RU2361888C1 - Method of producing catalyst for polymerisation and copolymerisation of conjugated dienes - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention involves reacting hydrocarbon solutions of a compound of lanthanide A, conjugated diene B and organoaluminium C at molar ratio A:B:C equal to 1:[5-100]:[5-40] for 5-120 minutes, further addition of hydrocarbon solutions of a source of halogen E, alkylalumoxane D and catalyst activation by addition into a hydrocarbon solvent, of a complex of organoaluminium C and a Lewis base F with overall molar ratio of components A:B:C:D (in terms of aluminium): E:F equal to 1:[5-100]:[20-100]:[1-100]:[0.3-6]:[0.1-100].

EFFECT: design of a method of producing catalyst with high activity and stereoselectivity during polymerisation and copolymerisation of conjugated dienes.

7 cl, 20 ex, 1 tbl

Description

The invention relates to methods for producing polymerization and copolymerization catalysts of conjugated dienes and can be used in the synthetic rubber industry.

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 elements (REE) or mixtures thereof with an organohalogen compound selected from the group of primary, secondary or tertiary alkyl, cycloalkyl, aryl, alkylaryl, vinyl , alkoxy, epoxyhalides, and trialkylaluminum or diisobutylaluminum hydride (US Patent No. 4444903, MKI C08F 4/62, publ. 1984). The molar ratio of lanthanide: aluminum: halogen is in the range 1: 30-200: 0.5-3. atalizator prepared by mixing the components at room temperature in any order in the presence or absence of monomer and held for 15 minutes.

Despite the use of affordable and cheap halogenated compounds in the formation of the catalyst, the resulting polymers are characterized by a high content of cis units (up to 99%). Moreover, the catalyst prepared by this method does not have a sufficiently high activity (the output of polybutadiene is only 280 kg / g · atom of neodymium).

A known method of producing a catalyst for the polymerization of conjugated dienes by mixing in a hydrocarbon solvent the reaction product of a compound of a rare-earth element and a Lewis base with an organoaluminum compound (AOC) selected from among aluminum alkyls or alkylaluminium hydrides, with an aluminum halide or alkylaluminum halide in the presence of a conjugated diene (US Pat. 4/14, C08F 4/52, C08F 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 and allows to obtain polymers containing cis-1,4-units up to 97 ,one%.

However, the catalyst prepared by this method also does not have a sufficiently high activity (the yield of polyisoprene reaches 284 kg / g · atom of neodymium), and a significant consumption of organoaluminum compounds leads to an increased ash content in the polymer and limits its scope.

A known method of producing cis-1,4-polybutadiene and cis-1,4-copolymer of butadiene and isoprene in the presence of a catalyst obtained by the interaction of carboxylate compounds of rare earth elements with a halide-containing organoaluminum compound and an organoaluminum compound in the presence of a conjugated diene; as an organoaluminum compound, mixtures of dialkylaluminum hydride, trialkylaluminum, tetraalkyldiallyumoxane are used.

This method of producing a catalyst prepared using mixtures of organoaluminum compounds, allows to increase the activity of the catalyst in comparison with the use of individual AOS. The disadvantages of this method are the low conversion of monomer to 62.5% and the low polymer yield of not more than 247.4 kg / g · at REE (RF Patent No. 2087488, MKI C08F 136/06, 136/08, publ. 08/20/97, Bull . No. 23).

A known method of producing cis-1,4-polybutadiene and cis-1,4-copolymer of butadiene and isoprene under the influence of a Ziegler-Natta catalyst. The catalyst used is a complex preformed by reacting solvated REE salts with an organoaluminum compound in the presence of a conjugated diene. The method allows to obtain polymers with reduced ductility and cold flow (RF Patent No. 2127281, MKI C08F 36/06, 4/54, publ. 10.03.99, Bull. No. 7).

The disadvantages of the method are the need for mixing the components at a negative temperature, which complicates the technology for the preparation of the catalyst and insufficiently high (up to 264.8 kg / g · at REE) polymer yield.

