RU2765468C1 - Cobalt-containing catalyst component for polymerisation of ethylene into linear polyethylene wax containing terminal vinyl groups, catalyst and method for its preparation - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst component for the polymerisation of ethylene, a catalyst and a method of producing the catalyst. Catalyst component has a structure represented by general formula 1, where the cycloalkyl substituent is selected from a group comprising cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl (i.e. k = 1…10); and substitutes R¹ and R² are independently selected from a group, including alkyls C₁…C₄₀ and hydrogen atom, where an alkyl substituent is a monovalent substituent having composition C_nH_2n+1 (n is integer 1…40). Ethylene polymerisation catalyst contains at least one compound of general formula 1, at least one organoaluminium activator, optionally ethylene and at least one hydrocarbon solvent. Method of preparing the catalyst involves mixing, in any sequence, a suspension or solution of at least one compound of general formula 1, suspension or solution of at least one organoaluminium activator optionally in the presence of ethylene in the medium of at least one hydrocarbon solvent.

EFFECT: technical result of the present invention is the preparation of a catalyst component not described earlier and a catalyst containing said component, temperature maximum efficiency of which is in range of 60–70 °C, and use thereof to obtain linear polyethylene wax with MM 0.57–2.42 kg/mol with a fraction of macromolecules containing terminal vinyl groups of up to 95 %.

9 cl, 2 dwg, 1 tbl, 43 ex

Description

The invention relates to the production of polyethylene wax, namely: to a component of a catalyst for the polymerization of ethylene, to a catalyst (catalytic system) containing this component, a method for its preparation and use for obtaining a linear polyethylene wax with a narrow molecular weight distribution (MWD) containing terminal vinyl groups.

Polyethylene waxes include low molecular weight ethylene homopolymers, both linear and branched, as well as low molecular weight copolymers of ethylene with propylene and other α-olefins with a weight average molecular weight in the range of 500-10000 g/mol.

Polyethylene wax is used in a variety of industries, such as the production of electrical cables, the production of PVC compounds, the production of PVC profiles, pipes, fittings and other products from plasticized PVC, the production of molds in foundry production, the production of decorative and church candles, the production of hot melt adhesives and hot melt adhesives, production of waterproofing materials, production of phlegmatized explosives. Polyethylene wax is used in asphalt-bitumen and wood-polymer compositions, in creams for leather products, in lubricants for lining molds, in anti-friction lubricants, in mixtures for injection molding, in coatings for packaging paper, in anticoagulant compositions for coloring polymeric materials. in bulk. Application examples: Patent RU 2394292 Electrical insulating composition; Patent RU 2212421 PVC-based composition for profile products; Patent RU 2287399 Release agent for model rod equipment; Patent RU 2116335 Method for continuous production of candles; Patent RU 2488618 Hot melt adhesive; Patent RU 2088606 Waterproofing roll material; Patent RU 2514946 Phlegmatized explosive and method of its dry phlegmatization; Patent RU 2489462 Adhesion and cohesion modifiers for asphalt; Patent RU 2431648 Wood-polymer composition for products based on polyvinyl chloride; Patent RU 2119518 Cream for leather products; Patent RU 2036088 Method for manufacturing facing plates; Patent RU 2524267 Anti-friction lubricant; Patent RU 2315068 Multifunctional modifier.

Polyethylene wax can be obtained in the Fischer-Tropsch process by reacting hydrogen with carbon monoxide on catalysts containing iron and cobalt, during thermal degradation (cracking) of high-pressure polyethylene, and as a by-product in the purification of low-pressure polyethylene. The disadvantage of thermal degradation and the Fischer-Tropsch process is the use of high temperatures and pressures, which leads to difficulty in controlling the process, as well as the fact that these processes produce a heterogeneous product with a wide MWD. The availability of polyethylene wax released during the cleaning of low pressure polyethylene is gradually decreasing, since the improvement in the production technology of low pressure polyethylene, the driving reasons for which are the achievement of maximum efficiency and compliance with environmental requirements, has led to the fact that in modern processes for the production of low pressure polyethylene, the formation of low molecular weight impurities is significant. reduced to a level at which purification of the marketable product is not required. This source of polyethylene wax has no historical perspective due to the inevitable ubiquitous transition to high performance catalyst systems.

A separate group of methods for producing polyethylene wax is the polymerization of ethylene or the copolymerization of ethylene with α-olefins, aimed at obtaining polyethylene wax. The polymerization or copolymerization can be carried out at high pressure in the presence of peroxide initiators or at low pressure in the presence of Ziegler-Natta, metallocene or post-metallocene catalysts.

bei der Herstellung wachsartiger niedermolekularer

. 5. Патент US 3835107 Production of low molecular weight waxy polyethylenes. 6. Патент US 2387755 Hydrogen-modified polymers of ethylene]. С увеличением содержания водорода в этилене ММ, вязкость и температура размягчения продукта уменьшаются. A method for the production of polyethylene wax using a high pressure process using peroxides and/or oxygen as an initiator and hydrogen as a chain transfer agent is disclosed in patents, for example [ 1. Patent DE 10012775 Verfahren zur Herstellung von Polyethylenwachsen. 2. Patent US 2999856 Polyethylene waxes and process for preparing them. 3. Patent GB 1058967 Process for the production of wax-like ethylene polymers of low molecular weight. 4. Patent DE 1745547 Verfahren zum Vermeiden der Hydrierung von

bei der Herstellung wachsartiger niedermolekularer

. 5. Patent US 3835107 Production of low molecular weight waxy polyethylenes. 6. Patent US 2387755 Hydrogen-modified polymers of ethylene]. As the hydrogen content of ethylene MM increases, the viscosity and softening point of the product decrease.

