RU2667061C1 - Dilithium initiator for anionic (co)polymerization, method for preparing the same, method for producing diene rubbers based on the initiator - Google Patents

Abstract

FIELD: technological processes; chemistry.SUBSTANCE: invention relates to a dilithium initiator for anionic (co)polymerization. Initiator is a compound of general formula: Li-X-Li, where X is determined by one of following formulas: -B-C-B-, -D-, -A-D-A-, -A-B-C-B-A-, -B-A-D-A-B- or -B-A-B-C-B-A-B-, where "A" is a block formed by a branched or unbranched C4-C20 diene monomer, "B" is a block formed by a branched or unbranched C4-C20 diene monomer or alkylstyrene containing a heteroatom selected from silicon, nitrogen, phosphorus, tin; "C" is a block formed by alkenylstyrene C10-C40; "D" is a block formed by divinyl monomers containing a functional group, wherein the functional group of the divinyl monomer includes a heteroatom selected from nitrogen and silicon. Method for preparing a dilithium initiator and a method for preparing functionalized diene (co)polymers are also provided.EFFECT: invention allows preparing functionalized diene (co)polymers characterized by a statistical distribution of monomer units, a high content of vinyl units, such as 1,2-butadiene and/or 3,4-isoprene units, and a narrow molecular weight distribution.28 cl, 1 tbl, 27 ex

Description

FIELD OF THE INVENTION

The invention relates to the field of synthetic rubbers, in particular diene rubbers such as polybutadiene, polyisoprene and styrene butadiene rubber (BSK), styrene-isoprene-butadiene rubber (SIBK) used in the manufacture of tires, rubber products, bitumen modification, in electrical engineering and other areas. More specifically, the invention relates to an organilithium initiator of anionic (co) polymerization containing functional groups in its structure, and to a method for producing it, as well as to a method for producing functionalized diene (co) polymers using said initiator.

State of the art

The performance properties of rubber, such as rolling resistance, adhesion to the road surface, etc., are determined both by the properties of the rubber and the way this rubber interacts and combines with silicic fillers. The increase in the thermodynamic affinity of rubber and silicic acid fillers helps to reduce energy consumption during the mixing of these components and to significantly improve the basic properties of rubber. Silica fillers increase the indicators of rolling resistance, adhesion to the road surface, while reducing the performance of aquaplaning. The main disadvantage of silicic acid fillers is the poor thermodynamic affinity for general-purpose rubbers, which in turn has a negative effect on the physicomechanical characteristics of the resulting vulcanizates (rubbers) based on them.

Improving the thermodynamic affinity of rubber with silicic acid fillers is carried out by modifying rubber by polar groups. It is known from the prior art that the presence of functional groups in the rubber structure, for example, tin, silicon or nitrogen-containing groups, can improve the distribution of reinforcing fillers in the rubber matrix, which in turn leads to a decrease in hysteresis losses, an increase in the wear resistance and adhesion properties of rubber compounds based on rubber.

Modification of rubber by polar groups can be carried out in several ways:

• the use of functionalizing agents (such as Michler’s ketone, N-methylpyrrolidone, etc.) - compounds that can be incorporated into the macromolecule of the resulting rubber, which contain a functional group containing a heteroatom. Functionalizing agents are usually introduced into the rubber polymerizate at a conversion of the starting monomers of 95-100%, which allows the rubber to be functionalized at the ends of the macromolecules.

the use of monolithic, dilithium and multilithium initiators containing functional groups;

combined method (using an organolithium initiator containing functional groups, followed by the reaction of live rubber chains with functionalizing agents).