A known method of producing cis-1,4- (co) polymers of conjugated dienes by polymerizing or copolymerizing them together in a hydrocarbon solvent in the presence of a catalytic complex consisting of a compound of lanthanides, an organoaluminum compound, a conjugated diene and a halogen source, the catalytic complex is formed by introducing into a hydrocarbon solution of a conjugated diene, a hydrocarbon solution of a halogen-free organoaluminum compound, holding the resulting mixture for 5-15 minutes, introducing a hydrocarbon solution of a lanthanide compound selected from the group consisting of carboxylates, alcoholates and hydrocarbon-soluble halide complexes at a molar ratio of organoaluminum compound: lanthanide compound 3.1-6.0: 1 and a temperature of 20-50 ° C, activation of the complex by feeding diisobutylaluminium hydride followed by introducing the obtained soluble catalytic complex into a solution of monomers - conjugated dienes in a hydrocarbon solvent medium, in which halogen free was previously introduced organoaluminum compound with a total molar ratio of organoaluminum compound: lanthanide 5-100: 1 and additionally diisobutylaluminum hydride with a molar ratio of diisobutylaluminum hydride: lanthanide 2-10: 1 (RF Patent No. 2203289, MKI C08F 36/06, 136/06, 236/06, 4 / 44, publ. 04/27/03, Bull. No. 12).

The specified method for preparing the catalytic complex allows to obtain polymers with a narrow molecular weight distribution (up to 2.66), a high content of 1,4-cis units (up to 98.2%) with a high degree of monomer conversion of 89-99%. However, a high conversion of the monomer is achieved within 2-6 hours, and the maximum polymer yield is only 327.4 kg / g · at REE.

The closest in technical essence to the present invention is a method of producing a catalyst for the polymerization of butadiene and copolymerization of butadiene with conjugated dienes by the interaction of components including compounds of the rare-earth element, diisobutylaluminium hydride, tetraalkyldialumoxane, alkylaluminium halide and conjugated diene, first they are mixed with for 1-30 minutes, and then tetraalkyldiallyumoxane and alkylaluminium halide are added. The process is carried out with stirring in an atmosphere of inert gas (argon) and ambient temperature. The molar ratio of REE: DIBAG: tetraalkylaluminoxane: alkylaluminium halide (C1): conjugated diene is 1: 3-12: 6-12: 1,5-3: 2-20 (RF Patent No. 2267355, MKI C08F 36/06, 136 / 06, 4/52, publ. 10.01.06, Bull. No. 1).

The specified method for preparing the catalytic complex allows to obtain polymers with a narrow molecular weight distribution (up to 3.1) and a high content of 1,4-cis units (up to 99.1%). However, the maximum polymer yield is 975.5 kg / g · at REE.

An object of the present invention is to develop a method for producing a catalyst having high activity and stereoselectivity in the polymerization and copolymerization of conjugated dienes.

The problem is solved in that in the proposed method, the catalyst is formed by the interaction of hydrocarbon solutions of the compound of lanthanide (A), conjugated diene (B) and organoaluminum compound (C) with a molar ratio of A: B: C equal to 1: [5-100]: [5-40], for 5-120 minutes, the further introduction of hydrocarbon solutions of a source of halogen (E), alkylaluminoxane (D) and activation of the catalyst by introducing a complex of an organoaluminum compound (C) and a Lew base previously formed in a hydrocarbon solvent Isa (F) and the total molar ratio of components A: B: C: D (in terms of aluminum): E: F equal to 1: [5-100]: [20-100]: [1-100]: [0 3-6]: [0.1-100].

Salts formed by neodymium (Nd), praseodymium (Pr), lanthanum (La), cerium (Ce) or mixtures thereof with alpha-branched saturated C ₆ -C ₂₀ or naphthenic acids, preferably neodecanoate, are used as the lanthanide compound (A). neodymium (Nd (Ver) ₃ ), neodymium naphthenate (NdPh ₃ ), neodymium octanoate (Nd (Oct) ₃ ), praseodymium neodecanoate (Pr (Ver) ₃ ), praseodymium naphthenate (Pr ₃ ), praseodymium octanoate (Pr (Ost) ₃₎ neodecanoate lanthanum (La (Ver) ₃₎ octoate, lanthanum (La (Oct.) _3), cerium neodecanoate (Ce (Ver) ₃₎ octoate, cerium (Ce (Oct.) ₃₎ neodecanoate didymium (Di (V r) ₃₎ octanoate didymium (Di (Oct.) _3), didymium naphthenate (DiRh _3).

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

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

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

Alkylaluminoxanes are compounds containing alternating aluminum and oxygen atoms, usually these are compounds of formula (I)

where R can be the same or different, represent a C ₁ -C ₁₀ alkyl group, and p is an integer whose values are in the range from 0 to 40. In this connection, when calculating dosages, as a rule, use molar concentrations of alkylaluminoxanes, calculated on aluminum. Traditionally, the most widely used alkylaluminoxane is methylaluminoxane (MAO), which is an aluminoxane in which R is methyl groups.

