RU2422468C1 - Method of producing polymers and copolymers of conjugated dienes (versions) - Google Patents

Abstract

FIELD: chemistry. ^ SUBSTANCE: invention relates to methods of producing polymers and copolymers of conjugated dienes via (co)polymerisation and can be used in the industry of synthetic rubber. Described is a method of producing polymers and copolymers of conjugated dienes via (co)polymerisation of corresponding monomers in the medium of a hydrocarbon solvent in the presence of a catalyst system obtained by mixing lanthanide carboxylate (A1), unsaturated hydrocarbon (B) and an organoaluminium compound (C), further addition of a preformed complex of the organoaluminium compound (C) and a Lewis base (D), reaction of the obtained mixture with a halogen source (E), followed by activation of the catalyst system by adding alkylalumoxane (F). Overall molar ratio of components A1:B:C:D:E:F (in terms of aluminium) is equal to 1:[5-100]:[20-100]:[0-10]:[0.2-2.0]:[1-100]. Described also is a method where a catalyst system is obtained via alkylation of an alcohol solvate of a lanthanide chloride (A2) with a complex of an organoaluminium compound (C) and a Lewis base (D) prepared beforehand, further reaction of the mixture with an unsaturated hydrocarbon (B), followed by activation of the catalyst system by adding alkylalumoxane (F). Overall molar ratio A2:C:D:B:F (in terms of aluminium) is equal to 1:[10-25]:[0-1]:[1-10]:[2-15]. ^ EFFECT: obtaining polymers and copolymers of conjugated dienes with high output of the end product, having high content of cis-1,4-links and narrow molecular weight distribution. ^ 14 cl, 2 tbl, 20 ex

Description

The group of inventions relates to methods for producing polymers and copolymers of conjugated dienes and may find application in the synthetic rubber industry.

A known method of producing a catalyst for the polymerization of dienes by the interaction of hydrocarbon solutions of lanthanide carboxylate (atomic number from 57 to 60), triisobutylaluminum or diisobutialuminium hydride, an organohalogen compound from a series of aluminum halides, alkylaluminium halides and a conjugated diene and aged at room temperature (from 60 minutes to 37 days to several days for several days to 37 days, for several days to several days IPC C08F 1/14, publ. 1974). The molar ratios of lanthanide: aluminum: halogen: conjugated diene are maintained equal to 1: 4-200: 0.1-6: 5-500.

The disadvantage of this method is that the resulting polybutadiene is characterized by a low stereoregularity (cis-1,4-units content of about 97%), and the polymer yield when using this catalyst does not exceed 74 kg / g-cerium atom for 1 hour

A known method of producing a catalyst for the polymerization of conjugated dienes by reacting a preformed complex of hydrocarbon solutions of a rare-earth element and a Lewis base with an organoaluminum compound (AOC) selected from among aluminum alkyls or alkylaluminium hydrides, alkylaluminum halides or alkylaluminium halides and a conjugated diene at a temperature of US Pat. MKI C08F 4/14, 4/52, 2/06, publ. 1984). The resulting catalyst was incubated for 30 minutes and used for polymerization. If the optimal composition is observed at a molar ratio of the components, the neodymium compound: Lewis base: conjugated diene: aluminum: halogen is 1: 2: 10: 50: 2.5, the catalyst is characterized by time stability, however, the obtained polymer has a low stereo-regularity (cis-1 content , 4-links from 92.5 to 97.1%) and is characterized by an increased ash content due to the significant consumption of AOS.

A known method of producing a catalyst for the polymerization and copolymerization of conjugated dienes, consisting of an organoaluminum compound, neodymium alcoholate and aluminum halide or alkylaluminium halide. The catalytic complex is obtained by the interaction of the components directly in the hydrocarbon solution of the (co) monomer (US Patent No. 4429089, IPC C08F 004/72, 036 / 0.4, publ. 1984). The molar ratio of lanthanide: aluminum: halogen is in the range 1: 1-120: 0.1-10. The content of cis-1,4-units in the obtained polymer reaches 98.1%, however, the catalyst has insufficient activity — the polymer yield is not more than 200 kg / g-atom of neodymium in 1 hour.

A known method of producing cis-1,4- (co) polymers of conjugated dienes by polymerization, or their copolymerization in a hydrocarbon solvent under the action of a catalytic complex formed by reacting a mixture previously obtained and kept at a temperature of 20-50 ° C for 5-15 minutes consisting of hydrocarbon solutions of a conjugated diene and halogen-free AOC with a hydrocarbon solution of a lanthanide compound selected from the group consisting of carboxylates, alcoholates and hydrocarbon-soluble complexes ksy halides in a molar ratio of EPA: 3,1-6,0 lanthanide compound 1 and further activating complex diizobutilalyumininiygidrida feed. Before the catalyst is introduced into the monomer solution, halogen-free AOC is introduced at a total molar ratio of AOC: lanthanide 5-100: 1 and additionally diisobutylaluminium hydride at a molar ratio of diisobutylaluminium hydride: lanthanide 2-10: 1 (RF Patent No. 2203289, MKI C08F 36/06, 136 / 06, 236/06, 4/44, publ. 2003).

(Co) polymers of conjugated dienes obtained in the presence of the indicated catalyst have a narrow molecular weight distribution (up to 2.66) and are characterized by a high content of cis-1,4-units. The disadvantage of the described method is that a high conversion of monomer (89-99%) is achieved within 2-6 hours, and the maximum polymer yield is not more than 327.4 kg / g-atom of lanthanide in 1 hour.

A known method of polymerization of butadiene under the influence of a catalytic complex obtained from hydrocarbon solutions of rare-earth element (REE), diisobutylaluminium hydride, tetraisobutialumoxane, alkylaluminium halide and conjugated diene. When preparing the catalytic complex, a mixture of hydrocarbon solutions of the rare-earth element, diisobutylaluminium hydride and conjugated diene is held for 1-30 minutes, then hydrocarbon solutions of tetraisobutylaluminoxane and alkylaluminium halide are added, while the molar ratios of REE: diisobutylaluminium hydride: tetraalkyl aluminyl 1 : 3-12: 6-12: 1,5-3: 2-20. The resulting complex was incubated for 10-15 hours, and then used for the polymerization and copolymerization of butadiene (RF Patent No. 2267355, MKI C08F 36/06, 136/06, 4/52, publ. 10.01.06., Bull. No. 1).

The butadiene (co) polymer obtained according to this method is characterized by high stereoregularity (cis-1,4-units content is up to 99.1%), however, it has a high polydispersity of at least 3.1. In addition, the polymer yield is not more than 975.5 kg / g-atom of neodymium per 1 h.

