RU2753862C1 - Iron-containing catalyst component for ethylene polymerization into high-linear polyethylene, thermostable catalyst and method for its preparation - Google Patents

Abstract

FIELD: ethylene polymerization.

SUBSTANCE: invention relates to a catalyst component for the polymerization of ethylene, to a catalyst and a method for producing a catalyst. The catalyst component has the structure represented by the general formula 1, where 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 substituents R¹ and R² are independently selected from the group consisting of alkyl aromatic substituents of the formula CH_3-x(Ar)_x (1 ≤ x ≤ 3) and cycloalkyl substituents C_3-12. The catalyst for the polymerization of ethylene to obtain highly linear polyethylene comprises at least one compound of the general formula 1, at least one organoaluminum activator, optionally ethylene, and at least one hydrocarbon solvent. The method for preparing the catalyst 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 a medium of at least one hydrocarbon solvent.

EFFECT: obtaining a previously undescribed catalyst component and a catalyst containing this component, the temperature maximum of the efficiency of which is in the range 65-75°C, and using it to obtain highly linear polyethylene with a molecular weight of 4-187 kg/mol.

9 cl, 1 tbl, 37 ex

Description

The invention relates to the production of polyethylene, in particular to a catalyst component for ethylene polymerization, to a catalyst (catalytic system) containing this component, a method for its preparation and use for producing highly linear polyethylene with a narrow molecular weight distribution (MWD).

, H.H. Brintzinger, Berlin: Springer, 1995; 2. Polyolefins: 50 years after Ziegler and Natta II. Polyolefins by Metallocenes and Other Single-Site Catalysts / Ed. W. Kaminsky, Berlin: Springer, 2013; 3. Polymers and copolymers of higher α-olefins / Eds. B.A. Krentsel, Y.V. Kissin, V.I. Kleiner, L.L. Stotskaya, Munchen: Carl Hanser Verlag, 1997].The production of linear polyethylene is carried out by the method of ethylene polymerization using certain variants of Ziegler-Natta catalysts (supported, with a low titanium content, etc.) or metallocene complexes of transition metals in the presence of organoaluminum or organoboron compounds-activators [ 1. Ziegler Catalysts / Eds. G. Fink, R.

, HH Brintzinger, Berlin: Springer, 1995; 2. Polyolefins: 50 years after Ziegler and Natta II. Polyolefins by Metallocenes and Other Single-Site Catalysts / Ed. W. Kaminsky, Berlin: Springer, 2013; 3. Polymers and copolymers of higher α-olefins / Eds. BA Krentsel, YV Kissin, VI Kleiner, LL Stotskaya, Munchen: Carl Hanser Verlag, 1997].

The disadvantage of these methods is the fact that the resulting polyethylene contains a certain amount of short-chain branches, the content of which increases with an increase in the polymerization temperature, and to obtain highly linear polyethylene, it is required to carry out the polymerization process at a low temperature of -30 ... + 10 ° C. The disadvantage is also a decrease in the rate of polymerization with a decrease in the temperature of the process. Ziegler-Natta catalysts produce polyethylene with a wide molecular weight distribution, and metallocene catalysts, in addition to the complexity and high cost of their production, are highly sensitive to oxygen, moisture, and polar impurities in the monomer and solvent and require additional measures to purify the monomer and solvent.

A more attractive way to obtain linear polyethylene is the polymerization of ethylene on catalytic systems based on postmetallocene complexes [ 4. Ittel SD, Johnson LK, Brookhart M. Chem. Rev. 2000, V. 100, p. 1169; 5. Oleinik I.I. Chem. int. mouth development 2008, vol. 16, no. 6, p. 747; 6. Oleinik I.I. Advances in the design of postmetallocene catalytic systems of the arylimine type for ethylene polymerization // in the book: Chemistry of aromatic, heterocyclic and natural compounds (NIOCH SB RAS 1958-2008) / ed. ed. ac. V.N. Parmon, Novosibirsk: ZAO IPP "Offset", 2009. - p. 589-620; 7. 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; 8. Small, BL Acc. Chem. Res. 2015, 48, 2599-2611; 9. Wang, Z .; Solan, GA; Zhang, W .; Sun, W.-H. Coord. Chem. Rev. 2018, 363, p. 92-108], due to the ease of synthesis of such complexes, less sensitivity to oxygen, moisture and polar impurities in the monomer and solvent. The advantage of this method is the almost unlimited possibility of obtaining any combination of polymer characteristics by varying the structure of the complex and external conditions.

