fragment may be selected from the aliphatic series C1-C10, more preferably

or aromatic with C6-C24, more preferably

or a heteroaromatic compound with C1-C10 with one or three heteroatoms selected from O, S, N, P

A ₁ , the carbon-containing fragment may be selected from the aliphatic series C1-C10, preferably CH3, C2H5, C3H7, C4H9, or aromatic with C6-C24, preferably C6-C12, or a heteroaromatic compound with C1-C10 with one or three heteroatoms selected from O, S, N, P;

A ₂ carbon-containing fragment can be selected from the aliphatic series C1-C10, preferably CH3, C2H5, C3H7, C4H9, or aromatic with C6-C24, preferably C6-C12, or a heteroaromatic compound with C1-C10 with one or three heteroatoms selected from O, S, N, P;

k is 0 or 1;

m is 3 or 4;

n = 1 or 2.

As aluminum cocatalyst use any aluminum organic compounds with the General formula:

AlR _x Hal _y ,

where R is an alkyl radical of C ₁ -C ₉ ; Hal is a halogen from among Cl, Br or I; x is from 1 to 3, y = 3.

The cocatalyst is used with a ratio of vanadium / cocatalyst from 1: 1 to 1: 100.

The concentration of vanadium in the solution is from 0.001 to 0.01 g / l of solvent.

As a reactivator use any organochlorine compounds of the General formula:

where R is an alkyl radical C ₁ -C ₉

The reactant is used with a ratio of vanadium / reactant from 1: 1 to 1:20.

And as a molecular weight regulator, hydrogen, diethylzinc, diisobutylaluminum hydride and others are used.

Example 1

The process is carried out using a Buchi Glas Uster Polyclave type reactor with a 1 liter bowl volume. Thermostating is carried out using a Julabo thermostat.

The reactor is washed with hexane with triethyl aluminum distilled on a rotary evaporator (concentration of 25 wt% in toluene, volume 2.5 ml) at a temperature of 65 ° C and stirring at 500 rpm. Flushing time 2 hours. The washing of the reactor is repeated two times, between washing the reactor is filled with argon under a pressure of 0.15 MPa.

The solvent for polymerization, hexane, grade ХЧ, is distilled over triethylaluminium (concentration of 25% mass in toluene, volume 1 ml) in a stream of nitrogen at Т = 69 ° С into a Schlenk vessel. The solvent in a volume of 400 ml is poured into a bottle heated to 250 ° C and cooled in a stream of nitrogen for supply to the polymerization.

The washing solvent is drained from the reactor at 40 ° C in a stream of nitrogen and the hexane is passed through the lowering to polymerization. Turn on the stirrer - 500 rpm and cool the reactor to 20 ° C.

Within 1 minute, 3 times exchange the gas phase, blowing with propylene with the stirrer stopped.

For polymerization, ethylene and propylene of polymerization purity, which are in cylinders, are used. Dosage is carried out through a reactor flow meter system.

The mixer is turned on and 4 g of ethylene are metered at a feed rate of 0.4 g / min for 10 minutes using a flow meter. Next, propylene in the amount of 63 g is similarly dosed at a rate of 110 g / h for 34 minutes. After loading, the pressure in the apparatus is 0.37 MPa.

The preparation of the catalytic complex is carried out separately, using boxing equipment located under an argon pad. The catalyst used is a vanadium compound having the following structural formula:

The dosages of the components used are:

The vanadium compound of the general formula C ₄ H ₁₀ OSl ₃ V - 0.0125 g (0.048 mmol)

EASC - 0.1186 g (0.96 mmol)

ETHA - 0.0229 g (0.12 mmol).

The catalytic complex is transferred to the apparatus with propylene.

At the end of the polymerization, excess pressure is released to atmospheric pressure, after which the reaction mass is discharged through the bottom valve of the reactor. The polymer is then reprecipitated by adding 200 ml of ethanol. After that, the polymer is crushed, washed again with alcohol and dried to constant weight in a vacuum oven at a temperature of 70 ° C. The main parameters are determined using an Agillent 1200 gel permeation chromatograph with an evaporative light scattering detector on a PL gel mixed-C column with a molecular weight range of 200-3000000.