Closest to the proposed invention in technical essence and the achieved result is a method in which conjugated dienes (co) are polymerized in the presence of a catalyst obtained by the interaction of hydrocarbon solutions of a compound of lanthanide, a conjugated diene, an organoaluminum compound for 5-120 minutes, further introducing a source of halogen, alkylaluminoxane and activating the catalyst by introducing a preformed complex of the organoaluminum compound and Lewis base with a total molar ratio of components — lanthanide compound: conjugated diene: organoaluminum compound: alkylaluminoxane (in terms of aluminum): halogen source: Lewis base equal to 1: [5-100]: [20-100]: [1-100 ]: [0.3-6]: [0.1-100] (RF Patent No. 2361888, MKI C08F 36/06, 36/08, 4/44, publ. 20.07.09., Bull. No. 20).

The specified method allows to obtain (co) polymers of conjugated dienes with a high yield of up to 2948 kg / g-lanthanide atom per 1 h and stereo-regularity (cis-1,4-units content - up to 99.1%). However, the (co) polymers synthesized in this way have a wide molecular weight distribution of up to 4.0. High polydispersity leads to a significant decrease in the elasticity of the (co) polymer and vulcanizates based on it, worsening of the hysteresis properties of rubbers, and a decrease in tensile modulus. (Co) polymers with these characteristics cannot be used in the manufacture of high-tech tires.

A known method of producing cis- (co) polymers of dienes by their (co) polymerization in a hydrocarbon solvent in the presence of a catalyst consisting of a complex compound of a rare earth chloride with an electron donor, an organoaluminum compound and a conjugated diene. Ethyl alcohol, an organoaluminum compound — diisobutyl aluminum hydride, and a conjugated diene — piperylene are used as the electron donor. The interaction of the catalyst components is carried out under conditions of mechanical crushing in a vibrating mill for 3-30 hours at a molar ratio of lanthanide: aluminum: conjugated diene equal to 1: [0.2-5]: [1-5] (RF Patent No. 2049092, C08F 4 / 12, publ. 1995).

However, the resulting polymers have low stereoregularity, the content of cis-1,4 units from 92.0%, and low polymer yields of not more than 290 kg / g · at REE for 1 hour. The introduction of the stage of mechanical crushing of the catalyst components will significantly complicate the technological scheme of the process when implementing the method in industry.

A known method of polymerization of dienes in a hydrocarbon solvent or bulk in the presence of anhydrous lanthanide halides obtained by the interaction of hydrocarbon-soluble compounds of lanthanides and halides of the III-V groups of the Periodic system or alkyl aluminum halides (RF Patent No. 2139833 C01F 17/00, publ. 1999).

This method is characterized by a smaller number of components of the catalytic system, low consumption of organoaluminum compounds, high catalyst activity (up to 1169 kg / g · at REE for 1 hour) and ease of technical design. However, the resulting polymers are characterized by a low content of cis-1,4 units or the formation of polymers with a mixed microstructure.

A known method of producing cis-1,4-polyisoprene by polymerization of isoprene in a hydrocarbon aliphatic solvent in the presence of a catalyst, which is a complex comprising triisobutylaluminum or diisobutylaluminum hydride, a chlorine-containing coordination compound of an lanthanide having an atomic number from 57 to 60, with an organic ligand and conjugated diene. At the same time, in addition to the catalyst, additional triisobutylaluminium or diisobutylaluminum hydride is introduced into a solution of isoprene in an aliphatic solvent supplied for polymerization with a molar ratio of 1: 1 to 30: 1 to the lanthanide compound. Alcohol or tributyl phosphate is used as the organic ligand, and piperylene is used as the conjugated diene (RF Patent No. 2091400, С08F 136/08, 2/38, publ. 1997).

The resulting polymer contains at least 97.5% cis-1,4 units, in addition, the cis-1,4 units in the resulting polymer are attached exclusively by head-to-tail type. The disadvantages of the method include the increased consumption of the organoaluminum component of the catalyst and the low polymer yield of 516 kg / g · at REE for 1 h.

The closest in technical essence to the present invention is a method for producing cis-1,4-polyisoprene by polymerization of isoprene in the presence of a catalytic system prepared by mixing piperylene, a solvate of lanthanide chloride with a monohydric alcohol in a hydrocarbon solvent and the previously obtained product of the interaction of triisobutylaluminum with water, prepared at a temperature from minus 5 ° C to minus 10 ° C and a molar ratio of aluminum: water equal to 2: 1. The interaction is carried out at a temperature from minus 5 ° C to minus 40 ° C and a molar ratio of aluminum: piperylene: lanthanide [10-20]: [18-25]: 1, and then the reaction mixture is kept at room temperature for 6-15 hours (RF patent No. 2061546, MKI 6 B01J 37/04, C08F 136/08, 2/16, publ. 1996). The resulting rubber has a high stereoregularity (98.1-98.6% of cis-1,4 units). The catalyst is a homogeneous solution, the use of which increases the reproducibility of the resulting polymer.

However, the method is characterized by a low polymer yield (402 kg / g · at REE for 1 h), which in the case of industrial implementation will lead to a significant consumption of catalyst. The increased consumption of catalyst, in turn, will lead to an increase in the ash content in rubber and a limitation of its use in the food and medical industries. Also, the proposed method involves a stage of the interaction of triisobutylaluminum with water, which will complicate the technological scheme for preparing the catalyst, require the creation of special equipment, and most importantly increase the fire and explosion hazard of the process.

The technical task of the group of inventions is to develop a method for producing polymers and copolymers of conjugated dienes, with a high yield of the target product, having a high content of cis-1,4 units and a narrow molecular weight distribution.

The specified technical result is achieved by the fact that the proposed method for producing polymers and copolymers of conjugated dienes is carried out by (co) polymerizing the corresponding monomers in a hydrocarbon solvent in the presence of a catalytic system formed by mixing lanthanide carboxylate (A1), unsaturated hydrocarbon (B) and organoaluminum compound (C ), the further introduction of a preformed complex of the organoaluminum compound (C) and the Lewis base (D), the interaction obtained with a mixture with a source of halogen (E) and subsequent activation of the catalytic system by the introduction of alkylaluminoxane (F) with a total molar ratio of components A1: B: C: D: E: F (in terms of aluminum) equal to 1: [5-100]: [ 20-100]: [0-10]: [0.2-2.0]: [1-100].