Known catalytic systems based on bisarylimine complexes of iron and cobalt and organoaluminium compounds capable of producing linear polyethylene [ 10. Ivanchev SS, Tolstikov GA, Badaev VK, Oleinik II, Ivancheva NI. , Rogozin D.G., Oleinik I.V., Myakin S.V. Kinetics and Catalysis, 2004, V. 45, No. 2, p. 192-198; 11. Tolstikov G.A., Ivanchev S.S., Oleinik I.I., Ivancheva N.I., Oleinik I.V. Dokl. AN, 2005, T. 404, No. 2, p. 208-211; 12. Huang F., Zhang W., Yue E., Liang T., Hu X. Sun, W.-H. Dalton Trans. 2016, V. 45, p. 657-666; 13. Huang F., Xing Q., Yang W.-H., Hu X., Sun W.-H. Patent CN 105315309, 02/10/2016; 14. Suo H., Oleynik II, Bariashir C., Oleynik IV, Wang Z., Solan G., Ma Y., Liang T., Sun W.-H. Polymer 2018, V. 149, p. 45-54; 15. Guo J., Wang Z., Zhang W., Oleynik II, Vignesh A., Oleynik IV, Hu X., Sun Y., Sun W.-H. Molecules. 2019, V. 24, ID 1176. 16. Guo J., Zhang W., Oleynik II, Solan GA, Oleynik IV, Liang T., Sun W.-H. Dalton Transactions. 2020 V. 49, p. 136-146]. The advantage of such catalytic systems is that for the production of highly linear polyethylene it is not required to carry out the polymerization process at a low temperature, and a certain proportion of macromolecules contains a terminal vinyl group [ 17. Wang Z., Solan GA, Zhang W., Sun W.-H. Coord. Chem. Rev. 2018, V. 363, p. 92-108].

Close to the proposed invention is an ethylene polymerization catalyst containing a bisimine complex of cobalt chloride with the formula A , where R ¹ and R ^{2 are} independently selected from the group consisting of alkyls with the formula CH ₃ - _{(x + y + z)} (Alk ¹ ) _x (Alk ² ) _y (Alk ³ ) _z (0 ≤ x + y + z ≤ 3), and a hydrogen atom, and the cycloalkyl substituent is selected from the group consisting of cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and cyclododecyl (t i.e. g = 1, 2, 3, 4, 5, 6, 8) [18. Oleinik I.I., Oleinik I.V., Sun Wen-Hua. RF patent 2704263, 10/25/2019 ] , as well as a catalyst containing a bisimine complex of ferric chloride with formula B , where the substituents R ¹ and R ^{2 are} independently selected from the group consisting of alkyls and a hydrogen atom, and the cycloalkyl substituent in the compound of the general formula B is selected from the group consisting of cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and cyclododecyl (i.e. g = 1, 2, 3, 4, 5, 6, 8) [19. Oleinik I.I., Oleinik I.V., Sun Wen-Hua. RF patent 2729622, 08/11/2020 ] .

The catalytic system based on compounds of general formula A , depending on the external conditions of polymerization in the temperature range of 10 ... 80 ° C, has an activity of 0.96 ... 8.12 t _pe / mol _Co × h and makes it possible to obtain a monomodal highly linear polyethylene with a molecular weight of 6.41 ... 25.96 kg / mol, narrow molecular weight distribution 2.00 ... 4.50 and high melting point 128.1 ... 133.7 ° С. The maximum productivity of the catalyst is observed at a temperature of 40 ... 50 ° C [ 18 ].

The catalytic system based on compounds of the general formula B , depending on the external conditions of polymerization, has an activity of 2.9 ... 38.8 t _pe / mol _Fe × h and makes it possible to obtain highly linear polyethylene with an MM of 2.4 ... 166.0 kg / mol, an MWD of 1.7 ... 50.4 and a high melting point of 122.1 ... 133.8 ° C. The maximum productivity of the catalyst is observed at a temperature of 70 ... 80 ° C [ 19 ].

Closest to the proposed invention is an ethylene polymerization catalyst containing a bisimine complex of cobalt chloride with the formula B , where R ¹ and R ^{2 are} independently selected from the group consisting of alkyl aromatic substituents with the formula CH ₃ - _x (Ar) _x (1 ≤ x ≤ 3) and cycloalkyl substituents with the formula C _n H _2n - ₁ (3 ≤ n ≤ 12), and the cycloalkyl substituent at position 6 is selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl (ie k = 1 ... 10) [ 20. Oleinik II, Oleinik IV, Sun Wen-Hua. RF patent 2739765, 28.12.2020 ] .

The described catalytic system based on compounds of general formula B , depending on the external conditions of polymerization in the temperature range of 10 ... 80 ° C in the presence of alkylaluminoxanes (MAO or MMAO), has an activity of 0.04 ... 3.70 t _pe / mol _Co × h and makes it possible to obtain highly linear polyethylene with MM 12.3 ... 598.5 kg / mol, narrow molecular weight distribution 1.08 ... 3.01 and high melting temperature 130.3 ... 136.5 ° С. The maximum productivity of the catalyst is observed at a temperature of 50-60 ° C.

