RU2254923C1 - Method of preparing catalysts for polymerization and copolymerization of conjugated dienes - Google Patents

Abstract

FIELD: polymerization catalysts.

SUBSTANCE: catalysts, which may, in particular, be used in production of cis-1,4-homopolymers and cis-1,4-copolymers in synthetic rubber industry, are prepared by reaction of rare-earth element compound and conjugated diene in hydrocarbon solvent with preliminarily formed complex, the latter being prepared by chlorination agent-alkylation agent-Lewis base triple interaction.

EFFECT: increased activity and stereoselectivity of catalyst.

10 cl, 1 tbl, 20 ex

Description

The invention relates to methods for producing polymerization and copolymerization catalysts of conjugated dienes and may find application in the production of cis-1,4 homopolymers and cis-1,4 copolymers in the synthetic rubber industry.

A method of producing a polymerization catalyst dienes by pre-contact in the hydrocarbon solvent carboxylate lanthanide having atomic number from 57 to 60, with triisobutylaluminum or diisobutyl aluminum hydride, organohalogen compound selected from among the aluminum halides, alkylaluminum halides, and conjugated diene (U.S. Patent № 3794604, IPC ² C 08 F 1/14, publ. 1974). The molar ratio of lanthanide: aluminum: halogen: conjugated diene is in the range 1: 4-200: 0.1-6: 5-500. The mixture is kept at room temperature from several minutes to several days, and then used in the polymerization of dienes at 50 ° C.

The catalyst thus obtained is characterized by stability over time, but it has low activity (polybutadiene yield is only 74 kg / g · cerium) and relatively low stereoselectivity (cis-1.4 units in the polymer is about 97%).

A known method of producing a catalyst for the polymerization of conjugated dienes by reacting them in a hydrocarbon solvent with compounds of individual rare earth metals or a mixture thereof with an organohalogen compound selected from the group of primary, secondary or tertiary alkyl, cycloalkyl, aryl, alkylaryl, vinyl, alkoxy , epoxyhalides, and trialkylaluminium or diisobutylaluminum hydride (US Patent No. 4444903, MKI ³ C 08 F 4/62, publ. 1984). The molar ratio of lanthanide: aluminum: halogen is in the range 1: 30-200: 0.5-3. The catalyst was prepared by mixing at room temperature in any order in the presence or absence of monomer and held for 15 minutes.

Despite the use of the most affordable and cheapest halogen compounds in the formation of the catalyst, the obtained polymers are characterized by a high content of cis units (up to 99%), the catalytic complex prepared by this method has insufficient activity (the output of polybutadiene is only 280 kg / g · at neodymium )

The closest in technical essence to the proposed one is a method for producing a polymerization catalyst for conjugated dienes by mixing in a hydrocarbon solvent the product of the interaction of a compound of a rare-earth element and a Lewis base with an organoaluminum compound selected from among aluminum alkyls or alkylaluminium hydrides with an aluminum halide or an alkylaluminum halide in the presence of a conjugated US No. 4461883, MKI ³ C 08 F 4/14, C 08 F 4/52, C 08 F 2/06, publ. 1984).

The catalyst is prepared by mixing the components at a temperature of 50 ° C and incubated for 30 minutes Obtained at optimal molar ratios, the neodymium compound: Lewis base: conjugated diene: aluminum: halogen equal to 1: 2: 10: 50: 2.5, the catalyst is stable in time, has good activity (the yield of polyisoprene reaches 284 kg / g · at neodymium ), allows to obtain polymers with a cis-1.4 content of up to 97.1%.

However, the method has several disadvantages, namely, insufficiently high activity and stereoselectivity of the catalyst. In addition, the high consumption of organoaluminum compounds leads to an increased ash content in the polymer and limits its scope.

The objective of the invention is to develop a method that can significantly increase the activity of the catalyst, as well as making it possible to obtain polymers with a high content of cis-1,4-units.

The problem is solved by developing a method for producing a polymerisation and copolymerization catalyst of conjugated dienes by mixing in a hydrocarbon solvent a compound of a rare-earth element (A) and a conjugated diene (B) with a preformed complex resulting from the interaction of a chlorinating agent (C), an alkylating agent (D), and Lewis Foundation (E).

Butadiene, isoprene, piperylene or mixtures thereof are used as conjugated diene (B).