the use of monomers containing functional groups (such as aminostyrene, etc.), compounds capable of entering into the polymerization process (i.e., capable of incorporating into the macromolecule of the resulting rubber), which include functional groups containing a heteroatom. Monomers containing functional groups are usually introduced into the polymerization system either together with the starting monomers, or up to the conversion of the starting monomer of 50%, which allows functionalization of rubber macromolecules along the chain, or during the conversion of the starting monomer 95-100%, which is the same as in the case of using a functionalizing agent, allows you to functionalize the rubber at the ends of the macromolecules [1. VR-S. Quiteria, CA Sierra, JM Gómez-Fatou, C. Galán, LM Fraga. Tin-coupled styrene-butadiene rubbers (SBRs). Relationship between coupling type and properties // Macromolecular Materials and Engineering, 1999. 246. 2025-2032 p. 2. CA Uraneck, JN Short. Solution-polymerized rubbers with superior breakdown properties // J. Appl.Polym. Sci, 2003. -1421-1432 p. 3 . Takashi Ishizone, Akira Hirao, Seiichi Nakahama. Anionic polymerization of monomers containing functional groups. 2. Anionic living polymerization of 4-cyanostyrene // Macromolecules, 1991. No. 24. pp. 625-626 4 . Takashi Ishizone, Nobuyuki Sueyasu, Kenji Sugiyama, Akira Hirao, and Seiichi Nakahama. Anionic polymerization of monomers containing functional groups. 7. Anionic polymerizations of N-alkyl-N- (4-vinylbenzylidene) amines // Macromolecules, 1993. No. 26. -pp. 6976-6984 5 . Takashi Ishizone, Yukiko Okazawa, Kenji Ohnuma, Akira Hirao, and Seiichi Nakahama. Anionic polymerization of monomers containing functional groups. 8. Anionic living polymerization of 4-cyano-α-methylstyrene // Macromolecules, 1997. No. 30. pp. 757-763

US 8,362,164 discloses multifunctional aminolithium initiators containing at least two aminolithium groups, as well as a process for producing polymers using such initiators.

This source describes a method for producing an aminodilithium initiator of the following general formula:

where Q represents a methylene group, oxygen, sulfur; R1 and R2 may be the same or different and are alkyl, cycloalkyl or aralkyl groups containing 1-20 carbon atoms.

The initiator described in US 8362164 is prepared in situ, i.e. directly in the reactor by reacting an amine-containing compound with butyl lithium. Synthesis of styrene-butadiene rubber is carried out in a hydrocarbon solvent at a temperature of 50 ^C. As the electron donor is 2-bis (2'-tetrahydrofuranyl) propane or N, N, N ', N'- tetramethylethylenediamine (TMEDA). Cyclohexanecarboxaldehyde homopiperidihydrazone (CyAHPH) is used as the terminal modifier.

A method for producing a polymer by anionic polymerization according to US 8362164 includes the steps of preparing at least one conjugated diene monomer (I), to obtain an in situ initiator, i.e. directly in the reactor, by reacting an amine-containing compound with butyl lithium (II), and the step of reacting the monomer with initiator (III).

Among the disadvantages of the method of obtaining the initiator according to US 8362164 it should be noted the low speed of the polymerization process, because the N-Li bond is less active in the processes of anionic (co) polymerization than C-Li. To increase the speed of the process, it is necessary to increase the synthesis temperature and, accordingly, the amount of electron-donating compound (to obtain the desired microstructure), which, in turn, leads to a rise in the cost of the process.

The prior art also describes a bifunctional organolithium initiator containing functional groups in its structure:

- see patent EP 2336137A2. This source is considered as the closest analogue (prototype) of the present invention.

The advantage of this initiator is its stability over a long time, the homogeneity of the solution. The disadvantages include the fact that the initiator is soluble only in polar solvents or in aromatic solvents with the addition of polar ones (such as TMEDA), which are used in the synthesis of rubbers as electron donors, which makes it impossible to control the microstructure of rubbers.

Among the disadvantages of this method should also be noted its low manufacturability - multi-stage, long cooking time. This leads to a rise in the cost of the initiator several times. Another disadvantage is the high probability of the formation of a mixture of different products: in addition to di-forms, mono-, tri- or tetraforms of the initiator may be contained, which also complicates the process of controlling the properties of rubbers.

The synthesis of styrene-butadiene rubber using the initiator described above is carried out in a hydrocarbon solvent at a temperature of 50 ° C. The concentration of monomers in the mixture is 14% (mass.), And their ratio in the mixture is as follows: styrene - 20% (mass.), Butadiene - 80% (mass.). The dosage of the initiator is 2.3 mmol / 100 g of monomers.

Rubber compounds based on styrene-butadiene rubber obtained on the initiator described above have improved physical and mechanical characteristics, but at the same time, the elastic-hysteresis properties of the rubber are deteriorated.

In connection with the foregoing, the objective of the present invention is to develop an effective method for producing functionalized diene (co) polymers characterized by a statistical distribution of monomer units, a high content of vinyl units (1,2-butadiene and / or 3,4-isoprene units (more than 60%) ) and a narrow molecular weight distribution (1.4-1.7), as well as having an optimal set of properties, namely improved physicomechanical and elastic-hysteresis characteristics.