The consumer characteristics of high-linear polyethylene are determined by the value of MM and MMR. With an increase in the molecular mass of highly linear polyethylene, the strength and hardness increase, and the beginning of the plastic flow of such polymers shifts to the region of higher temperatures. As the MWD increases, the physicomechanical properties of the polymer tend to deteriorate, making it easier to process reactor powders by injection molding, extrusion, and extrusion blowing methods. To achieve high efficiency in the industrial production of highly linear polyethylene, it is desirable to have a highly active (high-performance) catalytic system at your disposal, which allows, by varying the external conditions of polymerization, to control the molecular mass of the resulting polymer in a wide range, since in this case the transition to the production of a polymer with a different desired molecular mass is possible without readjustment of production equipment, which is inevitable when replacing the catalytic system. It is desirable that the maximum activity of the catalytic system be in the range of 60 ... 110 ° C, which ensures the optimal operating mode of industrial plants. From this point of view, the disadvantage of the prototype catalyst B is its low activity, which lies in the range of 0.04 ... 3.70 t _pe / mol _Co × h.

Since the problem of producing linear polyethylene with any desired MM is still urgent, the technical problem of the invention is to create a new catalyst component for ethylene polymerization, a new catalyst (catalytic system) containing this component, superior in activity and thermal stability (temperature maximum efficiency) to the prototype and use it for obtaining highly linear polyethylene with MM 4 ... 187 kg / mol, MMR 2.3 ... 4.7 and high melting temperature 126 ... 135 ° С.

The technical result of the invention is to obtain a previously undescribed catalyst component and a catalyst for ethylene polymerization containing this component, the temperature maximum efficiency of which is in the range of 65 ... 75 ° C.

The solution to this problem is achieved by the fact that it is proposed to use previously unknown bisaryliminopyridine complexes of iron dichloride as a catalyst component for the polymerization of ethylene into highly linear polyethylene, namely: {2- [1- (2-R ¹ -4-R ² -6-cycloalkylphenylimino ) ethyl] -9- (2-R ¹ -4-R ² -6-cycloalkylphenylimino) -5,6,7,8-tetrahydro-9H-cyclohepta [b] pyridine} iron (II) dichlorides having the structure shown 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 alkyl aromatic substituents with the formula CH ₃ - _x (Ar) _x (1 ≤ x ≤ 3) and cycloalkyl substituents with the formula C _n H _2n - ₁ (3 ≤ n ≤ 12); where the notation Ar means the monovalent radical of benzene and its homologues with the formula С ₆ H ₅ - _{(y + z)} (Alk ¹ ) _y (Alk ² ) _z (0 ≤ y + z ≤ 5), where the notation Alk ¹ and Alk ² means different C ₁ ... C ₄₀ alkyls, and by alkyl (as well as an alkyl substituent) is meant a monovalent substituent having the composition C _m H _{2m + 1} ; (x, y, z, n, m are integers).

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 (ie, k = 1 ... 10).

Preferred combinations of R ¹ , R ² and cycloalkyl substituents include: R ¹ = diphenylmethyl, R ² = diphenylmethyl, cycloalkyl = cyclopentyl ( I ); R ¹ = diphenylmethyl, R ² = diphenylmethyl, cycloalkyl = cyclohexyl ( II ); R ¹ = diphenylmethyl, R ² = diphenylmethyl, cycloalkyl = cyclooctyl ( III ); R ¹ = diphenylmethyl, R ² = diphenylmethyl, cycloalkyl = cyclododecyl ( IV ); R ¹ = cyclopentyl, R ² = diphenylmethyl, cycloalkyl = cyclopentyl ( V ). Further in the text, to designate a specific bisaryliminopyridine complex of iron dichloride, a two-link code is used, for example 1 - II , referring to a compound of general formula 1 with R ¹ = CH (C ₆ H ₅ ) ₂ , R ² = CH (C ₆ H ₅ ) ₂ , cycloalkyl = cyclohexyl (combination II ), i.e. to {2- [1- (2,4-bis (diphenylmethyl) -6-cyclohexylphenylimino) ethyl] -9- (2,4-bis (diphenylmethyl) -6-cyclohexylphenylimino) -5,6,7,8-tetrahydro -9H-cyclohepta [b] pyridine} iron (II) dichloride.