Polymerization time 1 minute.

The results of the experiment in table 1

The vanadium complex 1 is synthesized by reacting vanadium oxychloride and 1,2-dimethoxyethane in hexane. Yield 98%. The product is a dark brown solid.

Example 2

Perform the same way as example 1, but the polymerization time is 2 minutes.

The results of the experiment in table 1.

Example 3

Perform the same way as example 1, but the polymerization time is 5 minutes.

The results of the experiment in table 1.

Example 4

Perform the same way as example 1, but the polymerization time is 10 minutes.

The results of the experiment in table 1.

Example 5

Perform the same way as example 1, but the polymerization time is 15 minutes.

The results of the experiment in table 1.

Example 6

Perform the same way as example 1, but the polymerization time is 30 minutes.

The results of the experiment in table 1.

Example 7

Perform the same way as example 1, but the polymerization time is 60 minutes.

The results of the experiment in table 1.

Example 8

Perform the same way as example 1, but as α-olefin instead of propylene use hexene-1 in an amount of 60 g

The results of the experiment in table 1.

Example 9

Perform the same way as example 1, but instead of propylene use octene-1 in an amount of 100 g

The results of the experiment in table 1.

Example 10

Perform the same way as example 1, but as a catalyst using a vanadium compound having the following structural formula:

The vanadium compound of the general formula C ₃₂ H ₂₈ N ₂ O ₅ V - 0.027 g (0.048 mmol)

EASC - 0.5928 g (4.8 mmol)

ETHA - 0.0229 g (0.12 mmol).

The results of the experiment in table 1.

Vanadium complex 2 was synthesized by reacting vanadyl sulfate pentahydrate and 2- [4′-allyloxyphenylimino] phenol in methanol. Yield 75%. The product is a yellow brown solid.

Example 11

Perform the same way as example 1, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the components used are:

The vanadium compound of the general formula C ₆ H ₁₆ N ₂ OSl ₃ V - 0.014 g (0.048 mmol)

EASC - 0.5928 g (4.8 mmol)

ETHA - 0.0229 g (0.12 mmol).

The ratio of EASC: ETHA: C ₆ H ₁₆ N ₂ OCl ₃ V = 100: 2.5: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 3 was synthesized by reacting vanadium oxychloride and NNNN-tetramethylethylenediamine in hexane. Yield 95%. The product is a yellow-green solid.

Example 12

Perform the same way as example 1, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the components used are:

The vanadium compound of the general formula C ₁₀ H ₂₂ O ₇ Cl ₆ V ₂ - 0.013 g (0.023 mmol) EACh - 0.3409 g (2.76 mmol)

ETHA - 0.011 g (0.0575 mmol).

The ratio of EASC: ETHA: C ₁₀ H ₂₂ O ₇ Cl ₆ V ₂ = 120: 2.5: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 4 was synthesized by the interaction of vanadium oxychloride and dimethoxytriethylene glycol in hexane. Yield 80%. The product is a black solid.

Example 13

Perform the same way as example 1, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the components used are:

The vanadium compound of the general formula C ₈ H ₁₀ O ₃ Cl ₃ V is 0.015 g (0.048 mmol)

EASC - 0.2371 g (1.92 mmol)

ETHA - 0.0229 g (0.12 mmol).

The ratio of EASC: ETHA: C ₈ H ₁₀ O ₃ Cl ₃ V = 40: 2.5: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 5 was synthesized by reacting vanadium oxychloride and 1,2-dimethoxybenzene in hexane. Yield 90%. The product is a black solid.

Example 14

Perform the same way as example 1, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the components used are:

The vanadium compound of the general formula C ₄ H ₁₀ O ₂ Cl ₁₄ V is 0.012 g (0.042 mmol)

EASH-0.3137 g (2.54 mmol)

ETHA - 0.0201 g (0.105 mmol).