As the compound of the rare-earth element (A), salts formed by neodymium (Nd), praseodymium (Pr), lanthanum (La), cerium (Ce) or their mixtures with alpha-branched saturated C ₆ -C ₂₀ or naphthenic acids are used, preferably using neodymium neodecane (Nd (Ver) ₃ ), neodymium naphthenate (NdPh ₃ ), neodymium octanoate (Nd (Oct) ₃ ), praseodymium neodecane (Pr (Ver) ₃ ), praseodymium naphthenate (Pr ₃ ), praseodymium octanoate (Pr (Ot ) ₃ ), lanthanum neodecane (La (Vеr) ₃ ), lanthanum octanoate (La (Ost) ₃ ), cerium neodecane (Ce (Ver) ₃ ), cerium octanoate (Ce (Ost) ₃ ), neodecane Didim (Di (Ver) ₃ ), Didyme naphthenate (DiPh ₃ ), Didim octanoate (Di (Oct) ₃ ).

As the chlorinating agent (C) selected compound from the group consisting of diethylaluminum chloride (DEAC), ethylaluminum sesquichloride (EASKH), ethylaluminum dichloride (EADC), diisopropylaluminum chloride (DIPAH) izopropilalyuminiyseskvihlorid (IPASKH), isopropylaluminum (IPADH) diisobutylaluminum chloride (Diebach) izobutilalyuminiyseskvihlorid ( IBASCH), isobutylaluminium dichloride (IBADC), carbon tetrachloride (CCl ₄ ), tert-butyl chloride, silicon tetrachloride (SiCl ₄ ), tin tetrachloride (SnCl ₄ ), aluminum chloride (AlCl ₃ ).

As the alkylating agent (D), a compound of the formula R ¹ R ² R ³ Al is used, where R ¹ , R ² is an aliphatic C ₂ -C ₈ or an aromatic hydrocarbon radical or hydrogen, R ³ is an aliphatic C ₂ -C ₈ or aromatic hydrocarbon radical or AlR ¹ R ² , preferably using triisobutylaluminum (TIBA), diisobutylaluminum hydride (DIBAG), triethylaluminum (TEA).

As the Lewis base (E), a compound selected from the group consisting of acetylacetone, phenylacetylacetone, ethylacetylacetone, tert-butylacetylacetone, propylacetylacetone, pyridine, tetrahydrofuran, dimethylformamide, thiophene, diphenyl ether, methylphenyl ether, triethylphosphine, triethylphenyl triethyl triphenyl triphenyl triethyl triphenyl triphenyl triethyl triphenyl triethyl triethyl triethyl triethyl triethyl triethyl triethyl triethyl triethyl diphenyl triethyl diphenyl triethyl triethyl diphenyl methanol, ethanol, isopropanol, isobutanol.

The molar ratios of the components are kept equal: component (A): component (B) - 1: 1-100; component (A): component (C) - 1: 0.5-6; component (A): component (D) - 1: 10-150; component (A): component (E) -1: 0.1-100.

Preliminary formation of the Lewis base complex (E) with an alkylating agent (D) and a chlorinating agent (C) leads to the destruction of the associates of the latter. In this case, the best alkylation, halogenation of the rare-earth metal compound (A) occurs, the activity of the catalytic complex increases by 30-50%, the regulation of the molecular weight of the obtained polymer improves.

The application of the proposed method for the formation of the catalyst leads to an increase in its solubility in hydrocarbons, which improves the molecular weight distribution, the homogeneity of the obtained polymer and increases the dosage accuracy of the catalytic complex.

An additional advantage of the proposed method is that during the preliminary formation of the Lewis base complex (E) with an alkylating agent (D), a chlorinating agent (C) and its further interaction with the catalyst components, the maximum activity of the catalytic complex is achieved at lower ratios of rare-earth metal: organoaluminum compound, this reduces the consumption rate of organoaluminum compounds per ton of rubber produced.

The polymerization is carried out in aliphatic, alicyclic and aromatic hydrocarbons at a temperature of 0-120 ° C, preferably 20-110 ° C. The viscosity of the polymer can be controlled by a known method — introducing monomer in a hydrocarbon solvent into a solution before feeding diisobutyl aluminum hydride catalyst. At the end of the polymerization, the catalyst is deactivated, and the polymer is precipitated by the introduction of ethanol containing an antioxidant. The polymer is dried in vacuo to constant weight.

The activity of the catalyst is estimated in kg of polymer per 1 g · atom of rare earth metal for 1 hour.

The following are examples illustrating the invention.