To achieve the specified technical result, a new catalyst (catalytic system) for polymerization of ethylene into highly linear polyethylene is also proposed, comprising 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- (2,4-bis (diphenylmethyl) -6-cyclopentylphenylimino) ethyl] -9- [2,4-bis (diphenylmethyl) -6-cyclopentylphenylimino] -5,6,7,8-tetrahydro-9H-cyclohepta [b] pyridine} iron (II) dichloride; {2- [1- (2,4-bis (diphenylmethyl) -6-cyclohexylphenylimino) ethyl] -9- [2,4-bis (diphenylmethyl) -6-cyclohexylphenylimino] -5,6,7,8-tetrahydro- 9H-cyclohepta [b] pyridine} iron (II) dichloride; {2- [1- (2,4-bis (diphenylmethyl) -6-cyclooctylphenylimino) ethyl] -9- [2,4-bis (diphenylmethyl) -6-cyclooctylphenylimino] -5,6,7,8-tetrahydro- 9H-cyclohepta [b] pyridine} iron (II) dichloride; {2- [1- (2,4-bis (diphenylmethyl) -6-cyclododecylphenylimino) ethyl] -9- [2,4-bis (diphenylmethyl) -6-cyclododecylphenylimino] -5,6,7,8-tetrahydro- 9H-cyclohepta [b] pyridine} iron (II) dichloride; {2- [1- (4-diphenylmethyl-2,6-dicyclopentylphenylimino) ethyl] -9- (4-diphenylmethyl-2,6-dicyclopentylphenylimino) -5,6,7,8-tetrahydro-9H-cyclohepta [b] pyridine} iron (II) dichloride.

As the organoaluminum activator, at least one organoaluminum compound is used, specific examples of which include methylaluminoxane (MAO), modified versions of MAO (including, but not limited to, polymethylalumoxane with improved characteristics, designated by the manufacturers as PMAO-IP; modified methylalumoxane type 3A, designated as a MMAO-3A, modified methylaluminoxane type 12, designated as MMAO-12) and trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n -butilalyuminy, tri- n -geksilalyuminy, tri- n - octylaluminum, dimethylaluminum chloride (DMAX), diethylaluminum chloride (DEAC), diisobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride. Can be used and other similar organoaluminum compounds or mixtures thereof in any combination.

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, trimethylbenzene camphene, tetralin, gasoline, naphtha, kerosene. Solvents can be used singly or in combination of two or more solvents.

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

The method for preparing the catalyst in accordance with the present invention includes contacting at least one compound of general formula 1 with at least one organoaluminum activator, optionally in the presence of ethylene in the medium 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 can 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 portions 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 immediately or in portions to a 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 contacting, ease of loading and dosing, it is preferable to carry out contacting the compound of general formula 1 taken in the form of a suspension or solution in at least one hydrocarbon solvent with a solution or suspension of an organoaluminum activator in a hydrocarbon solvent. The contacting of 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 an organoaluminum activator is saturated with ethylene at an overpressure of ethylene from 0.01 to 10 ati and temperatures 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 overpressure of ethylene from 0.01 to 10 atm and a temperature from 10 to 120 ° C. In the case where a combination of two or more compounds of general formula 1 is used , they can be added separately in any order or as a mixture of two or more components taken in the form of a suspension or solution. In the case where a combination of two or more organoaluminum activators is used, they can be added separately in any order or as a mixture of two or more components taken in the form of a suspension or solution, not necessarily in the presence of ethylene.

A preferred embodiment of the method for preparing a catalyst in accordance with the present invention consists in 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, and then at least one catalyst component described by the general formula 1 , in the form of a suspension or solution in a hydrocarbon solvent, for example, toluene, or sequentially injected into the reactor certain amounts of at least one hydrocarbon solvent, for example, toluene, one or more catalyst components described by the general formula 1 , in the form of a suspension or solution in a hydrocarbon solvent such as toluene, and then a solution of one or more organoaluminum activators in a hydrocarbon solvent such as toluene is introduced. Then the mixture is saturated with ethylene (creating a constant overpressure of ethylene from 1.0 to 10 atm) at a certain temperature (from 10 to 120 ° C). The concentration of the catalyst component of the 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 molar ratio of Al / Fe is in the range from 100 to 5000, preferably 500-3000. The catalyst is then ready to be used for ethylene polymerization.

Another preferred embodiment of the method for preparing the catalyst in accordance with the present invention consists in the sequential implementation of the following steps. 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 the overpressure of ethylene from 0.01 to 10 atm) at a certain temperature (from 10 to 120 ° C) and then add 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; 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 overpressure of ethylene from 0.01 up to 10 atm) at a certain temperature (from 10 to 120 ° C) and then a suspension or a solution of one or more organoaluminum activators in at least one hydrocarbon solvent, for example, toluene, is introduced. The concentration of the catalyst component of the 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 molar ratio of Al / Fe is in the range from 100 to 5000, preferably 500-3000. The catalyst is then ready to be used for ethylene polymerization.