SUMMARY OF THE INVENTION

The problem is solved and the desired technical result is achieved using the present invention, according to which the rubber is produced in a hydrocarbon medium in the presence of a dilithium initiator for anionic (co) polymerization, which is a compound of the general formula:

Li-X-Li,

where X means one of the following groups: -B-C-B-, -D-, -A-D-A-, -A-B-C-B-A-, -B-A-D-A-B, B-A-B-C-B-A-B-,

where "A" means a block formed by a branched or unbranched C4-C20 diene monomer, "B" means a block formed by a branched or unbranched C4-C20 diene monomer or alkyl styrene containing a heteroatom selected from the following: silicon, nitrogen, phosphorus, tin; "C" means a block formed by alkenylstyrene C10-C40, "D" means a block formed by divinyl monomers containing a functional group.

Said initiator can be synthesized in a mixed organic solvent medium (aliphatic or aromatic + polar solvent) by reacting an organolithium compound with alkenylstyrene or with divinyl monomers containing a functional group.

The present invention also relates to a method for producing functionalized diene (co) polymers by polymerizing dienes or copolymerizing them with each other and / or with alpha-olefins in a hydrocarbon solvent in the presence of an organolithium initiator of anionic (co) polymerization and electron-donating additive, and as an anionic initiator (co) polymerization using the above organolithium initiator.

DETAILED DESCRIPTION OF THE INVENTION

The present invention discloses a dilithium initiator for anionic (co) polymerization, which is a compound of the general formula:

Li-X-Li,

where X means one of the following groups: -B-C-B-, -D-, -ADA-, -A-B-C-BA-, -BADAB, BABCBAB-, where “A” means a block formed by a branched or unbranched C4-C20 diene monomer, "B" means a block formed by a branched or unbranched C4-C20 diene monomer or alkyl styrene containing a heteroatom selected from the following: silicon, nitrogen, phosphorus, tin; "C" means a block formed by alkenylstyrene C10-C40, "D" means a block formed by divinyl monomers containing a functional group.

As a branched or unbranched C4-C20 diene monomer (block A), a compound selected from the group consisting of 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 2-methyl can be used -3-ethyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-methyl-3-ethyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene , 2-methyl-1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 1,1 ', 4,4'-tetraphenyl-1,3-butadiene, 3-methyl-1 , 3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-butadiene, 4,5-diethyl -1,3-octadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-isoprop L-1,3-butadiene or a mixture thereof.

As a branched or unbranched C4-C20 diene monomer or alkyl styrene containing heteroatoms, namely silicon, and / or nitrogen, and / or phosphorus, and / or tin (block B), a compound selected from the group may be used including silicon-containing, phosphorus-containing, silicon-nitrogen-containing, nitrogen-containing or tin-containing compound, in particular, such as, for example, 2-dimethylaminopropyl-1,3-butadiene, 2-triethylsilylpropyl-1,3-butadiene or dimethylaminomethylmethyl styrene, N-trimethyl - (trimethylsilyl) ami nomethylstyrene, 4-diphenylphosphine styrene, 4-triphenyltin-styrene or a mixture thereof.

As alkenylstyrene C10-C40 (block C), a compound selected from the group consisting of divinylbenzene, diisopropenylbenzene, p -2-propenylstyrene, p -2-butenyl-α-methylstyrene, p -2-propenyl-α- can be used methyl styrene, p -2-methyl-2-propenylstyrene, p -2-butenylstyrene, p -2-methyl-2propenyl-α-methylstyrene, 8- ( p- vinylphenyl) -1-octene, 2-methyl-7- ( p vinylphenyl) -1-heptene .

As the divinyl monomer containing a functional group (block D), a compound selected from the group consisting of: alkylalkenylamine, in particular methyldialkenylamine, butyl dialkylamine, can be used; alkylallylsilane, in particular diethyl diallyl silane, dipropyl diallyl silane, methyltriallyl silane.

The dilithium initiator according to the present invention is obtained in a mixed organic solvent medium (aliphatic or aromatic + polar solvent) by reacting an organolithium compound with alkenylstyrene or with divinyl monomers containing a functional group.

Each monomer is individually added dropwise to a reaction medium consisting of a mixed solvent and an organolithium compound. At the end of the synthesis, the polar solvent is distilled off in vacuo.

As an aliphatic solvent, a compound selected from the group consisting of: acyclic saturated hydrocarbons of linear and branched structure and cyclic saturated hydrocarbons is used. As an aromatic solvent, a compound selected from the group consisting of benzene, toluene, xylene, ethylbenzene is used. As a polar solvent, a compound selected from the group consisting of diethyl ether, tetrahydrofuran, trimethylamine, etc. is used.