The disadvantages of the process at high pressure are the use of high temperatures (up to 350°C) and pressure (300-1000 atm.), Which leads to difficulties in controlling the process. As a molecular weight regulator, an additive of hydrogen to ethylene (5-60 vol.%) is used. Since hydrogen is consumed at high temperature for hydrogenation of ethylene, this leads to the accumulation of ethane in the gas mixture and creates difficulties in maintaining a constant partial pressure of hydrogen and ethylene, which provides the required molecular weight and molecular weight distribution. At high temperatures, the diffusion of hydrogen into the reactor wall causes a decrease in the strength of the steel and creates the risk of cracking and rupture of the reactor. The use of high-alloy special steels reduces risks, but significantly increases the cost of production and does not eliminate the need for periodic shutdown of the reactor for inspection.

. 8. Патент DE 1940686 Verfahren zum kontinuierlichen Herstellen von wachsartigem, niedermolekularem

aus festem, hochmolekularem

. 9. Патент US 4039560 Method of producing modified polyethylene wax.].A method for the production of polyethylene wax in the presence of Ziegler-Natta catalysts and hydrogen as a molecular weight regulator is disclosed in patents, for example [ 7. Patent DE 2257917 Verfahren zur Aufarbeitung von

. 8. Patent DE 1940686 Verfahren zum kontinuierlichen Herstellen von wachsartigem, niedermolekularem

aus festem, hochmolekularem

. 9. Patent US 4039560 Method of producing modified polyethylene wax.].

When using Ziegler-Natta catalysts to produce polyethylene wax, the addition of hydrogen to ethylene at high partial pressure is also used as a molecular weight regulator. This leads to the formation of a significant amount of oligomers and the expansion of the molecular weight distribution.

Polyethylene wax having a narrow molecular weight distribution can be obtained using metallocene catalysts [ 10. Patent US 4914253 Method for preparing polyethylene wax by gas phase polymerization. 11. Patent KR 0137960 Method for preparing polyethylene wax by gas phase polymerization. 12. Patent US 5750813 Process for the preparation of polyolefin waxes. 13. Patent EP 2748210 A process for the preparation of polyethylene wax using metallocene catalyst. 14. Lamb JV, Buffet J.-C., Turner ZR, Khamnaen T., O'Hare D. Metallocene Polyethylene Wax Synthesis. Macromolecules 2020, V. 53, p. 5847-5856].

In addition to the complexity and high cost of their production, metallocene catalysts are highly sensitive to oxygen, moisture, and polar impurities in the monomer and solvent and require additional measures to purify the monomer and solvent. In addition, the desired reduction in polymer molecular weights observed in the presence of hydrogen is accompanied by an undesirable reduction in catalyst activity. Since MW control is achieved with hydrogen using Ziegler-Natta and metallocene catalysts, the resulting polyethylene waxes do not contain terminal (terminal) vinyl groups.

A more attractive way to obtain polyethylene wax is the polymerization of ethylene on catalytic systems based on post-metallocene complexes due to the ease of synthesis of such complexes, lower sensitivity to oxygen, moisture and polar impurities in the monomer and solvent [ 15. Oleinik I.I. Chem. int. mouth development 2008, Vol. 16, Issue. 6, p. 747. 16. Oleinik I.I. Advances in the design of post-metallocene catalytic systems of the arylimine type for the polymerization of ethylene // in the book: Chemistry of aromatic, heterocyclic and natural compounds (NIOC SB RAS 1958-2008) / ed. ed. ak. V.N. Parmon, Novosibirsk: ZAO IPP Offset, 2009. - p. 589-620. 17. Gibson VC, Solan GA Olefin Oligomerizations and Polymerizations Catalyzed by Iron and Cobalt Complexes Bearing Bis(imino)pyridine Ligands // in: Catalysis without Precious Metals, Bullock M., Ed.; Wiley-VCH: Weinheim, Germany, 2010, p. 111-141. 18. Small BL Acc. Chem. Res. 2015, V. 48, p. 2599-2611. 19. Wang Z., Solan GA, Zhang W., Sun W.-H. Coord. Chem. Rev. 2018, V. 363, p. 92-108].

Known catalytic systems based on arylimine complexes of nickel and cobalt and organoaluminum compounds capable of producing polyethylene wax [ 20. Huang F., Zhang W., Yue E., Liang T., Hu X. Sun, W.-H. Dalton Trans. 2016, V. 45, p. 657-666. 21. Sun Z., Huang F., Qu M., Yue E., Oleynik IV, Oleynik II, Zeng Y., Liang T., Li K., Zhang W., Sun W.-H. RSC Adv., 2015, v. 5, p. 77913-77921. 22. Sun Z., Erlin Y., Qu M., Oleynik IV, Oleynik II, Li K., Liang T., Zhang W., Sun W.-H. inorg. Chem. front. 2015, v. 2, p. 223-227. 23. Oleinik I.I., Oleinik I.V., Sun Wen-Hua. Patent RU 2704263, 10/25/2019. 24. Oleinik I.I., Oleinik I.V., Sun Wen-Hua. Patent RU 2729622, 08/11/2020.].

The advantage of such catalytic systems is that the production of polyethylene wax is carried out in the absence of hydrogen as a chain transfer agent, and the molecular weight, MWD, degree of branching, and the proportion of macromolecules containing a terminal vinyl group are controlled by varying the structure of the complex and external conditions. The content of terminal vinyl groups in the resulting polymer depends on the ratio of the rates of the transfer of a hydrogen atom from the β -position of the macroalkyl group to the central transition metal atom of the catalyst and the transfer of the macroalkyl group to the aluminum atom of the organoaluminum activator.