In accordance with the present invention, there is proposed the use of a catalyst component - a compound of general formula 1 , a catalyst containing said component for the polymerization of ethylene to a highly linear polyethylene with a narrow MWD, described as a method for producing a highly linear polyethylene with a narrow MWD.

The method for producing highly linear polyethylene with narrow MWD according to the present invention includes the step of polymerizing ethylene in the presence of the catalyst described in the present invention.

Polymerization to obtain a highly linear polyethylene 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 atm, duration process in the range from 10 minutes to 8 hours, preferably from 30 minutes to 5 hours, the rotation speed of the paddle mixer 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 conditions of polymerization has an activity of 0.3 ... 24 t _pe / mol _Fe × h and makes it possible to obtain unimodal highly linear polyethylene with MM 4 ... 187 kg / mol, MMR 2.3 ... 4.7, high melting point 126 ... 135 ° C. The temperature maximum of the efficiency of the catalytic system based on compounds of general formula 1 is in the range 65 ... 75 ° C. In terms of the totality of indicators, the catalytic system based on compounds of general formula 1 is superior to the catalytic system-prototype based on compounds of general formula B [20] .

The synthesis of bisaryliminopyridine complexes of iron dichloride having a structure represented by general formula 1 was carried out according to a one-step scheme, including the condensation of 2-acetyl-5,6,7,8-tetrahydro-9H-cyclohepta [b] pyridin-9-one with 2-R ¹ -4-R ² -6-cycloalkylanilines or their hydrochlorides in the presence of iron dichloride tetrahydrate FeCl ₂ × 4H ₂ O according to a unified procedure.

Synthesis of {2 - [1 - (2 - R ¹ - 4 - R ² - 6 - cycloalkylphenylimino) ethyl] - 9 - (2 - R ¹ - 4 - R ² - 6 - cycloalkylphenylimino) - 5,6,7,8 - tetrahydro - 9H - cyclohepta [b] pyridine} iron (II) dichlorides. General methodology.

A mixture of 1.0 mmol (0.204 g) of 2-acetyl-5,6,7,8-tetrahydro-9H-cyclohepta [b] pyridin-9-one, 2.2 mmol of 2-R ¹ -4-R ² -6-cycloalkylaniline, 1.0 mmol (0.199 g) of iron dichloride tetrahydrate FeCl ₂ × 4H ₂ O, and 60 ml of anhydrous acetic acid were boiled with stirring under reflux for 3 ... 4 h, the volume of the reaction mass was halved by distilling off acetic acid in vacuum (15 ... 18 mm rt.st.). After cooling the reaction mixture to room temperature, 100 ml of diethyl ether was added, the precipitate was filtered off, washed on the filter with diethyl ether (4 × 15 ml), and kept in vacuum. Received target {2- [1- (2-R ¹ -4-R ² -6-cycloalkylphenylimino) ethyl] -9- (2-R ¹ -4-R ² -6-cycloalkylphenylimino) -5,6,7, 8-tetrahydro-9H-cyclohepta [b] pyridine} iron (II) dichloride.

{2 - [1 - (2,4 - bis (diphenylmethyl) - 6 - cyclopentylphenylimino) ethyl] - 9 - [2,4 - bis (diphenylmethyl) - 6 - cyclopentylphenylimino] - 5,6,7,8 - tetrahydro - 9H - cyclohepta [b] pyridine} iron (II) dichloride (1 - I). Green powder. The yield is 53%. IR spectrum (KBr), ν, cm ^-1 : 3025 (w), 2946 (m), 2865 (w), 1598 (m, ν _{C = N} ), 1569 (m), 1492 (s .), 1448 (c.), 1030 (c.), 840 (f.), 744 (c.), 698 (c.), 613 (c.). Found,%: C 80.44; H 6.16; N 3.40. C ₈₆ H ₇₉ Cl ₂ FeN ₃ (1281.34). Calculated,%: C, 80.61; H, 6.21; N, 3.28.

{2 - [1 - (2,4 - bis (diphenylmethyl) - 6 - cyclohexylphenylimino) ethyl] - 9 - [2,4 - bis (diphenylmethyl) - 6 - cyclohexylphenylimino] - 5,6,7,8 - tetrahydro - 9H - cyclohepta [b] pyridine} iron (II) dichloride (1 - II). Green powder. Yield 58%. IR spectrum (KBr), ν, cm ^-1 : 3025 (w), 2927 ( _{m), 1599 (m, ν C = N} ), 1572 (m), 1493 (s), 1447 (s .), 1261 (c.), 1030 (c.), 744 (c.), 698 (c.), 614 (c.). Found,%: C 80.48; H 6.33; N 3.44. C ₈₈ H ₈₃ Cl ₂ FeN ₃ (1309.40). Calculated,%: C, 80.72; H, 6.39; N, 3.21.