 The organolithium compound used may be, in particular, an alkyl lithium compound, preferably C4-C6 alkyl lithium, more preferably n-butyllithium, sec-butyl lithium, tert-butyl lithium, isopropyl lithium.

In one embodiment of the method of the present invention, in the case where X = —B — C — B— the ratio of the components C: B can be 1:30, 1:20 or 1:10.

In another embodiment of the method of the present invention, in the case where X = -ADA- the ratio of the components D: A can be 1:30, 1:20 or 1:10.

In yet another embodiment of the method of the present invention, in the case where X = -A-B-C-B-A- the ratio of components A: B: C may be: 20: 15: 1, or 15: 10: 1 , or 10: 4: 1.

In yet another embodiment of the method of the present invention, in the case where X = -BADAB- the ratio of components A: B: D may be: 20: 15: 1, or 15: 10: 1, or 10: 4: 1.

In yet another embodiment of the method of the present invention, in the case where X = -BABCBAB- the ratio of components A: B: C may be: 20: 15: 1, or 15: 10: 1, or 10: 4: 1.

The reaction of the organolithium compound with alkenylstyrene or with divinyl monomers containing a functional group in a mixed organic solvent is usually carried out at a temperature of -20-80 ° C, preferably -10-60 ° C, more preferably 0-20 ° C.

The reaction is usually carried out over a period not exceeding 5 hours, preferably from 60 to 300 minutes, more preferably from 120-180 minutes.

The polymerization of dienes or their copolymerization between themselves and / or with alpha-olefins according to the present invention is carried out in a hydrocarbon solvent in the presence of an organolithium initiator described above and an electron-donating additive. However, conjugated dienes, especially C4-C12, such as butadiene and / or isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, are preferably used as dienes , 3-methyl-1,3-pentadiene, 2-methyl-3-ethyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene , 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, 3,4-dimethyl-1 , 3-hexadiene, 3-n-propyl-1,3-butadiene, 4,5-diethyl-1,3-octadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-isopropyl-1 , 3-butadiene, or a mixture thereof.

As the alpha olefin, C8-C40 aryl vinyl compounds can be used. In particular, vinylbenzenes, in particular styrene, alpha-methylstyrene; vinyl biphenyls, in particular vinyl diphenyl; vinyl naphthalenes, in particular 1-vinyl naphthalene, 1-methyl vinyl naphthalene; vinylanthracenes, in particular 9-vinyl anthracene.

In one embodiment of the method of the present invention, the ratio of alpha olefin to diene is from 5:95 to 10:90. In other embodiments of the method of the present invention, this ratio may be from 15:85 to 20:80 or from 20:80 to 24:76 .

As the organolithium initiator, the dilithium initiator for anionic (co) polymerization according to the present invention is used, which is a compound of the general formula:

Li-X-Li, where X is defined as described above.

The electron donor additive used according to the present invention is a compound containing at least one heteroatom and / or its mixture with alkoxides of alkali or alkaline earth metals. The heteroatom in the compound containing at least one heteroatom is preferably N or O.

In particular, such compounds containing at least one heteroatom may be compounds represented by one of the following formulas:

where n = 1-20; R, R '= CH ₃ , C ₂ H ₅ , n -C ₃ H ₇ , i -C ₃ H ₇ , n -C ₄ H ₉ , s -C ₄ H ₉ , t -C ₄ H ₉ , i - C ₄ H ₉ , C ₅ H ₁₁ , C ₆ H ₁₃ , C ₇ H ₁₅ , C ₈ H ₁₇ , C ₉ H ₁₉ , C ₁₀ H ₂₁ , C ₆ H ₅ , o -C ₆ H ₄ CH ₃ , m -C ₆ H ₄ CH ₃ , p -C ₆ H ₄ CH ₃ , o -C ₆ H ₄ C ₂ H ₅ , m -C ₆ H ₄ CH ₃ , or p -C ₆ H ₄ CH ₃ , and