Salts formed by neodymium (Nd), praseodymium (Pr), lanthanum (La), cerium (Ce) or their mixtures with saturated alpha branched or naphthenic acids are used as the carboxylate of lanthanide (Al). Preferred are neodymium neodecanoate (Nd (Ver) ₃ ), neodymium naphthenate (NdPh ₃ ), neodymium octanoate (Nd (Oct) ₃ ), praseodymium neodecanoate (Pr (Ver) ₃ ), praseodymium naphthenate (PrPh ₃ ), praseodymium octanoate (Pr (Oct) ₃ ), lanthanum neodecanoate (La (Ver) ₃ ), lanthanum octanoate (La (Oct) ₃ ), lanthanum naphthenate (La (Ph) ₃ ), or mixtures thereof.

Butadiene, isoprene, piperylene or mixtures thereof are used as unsaturated hydrocarbon (B).

As the organoaluminum compound (C), diisobutylaluminum hydride (DIBAG), triisobutylaluminum (TIBA), triethylaluminum (TEA) or mixtures thereof are used.

As the Lewis base (D), a compound selected from the group consisting of acetylacetone, diphenyl ether, methylphenyl ether, triphenylphosphine, phenylacetylacetone is used.

As the halogen source (E) is selected compound from the group consisting of diethylaluminum chloride (DEAC), ethylaluminum sesquichloride (EASKH) diisobutylaluminum chloride (Diebach) izobutilalyuminiyseskvihlorid (IBASKH), isobutylaluminum dichloride (IBADH), carbon tetrachloride (CCl _4), tert-butyl (TBH) silicon tetrachloride (SiCl ₄ ), hexachloro-p-xylene (HCFC), chlorobenzene (CB).

As alkylaluminoxane (F), methylaluminoxane (MAO), ethylaluminoxane (EAO), isobutylaluminoxane (IBAO) or mixtures thereof are used.

As an option, the stated problem is solved by the fact that the proposed method for producing polymers and copolymers of conjugated dienes is carried out by (co) polymerizing the corresponding monomers in a hydrocarbon solvent in the presence of a catalytic system formed by alkylating an alcohol solvate of lanthanide chloride (A2) with a pre-prepared complex of organoaluminum compound (C) and Lewis base (D), further interaction of the mixture with an unsaturated hydrocarbon (B), and subsequent activation of the catalytic system topics the introduction of alkylaluminoxane (F) with a total molar ratio of A2: C: D: B: F (in terms of aluminum) equal to 1: [10-25]: [0-1]: [1-10]: [2- fifteen].

As the alcohol solvate of lanthanide chloride (A2), a salt formed by the interaction of neodymium chloride (NdCl ₃ ), praseodymium (PrCl ₃ ), lanthanum (LaCl ₃ ) or mixtures thereof with a monohydric alcohol is used.

Ethyl alcohol (ES), n-propyl alcohol (NPS), isopropyl alcohol (IPS), n-butyl alcohol (NBS), isobutyl alcohol (IHD), cyclohexyl alcohol (CHS) and octyl alcohol (OC) are used as monohydric alcohols. .

As the organoaluminum compound (C), diisobutyl aluminum hydride (DIBAG), triisobutylaluminum (TIBA), triethylaluminum (TEA), or mixtures thereof, are used.

As the Lewis base (D), a compound selected from the group consisting of acetylacetone, diphenyl ether, methylphenyl ether, triphenylphosphine, phenylacetylacetone is used.

Butadiene, isoprene, piperylene or mixtures thereof are used as unsaturated hydrocarbon (B).

As alkylaluminoxane (E), methylaluminoxane (MAO), ethylaluminoxane (EAO), isobutylaluminoxane (IBAO) or mixtures thereof are used.

Carrying out the process of (co) polymerization of conjugated dienes using a catalytic system obtained in accordance with the specified component composition, molar ratio of components and the order of their interaction allows to obtain (co) polymers with a high yield of the target product with a high content of cis-1,4 units and narrow molecular weight distribution.

As conjugated dienes, as a rule, butadiene and / or isoprene are used. (Co) polymerization of butadiene and / or isoprene is carried out in aliphatic and aromatic hydrocarbons at a temperature of 0-120 ° C, preferably at 60 ° C. The viscosity of the (co) polymer, if necessary, is controlled by a known method — introducing monomer in a hydrocarbon solvent into the solution before feeding the catalytic system of diisobutylaluminum hydride. At the end of the (co) polymerization, the catalyst system is deactivated, and the (co) polymer is precipitated by the introduction of ethanol containing an antioxidant. Next, the (co) polymer is dried in vacuo to constant weight.

The activity of the catalytic system is evaluated in kg (co) polymer per 1 g · REE atom for 1 h. The microstructure is determined by infrared spectroscopy, polydispersity by gel permeation chromatography.

The invention is illustrated by the following examples.

Example 1. In a glass reactor, preheated in a vacuum and filled with dry nitrogen, with constant stirring, 0.5 ml (0.36 mmol) of a solution of neodymium neodecanoate in hexane, 1.45 ml (1.80 mmol) of a toluene piperylene solution and 4.25 ml (3.61 mmol) of a toluene solution of diisobutylaluminum hydride was incubated for 30 minutes, while the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound was 1: 5: 10. To the resulting mixture was added a preformed complex obtained by mixing 6.0 ml (3.60 mmol) of a toluene solution of triisobutylaluminum and 0.60 ml (0.36 mmol) of a toluene solution of diphenyl ether, then 0.18 ml (0.072 mmol) was added toluene solution of hexachloroparaxylene. The prepared catalyst system is activated by introducing 5.85 ml (14.39 mmol) of a methylaluminoxane toluene solution. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: Lewis base: halogen source: alkylaluminoxane (in terms of aluminum) is 1: 5: 20: 1: 0.2: 40.

The resulting catalytic system with a neodymium ion concentration of 0.019 g · at / L is used in the polymerization of butadiene. 40 ml of a hexane solution containing 3.24 g of butadiene are loaded into a glass ampoule preheated in vacuum at 150-200 ° C and filled with dry nitrogen with a self-tightening rubber stopper, the ampoule is thermostated at 60 ° C and 0.26 ml of catalytic is added using a syringe system. The molar ratio of butadiene to neodymium is equal to 12000.