Close to the proposed invention is a catalyst for the polymerization of ethylene containing a biimine complex of chromium chloride with the formula A , where R ¹ = Me, Et, i-Pr; R ² = H, Me [25. Huang C., Zhang, Y., Solan GA, Ma, Y., Hu X., Sun Y., Sun W.-H. European Journal of Inorganic Chemistry 2017, V. 2017, p. 4158 - 4166 ] , as well as a catalyst containing a bisimine complex of iron chloride with the formula B , where R ¹ = Me, Et, i-Pr; R ² = H, Me [26. Patent CN 102731578. 27. Zhang W., Chai W., Sun W.-H., Hu X., Redshaw C., Hao X. Organometallics 2012, v. 31, p. 5039-5048 .] .

The catalytic system based on compounds of general formula A , depending on the external conditions of polymerization in the temperature range of 20…100°C, has an activity of 0.19…15.9 _tpe /mol _Cr ×h and makes it possible to obtain a monomodal linear polyethylene wax with an MM of 0.4…8.39 kg/mol, narrow molecular weight distribution 1.04…1.99 and melting point 85.5…130.5°С. The proportion of macromolecules containing a terminal vinyl group is 64–77%. The maximum productivity of the catalyst is observed at a temperature of 70–80°C [ 25 ].

The catalytic system based on compounds of general formula B , depending on the external conditions of polymerization, has an activity of 1.6…24.0 _tpe /mol _Fe ×h and makes it possible to obtain linear polyethylene without vinyl groups with MM 8.1…203.4 kg/mol, MWD 2.7…35.9 and high temperature melting point 120.5…135.5°C. The maximum productivity of the catalyst is observed at a temperature of 50°C [ 27 ].

Closest to the proposed invention is an ethylene polymerization catalyst containing a biimine complex of cobalt chloride with the formulaV, where R^one = Me, Et, i-Pr; R² = H, Me[26. Patent CN 102731578.28. Sun W.-H., Kong S., Cha, W., Shiono T., Redshaw C., Hu X., Guo C., Hao X. Applied Catalysis A: General 2012, v. 447-448, p. 67 - 73].

The described catalytic system based on compounds of general formula B , depending on the external conditions of polymerization in the temperature range of 30–70°C in the presence of alkylalumoxanes (MAO or MMAO), has an activity of 0.78–19.3 _tpe /mol _Co ×h and makes it possible to obtain linear polyethylene wax without vinyl groups with MM 0.83...10.2 kg/mol, narrow molecular weight distribution 1.4...2.0 and melting point 89.2...129.1°C. The maximum productivity of the catalyst is observed at a temperature of 60°C [ 28 ].

The performance characteristics of a linear polyethylene wax obtained from the catalytic polymerization of ethylene can be modified by post-polymerization functionalization. For example, oxidized polyethylene wax is almost insoluble in most solvents. Since commercially available polyethylene waxes are produced using Ziegler-Natta and metallocene catalysts and do not contain terminal vinyl groups, functionalization is carried out under harsh conditions: oxidation is carried out at 150-200°C at a pressure of up to 10 atm., and the interaction of acrylic acids in the presence of organic peroxides - at a temperature of 250°C. In contrast, post-polymerization functionalization of vinyl-terminated polyethylene waxes using epoxidation, thiol addition, metathesis with acrylates, etc., can be carried out under mild conditions. Given this, it is desirable to obtain a polyethylene wax with a high content of vinyl groups, because at a high content of vinyl groups, post-polymerization functionalization can cause a more significant modification of the properties of the polyethylene wax. From this point of view, the disadvantage of the prototype catalyst is the production of polyethylene wax without terminal vinyl groups.

Since the task of producing a linear polyethylene wax with a high content of terminal vinyl groups is still relevant, the technical problem of the invention is to create a new component of the ethylene polymerization catalyst, a new catalyst (catalyst system) containing this component, producing a linear polyethylene wax containing terminal vinyl groups, with MM 0.5...2.4 kg/mol, MWD 1.8...2.4 and melting point 116...125°C.

The technical result of the invention is the production of a previously undescribed catalyst component and an ethylene polymerization catalyst containing this component, producing, in contrast to the prototype catalyst based on compounds B , a linear polyethylene wax containing terminal vinyl groups.

The solution of this problem is achieved by the fact that as a component of the catalyst for the polymerization of ethylene into a linear polyethylene wax containing terminal vinyl groups, it was proposed to use previously unknown bisaryl-iminopyridine complexes of cobalt dichloride, namely: {2-[1-(2-R ¹ -4-R ² -6-cyclo-alkylphenylimino)ethyl]-8-(2-R ^1-4 -R ² -6-cycloalkylphenylimino)-5,6,7,8-tetrahydro-quinoline}cobalt(II) dichlorides , having the structure represented by the general formula 1 .

The substituents R ¹ and R ² in the compound of general formula 1 are independently selected from the group consisting of C ₁ ... C ₄₀ alkyls and a hydrogen atom (by alkyl, alkyl substituent is meant a monovalent substituent having the composition C _n H _2n+1 (n - integer 1 ... 40; alkyl, alkyl substituent is primary if the carbon atom of the substituent, which forms a bond with the fragment of the molecule, in relation to which alkyl is a substituent, in addition to this bond has three bonds with three hydrogen atoms or has only one bond with one a carbon atom and two bonds to two hydrogen atoms; secondary if it has two bonds to two carbon atoms and one bond to a hydrogen atom; and tertiary if it has three bonds to three carbon atoms).

The cycloalkyl substituent in the compound of general formula 1 at position 6 is selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl (i.e. k = 1...10).