Example 1

0.5 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.2 ml (0.045 mmol) of a toluene solution of diisobutylaluminium chloride, 0.45 ml (0.0225) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring mmol) of a toluene solution of diphenyl ether, incubated for one hour at a temperature of 40 ° C. Then, 0.3 ml (0.0225 mmol) of neodymium neodecane solution and 0.1 ml (0.11 mmol) of piperylene toluene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of neodymium ions in the catalytic complex is 0.016 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 2

0.5 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.2 ml (0.045 mmol) of a toluene solution of diethylaluminium chloride, 0.0045 ml (0.00225) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring mmol) of toluene solution of acetylacetone, incubated for one hour at a temperature of 25 ° C. Then, 0.2 ml (0.015 mmol) of neodymium neodecane, 0.1 ml (0.0075 mmol) of neodymium octanoate and 0.1 ml (0.11 mmol) of piperylene toluene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The resulting catalyst with a neodymium ion concentration of 0.0116 g · at / L is used for the copolymerization of butadiene and isoprene. In a glass ampoule pre-heated in vacuum at 150-200 ° C and filled with dry nitrogen with a self-tightening rubber stopper, 40 ml of a cyclohexane solution containing 2.16 g of butadiene and 1.36 g of isoprene are loaded, the ampoule is thermostated at 60 ° C and added using syringe 0.34 ml of catalyst.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 3

1.1 ml (1.125 mmol) of a toluene solution of triethyl aluminum, 0.12 ml (0.029 mmol) of a toluene solution of ethyl aluminum sesquichloride, 0.1 ml (0.045 mmol) of a toluene solution are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring phenylacetylacetone, incubated for one hour at a temperature of 25 ° C. Then, 0.3 ml (0.0225 mmol) of neodymium naphthenate and 0.1 ml (0.11 mmol) of isoprene toluene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The resulting catalyst with a neodymium concentration of 0.0116 g · at / L is used for the polymerization of isoprene. 40 ml of a toluene solution containing 3.84 g of isoprene are pre-heated in a vacuum at 150-200 ° C and filled with dry nitrogen with a self-tightening rubber stopper, the ampoule is thermostated at 60 ° C and 0.343 ml of catalyst is added using a syringe.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 4

3.4 ml (3.375 mmol) of a toluene solution of triisobutylaluminum, 0.1 ml (0.0225 mmol) of a toluene solution of ethylaluminium dichloride, 0.1 ml (0.045 mmol) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring a toluene solution of ethylacetylacetone, incubated for one hour at a temperature of 25 ° C. Then, 0.1 ml (0.0075 mmol) of neodymium octanoate, 0.1 ml (0.0075 mmol) of cerium neodecane, 0.1 ml (0.0075 mmol) of praseodymium neodecane and 1.8 ml are added to the resulting complex with stirring (2.25 mmol) butadiene toluene solution.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The total concentration of rare earth ions in the catalytic complex is 0.0116 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 5

0.5 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.23 ml (0.0563 mmol) of a toluene solution of diisopropylaluminium chloride, 0.22 ml (0) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring , 1125 mmol) of a toluene solution of tert-butylacetylacetone, incubated for one hour at a temperature of 25 ° C. Then, 0.3 ml (0.0225 mmol) of praseodymium neodecane and 0.18 ml (0.225 mmol) of isoprene toluene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of praseodymium ions in the catalytic complex is 0.01618 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 6

0.7 ml (0.675 mmol) of a toluene solution of diisobutylaluminium hydride, 0.19 ml (0.045 mmol) of a toluene solution of isopropylaluminium sesquichloride, 0.18 ml (0.09 mmol) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring a toluene solution of propylacetylacetone, incubated for one hour at a temperature of 25 ° C. Then, 0.3 ml (0.0225 mmol) of praseodymium naphthenate, 0.05 ml (0.055 mmol) of piperylene toluene solution and 0.05 ml (0.055 mmol) of isoprene toluene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of praseodymium ions in the catalytic complex is 0.0157 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 7

0.5 ml (0.45 mmol) of a toluene solution of triethyl aluminum, 0.14 ml (0.0338 mmol) of a toluene solution of isopropyl aluminum dichloride, 0.0045 ml (0) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring , 0023 mmol) of a toluene solution of pyridine, incubated for one hour at a temperature of 25 ° C. Then, to the resulting complex, 0.3 ml (0.0225 mmol) of praseodymium octanoate, 0.04 ml (0.04 mmol) of piperylene toluene solution, 0.04 ml (0.04 mmol) of isoprene toluene solution and 0.031 ml are added with stirring (0.031 mmol) butadiene toluene solution.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of praseodymium ions in the catalytic complex is 0.0228 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 8

0.5 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.28 ml (0.0675 mmol) of a toluene solution of diisobutylaluminium chloride, 0.045 ml (0.0225) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring mmol) of a toluene solution of tetrahydrofuran, incubated for one hour at a temperature of 25 ° C. Then, to the resulting complex, 0.3 ml (0.0225 mmol) of didim neodecane and 0.1 ml (0.112 mmol) of toluene piperylene solution are added with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of didim ions in the catalytic complex is 0.0192 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 9