After 30 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 2. In a glass reactor, preheated in vacuum and filled with dry nitrogen, with constant stirring, 0.5 ml (0.36 mmol) of a solution of neodymium octonate in hexane, 6.0 ml (7.2 mmol) of a toluene solution of piperylene mixture (3.6 mmol) and butadiene (3.6 mmol) and 9.85 ml (7.19 mmol) of a toluene solution of triethylaluminum, incubated for 30 minutes, while the molar ratio of the compound of the lanthanide: conjugated diene: organoaluminum compound is 1: 20:20. To the resulting mixture was added a preformed complex obtained by mixing 4.25 ml (3.61 mmol) of a toluene solution of diisobutial aluminum hydride and 12.00 ml (3.6 mmol) of a toluene solution of triphenylphosphine, then 1.2 ml (0.72 mmol) ) toluene solution of chlorobenzene. The prepared catalyst system is activated by introducing 9.0 ml of a toluene solution of a mixture of methylaluminoxane (9.0 mmol) and isobutylaluminoxane (9.0 mmol). The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: Lewis base: halogen source: alkylaluminoxane (in terms of aluminum) is 1: 20: 30: 10: 2.0: 50.

The resulting catalytic system with a neodymium ion concentration of 0.008 g · at / L is used in the polymerization of butadiene. The polymerization of butadiene is carried out according to example 1. The volume of the introduced catalyst system is 0.55 ml. The molar ratio of butadiene to neodymium is equal to 13000.

After 30 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 3. In a glass reactor, preheated in a vacuum and filled with dry nitrogen, with constant stirring, 0.5 ml (0.36 mmol) of a solution of neodymium naphthenate in hexane, 32.14 ml (36.00 mmol) of a toluene solution of butadiene and 6.0 ml (3.6 mmol) of a toluene solution of triisobutylaluminum is incubated for 30 minutes, while the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound is 1: 100: 10. To the resulting mixture were added 4.24 ml (3.60 mmol) of a toluene solution of diisobutylaluminum hydride and 0.29 ml (0.23 mmol) of a toluene solution of ethylaluminium sesquichloride. The prepared catalyst system is activated by the addition of 19.45 ml (35.98 mmol) of a toluene solution of a mixture of ethylaluminoxane. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: source of halogen: alkylaluminoxane (in terms of aluminum) is 1: 100: 20: 0.65: 100.

The resulting catalytic system with a neodymium ion concentration of 0.006 g · at / L is used in the polymerization of butadiene. The polymerization of butadiene is carried out as in example 1. The volume of the introduced catalyst system is 0.70 ml. The molar ratio of butadiene to neodymium is equal to 15,000.

After 45 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 4. In a glass reactor, preheated in a vacuum and filled with dry nitrogen, with constant stirring, 0.5 ml (0.36 mmol) of a solution of praseodymium naphthenate in hexane, 9.0 ml (10.80 mmol) of a toluene solution of piperylene mixture are introduced (10.00 mmol) and isoprene (0.80 mmol), 2.47 ml of a toluene solution of a mixture of triisobutylaluminum (0.90 mmol) and diisobutylaluminum hydride (0.90 mmol) was incubated for 30 min, while the molar ratio of the lanthanide compound : conjugated diene: organoaluminum compound is 1: 30: 5. To the resulting mixture was added a preformed complex obtained by mixing 6.35 ml (5.40 mmol) of a toluene solution of diisobutial aluminum hydride and 2.7 ml (0.54 mmol) of a toluene solution of phenylacetylacetone, then 0.65 ml (0.72 mmol ) toluene solution of diethylaluminium chloride. The prepared catalyst system is activated by introducing 1.46 ml (3.59 mmol) of a methylaluminoxane toluene solution. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: Lewis base: halogen source: alkylaluminoxane (in terms of aluminum) is 1: 30: 20: 1,5: 2,0: 10.

The resulting catalytic system with a neodymium ion concentration of 0.016 g · at / L is used in the polymerization of butadiene. The polymerization of butadiene is carried out according to example 1. The volume of the introduced catalyst system is 0.30 ml. The molar ratio of butadiene to neodymium is equal to 13000.

After 30 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 5. In a glass reactor, preheated in vacuum and filled with dry nitrogen, with constant stirring, 0.5 ml (0.36 mmol) of a solution of praseodymium neodecanoate in hexane, 2.9 ml (3.6 mmol) of toluene piperylene solution, 4.25 ml (3.61 mmol) of a toluene solution of diisobutyl aluminum hydride was held for 30 minutes, while the molar ratio of lanthanide compound: conjugated diene: organic aluminum compound was 1:10:10. To the resulting mixture was added a preformed complex obtained by mixing 6.0 ml (3.6 mmol) of a toluene solution of triisobutylaluminum and 0.36 ml (0.18 mmol) of a toluene solution of acetylacetone, then 0.30 ml (0.18 mmol ) toluene solution of silicon tetrachloride. The prepared catalyst system is activated by introducing 3.63 ml of a toluene solution of a mixture of methylaluminoxane (5.19 mmol) isobutialumoxane (1.0 mmol) and ethylaluminoxane (1.0 mmol). The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: Lewis base: halogen source: alkylaluminoxane (in terms of aluminum) is 1: 10: 20: 0.5: 0.5: 20.

The resulting catalytic system with a concentration of neodymium ions of 0.020 g · at / L is used in the polymerization of butadiene. The polymerization of butadiene is carried out according to example 1. The volume of the introduced catalyst system is 0.20 ml. The molar ratio of butadiene to neodymium is equal to 15,000.

After 30 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 6. 0.71 ml of a hexane solution of a mixture of neodymium octonate (0.20 mmol), praseodymium octonate (0.20 mmol) and lanthanum octonate (0, 11 mmol), 2.90 ml (3.60 mmol) of toluene piperylene solution, 17.00 ml (10.20 mmol) of triisobutylaluminum toluene solution, incubated for 30 min, while the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound is 1: 7: 20. To the resulting mixture was added a preformed complex obtained by mixing 6.00 ml (5.10 mmol) of a toluene solution of diisobutylaluminium hydride and 12.8 ml (2.56 mmol) of a toluene solution of phenylacetylacetone, then 0.9 ml (0.72 mmol) ) toluene solution of diisobutylaluminium chloride. The prepared catalyst system is activated by the introduction of 0.2 ml (0.49 mmol) of a toluene methylaluminoxane solution. In this case, the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound: Lewis base: halogen source: alkylaluminoxane (in terms of aluminum) is 1: 7: 30: 5: 1.4: 1.

The resulting catalytic system with a neodymium ion concentration of 0.013 g · at / L is used in the polymerization of butadiene. The polymerization of butadiene is carried out according to example 1. The volume of the introduced catalyst system is 0.37 ml. The molar ratio of butadiene to neodymium is equal to 13000.