Preferred combinations of R ¹ , R ² and cycloalkyl substituents include: R ¹ = Me, R ² = H, cycloalkyl = cyclopentyl ( I ); R ¹ = Me, R ² = H, cycloalkyl = cyclohexyl ( II ); R ¹ = Me, R ² = H, cycloalkyl = cyclooctyl ( III ); R ¹ = R ² = Me, cycloalkyl = cyclopentyl ( IV ); R ¹ = R ² = Me, cycloalkyl = cyclohexyl ( V ); R ¹ \u003d R ² \u003d Me, cycloalkyl \u003d cyclooctyl ( VI ). Hereinafter, a two-unit code is used to designate a specific bisaryliminopyridine complex of cobalt dichloride, for example 1-II , referring to a compound of general formula 1 with R ¹ = Me, R ² = H, cycloalkyl = cyclohexyl (combination II ), i.e. to {2-[1-(2-methyl-6-cyclohexylphenyl-imino)ethyl]-8-(2-methyl-6-cyclohexylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride.

To achieve this technical result, a new catalyst (catalytic system) for the polymerization of ethylene into a linear polyethylene wax is also proposed, including at least one compound of general formula 1 , at least one organoaluminum activator, not necessarily ethylene, and at least one hydrocarbon solvent.

Preferably, the compound of general formula 1 is selected from the group consisting of:

{2-[1-(2-methyl-6-cyclopentylphenylimino)ethyl]-8-(2-methyl-6-cyclopentylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride; {2-[1-(2-methyl-6-cyclohexylphenylimino)ethyl]-8-(2-methyl-6-cyclohexylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride; {2-[1-(2-methyl-6-cyclooctylphenylimino)ethyl]-8-(2-methyl-6-cyclooctylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride; {2-[1-(2,4-dimethyl-6-cyclopentylphenylimino)ethyl]-8-(2,4-dimethyl-6-cyclopentylphenylimino)-5,6,7,8-tetrahydroquino-line}cobalt( II) dichloride; {2-[1-(2,4-dimethyl-6-cyclohexylphenylimino)ethyl]-8-(2,4-dimethyl-6-cyclohexylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride; {2-[1-(2,4-dimethyl-6-cyclooctylphenylimino)ethyl]-8-(2,4-dimethyl-6-cyclooctylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride.

At least one organoaluminum compound is used as the organoaluminum activator, specific examples of which include methyl aluminoxane (MAO), modified MAO variants (including, but not limited to, improved polymethylalumoxane referred to by manufacturers as PMAO-IP; modified methylaluminoxane type 3A , designated as MMAO-3A; modified methylalumoxane type 12, designated as MMAO-12), as well as trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-butylaluminum, tri- n - hexylaluminum, tri- n- octylaluminum, dimethylaluminum chloride (DMAC), diethylaluminum chloride (DEAC), diisobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride. Other similar organoaluminum compounds or mixtures thereof in any combination can be used.

The hydrocarbon solvent is selected from individual aliphatic, alicyclic, alkylaromatic or aromatic compounds, their technical mixtures in any combination. Specifically, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, xylene, trimethylbenzene, cumene, cymene, camphene, tetralin, gasoline, naphtha, kerosene. Solvents may be used singly or in combination of two or more solvents.

In accordance with the present invention, a method for preparing a catalyst (catalyst system) for the polymerization of ethylene is provided.

The method for preparing a catalyst in accordance with the present invention includes the interaction, when contacting at least one compound of general formula 1 , at least one organoaluminum activator, optionally in the presence of ethylene, in an environment of at least one hydrocarbon solvent.

The contacting methods are not particularly limited as long as the beneficial effects of the invention can be obtained. For example, the method of contact may be such that the compound of general formula 1, taken in solid form, in the form of a suspension or solution in at least one hydrocarbon solvent, is added immediately or in parts to a solution or suspension of an organoaluminum activator in a hydrocarbon solvent, optionally in the presence of ethylene ; or a solution or suspension of an organoaluminum activator in a hydrocarbon solvent is added all at once or in parts to the compound of general formula 1 taken in solid form, in the form of a suspension or solution in at least one hydrocarbon solvent, optionally in the presence of ethylene. To ensure better contact, ease of loading and dosing, it is preferable to contact the compound of general formula 1 , taken as a suspension or solution in at least one hydrocarbon solvent, with a solution or suspension of an organoaluminum activator in a hydrocarbon solvent. Contacting a compound of general formula 1 with an organoaluminum compound can be carried out in the presence of ethylene dissolved in a hydrocarbon solvent, before adding a compound of general formula 1 if it is added to an organoaluminum activator, while the suspension or solution of the organoaluminum activator is saturated with ethylene at an excess pressure of ethylene from 0.01 to 10 ati and temperature from 10 to 120°C; or before adding a suspension or solution of an organoaluminum activator, if it is added to a suspension or solution of a compound of general formula 1 , while the suspension or solution of a compound of general formula 1 is saturated with ethylene at an excess pressure of ethylene from 0.01 to 10 atm and a temperature from 10 to 120 ° C. When a combination of two or more compounds of general formula 1 is used, they can be added individually in any order or as a mixture of two or more components taken as a suspension or solution. When a combination of two or more organoaluminum activators is used, they can be added individually in any order or as a mixture of two or more components taken as a suspension or solution, optionally in the presence of ethylene.