{2 - [1 - (2,4 - bis (diphenylmethyl) - 6 - cyclooctylphenylimino) ethyl] - 9 - [2,4 - bis (diphenylmethyl) - 6 - cyclooctylphenylimino] - 5,6,7,8 - tetrahydro - 9H - cyclohepta [b] pyridine} iron (II) dichloride (1 - III). Green powder. The yield is 62%. IR spectrum (KBr), ν, cm ⁻¹ : 3025 (w), 2916 (m), 2854 (m), 1599 (m, ν _{C = N} ), 1572 (s), 1493 (s .), 1446 (c.), 1261 (c.), 1030 (c.), 744 (c.), 697 (c.), 613 (c.). Found,%: C 80.71; H 6.90; N 3.12. C ₉₂ H ₉₁ Cl ₂ FeN ₃ (1365.51). Calculated,%: C, 80.92; H, 6.72; N, 3.08.

{2 - [1 - (2,4 - bis (diphenylmethyl) - 6 - cyclododecylphenylimino) ethyl] - 9 - [2,4 - bis (diphenylmethyl) - 6 - cyclododecylphenylimino] - 5,6,7,8 - tetrahydro - 9H - cyclohepta [b] pyridine} iron (II) dichloride (1 - IV). Green powder. The yield is 40%. IR spectrum (KBr), ν, cm ^-1 : 3025 (w), 2924 (m), 2856 (w), 1601 (m, ν _{C = N} ), 1571 (s), 1494 (s .), 1030 (c.), 744 (c.), 699 (c.), 614 (c.). Found,%: C 81.38; H 7.22; N 3.04. C ₁₀₀ H ₁₀₇ Cl ₂ FeN ₃ (1477.72). Calculated,%: C, 81.28; H, 7.30; N, 2.84.

{2 - [1 - (4 - diphenylmethyl - 2,6 - dicyclopentylphenylimino) ethyl] - 9 - (4 - diphenylmethyl - 2,6 - dicyclopentylphenylimino) - 5,6,7,8 - tetrahydro - 9H - cyclohepta [b] pyridine} -iron (II) dichloride (1 - V). Green powder. The yield is 55%. IR spectrum (KBr), ν, cm ^-1 : 3025 (w), 2948 (m), 2864 (m), 1598 (m, ν _{C = N} ), 1569 (s), 1491 (s .), 1029 (c.), 742 (c.), 700 (c.), 619 (c.). Found,%: C 77.76; H 6.80; N 3.52%. C ₇₀ H ₇₅ Cl ₂ FeN ₃ (1085.14). Calculated,%: C, 77.48; H, 6.97; N, 3.87.

The following examples 1 ... 37 illustrate options for a specific embodiment of the catalyst system for obtaining high linearity polyethylene. These examples should not be construed as limiting the scope of the invention. Process conditions in examples 1 ... 37: total volume of toluene, organoaluminum activator solution and complex solution - 100 ml, temperature, Al / Fe molar ratio, ethylene pressure are presented in Table 1. In examples 1 ... 18, a modified methylalumoxane solution is used as an organoaluminum activator MMAO-3A (1.93 M in heptane, Albemarle), in examples 19 ... 37 - a solution of methylaluminoxane MAO (1.46 M in toluene, Albemarle).

MW and molecular weight distribution for the obtained polyethylenes were determined on a PL-GPC 220 instrument at 150 ° C (solvent - 1,2,4-trichlorobenzene), _Tm and heat of fusion were determined using a Perkin Elmer DSC-7 instrument. ^{The 1} H and ¹³ C 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 NMR spectra data and the values of the temperature and heat of fusion confirm the high linearity of the obtained polyethylenes.