After 30 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 7. In a glass reactor, preheated in a vacuum and filled with dry nitrogen, 0.50 ml (0.36 mmol) of a hexane solution of lanthanum naphthenate, 32.73 ml (36.00 mmol) of isoprene toluene solution, 4 are introduced with constant stirring , 24 ml (3.60 mmol) of a toluene solution of diisobutylaluminium hydride is held for 30 minutes, while the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound is 1: 100: 10. To the resulting mixture was added a preformed complex obtained by mixing 6.00 ml (3.60 mmol) of a toluene solution of triisobutylaluminum and 2.70 ml (1.08 mmol) of a toluene solution of methylphenyl ether, then 1.37 ml (0.69 mmol) of a toluene solution of tert-butyl chloride. The prepared catalyst system is activated by introducing 3.63 ml of a toluene solution of a mixture of methylaluminoxane (5.19 mmol), ethylaluminoxane (1.0 mmol) and isobutialumoxane (1.0 mmol). The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: Lewis base: halogen source: alkylaluminoxane (in terms of aluminum) is 1: 100: 20: 3: 1.9: 20.

The resulting catalytic system with a neodymium ion concentration of 0.007 g · at / L is used in the copolymerization of butadiene and isoprene. 40 ml of a hexane solution containing 2.16 g of butadiene and 1.08 g of isoprene are loaded into a glass ampoule previously preheated in vacuum at 150-200 ° C and filled with dry nitrogen with a self-tightening rubber stopper, the ampoule is thermostated at 60 ° C and added using 0.5 ml syringe catalytic system. The molar ratio of monomers to neodymium is equal to 15,000.

After 30 minutes, the copolymer is isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 8. In a glass reactor, preheated in a vacuum and filled with dry nitrogen, 0.50 ml (0.33 mmol) of a hexane solution of lanthanum octonate, 5.8 ml (6.50 mmol) of a toluene solution of butadiene, 3 are introduced with constant stirring 82 ml (3.25 mmol) of a toluene solution of diisobutylaluminium hydride is held for 30 minutes, while the molar ratio of lanthanide compound: conjugated diene: organic aluminum compound is 1:20:10. To the resulting mixture was added a preformed complex obtained by mixing 5.41 ml (3.25 mmol) of a toluene solution of triisobutyl aluminum and 1.09 ml (0.65 mmol) of a toluene solution of diphenyl ether, then 0.12 ml (0.10 mmol) of a toluene solution of carbon tetrachloride. The prepared catalyst system is activated by introducing 9.97 ml (16.25 mmol) of isobutylaluminoxane toluene solution. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: Lewis base: halogen source: alkylaluminoxane (in terms of aluminum) is 1: 20: 20: 2: 0.3: 50.

The resulting catalytic system with a neodymium ion concentration of 0.012 g · at / L is used in the polymerization of butadiene. The polymerization of butadiene is carried out according to example 1. The volume of the introduced catalyst system is 0.41 ml. The molar ratio of butadiene to neodymium is equal to 12000.

After 30 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 9. In a glass reactor, preheated in a vacuum and filled with dry nitrogen, 0.50 ml (0.36 mmol) of a hexane solution of lanthanum neodecanoate, 2.03 ml (2.52 mmol) of toluene piperylene solution, 3 are introduced with constant stirring , 40 ml (2.89 mmol) of a toluene solution of diisobutylaluminium hydride is held for 30 minutes, while the molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound is 1: 7: 8. To the resulting mixture was added a preformed complex obtained by mixing 7.20 ml (4.32 mmol) of a toluene solution of triisobutylaluminum and 12 ml (3.60 mmol) of a toluene solution of triphenylphosphine, then 1.08 ml (0.32 mmol) of toluene solution of isobutylaluminium sesquichloride. The prepared catalyst system is activated by introducing 1.46 ml (3.59 mmol) of a methylaluminoxane toluene solution. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: Lewis base: halogen source: alkylaluminoxane (in terms of aluminum) is 1: 7: 20: 10: 0.9: 10.

The resulting catalytic system with a neodymium ion concentration of 0.013 g · at / L is used in the polymerization of butadiene. The polymerization of butadiene is carried out according to example 1. The volume of the introduced catalyst system is 0.31 ml. The molar ratio of butadiene to neodymium is equal to 15,000.

After 45 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 10. In a glass reactor, preheated in vacuum and filled with dry nitrogen, 0.50 ml (0.36 mmol) of a hexane solution of neodymium neodecanoate, 14.52 ml (18.00 mmol) of a toluene piperylene solution, 4 are introduced with constant stirring 25 ml (3.61 mmol) of a toluene solution of diisobutylaluminium hydride is held for 30 minutes, while the molar ratio of lanthanide compound: conjugated diene: organic aluminum compound is 1:50:10. To the resulting mixture were added 54.00 ml (32.40 mmol) of a toluene solution of triisobutylaluminum and 0.71 ml (0.36 mmol) of a toluene solution of ethylaluminium sesquichloride. The prepared mixture was incubated for 24 hours at a temperature of 25 ° C and activated by the introduction of 0.29 ml (0.71 mmol) of a toluene methylaluminoxane solution. The molar ratio of lanthanide compound: conjugated diene: organoaluminum compound: Lewis base: halogen source: alkylaluminoxane (in terms of aluminum) is 1: 50: 100: 0: 1: 2.

The resulting catalytic system with a neodymium ion concentration of 0.005 g · at / L is used in the polymerization of isoprene. 40 ml of isopentane containing 4.1 g of isoprene are loaded into a glass ampoule pre-heated in vacuum at 150-200 ° C and filled with dry nitrogen with a self-tightening rubber stopper, the ampoule is thermostated at 60 ° C and 1.23 ml of the catalytic system is added via syringe . The molar ratio of isoprene to neodymium is equal to 13000.

After 30 minutes, the polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 11. In a glass reactor with a magnetic stirrer, 5 ml of a toluene suspension of NdCl ₃ solvate with IPA containing 0.5 mmol of REE is introduced. Then, with constant stirring, 10 ml of a solution of a previously prepared complex of TIBA (7.5 mmol) with TEU (0.1 mmol) in toluene, 0.9 ml of a solution of piperylene (1 mmol) in hexane are introduced into the suspension. The resulting reaction mass is activated by introducing 1 ml of a solution of MAO (2.5 mmol) in toluene. The molar ratio of lanthanide: organoaluminum compound: electron donor: conjugated diene: alkylaluminoxane (in terms of aluminum) is 1: 15: 0.2: 2: 5.