As a source of halogen (E) is 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 (TBH), silicon tetrachloride (SiCl ₄ ), tin tetrachloride (SnCl ₄ ), aluminum chloride (AlCl ₃ ), hexachlor-p-chloride HCCH), p-methyltrichloromethylbenzene (MTXMB), dichloro-p-xylene (DHPC).

As the Lewis base (F), a compound selected from the group consisting of acetylacetone (AA), diphenyl ether (DFO), diethyl ether (DEE), methylphenyl ether (MPE), phenylacetylacetone (FAA), ethylacetylacetone (EAA), tert- butylacetylacetone (TBAA), propylacetylacetone (PAA), pyridine, tetrahydrofuran (THF), dimethylformamide (DMF), thiophene, triethylphosphine (TEF), tripropylphosphine (TPF), triisobutylphosphine (TIFPH, ethanol, triphenylphosphine, triphenol) isobutanol.

The indicated order, component composition and molar ratio of components allows one to obtain a catalyst with high activity (up to 2981 kg / g · at REE) and stereoselectivity (up to 99.2%) of the action during polymerization and copolymerization of conjugated dienes. By varying the molar ratio of the components and the dosage of the catalyst, it is possible to effectively control the molecular weight characteristics of the polymer formed during the polymerization and copolymerization, and activation of the catalyst by a preformed complex of the organoaluminum compound (C) and the Lewis base (F) leads to the destruction of the associates of the organoaluminum components of the catalyst, while alkylation of the lanthanide compound (A), which significantly increases the activity of the catalyst.

The polymerization is carried out in aliphatic, alicyclic and aromatic hydrocarbons at a temperature of 0-120 ° C, preferably 20-110 ° C. Conjugated dienes such as butadiene, isoprene or mixtures thereof are used as monomers. The viscosity of the polymer can be controlled by a known method - introducing into the solution of the monomer in a hydrocarbon solvent before feeding the catalyst - diisobutylaluminium hydride. 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 evaluated in kilograms per 1 g · lanthanide atom for 1 hour.

The following are examples illustrating the invention.

Example 1

0.5 ml (0.34 mmol) of a solution of neodymium neodecanoate in hexane, 1.4 ml (1.70 mmol) of a toluene piperylene solution and 3.0 ml are placed in a glass reactor, preheated in a vacuum and filled with dry nitrogen, with stirring (2.73 mmol) of a toluene solution of diisobutylaluminium hydride was incubated for 60 minutes, while the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound was 1: 5: 8. To the resulting mixture, with stirring, add 0.5 ml (0.1 mmol) of a toluene solution of hexachloro-para-xylene, 2.5 ml (3.40 mmol in terms of aluminum) of a toluene solution of methylaluminoxane. Then, to activate the catalyst, a previously prepared complex is introduced, obtained by mixing 7.2 ml (4.10 mmol) of a toluene solution of triisobutylaluminum and 10.0 ml (17.00 mmol) of a toluene solution of diphenyl ether. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 5: 20: 0.3: 10: 50.

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 0.014 g · at / L is used in the polymerization of butadiene. 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 hexane solution containing 3.24 g of butadiene are loaded, the ampoule is thermostated at 60 ° C and 0.22 ml of catalyst is added using a syringe . The molar ratio of butadiene to neodymium is equal to 20,000.

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

Example 2

0.3 ml (0.23 mmol) of a solution of neodymium neodecanoate in hexane, 0.2 ml (0.11 mmol) of a solution of praseodymium neodecanoate in hexane are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring, 1, 4 ml (1.7 mmol) of a toluene solution of piperylene and 1.9 ml (1.7 mmol) of a toluene solution of diisobutylaluminium hydride are held for 60 minutes, while the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound is 1: 5: 5 . To the resulting mixture, 0.3 ml (0.45 mmol) of a toluene solution of ethyl aluminum sesquichloride, 0.25 ml (0.34 mmol Al) of a toluene solution of methylaluminoxane are added with stirring. Then, to activate the catalyst, a previously prepared complex is introduced, obtained by mixing 8.8 ml (5.1 mmol) of a toluene solution of triisobutylaluminum and 0.1 ml (0.034 mmol) of a toluene solution of acetylacetone. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 5: 20: 1.3: 1: 0.1.

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 concentration of neodymium ions of 0.025 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 is 0.16 ml. The molar ratio of butadiene to neodymium is 15,000.