0.5 ml (0.45 mmol) of a toluene solution of triethyl aluminum, 0.14 ml (0.0338 mmol) of a toluene solution of isobutylaluminium sesquichloride, 0.022 ml (0.0113) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring mmol) of toluene solution of dimethylformamide, incubated for one hour at a temperature of 25 ° C. Then, 0.3 ml (0.0225 mmol) of Didim naphthenate and 0.18 ml (0.225 mmol) of piperylene toluene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of didim ions in the catalytic complex is 0.0205 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 10

0.5 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.09 ml (0.0225 mmol) of a toluene solution of isobutylaluminium dichloride, 0.045 ml (0.0225) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring mmol) of toluene solution of thiophene, incubated for one hour at a temperature of 25 ° C. Then, 0.3 ml (0.0225 mmol) of didim octanoate and 0.09 ml (0.1125 mmol) of toluene piperylene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex. The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of didim ions in the catalytic complex is 0.0229 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 11

0.5 ml (0.45 mmol) of a toluene solution of triisobutylaluminum, 0.56 ml (0.135 mmol) of a toluene solution of tert-butyl chloride, 0.045 ml (0.0225 mmol) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen. toluene solution of methylphenyl ether, incubated for one hour at a temperature of 25 ° C. Then, 0.2 ml (0.015 mmol) of neodymium neodecane, 0.1 ml (0.0075 mmol) of cerium octanoate and 0.09 ml (0.1125 mmol) of toluene piperylene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex. The polymerization of butadiene-1,3 is carried out according to example 1. The total concentration of rare earth ions in the catalytic complex is 0.0116 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 12

0.225 ml (0.225 mmol) of a toluene solution of diisobutylaluminium hydride, 0.08 ml (0.018 mmol) of a toluene solution of silicon tetrachloride, 0.0045 ml (0.0022 mmol) of toluene are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring a solution of diethyl ether, incubated for one hour at a temperature of 25 ° C. Then, 0.3 ml (0.0225 mmol) of neodymium neodecane and 0.18 ml (0.225 mmol) of toluene piperylene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of neodymium ions in the catalytic complex is 0.0286 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 13

0.45 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.13 ml (0.0304 mmol) of a toluene solution of tin tetrachloride, 0.36 ml (0.46 ml) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring 0.18 mmol) of a toluene solution of triethylphosphine, incubated for one hour at a temperature of 25 ° C. Then, to the obtained complex, 0.3 ml (0.0225 mmol) of cerium neodecane 0.18 ml (0.225 mmol) of toluene piperylene solution are added with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of cerium ions in the catalytic complex is 0.0158 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 14

0.45 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.12 ml (0.0299 mmol) of a toluene solution of carbon tetrachloride, 0.36 ml (0.46 ml) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring 0.18 mmol) of toluene solution of tripropylphosphine, incubated for one hour at a temperature of 25 ° C. Then, to the resulting complex, 0.3 ml (0.0225 mmol) of lanthanum neodecane 0.18 ml (0.225 mmol) of toluene piperylene solution are added with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of lanthanum ions in the catalytic complex is 0.01494 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 15

0.45 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.09 ml (0.0225 mmol) of a toluene solution of aluminum chloride, 0.675 ml (0.3375) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen. mmol) of a toluene solution of triisobutylphosphine, incubated for one hour at a temperature of 25 ° C. Then, to the obtained complex, 0.3 ml (0.0225 mmol) of lanthanum octanoate 0.18 ml (0.225 mmol) of toluene piperylene solution are added with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of lanthanum ions in the catalytic complex is 0.01323 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 16

0.45 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.19 ml (0.045 mmol) of a toluene solution of diisobutylaluminium chloride, 0.45 ml (0.225 mmol) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring toluene solution of triphenylphosphine, incubated for one hour at a temperature of 25 ° C. Then, 0.3 ml (0.0225 mmol) of neodymium neodecane and 0.18 ml (0.225 mmol) of toluene piperylene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of neodymium ions in the catalytic complex is 0.01434 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 17

0.45 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.19 ml (0.045 mmol) of a toluene solution of diisobutylaluminium chloride, 0.02 ml (0.0113) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring mmol) of a toluene solution of methanol, incubated for one hour at a temperature of 25 ° C. Then, 0.3 ml (0.0225 mmol) of neodymium neodecane and 0.18 ml (0.225 mmol) of toluene piperylene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of neodymium ions in the catalytic complex is 0.01971 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 18