where n = 1-20; m is 1-4; Me = Li, Na, K; X = -CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C ₅ H ₁₀ -, -C ₆ H ₁₂ -, -C ₇ H ₁₄ -, or -C ₈ H ₁₆ -; R = CH _3, C ₂ H _5, n -C ₃ H _7, i -C ₃ H _7, n -C ₄ H _9, s -C ₄ H _9, t -C ₄ H _9, i -C ₄ H ₉ , C ₅ H ₁₁ , C ₆ H ₁₃ , C ₇ H ₁₅ , C ₈ H ₁₇ , C ₉ H ₁₉ , C ₁₀ H ₂₁ , C ₆ H ₅ , o -C ₆ H ₄ CH ₃ , m -C ₆ H ₄ CH ₃ , p -C ₆ H ₄ CH ₃ , o -C ₆ H ₄ C ₂ H ₅ , m -C ₆ H ₄ CH ₃ , or p -C ₆ H ₄ CH ₃ . It is also possible to use such compounds as N, N, N ', N'-tetramethylethylenediamine, trimethylamine, sodium or potassium tetrahydrofurfurfurylate, calcium butylate, ethylene glycol ethyl tert-butyl ether, ethylene glycol ditetrahydrofuryl propane, ethylene glycol di-tert-butyl ether or a mixture thereof.

In this case, the molar ratio of the organolithium initiator to the compound containing at least one heteroatom is usually 1: (0.1 ÷ 20.0), and the molar ratio of the organolithium initiator to the alkali and / or alkaline-earth metal alkoxide is 1: (0.1 ÷ 20.0). The indicated limits of molar ratios are determined by the need to obtain a given value of the vinyl groups (at least 50 mass%) in the butadiene component of the polymer chain, controlling the degree of statistical distribution (microblockness) of alpha-olefins in rubber, for example styrene or its derivatives, if used as diene comonomers

The (co) polymerization process according to the present invention is carried out at a temperature of 0-80 ° C, preferably 20-70 ° C, more preferably 40-60 ° C.

After the synthesis is carried out, the catalyst is deactivated and the rubber is stabilized by introducing into the polymerizate a solution of an antioxidant, for example, agidol-2 or another type in an amount of 0.2-0.6 mass. % Then rubber is separated by known methods, such as steam and gas degassing and roller drying.

To further improve the properties of the resulting rubber, it is possible to carry out its additional functionalization. Such additional functionalization is carried out upon reaching 95-100% conversion by introducing functionalizing agents into the polymerization system. Moreover, functionalizing agents are used to functionalize rubber macromolecules at the ends of the chain. In another embodiment, additional functionalization is carried out by introducing into the polymerization system monomers containing functional groups that are introduced simultaneously with the starting monomers or during the polymerization reaction up to the conversion of the starting monomers up to 50%, including, in some cases, during the conversion of the starting monomers 95 -one hundred%. Functional containing monomers are used to functionalize rubber macromolecules both along the chain and, in some cases, at the ends of the chain.

As functionalizing agents, compounds selected from the group consisting of: N, N-di-substituted aminoalkyl acrylamides and N, N-di-substituted aminoalkyl methacrylamides, in particular, such as N, N-dimethylaminopropyl acrylamide and N, N-dimethylaminopropyl methacrylamide; N-substituted cyclic amides, such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-methyl-epsilon-caprolactam; N-substituted cyclic ureas such as 1,3-dimethylethylene urea and 1,3-diethyl-2-imidazolidinone; as well as N-substituted aminoketones, such as, for example, N, N'-bis- (dimethylamino) benzophenone (Michler's ketone) and N, N'-bis- (diethylamino) benzophenone. The functionalizing agent is used in a molar ratio to the dilithium initiator of 0.01-2.0, preferably 0.1-1.5, more preferably 0.5-1.0.

As the monomers containing functional groups, use is made of compounds selected from the group consisting of: silicon-containing, phosphorus-containing, silicon-nitrogen-containing, nitrogen-containing, tin-containing compounds, in particular, N, N-dimethylaminoethyl styrene and N, N-diethylaminoethyl styrene, 2-dimethylaminopropyl , 3-butadiene, 2-triethylsilylpropyl-1,3-butadiene or dimethylaminomethylstyrene), trimethylsilyl styrene, N, N'-bis- (trimethylsilyl) aminomethyl styrene, 4-diphenylphosphine styrene, 4-triphenyltin styrene or a mixture thereof. The monomer containing functional groups is added in an amount of 0.01-70.0%, preferably 1-60 mass. %, more preferably 20-40 mass. % based on the weight of the polymer. The functionalization is preferably carried out at a temperature of 30-100 ° C, preferably at a temperature of 40-80 ° C or 60-80 ^° C, more preferably at a temperature of 50-70 ° C, for 15-60 minutes.

Using the claimed method allows to obtain functionalized (co) polymers of dienes with a statistical distribution of monomer units, narrow MMP and a high content of vinyl units (1,2-butadiene and / or 3,4-isoprene units (more than 50%), as well as with an improved complex properties, namely physico-chemical and elastic-hysteresis characteristics.