The resulting catalytic system is used for the polymerization of isoprene. For this purpose, 800 ml of an isopentane solution containing 74.8 g of isoprene (1.1 mol) and 0.37 ml of DIBAG solution (0.28) are introduced into a 1 dm ³ metal apparatus equipped with a mixing device and a jacket to maintain a predetermined temperature. mmol) in toluene. The apparatus is thermostated and a catalytic system is introduced; polymerization is carried out at 50 ° C.

After 60 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 12. In a glass reactor with a magnetic stirrer, 5 ml of a toluene suspension of Md NdCl ₃ with ES containing 0.5 mmol REE. Then, with constant stirring, 13.4 ml of a solution of the previously prepared TIBA complex (10 mmol) with AA (0.2 mmol) in toluene, 2.1 ml of piperylene solution (2.5 mmol) in hexane are introduced into the suspension. The resulting reaction mass is activated by introducing 2 ml of a solution of MAO (5 mmol) in toluene. The molar ratio of lanthanide: organoaluminum compound: electron donor: conjugated diene: alkylaluminoxane (in terms of aluminum) is 1: 20: 0.4: 5: 10.

The resulting catalytic system is used for the polymerization of isoprene. For this purpose, 800 ml of a hexane solution containing 74.8 g of isoprene (1.1 mol) and 0.37 ml of DIBAG solution (0.28) are introduced into a 1 dm ³ metal apparatus equipped with a mixing device and a jacket to maintain a given temperature mmol) in toluene. The apparatus is thermostated and a catalytic system is introduced; polymerization is carried out at 50 ° C.

After 60 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 13. In a glass reactor with a magnetic stirrer, 5 ml of a toluene solvate of LaCl ₃ solvate with NPS containing 0.5 mmol of REE are introduced. Then, with constant stirring, 18.6 ml of a solution of a previously prepared complex of DIBAG (12.5 mmol) with FAA (0.05 mmol) in toluene, 1.7 ml of a solution of piperylene (2 mmol) in hexane are introduced into the suspension. The resulting reaction mass is activated by introducing 2 ml of a solution of EAO (5 mmol) in toluene. The molar ratio of lanthanide: organoaluminum compound: electron donor: conjugated diene: alkylaluminoxane (in terms of aluminum) is 1: 25: 0.1: 4: 10.

The resulting catalytic system is used for the polymerization of isoprene. For this purpose, 800 ml of an isopentane solution containing 74.8 g of isoprene (1.1 mol) is introduced into a 1 dm ³ metal apparatus equipped with a mixing device and a jacket to maintain a given temperature. The apparatus is thermostated and a catalytic system is introduced; polymerization is carried out at 70 ° C.

After 120 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 14. In a glass reactor with a magnetic stirrer, 5 ml of a toluene suspension of NdCl ₃ solvate with IHD containing 0.5 mmol of REE is introduced. Then, with constant stirring, 13.4 ml of a solution of the previously prepared TIBA complex (10 mmol) with TEU (0.25 mmol) in toluene, 0.4 ml of a solution of butadiene (0.4 mmol) in hexane are introduced into the suspension. The resulting reaction mass is activated by introducing 0.4 ml of a solution of MAO (1 mmol) in toluene. The molar ratio of lanthanide: organoaluminum compound: electron donor: conjugated diene: alkylaluminoxane (in terms of aluminum) is 1: 20: 0.5: 1: 2.0.

The resulting catalytic system is used for the polymerization of isoprene. For this purpose, 800 ml of a cyclohexane solution containing 74.8 g of isoprene (1.1 mol) and 0.49 ml of DIBAG solution (0.37) are introduced into a 1 dm ³ metal apparatus equipped with a mixing device and a jacket to maintain a predetermined temperature. mmol) in toluene. The apparatus is thermostated and a catalytic system is introduced; polymerization is carried out at 20 ° C.

After 60 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 15. In a glass reactor with a magnetic stirrer, 5 ml of a toluene suspension of a NdCl ₃ solvate with CHS containing 0.5 mmol of REE are introduced. Then, with constant stirring, 6.7 ml of a toluene solution of a mixture of TIBA (2.5 mmol) and DIBAG (2.5 mmol), 2.1 ml of a solution of piperylene (2.5 mmol) in hexane are introduced into the suspension. The resulting reaction mass is activated by introducing 2 ml of a solution of EAO (5 mmol) in toluene. The molar ratio of lanthanide: organoaluminum compound: electron donor: conjugated diene: alkylaluminoxane (in terms of aluminum) is 1: 10: 0: 5: 10.

The resulting catalytic system is used for the polymerization of isoprene. For this purpose, 800 ml of an isopentane solution containing 74.8 g of isoprene (1.1 mol) and 0.37 ml of DIBAG solution (0.28) are introduced into a 1 dm ³ metal apparatus equipped with a mixing device and a jacket to maintain a predetermined temperature. mmol) in toluene. The apparatus is thermostated and a catalytic system is introduced; polymerization is carried out at 50 ° C.

After 90 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 16 In a glass reactor with magnetic stirrer administered 5 ml toluene suspension solvate NdCl ₃ OS and solvate RrSl ₃ OS, containing 0.5 mmol of REE. Then, with constant stirring, 13.4 ml of a solution of the previously prepared DIBAG complex (10 mmol) with AA (0.25 mmol) in toluene, 3.4 ml of a solution of isoprene (4 mmol) in hexane are introduced into the suspension. The resulting reaction mass is activated by introducing 1 ml of a solution of MAO (2.5 mmol) in toluene. The molar ratio of lanthanide: organoaluminum compound: electron donor: conjugated diene: alkylaluminoxane (in terms of aluminum) is 1: 20: 0.5: 8: 5.

The resulting catalytic system is used for the polymerization of isoprene. For this purpose, 800 ml of a toluene solution containing 74.8 g of isoprene (1.1 mol) is introduced into a 1 dm metal apparatus equipped with a mixing device and a jacket to maintain a given temperature. The apparatus is thermostated and a catalytic system is introduced; polymerization is carried out at 80 ° C.

After 90 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 17. In a glass reactor with a magnetic stirrer injected 5 ml of a toluene suspension of a solvate of NdCl ₃ with IPA containing 0.5 mmol REE. Then, with constant stirring, 6.7 ml of a solution of the previously prepared TIBA complex (5 mmol) with TPP (0.4 mmol) in toluene, 2.1 ml of piperylene solution (2.5 mmol) in hexane are introduced into the suspension. The resulting reaction mass is activated by introducing 3 ml of a solution of MAO (7.5 mmol) in toluene. The molar ratio of lanthanide: organoaluminum compound: electron donor: conjugated diene: alkylaluminoxane (in terms of aluminum) is 1: 10: 0.8: 5: 15.