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

Example 3

0.5 ml (0.34 mmol) of a solution of neodymium naphthenate in hexane, 0.7 ml (6.0 mmol) of a toluene solution of butadiene, 0.7 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (2.5 mmol) of a toluene solution of isoprene and 2.1 ml (1.7 mmol) of a toluene solution of triethylaluminum, incubated for 60 minutes, while the molar ratio of the compound of the lanthanide: conjugated diene: organoaluminum compound is 1: 25: 5. To the resulting mixture, 0.4 ml (0.68 mmol) of a toluene solution of diethylaluminium chloride, 3.7 ml (5.1 mmol in terms of aluminum) of a toluene solution of methylaluminoxane are added with stirring. Then, to activate the catalyst, a previously prepared complex is introduced, obtained by mixing 20.5 ml (11.9 mmol) of a toluene solution of triisobutylaluminum and 0.2 ml (0.68 mmol) of a toluene solution of methylphenyl ether. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 25: 40: 2: 15: 2.

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 0.012 g · at / L is used in the polymerization of butadiene. 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 toluene solution containing 4.1 g of butadiene are loaded, the ampoule is thermostated at 60 ° C and 0.26 ml of catalyst is added using a syringe . The molar ratio of butadiene to neodymium is 25,000.

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

Example 4

0.5 ml (0.36 mmol) of a solution of neodymium octanoate in hexane, 2.9 ml (3.6 mmol) of toluene piperylene solution and 4.5 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (3.6 mmol) of a toluene solution of triisobutylaluminum, incubated for 60 minutes, while the molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound is 1:10:10. To the resulting mixture, 0.3 ml (0.5 mmol) of a toluene solution of ethylaluminium dichloride, 16.4 ml (18.0 mmol in terms of aluminum) of a toluene solution of ethylaluminoxane are added with stirring. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 4.0 ml (3.6 mmol) of a toluene solution of diisobutylaluminium hydride and 0.2 ml (0.72 mmol) of a toluene solution of diethyl ether. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 10: 20: 1.3: 50: 2.

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 0.013 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 is 0.32 ml. The molar ratio of butadiene to neodymium is 15,000.

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

Example 5

0.4 ml (0.3 mmol) of a solution of praseodymium octanoate in hexane, 1.0 ml (1.5 mmol) of isoprene toluene solution and 2.2 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (1.8 mmol) of a toluene solution of diisobutylaluminum hydride, incubated for 60 minutes, while the molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound is 1: 5: 6. To the resulting mixture, 0.9 ml (0.7 mmol) of a toluene solution of diisopropylaluminium chloride, 19.7 ml (23.6 mmol in terms of aluminum) of a toluene solution of isobutylaluminoxane are added with stirring. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 7.1 ml (4.2 mmol) of a toluene solution of triisobutylaluminum and 0.1 ml (1.5 mmol) of a toluene solution of phenylacetylacetone. In this case, the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 5: 20: 2.4: 80: 5.

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 concentration of neodymium ions of 0.009 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 is 0.42 ml. The molar ratio of butadiene to neodymium is 15,000.

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

Example 6

0.4 ml (0.3 mmol) of praseodymium naphthenate solution in hexane, 21.2 ml (29.7 mmol) of butadiene toluene solution and 3.3 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (2.7 mmol) of a toluene solution of diisobutylaluminum hydride, incubated for 60 minutes, while the molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound is 1: 100: 9. To the resulting mixture, 0.6 ml (0.6 mmol) of toluene solution of isopropylaluminium sesquichloride and 1.5 ml (2.1 mmol in terms of aluminum) of toluene solution of methylaluminoxane are added with stirring. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 10.7 ml (6.2 mmol) of a toluene solution of triisobutylaluminum and 0.1 ml (1.2 mmol) of a toluene solution of ethyl acetate. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 100: 30: 2: 7: 4.

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 concentration of neodymium ions 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 is 0.38 ml. The molar ratio of butadiene to neodymium is equal to 20,000.

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

Example 7

0.4 ml (0.3 mmol) of a solution of praseodymium octanoate in hexane, 1.2 ml (1.5 mmol) of toluene piperylene solution and 1.8 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (1.5 mmol) of a toluene solution of diisobutylaluminum hydride, incubated for 60 minutes, while the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound is 1: 5: 5. To the resulting mixture, 0.4 ml (0.45 mmol) of toluene solution of isopropylaluminium dichloride, 8.7 ml (11.8 mmol in terms of aluminum) of toluene solution of methylaluminoxane are added with stirring. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 17.8 ml (10.3 mmol) of a toluene solution of triisobutylaluminum and 0.1 ml (0.03 mmol) of a toluene solution of tert-butylacetylacetone. In this case, the molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum), the Lewis base is 1: 5: 40: 1.5: 40: 0.1.