Examples

Example 1

50 ml of absolute cyclohexane and 10 ml of n- butyllithium (1.6 M) are placed in a 250 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel 1.5 ml of 1,3-diisopropenylbenzene and 6 ml of THF. Next, 1.5 ml of dimethylaminomethylstyrene are also added via a dropping funnel. Then 5 ml of isoprene are added to the reaction solution. Upon completion of the addition of monomers, the reaction mixture was warmed to room temperature and stirred for another 30 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.35 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a 1 liter glass reactor equipped with devices for measuring temperature and pressure, loading and unloading, an agitator and a jacket, a charge consisting of 350 g of nephras, previously dried and deoxygenated, 46 g of butadiene and 12 g of styrene (mass ratio of monomers to reaction medium 79:21). The flow temperature of the charge in the reactor minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of a dilithium initiator prepared above and the electron donor additive. The electron-donor additive includes ditetrahydrofurylpropane (DTGFP) in the form of a solution in nephras concentration of 0.054 M, calculated as DTGFP / Lithium = 0.2 mol / mol. The dilithium initiator is fed into the reactor as a solution in toluene (concentration 0.35 M) at the rate of 1.4 mmol per 100 g of monomers. The copolymerization process is carried out at a temperature of 50 ° C to a conversion of 100%. Upon conversion, an antioxidant is added. As an antioxidant use agidol-2 in an amount of 0.5% of the mass.

The resulting product is characterized by the following characteristics: styrene content - 21% of the mass .; the content of 1,2-butadiene units per polybutadiene - 66% of the mass .; glass transition temperature - -21 ^о С; Mn = 146000; polydispersity - 1.4; Mooney viscosity - 50 units.

Rubber compounds based on the rubber obtained have an improved set of properties, namely, physicochemical and elastic-hysteresis characteristics.

Example 2

50 ml of absolute cyclohexane and 10 ml of n- butyllithium (1.6 M) are placed in a 250 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel 1.5 ml of 1,3-diisopropenylbenzene and 6 ml of THF. Next, 1.5 ml of diethylaminomethylstyrene are also added via a dropping funnel. Upon completion of the addition of monomers, the reaction mixture was warmed to room temperature and stirred for another 30 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.45 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a glass reactor with a volume of 1 liter, equipped with devices for measuring temperature and pressure, loading and unloading, a stirrer and a jacket, a charge is introduced, consisting of 350 g of nephras, previously dried and deoxygenated and 54 g of butadiene. The flow temperature of the charge in the reactor minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of a dilithium initiator prepared above, and the electron donor additive. The electron-donor additive includes sodium tetrahydrofurfurylate (THF) in the form of a solution in toluene with a concentration of 0.060 M based on the calculation of THF / Lithium = 0.2 mol / mol. Dilithium initiator is fed into the reactor at the rate of 1.6 mmol per 100 g of monomers. The copolymerization process is carried out at a temperature of 55 ° C to a conversion of 100%. Upon conversion, the polymerization mixture is mixed with a solution of antioxidant in nephras. As an antioxidant use agidol-2 in an amount of 0.5% of the mass.

The resulting product contains 50% - 1,2-butadiene units, glass transition temperature -25 ^о С, Мn = 155000, polydispersity - 1.6, Mooney viscosity - 50 units.

Example 3

50 ml of absolute cyclohexane and 10 ml of sec- butyl lithium are placed in a 200 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel metildialkenilamin 3 ml and 6 ml of THF. Upon completion of the monomer addition, the reaction mixture was warmed to room temperature and stirred for another 30 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.25 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a 1 liter glass reactor equipped with devices for measuring temperature and pressure, loading and unloading, an agitator and a jacket, a charge is introduced consisting of 350 g of nephras previously dried and deoxygenated, 54 g of isoprene and 16 g of styrene. The flow temperature of the charge in the reactor minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of a dilithium initiator prepared above, and the electron donor additive. The electron donor additive includes calcium butylate in the form of a solution in toluene with a concentration of 0.056 M based on the calculation of calcium butylate / lithium = 0.8 mol / mol. The dilithium initiator is fed into the reactor at the rate of 1.5 mmol per 100 g of monomers. The copolymerization process is carried out at a temperature of 50 ° C to a conversion of 100%. Upon conversion, the polymerization mixture is mixed with a solution of antioxidant in nephras. As an antioxidant use agidol-2 in an amount of 0.5% of the mass.

The resulting product contains 50% - 3,4-isoprene units, glass transition temperature -25 ^о С, Мn = 168000, polydispersity - 1.7, Mooney viscosity - 59 units.