A preferred embodiment of the method for preparing a catalyst in accordance with the present invention is to sequentially carry out the following operations. Certain amounts of at least one hydrocarbon solvent, for example, toluene and a suspension or solution of one or more organoaluminum activators in at least one hydrocarbon solvent, for example, toluene, are sequentially introduced into the reactor, and then at least one catalyst component is introduced, described by the general formula 1 , in the form of a suspension or solution in a hydrocarbon solvent, for example, toluene, or certain amounts of at least one hydrocarbon solvent, for example, toluene, one or more catalyst components described by the general formula 1 , are sequentially introduced into the reactor in the form of a suspension or solution in hydrocarbon solvent, for example, toluene, and then a solution of one or more organoaluminum activators in a hydrocarbon solvent, for example, toluene, is introduced. Then the mixture is saturated with ethylene (the creation of a constant value of the excess pressure of ethylene from 1.0 to 10 atm) at a certain temperature (from 10 to 120°C). The concentration of the catalyst component of general formula 1 in the catalytic system is in the range from 0.1 to 100 µmol/l, preferably from 10 to 40 µmol/l, the Al/Co molar ratio is in the range from 100 to 5000, preferably 500-3500. The catalyst is then ready to be used for the polymerization of ethylene.

Another preferred variant of the process for preparing a catalyst in accordance with the present invention is the sequential implementation of the following operations. Certain amounts of at least one hydrocarbon solvent, for example, toluene and a suspension or solution of one or more organoaluminum activators in at least one hydrocarbon solvent, for example, toluene, are sequentially introduced into the reactor, the mixture is saturated with ethylene (creating a constant value of ethylene excess pressure from 0.01 to 10 ati) at a certain temperature (from 10 to 120°C) and then at least one component of the catalyst of general formula 1 is introduced, in the form of a suspension or solution in a hydrocarbon solvent, for example, toluene; or sequentially introduce into the reactor certain amounts of a hydrocarbon solvent, for example, toluene, introduce at least one component of the catalyst of general formula 1 , in the form of a suspension or solution in a hydrocarbon solvent, for example, toluene, saturate the mixture with ethylene (creating a constant value of excess pressure of ethylene from 0.01 up to 10 ati) at a certain temperature (from 10 to 120°C) and then a suspension or solution of one or more organoaluminum activators is introduced in at least one hydrocarbon solvent, for example, toluene. The concentration of the catalyst component of general formula 1 in the catalytic system is in the range from 0.1 to 100 µmol/l, preferably from 10 to 40 µmol/l, the Al/Co molar ratio is in the range from 100 to 5000, preferably 500-3500. The catalyst is then ready to be used for the polymerization of ethylene.

In accordance with the present invention, it is proposed to use a catalyst component - a compound of general formula 1 , a catalyst containing the specified component, for the polymerization of ethylene into a linear polyethylene wax containing terminal vinyl groups, with a narrow MWD, described as a method for producing a linear polyethylene wax containing terminal vinyl groups. groups with narrow MWD.

The method for producing a narrow MWD linear vinyl-terminated polyethylene wax of the present invention includes the step of polymerizing ethylene in the presence of the catalyst described in the present invention.

The polymerization to obtain a linear polyethylene wax containing terminal vinyl groups with a narrow MWD is carried out under the following conditions: temperature in the range from 10 to 120°C, preferably from 30 to 80°C, ethylene pressure in the range from 1 to 15 atm, preferably from 1 to 10 ati, the duration of the process is in the range from 10 minutes to 8 hours, preferably from 30 minutes to 5 hours, the rotation speed of the paddle mixer is in the range from 50 to 2000 rpm, preferably from 100 to 1000 rpm.

The described catalytic system based on compounds of general formula 1 under optimal external polymerization conditions has an activity of 0.28...39 _tpe /mol _Co h and makes it possible to obtain unimodal linear polyethylene wax with MM 0.57...2.42 kg/mol, MWD 1.8...2.4, melting point 116 …125°C with up to 95% of macromolecules containing terminal vinyl groups. The temperature maximum efficiency of the catalytic system based on the compounds of General formula 1 is in the range of 60-70°C. The set of indicators of the catalytic system based on the compounds of General formula 1 is superior to the prototype catalytic system based on compounds of General formula B [28] .

The synthesis of bisaryliminopyridine complexes of cobalt dichloride, having the structure represented by the general formula 1 , was carried out according to a one-stage scheme, including the condensation of 2-acetyl-8-oxo-5,6,7,8-tetrahydroquinoline with 2-R ¹ -4-R ² -6 -cycloalkylanilines or their hydrochlorides in the presence of anhydrous cobalt dichloride CoCl ₂ according to a unified method.

Synthesis {2-[1-(2-R ^one -4-R ² -6-cycloalkylphenylimino)ethyl]-8-(2-R ^one -4-R ² -6-cycloal-kylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt (II) dichlorides. General methodology.

A mixture of 1.0 mmol (0.190 g) 2-acetyl-8-oxo-5,6,7,8-tetrahydroquinoline, 2.0 mmol 2-R ¹ -4-R ² -6-cycloalkylaniline hydrochloride, 0.9 mmol (0.117 g) anhydrous dichloride cobalt CoCl ₂ , and 20 ml of anhydrous acetic acid were boiled with stirring under reflux for 3...4 h, the volume of the reaction mass was reduced by half, distilling acetic acid in a vacuum (15...18 mm Hg). After the reaction mixture was cooled to room temperature, 100 ml of diethyl ether was added, the precipitate was filtered off, washed on the filter with diethyl ether (3 × 15 ml), and kept in a vacuum. Received target {2-[1-(2-R ¹ -4-R ² -6-cycloalkylphenylimino)ethyl]-8-(2-R ¹ -4-R ² -6-cycloalkylphenylimino)-5.6, 7,8-tetrahydroquinoline}cobalt(II) dichloride.