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 0.010 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 is 0.31 ml. The molar ratio of butadiene to neodymium is equal to 20,000.

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

Example 8

0.4 ml (0.3 mmol) of a solution of versatate didim in hexane, 2.4 ml (3.0 mmol) of a toluene piperylene solution and 3.7 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (3.0 mmol) of a toluene solution of diisobutylaluminum hydride, incubated for 60 minutes, while the molar ratio of the compound of the lanthanide: conjugated diene: organoaluminum compound is 1:10:10. To the resulting mixture, 0.7 ml (0.9 mmol) of a toluene solution of diisobutylaluminium chloride, 4.4 ml (5.9 mmol in terms of aluminum) of a toluene solution of methylaluminoxane are added with stirring. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 5.1 ml (3.0 mmol) of a toluene solution of triisobutylaluminum and 0.2 ml (0.3 mmol) of a toluene solution of propylacetylacetone. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 10: 20: 3: 20: 1.

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 0.018 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 is 0.11 ml. The molar ratio of butadiene to neodymium is equal to 30,000.

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

Example 9

0.4 ml (0.3 mmol) of a solution of Didim naphthenate in hexane, 2.4 ml (3.0 mmol) of a toluene piperylene solution and 3.7 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen. (3.0 mmol) of a toluene solution of triethylaluminum, incubated for 60 minutes, while the molar ratio of the compound of the lanthanide: conjugated diene: organoaluminum compound is 1:10:10. To the resulting mixture, 0.5 ml (0.45 mmol) of isobutylaluminium sesquichloride toluene solution, 2.2 ml (3.0 mmol in terms of aluminum) of toluene methylaluminoxane solution are added with stirring. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 5.1 ml (3.0 mmol) of a toluene solution of triisobutylaluminum and 0.1 ml (0.15 mmol) of a toluene solution of pyridine. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 10: 20: 1.5: 10: 0.5.

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 concentration of neodymium ions of 0.021 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 is 0.12 ml. The molar ratio of butadiene to neodymium is 25,000.

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

Example 10

0.4 ml (0.3 mmol) of a solution of Didim octanoate in hexane, 1.2 ml (1.5 mmol) of a toluene piperylene solution and 1.8 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen. (1.4 mmol) of a toluene solution of diisobutylaluminum hydride, incubated for 60 minutes, while the molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound is 1: 5: 5. To the resulting mixture, 0.2 ml (0.3 mmol) of isobutylaluminium dichloride toluene solution, 0.2 ml (0.3 mmol in terms of aluminum) of methylaluminoxane toluene solution, 0.9 ml (1.1 mmol in terms of aluminum) isobutylaluminoxane toluene solution. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 7.2 ml (4.2 mmol) of a toluene solution of triisobutylaluminum and 0.1 ml (0.3 mmol) of a toluene solution of tetrahydrofuran. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 5: 20: 1: 5: 1.

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 concentration of neodymium ions of 0.024 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 is 0.13 ml. The molar ratio of butadiene to neodymium is equal to 20,000.

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

Example 11

0.1 ml (0.15 mmol) of a solution of cerium neodecanoate in hexane, 0.2 ml (0.1 mmol) of a solution of neodycanoate neodymium in hexane are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring, 0, 2 ml (0.1 mmol) of praseodymium neodecanoate solution in hexane, 0.7 ml (1.7 mmol) of piperylene toluene solution, 0.7 ml (1.8 mmol) of isoprene toluene solution, 6.0 ml (3.5 mmol) of a toluene solution of triisobutylaluminum and 4.4 ml (3.6 mmol) of a toluene solution of triethylaluminum, incubated for 60 minutes, while the molar ratio lanthanide compound: conjugated diene: organoaluminum compound is 1:10:20. To the resulting mixture, 3.5 ml (2.1 mmol) of a toluene solution of tert-butyl chloride, 5.1 ml (7.0 mmol in terms of aluminum) of a toluene solution of methylaluminoxane are added with stirring. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 8.7 ml (7.0 mmol) of a toluene solution of diisobutylaluminium hydride and 0.3 ml (0.35 mmol) of a toluene solution of dimethylformamide. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 5: 40: 6: 20: 1.

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 0.011 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 is 0.27 ml. The molar ratio of butadiene to neodymium is equal to 20,000.