Example 4

50 ml of absolute cyclohexane and 5 ml of t- butyllithium are placed in a 250 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel 2.0 ml dimetildiallilsilan and 3 ml of diethyl ether. Then, 10 ml of 2-phenyl-1,3-butadiene is added to the reaction solution. Upon completion of the addition of monomers, the reaction mixture was warmed to room temperature and stirred for another 30 minutes. Then, under reduced pressure, diethyl ether was removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.45 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

A charge consisting of 2273 g of nephras, 348 g of butadiene and 92 g of styrene is introduced into a 5-liter metal reactor equipped with devices for measuring temperature and pressure, loading and unloading, a stirrer and a jacket. The batch feed temperature to the reactor is minus 10 ^о С, when the reactor reaches 15 ° C, a catalytic system is introduced, consisting of the dilithium initiator obtained above and a mixture of electron-donating additives, dilithium initiator is supplied at the rate of 1.6 mmol per 100 g of monomers. The mixture of electron-donor additives includes tetramethylethylenediamine (TMEDA) in the form of a solution in nephras with a concentration of 0.36 M from the calculation of TMEDA / lithium = 0.5 mol / mol and a solution of potassium amylate in nephras with a concentration of 0.30 M from the calculation of AK / lithium = 0 1 mol / mol. Copolymerization process is carried out at a temperature of 50 ^o C. As the antioxidant used Agidol-2 in an amount of 0.5% by weight.

The resulting product is characterized by the following characteristics: styrene content - 20% of the mass .; the content of 1,2-butadiene units per polybutadiene - 67% of the mass .; glass transition temperature - -20 ^о С; Mn = 160000; polydispersity - 1.6; Mooney viscosity - 53 units.

Example 5

50 ml of absolute cyclohexane and 10 ml of sec- butyl lithium are placed in a 250 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel 1.5 ml of 1,3-divinyl benzene and 2 ml of THF. Next, 4 ml of 4-trimethylsilyl styrene is also added via a dropping funnel. Upon completion of the addition of monomers, the reaction mixture was warmed to room temperature and stirred for another 30 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.50 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a glass reactor with a volume of 1 liter, equipped with devices for measuring temperature and pressure, loading and unloading, a stirrer and a jacket, a charge is introduced, consisting of 350 g of nephras, previously dried and deoxygenated, 17 g of styrene, 20 g of butadiene and 20 g of isoprene. The flow temperature of the charge in the reactor minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of a dilithium initiator prepared above mixture electron additives. The mixture of electron-donor additives includes tetramethylethylenediamine in the form of a solution in nephras with a concentration of 0.066 M from the calculation of TMEDA / lithium = 0.25 mol / mol and a solution of sodium tetrahydrofurfurylate in toluene with a concentration of 0.07 M from the calculation of THF / lithium = 0.1 mol / mol . The dilithium initiator is fed to the reactor at the rate of 1.4 mmol per 100 g of monomers. The copolymerization process is carried out at a temperature of 60 ^o C. As an antioxidant using agidol-2 in an amount of 0.5% of the mass.

The resulting product is characterized by the following characteristics: styrene content - 30% of the mass .; the content of 1,2-butadiene units per polybutadiene - 48% of the mass .; the content of 3,4-isoprene units on polyisoprene - 53%; glass transition temperature - -20 ^о С; Mn = 186,000; polydispersity - 1.7; Mooney viscosity - 66 units.

Example 6

50 ml of absolute toluene and 10 ml of n- butyllithium (1.6 M) are placed in a 250 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel 1.5 ml of 1,3-divinyl benzene and 10 ml of THF. Then, 6.0 ml of N, N'-bis- (trimethylsilyl) aminomethylstyrene is also added via a dropping funnel. Then 10 ml of butadiene are added to the reaction solution. Upon completion of the addition of monomers, the reaction mixture was warmed to room temperature and stirred for another 30 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.55 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, for 1 month the concentration of active lithium does not change.

In a 1 liter glass reactor equipped with devices for measuring temperature and pressure, loading and unloading, an agitator and a jacket, a charge consisting of 350 g of nephras, previously dried and deoxygenated, 46 g of butadiene and 12 g of styrene (mass ratio of monomers to reaction medium 79:21). The flow temperature of the charge in the reactor minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of a dilithium initiator prepared above, and the electron donor additive. The electron-donor additive includes tetramethylethylenediamine in the form of a solution in nephras with a concentration of 0.066 M based on the calculation of TMEDA / Lithium = 1.0 mol / mol. The dilithium initiator is fed to the reactor at the rate of 1.0 mmol per 100 g of monomers. The copolymerization process is carried out at a temperature of 55 ° C to a conversion of 100%. Upon conversion, an antioxidant is added. As an antioxidant use agidol-2 in an amount of 0.5% of the mass.