{2-[1-(2-methyl-6-cyclopentylphenylimino)ethyl]-8-[2-methyl-6-cyclopentylphenylimino]-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride (1- I). Green powder. Yield 77%. IR spectrum (KBr), ν, cm ^-1 : 2949 (s.), 2864 (av.), 1620 (v _C=N , s.), 1582 (s.), 1451 (s.), 1368 (av. .), 1242 (s.), 1211 (s.), 1192 (s.), 1133 (s.), 1040 (s.), 927 (s.), 777 (s.). Found, %: C 66.01; H 6.89; No. 6.52. C ₃₅ H ₄₁ Cl ₂ CoN ₃ (633.57). Calculated, %: C, 66.35; H, 6.52; N, 6.63.

{2-[1-(2-methyl-6-cyclohexylphenylimino)ethyl]-8-[2-methyl-6-cyclohexylphenylimino]-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride (1- II). Green powder. Yield 59%. IR spectrum (KBr), ν, cm ^-1 : 2922 (s.), 2850 (av.), 1622 (v _C=N , av.), 1583 (av.), 1470 (av.), 1447 (s .), 1370 (cf.), 1266 (c.), 1246 (c.), 1189 (cf.), 1131 (cf.), 1041 (cf.), 927 (cf.), 781 (cf.) . Found, %: C 67.39; H 6.99; N 6.02. C ₃₇ H ₄₅ Cl ₂ CoN ₃ (661.62). Calculated, %: C, 67.17; H, 6.86; N, 6.35.

{2-[1-(2-methyl-6-cyclooctylphenylimino)ethyl]-8-[2-methyl-6-cyclooctylphenylimino]-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride (1- III). Green powder. Yield 64%. IR spectrum (KBr), ν, cm ^-1 : 2913 (s.), 2863 (s.), 1622 (v _C=N , s.), 1585 (s.), 1467 (av.), 1448 (av. .), 1371 (cf.), 1267 (cf.), 1245 (cf.), 1157 (cf.), 1040 (cf.), 927 (cf.), 837 (cf.), 772 (cf.) . Found, %: C 68.39; H 7.36; N 6.02. C ₄₁ H ₅₃ Cl ₂ CoN ₃ (717.73). Calculated, %: C, 68.61; H, 7.44; N, 5.85.

{2-[1-(2,4-dimethyl-6-cyclopentylphenylimino)ethyl]-8-[2,4-dimethyl-6-cyclopentylphenylimino]-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride (1-IV). Green powder. Yield 60%. IR spectrum (KBr), ν, cm ^-1 : 2947 (s.), 2864 (av.), 1621 (v _C=N , s.), 1557 (s.), 1541 (av.), 1476 (s .), 1449 (s.), 1370 (cf.), 1248 (s.), 1209 (cf.), 1141 (cf.), 1038 (sl.), 928 (sl.), 855 (s.) , 769 (f.). Found, %: C 66.89; H 6.99; No. 6.54. C ₃₇ H ₄₅ Cl ₂ CoN ₃ (661.62). Calculated, %: C, 67.17; H, 6.86; N, 6.35.

{2-[1-(2,4-dimethyl-6-cyclohexylphenylimino)ethyl]-8-(2,4-dimethyl-6-cyclohexylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride (1-V). Green powder. Yield 54%. IR spectrum (KBr), ν, cm ^-1 : 2922 (s.), 2850 (av.), 1628 (v _C=N , av.), 1584 (av.), 1567 (av.), 1473 (av. .), 1448 (s.), 1369 (cf.), 1268 (cf.), 1244 (s.), 1204 (cf.), 1149 (cf.), 1041 (cf.), 926 (f.) , 852 (p.), 769 (f.). Found, %: C 68.29; H 7.02; N 6.02%. C ₃₉ H ₄₉ Cl ₂ CoN ₃ (689.68). Calculated, %: C, 67.92; H, 7.16; N, 6.09.

{2-[1-(2,4-dimethyl-6-cyclooctylphenylimino)ethyl]-8-(2,4-dimethyl-6-cyclooctylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride (1-VI). Green powder. Yield 56%. IR spectrum (KBr), ν, cm ^-1 : 2914 (s.), 2856 (av.), 1623 (v _C=N , s.), 1583 (av.), 1471 (av.), 1446 (av. .), 1368 (Wed), 1236 (Wed), 1146 (Wed), 1075 (Wed), 1043 (Wed), 923 (Wed), 857 (Wed), 731 (Wed) . Found, %: C 69.39; H 7.56; N 5.77%. C ₄₃ H ₅₇ Cl ₂ CoN ₃ (745.78). Calculated, %: C, 69.25; H, 7.70; N, 5.63.

The following examples 1-43 illustrate embodiments of a specific catalyst system for the production of linear vinyl-terminated polyethylene wax. These examples should not be construed as limiting the scope of the invention. Process conditions in examples 1...43: the total volume of toluene, a solution of an organoaluminum activator and a solution of the complex - 100 ml, temperature, molar ratio Al/Co, ethylene pressure are presented in Table 1. In examples 1...22, a solution of methylalumoxane MAO is used as an organoaluminum activator (1.46 M in toluene, Albemarle), in examples 23 ... 43 - a solution of modified methylalumoxane MMAO-3A (1.93 M in heptane, Albemarle).

MW and molecular weight distribution for the resulting polyethylenes were determined on a PL-GPC 220 instrument at 150°C (solvent - 1,2,4-trichlorobenzene), T _pl and heat of fusion were determined using a Perkin Elmer DSC-7 instrument. The 1H and 13C NMR spectra ^of the obtained polyethylenes were recorded ^on a Bruker DMX 300 MHz spectrometer at 100°C in 1,1,2,2-tetrachloroethane-d ₂ . The data of the NMR spectra confirm the high linearity of the obtained polyethylenes. The mole fraction of macromolecules containing terminal vinyl groups was calculated using the formula X = 3/(1.5 + N), where N is the ratio of the integrated signal intensity in the 1H NMR spectrum at 0.96 ^ppm . and 5.00 ppm corresponding to the terminal methyl groups and terminal methylidene groups. For example, for the wax in example 4, the mole fraction X = 0.95 (N = 3.68/2.00; see Fig. 1), for the wax in example 26, the mole fraction X = 0.90 (N = 2.50/2.12; see Fig. 2).