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

Example 12

0.3 ml (0.27 mmol) of a solution of cerium neodecanoate in hexane, 2.2 ml (2.7 mmol) of a toluene piperylene solution, 5.0 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (4.1 mmol) of a toluene solution of diisobutylaluminum hydride and 1.7 ml (1.4 mmol) of a toluene solution of triethylaluminum, incubated for 60 minutes, while the molar ratio of the compound of the lanthanide: conjugated diene: organoaluminum compound is 1:10:20. To the resulting mixture, 0.1 ml (0.135 mmol) of a toluene solution of silicon tetrachloride, 4.0 ml (5.5 mmol in terms of aluminum) of a toluene solution of methylaluminoxane are added with stirring. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 28.0 ml (16.2 mmol) of a toluene solution of triisobutylaluminum and 0.1 ml (0.027 mmol) of a toluene solution of thiophene. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 10: 80: 0.5: 20: 0.1.

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 0.007 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 is 0.31 ml. The molar ratio of butadiene to neodymium is equal to 30,000.

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

Example 13

0.5 ml (0.34 mmol) of a solution of neodymium neodecanoate in hexane, 2.8 ml (3.4 mmol) of a toluene piperylene solution and 3.7 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (3.4 mmol) of a toluene solution of diisobutylaluminum hydride, incubated for 60 minutes, while the molar ratio of the compound of the lanthanide: conjugated diene: organoaluminum compound is 1:10:10. To the resulting mixture, 0.2 ml (0.28 mmol) of toluene solution of tin tetrachloride, 1.3 ml (1.8 mmol in terms of aluminum) of toluene solution of methylaluminoxane are added with stirring. Then, in order to activate the catalyst, a previously prepared complex is introduced, obtained by mixing 11.7 ml (6.8 mmol) of a toluene solution of triisobutylaluminum and 0.2 ml (2.72 mmol) of a toluene solution of triethylphosphine. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: source of halogen: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 10: 30: 0.8: 5: 8.

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 0.017 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 is 0.24 ml. The molar ratio of butadiene to neodymium is equal to 15,000.

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

Example 14

0.5 ml (0.34 mmol) of a solution of lanthanum neodecanoate in hexane, 0.8 ml (1.0 mmol) of toluene piperylene solution, 0.5 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (0.7 mmol) of a toluene solution of butadiene and 1.9 ml (1.7 mmol) of a toluene solution of diisobutylaluminium hydride was incubated for 60 minutes, while the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound was 1: 5: 5. To the resulting mixture, with stirring, add 0.2 ml (0.22 mmol) of a toluene solution of carbon tetrachloride, 1.6 ml (1.8 mmol in terms of aluminum) of a toluene solution of ethylaluminoxane, 1.5 ml (1.8 mmol in terms of on aluminum) toluene solution of isobutylaluminoxane. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 8.8 ml (5.1 mmol) of a toluene solution of triisobutylaluminum and 0.2 ml (3.4 mmol) of a toluene solution of tripropylphosphine. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: source of halogen: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 5: 20: 0.6: 10: 10.

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 concentration of neodymium ions of 0.022 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 is 0.14 ml. The molar ratio of butadiene to neodymium is equal to 20,000.

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

Example 15

0.5 ml (0.33 mmol) of a solution of lanthanum octanoate in hexane, 1.3 ml (1.6 mmol) of toluene piperylene solution, 0.5 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (0.8 mmol) of isoprene toluene solution, 0.6 ml (0.8 mmol) of butadiene toluene solution, 1.1 ml (1.0 mmol) of diisobutylaluminum hydride toluene solution, 0.4 ml (0.3 mmol) of toluene solution triisobutylaluminum and 0.4 ml (0.3 mmol) of a toluene solution of triethylaluminum, incubated for 60 minutes, while the molar ratio union of a lanthanide: conjugated diene: an organoaluminum compound is 1: 10: 5. To the resulting mixture, 0.3 ml (0.33 mmol) of a toluene solution of aluminum chloride, 9.5 ml (13.0 mmol in terms of aluminum) of a toluene solution of methylaluminoxane, 5.4 ml (6.5 mmol in terms of aluminum) a toluene solution of isopropylaluminoxane, 5.9 ml (5.9 mmol in terms of aluminum) of a toluene solution of ethylaluminoxane Then, to activate the catalyst, a previously prepared complex is introduced, obtained by mixing 8.6 ml (5.0 mmol) of a toluene solution of triisobutylaluminium and 0, 1 ml (5.0 mmol) of triisobutyl toluene solution phosphine. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 10: 20: 1: 80: 15.