The resulting catalyst system is used for the polymerization of butadiene. For this purpose, 800 ml of a hexane solution containing 59.4 g of butadiene (1.1 mol) and 0.37 ml of DIBAG solution (0.28) are introduced into a 1 dm ³ metal apparatus equipped with a mixing device and a jacket to maintain a given temperature mmol) in toluene. The apparatus is thermostated and a catalytic system is introduced; polymerization is carried out at 50 ° C.

After 60 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 18. In a glass reactor with a magnetic stirrer, 5 ml of a toluene suspension of NdCl ₃ solvate with IPA containing 0.5 mmol of REE is introduced. Then, with constant stirring, 6.7 ml of a solution of a pre-prepared complex of TIBA (5 mmol) with MFE (0.1 mmol) in toluene, 4.2 ml of a solution of piperylene (5 mmol) in hexane are introduced into the suspension. The resulting reaction mass is activated by introducing 2 ml of a solution of MAO (5 mmol) in toluene. The molar ratio of lanthanide: organoaluminum compound: electron donor: conjugated diene: alkylaluminoxane (in terms of aluminum) is 1: 10: 0.2: 10: 10.

The resulting catalyst system is used for the polymerization of butadiene. For this purpose, 800 ml of a hexane solution containing 59.4 g of butadiene (1.1 mol) and 0.37 ml of DIBAG solution (0.28) are introduced into a 1 dm ³ metal apparatus equipped with a mixing device and a jacket to maintain a given temperature mmol) in toluene. The apparatus is thermostated and a catalytic system is introduced; polymerization is carried out at 60 ° C.

After 60 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 19. In a glass reactor with a magnetic stirrer, 5 ml of a toluene suspension of Md NdCl ₃ with ES containing 0.5 mmol of REE is introduced. Then, with constant stirring, 13.4 ml of a toluene solution of a previously prepared complex of TIBA (5 mmol) and TEA (5 mmol) with DFE (0.5 mmol), 2.1 ml of a piperylene mixture solution (2.0 mmol) s are introduced into the suspension isoprene (0.5 mmol) in hexane. The resulting reaction mass is activated by introducing 2 ml of a solution of EAO (5 mmol) in toluene. The molar ratio of lanthanide: organoaluminum compound: electron donor: conjugated diene: alkylaluminoxane (in terms of aluminum) is 1: 20: 1: 5: 10.

The resulting catalytic system is used for the copolymerization of isoprene and butadiene. For this purpose, 800 ml of an isopentane solution containing 37.8 g of isoprene (0.56 mol), 37.8 g of butadiene (0.7 mol) are introduced into a 1 dm ³ metal apparatus equipped with a mixing device and a jacket to maintain a given temperature ) and 0.56 ml of a solution of DIBAG (0.42 mmol) in toluene. The apparatus is thermostated and a catalytic system is introduced; polymerization is carried out at 50 ° C.

After 90 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Example 20. In a glass reactor with a magnetic stirrer, 5 ml of a toluene solvate of NdCl ₃ solvate with NBS containing 0.5 mmol of REE are introduced. Then, with constant stirring, 13.4 ml of a solution of the previously prepared TIBA complex (10 mmol) with TEU (0.15 mmol) in toluene, 2.1 ml of piperylene solution (2.5 mmol) in hexane are introduced into the suspension. The resulting reaction mass is activated by introducing 0.5 ml of a toluene solution of a mixture of MAO (1.0 mmol) and EAO (0.25 mmol). The molar ratio of lanthanide: organoaluminum compound: electron donor: conjugated diene: alkylaluminoxane (in terms of aluminum) is 1: 20: 0.3: 5: 2.5.

The resulting catalytic system is used for the copolymerization of isoprene and butadiene. For this purpose, 800 ml of an isopentane solution containing 37.8 g of isoprene (0.56 mol), 37.8 g of butadiene (0.7 mol) are introduced into a 1 dm ³ metal apparatus equipped with a mixing device and a jacket to maintain a given temperature ) and 0.56 ml of a solution of DIBAG (0.42 mmol) in toluene. The apparatus is thermostated and a catalytic system is introduced, polymerization is carried out at 30 ° C.

After 60 minutes, the (co) polymer was isolated, dried to constant weight. The synthesis conditions of the catalytic system are presented in table 1, the conditions of (co) polymerization and the properties of the obtained (co) polymer are presented in table 2.

Table 1 The conditions for the synthesis of the catalytic complex Example No. Catalytic System Components The molar ratio of components A1 A2 AT FROM C and D (pre-formed complex) E F A1: B: C: D: E: F A2: B: C: D: F one Nd (Ver) ₃ - Piperylene DIBAG TIBA and TEU GHPK MAO 1: 5: 20: 1: 0.2: 40 - 2 Nd (Oct) ₃ - Piperylene and butadiene Tea DIBAG and TFF HB MAO IBAO 1: 20: 30: 10: 2,0: 50 - 3 Nd (Ph) ₃ - Butadiene Chiba DIBAG EASH EAO 1: 100: 20: 0: 0.65: 100 - four Pr (Ph) ₃ - Piperylene and isoprene DIBAG and CHIBA DIBAG and FAA DEAH MAO 1: 30: 20: 1,5: 2,0: 10 - 5 Pr (Ver) ₃ - Piperylene DIBAG Chiba and AA SiCl ₄ MAO, IBAO, EAO 1: 10: 20: 0,5: 0,5: 20 - 6 Nd (Oct) ₃ Pr (Oct) ₃ La (Oct) ₃ Piperylene Chiba DIBAG and FAA DIBAH MAO 1: 7: 30: 5: 1.4: 1 7 La (Ph) ₃ - Isoprene DIBAG TIBA and MFE TBH MAO, IBAO, EAO 1: 100: 20: 3: 1,9: 20 - 8 La (Oct) ₃ - Butadiene DIBAG TIBA and TEU CCl ₄ IBAO 1: 20: 20: 2: 0,3: 50 - 9 La (Ver) ₃ - Piperylene DIBAG TIBA and TFF IBASKH MAO 1: 7: 20: 10: 0.9: 10 - 10 Nd (Ver) ₃ - Piperylene DIBAG Chiba and EASH EASH MAO 1: 50: 100: 0: 1: 2 - eleven - NdCl ₃ and IPA Piperylene - TIBA and TEU - MAO - 1: 15: 0.2: 2: 5 12 - NdCl ₃ and ES Piperylene - Chiba and AA - MAO - 1: 20: 0.4: 5: 10