The ratio of EASC: ETHA: C ₄ H ₁₀ O ₂ C ₁₄ V = 60: 2.5: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 6 was synthesized by reacting vanadium tetrachloride and 1,2-dimethoxyethane in hexane. Yield 92%. The product is a dark brown solid.

Example 15

Perform the same way as example 1, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the components used are:

The vanadium compound of the general formula C ₂₁ H ₂₁ N ₃ Cl ₂ V is 0.02 g (0.046 mmol)

EASC - 0.8472 g (6.86 mmol)

ETHA - 0.022 g (0.115 mmol).

The ratio of EASC: ETHA: C ₂₁ H ₂₁ N ₃ Cl ₂ V = 150: 2.5: 1 (mol.).

The results of the experiment in table 1.

Vanadium complex 7 was synthesized by reacting vanadium tetrachloride and the dilithium salt of N-phenylbisaminopyridine in absolute tetrahydrofuran. Yield 70%. The product is a green solid.

Example 16

Perform as well as example 7, but diethylaluminium chloride was used as a cocatalyst.

The results of the experiment in table 1.

Example 17

Perform the same way as example 7, but as a cocatalyst use diisobutylaluminium chloride.

The results of the experiment in table 1.

Example 18

Perform the same way as example 7, but as a molecular weight regulator use hydrogen in an amount of 400 ml.

The results of the experiment in table 1.

Example 19

Perform the same way as example 7, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the used components of the vanadium catalyst system in this case are:

- Catalyst: vanadium compound of the general formula C ₄ H ₈ Cl ₃ O ₃ V — 0.0120 g (0.046 mmol).

- Socialization: EASC - 0.8472 g (2.76 mmol).

- Reactant: ETHA - 0.022 g (0.115 mmol).

The ratio of EASC: ETHA: C ₄ H ₈ Cl ₃ O ₃ V = 60: 2.5: 1 (mol.).

The results of the experiment in table 1.

Vanadium complex 8 was synthesized by reacting vanadium oxychloride and 1,4-dioxane in hexane. Yield 94%. The product is a dark purple solid.

Example 20

Perform the same way as example 7, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the used components of the vanadium catalyst system in this case are:

- Catalyst: vanadium compound of the general formula C ₅ H ₁₂ Cl ₃ O ₃ V — 0.0127 g (0.046 mmol).

- Socialization: EASC - 0.8472 g (2.76 mmol).

- Reactant: ETHA - 0.022 g (0.115 mmol).

The ratio of EASC: ETHA: C ₅ H ₁₂ Cl ₃ About ₃ V = 60: 2.5: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 9 was synthesized by reacting vanadium oxychloride and 1-methoxy, 2-ethoxyethane in hexane. Yield 90%. The product is a dark brown solid.

Example 21

Perform the same way as example 7, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the used components of the vanadium catalyst system in this case are:

- Catalyst: vanadium compound of the general formula C ₆ H ₁₄ Cl ₃ O ₃ V — 0.0134 g (0.046 mmol).

- Socialization: EASC - 0.8472 g (2.76 mmol).

- Reactant: ETHA - 0.022 g (0.115 mmol).

The ratio of EASC: ETHA: C ₆ H ₁₄ Cl ₃ O ₃ V = 60: 2.5: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 10 was synthesized by reacting vanadium oxychloride and 1-methoxy, 2-isopropoxyethane in hexane. Yield 91%. The product is a dark brown solid.

Example 22

Perform the same way as example 7, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the used components of the vanadium catalyst system in this case are:

- Catalyst: vanadium compound of the general formula C ₇ H ₁₆ Cl ₃ O ₃ V — 0.0140 g (0.046 mmol).

- Socialization: EASC - 0.8472 g (2.76 mmol).

- Reactant: ETHA - 0.022 g (0.115 mmol).

The ratio of EASC: ETHA: C ₇ H ₁₆ Cl ₃ About ₃ V = 60: 2.5: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 11 was synthesized by reacting vanadium oxychloride and 1-methoxy, 2-butoxyethane in hexane. Yield 93%. The product is a dark brown solid.