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 0.010 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 is 0.2 ml. The molar ratio of butadiene to neodymium is equal to 30,000.

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

Example 16

0.5 ml (0.34 mmol) of a solution of neodymium neodecanoate in hexane, 1.9 ml (2.6 mmol) of a toluene piperylene solution and 3.0 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (2.7 mmol) of a toluene solution of diisobutylaluminium hydride, incubated for 60 minutes, while the molar ratio of the compound of the lanthanide: conjugated diene: organoaluminum compound is 1: 7.5: 8. To the resulting mixture, 0.8 ml (1.03 mmol) of a toluene solution of methyltrichloromethylbenzene, 14.9 ml (20.4 mmol in terms of aluminum) of a toluene solution of methylaluminoxane are added with stirring. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 7.1 ml (4.1 mmol) of a toluene solution of triisobutylaluminum and 1.1 ml (34.0 mmol) of a toluene solution of triphenylphosphine. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 7.5: 20: 3: 60: 100.

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 0.012 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 is 0.17 ml. The molar ratio of butadiene to neodymium is equal to 30,000.

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

Example 17

In a glass reactor, preheated in a vacuum and filled with dry nitrogen, 0.5 ml (0.34 mmol) of a solution of neodymium neodecanoate in hexane, 2.1 ml (2.6 mmol) of toluene piperylene solution and 3.7 ml are placed with stirring (3.4 mmol) of a toluene solution of diisobutylaluminum hydride, incubated for 60 minutes, while the molar ratio of the compound of the lanthanide: conjugated diene: organoaluminum compound is 1: 7.5: 10. To the resulting mixture, 0.5 ml (0.65 mmol) of a toluene solution of dichloro-p-xylene, 10.0 ml (13.7 mmol in terms of aluminum) of a toluene solution of methylaluminoxane are added with stirring. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 5.8 ml (3.4 mmol) of a toluene solution of triisobutylaluminum and 0.2 ml (0.17 mmol) of a toluene solution of methanol. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 7.5: 20: 2: 40: 0.5.

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 0.014 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 is 0.13 ml. The molar ratio of butadiene to neodymium is equal to 30,000.

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

Example 18

0.2 ml (0.14 mmol) of a solution of neodymium octanoate in hexane, 0.3 ml (0.18 mmol) of a solution of praseodymium octanoate, 1.8 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (2.4 mmol) of a toluene solution of piperylene and 3.5 ml (3.2 mmol) of a toluene solution of diisobutylaluminium hydride, incubated for 60 minutes, while the molar ratio of the compound of the lanthanide: conjugated diene: organoaluminum compound is 1: 7.5: 10 . To the resulting mixture, 0.1 ml (0.13 mmol) of a toluene solution of hexachloro-para-xylene, 4.7 ml (6.4 mmol in terms of aluminum) of a toluene solution of methylaluminoxane are added with stirring. Then, to activate the catalyst, a pre-prepared complex is introduced, obtained by mixing 5.5 ml (3.2 mmol) of a toluene solution of triisobutylaluminum and 0.5 ml (0.29 mmol) of a toluene solution of ethanol. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 7.5: 20: 0.4: 20: 0.9.

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 0.019 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 is 0.10 ml. The molar ratio of butadiene to neodymium is equal to 30,000.

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

Example 19

In a glass reactor, preheated in a vacuum and filled with dry nitrogen, 0.5 ml (0.34 mmol) of a solution of neodymium neodecanoate in hexane, 2.1 ml (2.55 mmol) of toluene piperylene solution, 7.4 ml are placed with stirring (6.81 mmol) of a toluene solution of diisobutylaluminium hydride and 11.7 ml (6.79 mmol) of a toluene solution of triisobutylaluminum, incubated for 120 minutes, while the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound is 1: 7.5: 40 . To the resulting mixture, 0.57 ml (0.68 mmol) of a toluene solution of diisobutylaluminium chloride and 25 ml (34.00 mmol in terms of aluminum) of a toluene solution of methylaluminoxane are added with stirring. Then, to activate the catalyst, a previously prepared complex is introduced, obtained by mixing 6.0 ml (3.40 mmol) of a toluene solution of triisobutylaluminum and 0.45 ml (0.13 mmol) of a hexane solution of isopropanol. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 7.5: 50: 2: 100: 0.4.