Continuation of table 1 Example No. Catalytic System Components The molar ratio of components A1 A2 AT FROM C and D (pre-formed complex) E F A1: B: C: D: E: F A2: B: C: D: F 13 - LaCl ₃ and NPS Piperylene - DIBAG and FAA - EAO - 1: 25: 0,1: 4: 10 fourteen - NdCl ₃ and IHD Butadiene - TIBA and TEU - MAO - 1: 20: 0.5: 1: 2.0 fifteen - NdCl ₃ and CHS Piperylene - CHIBA + DIBAG EAO - 1: 10: 0: 5: 10 16 - NdCl ₃ + PrCl ₃ and OS Isoprene - DIBAG and AA - MAO - 1: 20: 0,5: 8: 5 17 - NdCl ₃ and IPA Piperylene - TIBA and TFF - MAO - 1: 10: 0.8: 5: 15 eighteen - NdCl ₃ and IPA Piperylene - TIBA and MFE - MAO - 1: 10: 0.2: 10: 10 19 - NdCl ₃ and ES Piperylene and isoprene - TIBA + TEA and TEU - EAO - 1: 20: 1: 5: 10 twenty - NdCl ₃ and NBS Piperylene - TIBA and TEU - MAO EAO - 1: 20: 0.3: 5: 2.5

table 2 Conditions for (co) polymerization and properties of the obtained (co) polymers Example No. The molar ratio of monomer / REE, mol / mol Monomer Solvent The polymerization time, min The polymer yield, kg / gag REE for 1 h The content of cis-1,4-units,% Polydispersity (M _w / M _n ) one 12000 butadiene hexane thirty 1037 97.0 1.9 2 13000 butadiene hexane thirty 983 97.9 2.5 3 15,000 butadiene hexane 45 972 97.1 1.9 four 13000 butadiene hexane thirty 1334 98.3 2.6 5 15,000 butadiene hexane thirty 1312 98.4 2.6 6 13000 butadiene hexane thirty 983 97.5 2.1 7 15,000 butadiene + isoprene hexane thirty 1409 98.5 2.6 8 12000 butadiene hexane thirty 985 97.2 1.9 9 15,000 butadiene hexane 45 1015 97.1 2.2 10 13000 isoprene isopentane thirty 1123 97.5 2.7 eleven 20000 isoprene isopentane 60 1224 99,2 2,3 12 20000 isoprene hexane 60 1210 98.9 2,3 13 15,000 isoprene isopentane 120 651 94.1 2.7 fourteen 15,000 isoprene cyclohexane 60 979 98.1 2,4 fifteen 20000 isoprene isopentane 90 612 98.4 2.6 16 15,000 isoprene toluene 90 721 97.1 2.6 17 20000 butadiene hexane 60 1307 98.9 2.5 eighteen 20000 butadiene hexane 60 1332 99.1 2,4 19 15,000 isoprene and butadiene isopentane 90 707 97.9 2.7 twenty 15,000 isoprene and butadiene isopentane 60 1006 99.0 2.5

Claims (14)

1. A method of producing polymers and copolymers of conjugated dienes by (co) polymerizing the corresponding monomers in a hydrocarbon solvent in the presence of a catalyst system based on a lanthanide compound, characterized in that the catalyst system is formed by mixing lanthanide carboxylate (A1), unsaturated hydrocarbon (B) and organoaluminum compound (C), the further introduction of a preformed complex of the aluminum-organic compound (C) and the Lewis base (D), the interaction of the obtained mixture si with a halogen source (E) and subsequent activation of the catalytic system by the introduction of alkylaluminoxane (F) with a total molar ratio of components A1: B: C: D: E: F (in terms of aluminum) equal to 1: [5-100]: 20-100]: [0-10]: [0.2-2.0]: [1-100]. 2. The method according to claim 1, characterized in that as the lanthanide carboxylate (A1) use salts formed by neodymium, praseodymium, lanthanum or mixtures thereof with saturated alpha branched or naphthenic acids. 3. The method according to claim 1, characterized in that butadiene, isoprene, piperylene or mixtures thereof are used as unsaturated hydrocarbon (B). 4. The method according to claim 1, characterized in that as the organoaluminum compound (C) diisobutylaluminum hydride, triisobutylaluminum, triethylaluminum or mixtures thereof are used. 5. The method according to claim 1, characterized in that as the Lewis base (D), a compound selected from the group consisting of acetylacetone, diphenyl ether, methylphenyl ether, triphenylphosphine, phenylacetylacetone is used. 6. The method according to claim 1, characterized in that diethylaluminium chloride, ethylaluminium sesquichloride, diisobutylaluminium chloride, isobutylaluminium sesquichloride, carbon tetrachloride, tert-butyl chloride, silicon tetrachloride, hexachloro-p-chloride are used as the source of halogen (E). 7. The method according to claim 1, characterized in that methylaluminoxane, ethylaluminoxane, isobutylaluminoxane or mixtures thereof are used as alkylaluminoxane (F). 8. A method for producing polymers and copolymers of conjugated dienes by (co) polymerizing the corresponding monomers in a hydrocarbon solvent in the presence of a catalytic system based on a lanthanide compound, characterized in that the catalytic system is formed by alkylating the alcohol solvate of lanthanide chloride (A2) with a pre-prepared complex of an organoaluminum compound ( C) and Lewis base (D), further interaction of the mixture with an unsaturated hydrocarbon (B), and subsequent activation of the catalytic with the introduction of alkylaluminoxane (F) with a total molar ratio of A2: C: D: B: F (in terms of aluminum) equal to 1: [10-25]: [0-1]: [1-10]: [2-15 ]. 9. The method according to claim 8, characterized in that the salt formed by the interaction of neodymium, praseodymium, lanthanum chloride or mixtures thereof with a monohydric alcohol is used as the alcohol solvate of the lanthanide chloride (A2). 10. The method according to claim 9, characterized in that ethanol, n-propanol, isopropanol, n-butanol, isobutanol, cyclohexanol and octanol are used as monohydric alcohols. 11. The method according to claim 8, characterized in that as the organoaluminum compound (C) diisobutylaluminum hydride, triisobutylaluminum, triethylaluminum or mixtures thereof are used. 12. The method according to claim 8, characterized in that as the Lewis base (D), a compound selected from the group consisting of acetyl acetone, diphenyl ether, methylphenyl ether, triphenylphosphine, phenylacetylacetone is used. 13. The method according to claim 8, characterized in that as the unsaturated hydrocarbon (B) use butadiene, isoprene, piperylene or mixtures thereof. 14. The method according to claim 8, characterized in that methylaluminoxane, ethylaluminoxane, isobutylaluminoxane or mixtures thereof are used as alkylaluminoxane (F).