Example 23

Perform the same way as example 7, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the used components of the vanadium catalyst system in this case are:

- Catalyst: vanadium compound of the general formula C ₆ H ₁₄ Cl ₃ O ₃ V — 0.0134 g (0.046 mmol).

- Socialization: EASC - 0.8472 g (2.76 mmol).

- Reactant: ETHA - 0.022 g (0.115 mmol).

The ratio of EASC: ETHA: C ₆ H ₁₄ Cl ₃ O ₃ V = 60: 2.5: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 12 was synthesized by reacting vanadium oxychloride and 1,2-diethoxyethane in hexane. Yield 97%. The product is a dark brown solid.

Example 24

Perform the same way as example 7, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the used components of the vanadium catalyst system in this case are:

- Catalyst: vanadium compound of the general formula C ₈ H ₁₈ Cl ₃ O ₃ V — 0.0147 g (0.046 mmol).

- Socialization: EASC - 0.8472 g (2.76 mmol).

- Reactant: ETHA - 0.022 g (0.115 mmol).

The ratio of EASC: ETHA: C ₃ H ₁₈ Cl ₃ O ₃ V = 60: 2.5: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 13 was synthesized by reacting vanadium oxychloride and 1,2-diisopropoxyethane in hexane. Yield 94%. The product is a dark brown solid.

Example 25

Perform the same way as example 7, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the used components of the vanadium catalyst system in this case are:

- Catalyst: vanadium compound of the general formula C ₁₀ H ₂₂ Cl ₃ O ₃ V — 0.0160 g (0.046 mmol).

- Socialization: EASC - 0.8472 g (2.76 mmol).

- Reactant: ETHA - 0.022 g (0.115 mmol).

The ratio of EASC: ETHA: C ₁₀ H ₂₂ Cl ₃ About ₃ V = 60: 2.5: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 14 was synthesized by reacting vanadium oxychloride and 1,2-dibutoxyethane in hexane. Yield 90%. The product is a dark brown solid.

Example 26

Perform the same way as example 7, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the used components of the vanadium catalyst system in this case are:

- Catalyst: vanadium compound of the general formula C ₁₆ H ₁₈ Cl ₃ O ₃ V — 0.0191 g (0.046 mmol).

- Socialization: EASC - 0.8472 g (2.76 mmol).

- Reactant: ETHA - 0.022 g (0.115 mmol).

The ratio of EASC: ETHA: C ₁₆ H ₁₈ Cl ₁₃ O ₃ V = 60: 2.5: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 15 was synthesized by reacting vanadium oxychloride and 1,2-dibenzyloxyethane in hexane. Yield 81%. The product is a black solid.

Example 27

Perform the same way as example 7, but as a catalyst using a vanadium compound having the following structural formula:

The dosages of the used components of the vanadium catalyst system in this case are:

- Catalyst: vanadium compound of the general formula C ₈ H ₁₄ Cl ₅ O ₅ V — 0.0190 g (0.046 mmol).

- Socialization: EASC - 0.8472 g (2.76 mmol).

The ratio of EASC: C ₈ H ₁₄ Cl ₅ O ₅ V = 60: 1 (mol.).

The results of the experiment in table 1.

The vanadium complex 16 was synthesized by reacting vanadium oxychloride and ethyl 2,2-dichloro- (2′-methoxyethoxy) propionate in hexane. Yield 60%. The product is a dark green solid.