0.45 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.19 ml (0.045 mmol) of a toluene solution of diisobutylaluminium chloride, 0.04 ml (0.0203) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring mmol) of a toluene solution of ethanol, incubated for one hour at a temperature of 25 ° C. Then, 0.3 ml (0.0225 mmol) of neodymium neodecane and 0.18 ml (0.225 mmol) of toluene piperylene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of neodymium ions in the catalytic complex is 0.01941 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 19

0.45 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.19 ml (0.045 mmol) of a toluene solution of diisobutylaluminium chloride, 0.018 ml (0.009 mmol) of toluene solution are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring isopropanol, incubated for one hour at a temperature of 25 ° C. Then, 0.3 ml (0.0225 mmol) of neodymium neodecane and 0.18 ml (0.225 mmol) of toluene piperylene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of neodymium ions in the catalytic complex is 0.01979 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

Example 20

0.45 ml (0.45 mmol) of a toluene solution of diisobutylaluminium hydride, 0.19 ml (0.045 mmol) of a toluene solution of diisobutylaluminium chloride, 0.02 ml (0.0113) are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring mmol) toluene solution of isobutanol, incubated for one hour at a temperature of 25 ° C. Then, 0.3 ml (0.0225 mmol) of neodecane and 0.18 ml (0.225 mmol) of toluene piperylene solution are added to the resulting complex with stirring.

The contents of the reactor are incubated for 24 hours at a temperature of 25 ° C until the complete maturation of the catalytic complex.

The polymerization of butadiene-1,3 is carried out according to example 1. The concentration of neodymium ions in the catalytic complex is 0.01971 g · at / L.

After 1 hour, the polymer is isolated, dried to constant weight. The experimental conditions and the data obtained are shown in the table.

As can be seen from the above examples, the proposed method can significantly increase the activity of the catalyst, as well as to obtain polymers with a high content of cis-1,4 units, which provides good technological properties and a high level of physico-mechanical properties of rubber.

Claims (10)

1. A method of obtaining a catalyst for the polymerization and copolymerization of conjugated dienes by mixing in a hydrocarbon solvent a compound of a rare-earth element (A), a conjugated diene (B), a chlorinating agent (C), an alkylating agent (D) and a Lewis base (E), characterized in that components (A) and (B) are mixed with a preformed complex resulting from the interaction of a chlorinating agent (C), an alkylating agent (D) and a Lewis base (E). 2. The method according to claim 1, characterized in that butadiene, isoprene, piperylene or mixtures thereof are used as the conjugated diene (B). 3. The method according to claim 1, characterized in that as the compound of the rare-earth element (A), salts formed by neodymium, praseodymium, lanthanum, cerium or mixtures thereof with alpha-branched saturated C ₆ -C ₂₀ or naphthenic acids are used. 4. A method according to claim 1, characterized in that as a chlorinating agent (C) a compound selected from the group consisting of aluminum chloride, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diisopropylaluminum chloride, izopropilalyuminiyseskvihlorid, isopropylaluminum chloride, diisobutylaluminum chloride, izobutilalyuminiyseskvihlorid, isobutylaluminum dichloride, carbon tetrachloride, tert butyl chloride, silicon tetrachloride, tin tetrachloride. 5. The method according to claim 1, characterized in that the alkylating agent (D) is a compound of the formula R ¹ R ² R ³ Al, where R ¹ , R ² is an aliphatic C ₂ -C ₈ , or an aromatic hydrocarbon radical, or hydrogen, R ³ is an aliphatic C ₂ -C ₈ , or an aromatic hydrocarbon radical, or OalR ¹ R ² . 6. The method according to claim 1, characterized in that as the Lewis base (E), a compound is selected from the group consisting of acetylacetone, phenylacetylacetone, ethylacetylacetone, tert-butylacetylacetone, propylacetylacetone, pyridine, tetrahydrofuran, dimethylformamide, thiophene, diphenyl ether, methylphenyl ether , diethyl ether, triethylphosphine, tripropylphosphine, triisobutylphosphine, triphenylphosphine, methanol, ethanol, isopropanol, isobutanol. 7. The method according to claim 1, characterized in that the molar ratio of component (A): component (B) is maintained equal to 1: 1 ÷ 100. 8. The method according to claim 1, characterized in that the molar ratio of component (A): component (C) is maintained equal to 1: 0.5 ÷ 6. 9. The method according to claim 1, characterized in that the molar ratio of component (A): component (D) is maintained equal to 1: 10 ÷ 150. 10. The method according to claim 1, characterized in that the molar ratio of component (A): component (E) is maintained equal to 1: 0.1 ÷ 100.