Example 1

Water with a temperature of 30.0°С. The reactor is evacuated to a residual pressure below 3.0×10 ^-2 mm Hg, the vacuum supply is shut off, and the reactor is filled with high purity argon grade 6.0. Vacuuming and filling the reactor with argon is repeated 2 more times. The reactor is evacuated again, the vacuum supply is shut off, and the reactor is filled with ethylene (OWC 99.99%). 25 ml of toluene, a solution of 0.00132 g (2.0 μmol) of complex 1-II in 25 ml of toluene, a mixture of 4.11 ml of a solution of MAO in toluene with a concentration of 1.46 mol/l, and 45.89 ml of toluene are loaded into the reactor with stirring. The molar ratio Al/Co = 3000, the temperature of the catalytic system is 30.0°C. Increase the rotation speed of the stirrer shaft to 500 rpm, this completes the preparation of the catalyst. Ethylene is supplied from the gas line to the reactor until a pressure of 10 atm is established. and the pressure of ethylene is maintained constant for 0.5 hours at 50.0°C. At the end of the exposure, the supply of ethylene to the reactor is automatically stopped, ethylene is vented into the ventilation duct. Deactivation of the catalytic system is carried out by introducing a mixture of 100 ml of ethanol with 10 ml of concentrated hydrochloric acid. The polymer is filtered off, washed with water until neutral and there is no chloride ion in the filtrate. The wet polymer is washed with ethanol (2 x 50 ml) and dried in vacuo to constant weight at 50-60°C. The characteristics of the catalytic system are given in the Table.

Examples 2-43

The catalyst is prepared analogously to example 1, but under the conditions presented in the Table. The characteristics of the catalytic system are given in the Table.

Table 1. Polymerization of ethylene in the presence of 2.0 µmol of compound 1 in toluene.

Example No. Complex Activator Al/Co Pressure, atm. Temperature, °C τ _pol. , min Yield, g Activity, _tpe /mol _Co h M _w , kg/mol M _w /M _n T _pl. , °С one 1-II MAO 3000 10 thirty thirty 5.50 5.50 2.07 2.14 122.8 2 1-II MAO 3000 10 40 thirty 8.95 8.95 1.64 1.96 121.8 3 1-II MAO 3000 10 50 thirty 11.70 11.70 1.59 2.13 122.8 4 1-II MAO 3000 10 60 thirty 13.70 13.70 1.57 2.20 122.5 5 1-II MAO 3000 10 70 thirty 11.80 11.80 1.39 2.06 121.1 6 1-II MAO 3000 10 80 thirty 9.09 9.09 1.42 2.05 120.8 7 1-II MAO 3000 10 90 thirty 6.75 6.75 1.29 1.93 121.5 eight 1-II MAO 2500 10 60 thirty 1.19 1.19 1.49 1.80 123.0 9 1-II MAO 2750 10 60 thirty 5.62 5.62 1.36 1.96 122.7 10 1-II MAO 3250 10 60 thirty 7.23 7.23 1.63 2.09 118.7 eleven 1-II MAO 3500 10 60 thirty 6.83 6.83 1.58 2.07 122.9 12 1-II MAO 3000 10 60 5 6.45 38.70 1.51 2.04 117.7 thirteen 1-II MAO 3000 10 60 15 9.10 18.20 1.48 2.12 117.6 14 1-II MAO 3000 10 60 45 13.98 9.32 1.53 2.20 117.8 15 1-II MAO 3000 10 60 60 14.24 7.12 1.48 2.14 121.5 sixteen 1-II MAO 3000 5 60 thirty 7.75 7.75 1.40 2.10 121.5 17 1-II MAO 3000 one 60 thirty 0.49 0.49 1.07 2.32 119.0 eighteen 1-I MAO 3000 10 60 thirty 6.61 6.61 1.70 2.03 123.1 nineteen 1-III MAO 3000 10 60 thirty 15.70 15.70 1.89 2.29 123.0 twenty 1-IV MAO 3000 10 60 thirty 17.10 17.10 1.08 2.09 121.5 21 1-V MAO 3000 10 60 thirty 13.50 13.50 0.57 1.94 116.1 22 1-VI MAO 3000 10 60 thirty 9.15 9.15 0.74 2.43 124.4 23 1-II MMAO 2000 10 thirty thirty 2.62 2.62 2.39 2.37 122.8 24 1-II MMAO 2000 10 40 thirty 3.37 3.37 2.32 2.32 122.6 25 1-II MMAO 2000 10 50 thirty 6.35 6.35 1.72 2.15 121.5 26 1-II MMAO 2000 10 60 thirty 10.20 10.20 1.48 2.16 121.5 27 1-II MMAO 2000 10 70 thirty 4.07 4.07 1.44 2.00 122.1 28 1-II MMAO 2000 10 80 thirty 0.34 0.34 1.78 1.97 124.7 29 1-II MMAO 1500 10 60 thirty 6.85 6.85 1.37 2.12 122.3 thirty 1-II MMAO 1750 10 60 thirty 7.64 7.64 1.37 2.02 121.3 31 1-II MMAO 2250 10 60 thirty 9.38 9.38 1.47 2.15 121.5 32 1-II MMAO 2500 10 60 thirty 7.28 7.28 1.65 2.16 121.6 33 1-II MMAO 2000 10 60 5 4.52 27.10 1.08 2.05 121.3 34 1-II MMAO 2000 10 60 15 9.10 18.20 1.39 2.19 117.9

End of Table 1.