Example 1

In the jacket of a stainless steel reactor with a volume of 250 ml, equipped with a thermocouple in the bottom and a lid with an installed magnetic drive of a paddle stirrer, controlled by a remote controller, and fittings connecting the reactor with a pressure sensor of a gas controller, a vacuum-gas line, water is supplied from the thermostat with a temperature 50.0 ° C. The reactor was evacuated to a residual pressure below 3.0 × 10- ² mm Hg, the vacuum supply is shut off and the reactor is filled with argon gas of high purity grade 6.0. The evacuation and filling of the reactor with argon are repeated 2 more times. The reactor is evacuated again, the vacuum supply is shut off, and the reactor is filled with ethylene (COV 99.99%). Into the reactor with stirring load 25 ml of toluene, a solution of 0.00262 g (2.0 μmol) of complex 1 - II in 25 ml of toluene, a mixture of 2.07 ml of a solution of MMAO-3A in heptane with a concentration of 1.93 mol / L and 47.93 ml of toluene. The molar ratio Al / Fe = 2000, the temperature of the catalytic system is 50.0 ° C. The speed of rotation of the stirrer shaft is increased to 500 rpm, at which the preparation of the catalyst is completed. Ethylene is fed from the gas line to the reactor until a pressure of 10 atm is established, and the ethylene pressure is maintained constant for 0.5 hour at 50.0 ° C. At the end of the holding, the supply of ethylene to the reactor is automatically stopped, ethylene is released 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 no chloride ion in the filtrate. The wet polymer is washed with ethanol (2 × 50 ml) and dried under vacuum to constant weight at 50-60 ° C. The characteristics of the catalytic system are shown in the Table.

Examples 2 - 37

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

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

Example No. Complex Activator Al / Fe Pressure, ati Temperature, ° С τ _floor , min Output, g Activity, t _pe / mol _Fe × h M _w , kg / mol M _w / M _n T _pl , ° С 1 1-II MMAO 2000 ten 50 thirty 4.20 4.20 7.00 2.7 127.4 2 1-II MMAO 2000 ten 60 thirty 7.90 7.90 9.40 3.0 128.6 3 1-II MMAO 2000 ten 70 thirty 11.2 11.2 12.2 3.1 130.3 4 1-II MMAO 2000 ten 80 thirty 8.80 8.80 7.20 2.3 127.5 5 1-II MMAO 2000 ten 90 thirty 7.50 7.50 9.30 2.3 126.4 6 1-II MMAO 1000 ten 70 thirty 7.40 7.40 31.1 4.5 132.6 7 1-II MMAO 1500 ten 70 thirty 9.40 9.40 21.8 3.7 131.9 eight 1-II MMAO 2500 ten 70 thirty 9.00 9.00 12.5 3.0 130.1 nine 1-II MMAO 3000 ten 70 thirty 7.80 7.80 9.40 2.8 128.4 ten 1-II MMAO 2000 ten 70 5 3.97 23.8 10.9 2.6 129.3 eleven 1-II MMAO 2000 ten 70 15 7.65 15.3 14.5 3.3 129.9 12 1-II MMAO 2000 ten 70 45 14.9 9.90 41.9 4.7 132.2 13 1-II MMAO 2000 ten 70 60 18.0 9.00 64.8 4.0 132.5 fourteen 1-II MMAO 2000 5 70 thirty 6.40 6.40 9.20 2.8 127.9 15 1-I MMAO 2000 ten 70 thirty 15.3 15.3 27.2 4.2 130.4 16 1-III MMAO 2000 ten 70 thirty 6.40 6.40 14.1 2.9 129.7 17 1-IV MMAO 2000 ten 70 thirty 0.50 0.50 4.60 2.8 125.7 eighteen 1-V MMAO 2000 5 70 thirty 14.6 14.6 37.5 4.0 128.7 19 1-II MAO 2000 ten thirty thirty 2.70 2.70 45.8 2.7 135.0 twenty 1-II MAO 2000 ten 40 thirty 2.90 2.90 90.6 3.0 132.6 21 1-II MAO 2000 ten 50 thirty 3.10 3.10 32.0 3.1 134.6 22 1-II MAO 2000 ten 60 thirty 3.30 3.30 103.5 2.3 131.9 23 1-II MAO 2000 ten 70 thirty 1.20 1.20 25.9 2.3 133.8 24 1-II MAO 2000 ten 80 thirty 1.00 1.00 24.7 4.5 131.1 25 1-II MAO 1000 ten 60 thirty 1.00 1.00 186.8 3.7 135.1 26 1-II MAO 1500 ten 60 thirty 2.90 2.90 41.6 3.0 132.2 27 1-II MAO 2500 ten 60 thirty 4.10 4.10 35.5 2.8 131.7 28 1-II MAO 3000 ten 60 thirty 2.70 2.70 13.6 2.6 130.3 29 1-II MAO 2500 ten 60 5 1.20 7.20 88.9 3.3 133.1 thirty 1-II MAO 2500 ten 60 15 2.80 5.60 52.8 4.7 132.3 31 1-II MAO 2500 ten 60 45 4.35 2.90 44.5 4.0 132.5 32 1-II MAO 2500 ten 60 60 4.80 2.40 71.2 2.8 134.2 33 1-II MAO 2500 5 60 thirty 1.20 1.20 28.8 3.2 133.0 34 1-I MAO 2500 ten 60 thirty 5.30 5.30 55.6 2.9 131.8

End of Table 1.