Claims (15)

1. Vanadium catalytic system for the copolymerization of ethylene and α-olefins with a hydrocarbon chain from 2 to 12 carbon atoms, consisting of a complex compound of vanadium, cocatalyst and a reactivator, characterized in that as a compound of vanadium using a complex of vanadium of the formula:

2. Vanadium catalytic system according to claim 1, characterized in that as the cocatalyst use an organoaluminum compound with the general formula:
AlRxHaly,
where R is an alkyl radical (C2) C1-C9; Hal is a halogen from among Cl, Br or I; x is from 1 to 3, y = 3.
with a ratio of vanadium / cocatalyst from 1: 1 to 1: 100. 3. The vanadium catalyst system according to claim 1, characterized in that the organochlorine compound of the general formula is used as a reactivator:

where R is an alkyl radical C1-C9
with a ratio of vanadium / reactivator from 1: 1 to 1:20. 4. Vanadium catalytic system for the copolymerization of ethylene and α-olefins with a hydrocarbon chain from 2 to 12 carbon atoms, consisting of a complex compound of vanadium, cocatalyst and a reactivator, characterized in that the vanadium complex is used as the vanadium compound by the formula:

5. The vanadium catalyst system according to claim 4, characterized in that the organoaluminum compound is used as the cocatalyst by the general formula:
AlRxHaly,
where R is an alkyl radical (C2) C1-C9; Hal is a halogen from among Cl, Br or I; x is from 1 to 3, y = 3.
with a ratio of vanadium / cocatalyst from 1: 1 to 1: 100. 6. Vanadium catalytic system according to claim 4, characterized in that as a reactivator, use organochlorine compound of the General formula:

where R is an alkyl radical C1-C9
with a ratio of vanadium / reactivator from 1: 1 to 1:20. 7. Vanadium catalytic system for the copolymerization of ethylene and α-olefins with a hydrocarbon chain of from 2 to 12 carbon atoms, consisting of a complex compound of vanadium, cocatalyst and reactivator, characterized in that the vanadium complex is used as the vanadium compound by the formula:

8. The vanadium catalyst system according to claim 7, characterized in that the organoaluminum compound is used as a cocatalyst with the general formula:
AlRxHaly,
where R is an alkyl radical (C2) C1-C9; Hal is a halogen from among Cl, Br or I; x is from 1 to 3, y = 3.
with a ratio of vanadium / cocatalyst from 1: 1 to 1: 100. 9. Vanadium catalytic system according to claim 7, characterized in that as a reactivator, an organochlorine compound is used with the general formula:

where R is an alkyl radical C1-C9
with a ratio of vanadium / reactivator from 1: 1 to 1:20. 10. Vanadium catalytic system for the copolymerization of ethylene and α-olefins with a hydrocarbon chain of from 2 to 12 carbon atoms, consisting of a complex compound of vanadium and cocatalyst, characterized in that a complex of vanadium is used as a compound of vanadium with the general formula:

,
where Alk is CH3, C2H5, C3H7, C4H9; 11. The vanadium catalyst system of claim 10, wherein the organoaluminum compound is used as a cocatalyst with the general formula:
AlRxHaly,
where R is an alkyl radical (C2) C1-C9; Hal is a halogen from among Cl, Br or I; x is from 1 to 3, y = 3.
with a ratio of V / cocatalyst from 1: 1 to 1: 100. 12. A method of obtaining a copolymer of ethylene and α-olefins with a hydrocarbon chain from 2 to 12 carbon atoms in a hydrocarbon solvent in the temperature range from 0 to 80 ° C and a monomer pressure in the range from 0.1 to 1.1 MPa in the presence of a molecular regulator mass and catalytic system, characterized in that as the catalytic system using a vanadium catalytic system according to claim 1 or according to claim 4 or according to claim 7. 13. The method according to p. 12, characterized in that hydrogen, diethylzinc or diisobutylaluminium hydride are used as the molecular weight regulator of the reaction product. 14. A method of obtaining a copolymer of ethylene and α-olefins with a hydrocarbon chain from 2 to 12 carbon atoms in a hydrocarbon solvent in the temperature range from 0 to 80 ° C and a monomer pressure in the range from 0.1 to 1.1 MPa in the presence of a molecular regulator mass and catalyst system, characterized in that the vanadium catalyst system of claim 10 is used as the catalyst system. 15. The method according to 14, characterized in that hydrogen, diethylzinc or diisobutylaluminium hydride are used as the molecular weight regulator of the reaction product.