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 concentration of neodymium ions of 0.007 g · at / L is used in the polymerization of 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 4.1 g of isoprene are loaded, the ampoule is thermostated at 60 ° C and 0.35 ml of catalyst is added using a syringe . The molar ratio of isoprene and neodymium is equal to 25,000.

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

Example 20

0.5 ml (0.34 mmol) of a solution of neodymium neodecanoate in hexane, 0.7 ml (0.87 mmol) of a toluene piperylene solution, 1.1 ml are placed in a glass reactor, previously heated in vacuum and filled with dry nitrogen, with stirring (0.65 mmol) of a toluene solution of isoprene and 3.74 ml (3.40 mmol) of a toluene solution of diisobutylaluminium hydride was incubated for 5 minutes, while the molar ratio of lanthanide compound: conjugated diene: organoaluminum compound was 1: 7.5: 10 . To the resulting mixture, 0.4 ml (0.68 mmol) of a toluene solution of diethylaluminium chloride, 12.5 ml (17.00 mmol in terms of aluminum) of a toluene solution of methylaluminoxane, 12.5 ml (17.00 mmol in terms of aluminum) toluene ethylaluminoxane solution. Then, in order to activate the catalyst, a previously prepared complex is introduced, obtained by mixing 25.50 ml (30.60 mmol) of a toluene solution of diisobutylaluminium hydride and 0.45 ml (0.13 mmol) of a hexane solution of isobutanol. The molar ratio of the lanthanide compound: conjugated diene: organoaluminum compound: halogen source: alkylaluminoxane (in terms of aluminum): Lewis base is 1: 7.5: 100: 2: 100: 0.4.

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 0.006 g · at / L is used in the copolymerization of isoprene and butadiene. 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 toluene solution containing 2.05 g of isoprene and 1.62 g of butadiene are loaded, the ampoule is thermostated at 60 ° C and added using syringe 0.58 ml of catalyst. The molar ratio of monomers to neodymium is equal to 20,000.

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

As can be seen from the above examples, the proposed method allows to obtain a catalyst with high activity and stereoselectivity in the polymerization and copolymerization of conjugated dienes.

Claims (7)

1. A method of obtaining a catalyst for the polymerization and copolymerization of conjugated dienes by reacting hydrocarbon solutions of the compound of lanthanide (A), conjugated diene (B) and organoaluminum compound (C) with a molar ratio of A: B: C equal to 1: [5-100]: [ 5-40], for 5-120 minutes, the further introduction of hydrocarbon solutions of a source of halogen (E), alkylaluminoxane (D) and activation of the catalyst by introducing a complex of an organoaluminum compound (C) and a Lewis base preformed in a hydrocarbon solvent a (F) with a total molar ratio of components A: B: C: D (in terms of aluminum): E: F equal to 1: [5-100]: [20-100]: [1-100]: [0 3-6]: [0.1-100]. 2. The method according to claim 1, characterized in that the salts of lanthanide (A) are salts formed by neodymium, praseodymium, lanthanum, cerium or mixtures thereof with alpha-branched saturated C ₆ -C ₁₀ or naphthenic acids. 3. The method according to claim 1, characterized in that butadiene, isoprene, piperylene or mixtures thereof are used as the conjugated diene (B). 4. The method according to claim 1, characterized in that diisobutylaluminum hydride, triisobutylaluminum, triethylaluminum and mixtures thereof are used as the organoaluminum compound (C). 5. The method according to claim 1, characterized in that as alkylaluminoxane (D) use methylaluminoxane, ethylaluminoxane, isobutylaluminoxane or mixtures thereof. 6. A method according to claim 1, characterized in that as the halogen source (E) is diethyl aluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diisopropylaluminum chloride, izopropilalyuminiyseskvihlorid, isopropylaluminum chloride, diisobutylaluminum chloride, izobutilalyuminiyseskvihlorid, isobutylaluminum dichloride, carbon tetrachloride, tert-butyl chloride, silicon tetrachloride, tin tetrachloride , aluminum chloride, hexachloro-p-xylene, p-methyltrichloromethylbenzene, dichloro-p-xylene. 7. The method according to claim 1, characterized in that the Lewis base (F) uses a compound selected from the group consisting of acetylacetone, diphenyl ether, methylphenyl ether, diethyl ether, phenylacetylacetone, ethylacetylacetone, tert-butylacetylacetone, propylacetylacetone, pyridine, tetrahydrofuran, dimethylformamide, thiophene, triethylphosphine, tripropylphosphine, triisobutylphosphine, triphenylphosphine, methanol, ethanol, isopropanol, isobutanol.