Example No. Complex Activator Al / Fe Pressure, ati Temperature, ° С τ _floor , min Output, g Activity, t _pe / mol _Fe × h M _w , kg / mol M _w / M _n T _pl , ° С 35 1-III MAO 2500 ten 60 thirty 1.60 1.60 11.2 2.8 131.3 36 1-IV MAO 2500 ten 60 thirty 0.30 0.30 5.10 4.0 129.6 37 1-V MAO 2500 ten 60 thirty 6.00 6.00 25.6 2.7 131.0

Claims (11)

1. Component of the catalyst for ethylene polymerization, namely {2- [1- (2-R ¹ -4-R ² -6-cycloalkylphenylimino) ethyl] -9- (2-R ¹ -4-R ² -6-cycloalkylphenylimino) -5,6,7,8-tetrahydro-9H-cyclohepta [b] pyridine} iron (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 substituents R ¹ and R ^{2 are} independently selected from the group consisting of alkyl aromatic substituents with the formula CH _3-x (Ar) _x (1 ≤ x ≤ 3) and cycloalkyl substituents with the formula C _n H _2n-1 (3 ≤ n ≤ 12), where the notation Ar means the monovalent radical of benzene and its homologues with the formula C ₆ H _{5- (y + z)} (Alk ¹⁾ _y (Alk ²⁾ _z (0 ≤ y + z ≤ 5), wherein under the designation of Alk ¹ and Alk ² are understood differing alkyls C ₁ ... C _40, and under the alkyl (and also alkyl substituent) refers to a monovalent substituent, and The variable composition C _m H _{2m + 1} (x, y, z, n, m are integers):

... 2. Catalyst for ethylene polymerization comprising at least one compound of general formula 1 according to claim 1, at least one organoaluminum activator of any structure, not necessarily ethylene, and at least one hydrocarbon solvent. 3. A catalyst according to claim 2, wherein the compound of general formula 1 is selected from the group consisting of: {2- [1- (2,4-bis (diphenylmethyl) -6-cyclopentylphenylimino) ethyl] -9- [2,4-bis (diphenylmethyl) -6-cyclopentylphenylimino] -5,6,7,8-tetrahydro- 9H-cyclohepta [b] pyridine} iron (II) dichloride; {2- [1- (2,4-bis (diphenylmethyl) -6-cyclohexylphenylimino) ethyl] -9- [2,4-bis (diphenylmethyl) -6-cyclohexylphenylimino] -5,6,7,8-tetrahydro- 9H-cyclohepta [b] pyridine} iron (II) dichloride; {2- [1- (2,4-bis (diphenylmethyl) -6-cyclooctylphenylimino) ethyl] -9- [2,4-bis (diphenylmethyl) -6-cyclooctylphenylimino] -5,6,7,8-tetrahydro- 9H-cyclohepta [b] pyridine} iron (II) dichloride; {2- [1- (2,4-bis (diphenylmethyl) -6-cyclododecylphenylimino) ethyl] -9- [2,4-bis (diphenylmethyl) -6-cyclododecylphenylimino] -5,6,7,8-tetrahydro- 9H-cyclohepta [b] pyridine} iron (II) dichloride; {2- [1- (4-diphenylmethyl-2,6-dicyclopentylphenylimino) ethyl] -9- (4-diphenylmethyl-2,6-dicyclopentylphenylimino) -5,6,7,8-tetrahydro-9H-cyclohepta [b] pyridine} iron (II) dichloride. 4. The catalyst according to claim 2, wherein the organoaluminum activator is methylalumoxane (MAO), modified versions of MAO (including, but not limited to, improved polymethylalumoxane, denoted PMAO-IP, modified methylalumoxane type 3A, denoted as MMAO-3A, modified methylalumoxane type 12, designated as MMAO-12), as well as trimethylaluminum (TMA), triethylaluminium (TEA), triisobutylaluminum (TIBA), tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octyl , dimethyl aluminum chloride (DMAX), diethyl aluminum chloride (DEAC), diisobutyl aluminum chloride, methyl aluminum sesquichloride, ethyl aluminum 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 molar ratio of Al / Fe is in the range from 100 to 5000, preferably 500-3000. 7. The catalyst according to PP. 2-6, characterized in that it is used for polymerizing ethylene to obtain highly linear polyethylene 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 atm, preferably from 1 to 10 atm, the duration of the polymerization process in the range from 10 minutes to 8 hours, preferably from 30 minutes to 5 hours, the rotation speed of the paddle stirrer in the range from 50 to 2000 rpm, preferably from 100 to 1000 rpm. 8. A method for preparing a catalyst according to any one of claims. 2-7 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 a medium of at least one hydrocarbon solvent. 9. The method according to claim 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 overpressure 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 overpressure 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.