Example No. Complex Activator Al/Co Pressure, atm. Temperature, °C τ _pol. , min Yield, g Activity, _tpe /mol _Co h M _w , kg/mol M _w /M _n T _pl ., °С 35 1-II MMAO 2000 10 60 45 12.69 8.46 1.27 2.17 121.2 36 1-II MMAO 2000 10 60 60 13.00 6.50 1.53 2.18 121.7 37 1-II MMAO 2000 5 60 thirty 4.07 4.07 1.31 1.91 121.9 38 1-II MMAO 2000 one 60 thirty 0.28 0.28 1.64 1.87 119.0 39 1-I MMAO 2000 10 60 thirty 5.53 5.53 1.82 2.03 123.0 40 1-III MMAO 2000 10 60 thirty 11.30 11.30 2.26 2.25 123.4 41 1-IV MMAO 2000 10 60 thirty 8.18 8.18 1.94 2.17 122.0 42 1-V MMAO 2000 10 60 thirty 11.70 11.70 1.54 2.02 117.4 43 1-VI MMAO 2000 10 60 thirty 8.73 8.73 2.42 2.28 123.6

Claims (11)

1. A component of the catalyst for the polymerization of ethylene, namely - {2-[1-(2-R ¹ -4-R ² -6-cycloalkylphenylimino)ethyl]-8-(2-R ¹ -4-R ² -6-cycloalkylphenylimino )-5,6,7,8-tetrahydro-quinoline}cobalt(II) dichloride having the structure represented by the general formula 1, in which the cycloalkyl substituent is selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl , cyclodecyl, cycloundecyl and cyclododecyl (i.e. k = 1…10); and the substituents R ¹ and R ² are independently selected from the group consisting of C ₁ ... C ₄₀ alkyls and a hydrogen atom, where the alkyl substituent is understood to be a monovalent substituent having the composition C _n H _2n+1 (n is an integer 1 ... 40 )

2. A catalyst for the polymerization of ethylene, comprising at least one compound of general formula 1 according to claim 1, at least one organoaluminum activator of any structure, optionally ethylene, and at least one hydrocarbon solvent. 3. The catalyst according to claim 2, where the compound of general formula 1 is selected from the group containing: {2-[1-(2-methyl-6-cyclopentylphenylimino)ethyl]-8-(2-methyl-6-cyclopentylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride; {2-[1-(2-methyl-6-cyclohexylphenylimino)ethyl]-8-(2-methyl-6-cyclohexylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride; {2-[1-(2-methyl-6-cyclooctylphenylimino)ethyl]-8-(2-methyl-6-cyclooctylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride; {2-[1-(2,4-dimethyl-6-cyclopentylphenylimino)ethyl]-8-(2,4-dimethyl-6-cyclopentylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride; {2-[1-(2,4-dimethyl-6-cyclohexylphenylimino)ethyl]-8-(2,4-dimethyl-6-cyclohexylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride; {2-[1-(2,4-dimethyl-6-cyclooctylphenylimino)ethyl]-8-(2,4-dimethyl-6-cyclooctylphenylimino)-5,6,7,8-tetrahydroquinoline}cobalt(II) dichloride. 4. Catalyst according to claim 2, characterized in that the organoaluminum activator is methylalumoxane (MAO), modified variants of MAO (including, but not limited to, improved polymethylalumoxane, referred to as PMAO-IP; modified methylalumoxane type 3A, referred to as MMAO-3A; modified methylalumoxane type 12, referred to as MMAO-12), as well as trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-butyl-aluminum, tri-n-hexylaluminum, tri-n -octylaluminum, dimethylaluminum chloride (DMAC), diethylaluminum chloride (DEAC), diisobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride and other similar compounds or mixtures thereof in any combination. 5. The catalyst according to claim 2, characterized in that the hydrocarbon solvent is selected from individual aliphatic, alicyclic, alkylaromatic or aromatic compounds, their technical mixtures in any combination. 6. The catalyst according to claim 2, characterized in that the concentration of the catalyst component according to claim 1 is in the range from 0.1 to 100 µmol/l, preferably from 10 to 40 µmol/l, the Al/Co molar ratio is in the range from 100 to 5000, preferably 500-3500. 7. The catalyst according to paragraphs. 2-6, characterized in that it is used for the polymerization of ethylene to obtain a linear polyethylene wax containing terminal vinyl groups with a narrow MWD under the following conditions: polymerization temperature in the range from 10 to 120°C, preferably 30-80°C, ethylene pressure in the range from 1 to 15 ati, preferably from 1 to 10 ati, the duration of the polymerization process in the range from 10 minutes to 8 hours, preferably from 30 minutes to 5 hours, the speed of rotation of the paddle mixer in the range from 50 to 2000 rpm, preferably from 100 to 1000 rpm. 8. The method of preparation of the catalyst according to any one of paragraphs. 2-7, which includes mixing in any sequence a suspension or solution of at least one compound of general formula 1, a suspension or solution of at least one organoaluminum activator, optionally in the presence of ethylene in an environment of at least one hydrocarbon solvent. 9. The method according to p. 8, characterized in that when mixed in the presence of ethylene, the suspension or solution of the organoaluminum activator is saturated with ethylene at an excess pressure of ethylene from 0.01 to 10 atm and a temperature from 10 to 120 ° C before adding a suspension or solution of a compound of the general formula 1, or by the fact that a suspension or solution of a compound of general formula 1 is saturated with ethylene at an excess pressure of ethylene from 0.01 to 10 atm and a temperature from 10 to 120°C before adding a suspension or solution of an organoaluminum activator to it.

Images