The resulting product is characterized by the following characteristics: styrene content - 21% of the mass .; the content of 1,2-butadiene units per polybutadiene - 64% of the mass .; glass transition temperature - -23 ^{° C;} Mn = 230,000; polydispersity - 1.7; Mooney viscosity - 76 units.

Rubber compounds based on the rubber obtained have an improved set of properties, namely, physicochemical and elastic-hysteresis characteristics.

Example 7

50 ml of absolute toluene and 11 ml of sec- butyl lithium are placed in a 250 ml glass reactor. The reactor is cooled to minus 20 ^° C. Then, 4.0 ml of dimethyldiallylsilane and 3 ml of THF are fed via a dropping funnel. Next, 8 ml of piperylene are also added via a dropping funnel. Upon completion of the addition of monomers, the reaction mixture was warmed to room temperature and stirred for another 30 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.65 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a glass reactor with a volume of 1 liter, equipped with devices for measuring temperature and pressure, loading and unloading, a stirrer and a jacket, a charge is introduced, consisting of 350 g of nephras, previously dried and deoxygenated, 54 g of butadiene and 4 g of isoprene. The flow temperature of the charge in the reactor minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of a dilithium initiator prepared above and the electron donor additive. As an electron-donating additive, triethylamine is used in the form of a solution in toluene with a concentration of 0.045 M based on the calculation of triethylamine / lithium = 20 mol / mol. The dilithium initiator is fed to the reactor at the rate of 1.7 mmol per 100 g of monomers. The copolymerization process is carried out at a temperature of 20 ° C to a conversion of 100%. Upon conversion, an antioxidant is added. As an antioxidant use agidol-2 in an amount of 0.5% of the mass.

The resulting product has the composition isoprene / butadiene = 7/93, 55% - 3,4-isoprene units, 60% - 1,2-butadiene units, glass transition temperature - -19 ^о С, М _n = 169000, polydispersity - 1.7 , Mooney viscosity - 56 units.

Example 8

50 ml of absolute toluene and 15 ml of n- butyllithium (1.6 M) are placed in a 250 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel 3.5 ml etildiallilamin and 5 mL THF. Next, 8.0 ml of 3-methyl-1,3-pentadiene are also added via a dropping funnel. Upon completion of the addition of monomers, the reaction mixture was warmed to room temperature and stirred for another 30 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.70 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a glass reactor with a volume of 1 liter, equipped with devices for measuring temperature and pressure, loading and unloading, a stirrer and a jacket, a charge is introduced, consisting of 350 g of nephras, previously dried and deoxygenated, 17 g of styrene, 20 g of butadiene and 20 g of isoprene. Low feed batch reactors minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of the dilithium initiator and the above electron donor additive. The electron-donor additive is a solution of ditetrahydrofurylpropane in nephras with a concentration of 0.050 M, calculated as DTGFP / lithium = 0.40 mol / mol. The dilithium initiator is fed into the reactor at the rate of 1.5 mmol per 100 g of monomers. The copolymerization process is carried out at a temperature of 80 ° C. As an antioxidant use agidol-2 in an amount of 0.5% of the mass.

The resulting product is characterized by the following characteristics: styrene content - 30% of the mass .; the content of 1,2-butadiene units per polybutadiene - 45% of the mass .; the content of 3,4-isoprene units on polyisoprene - 55%; glass transition temperature - -20 ^о С; Mn = 185,000; polydispersity - 1.7; Mooney viscosity - 60 units.

Example 9

60 ml of absolute toluene and 15 ml of n- butyllithium (1.6 M) are placed in a 250 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel dimetildiallilsilana 4 ml and 3 ml of THF. Upon completion of the monomer addition, the reaction mixture was warmed to room temperature and stirred for another 30 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.68 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

A charge consisting of 2273 g of nephras, 348 g of butadiene and 92 g of styrene is introduced into a 5-liter metal reactor equipped with devices for measuring temperature and pressure, loading and unloading, a stirrer and a jacket. The temperature of the reactor feed blend minus 10 ^{° C,} the reactor reaches 15 ° C is introduced catalytic system consisting of a dilithium initiator, and the mixture obtained above electron additives dilithium initiator is fed at the rate of 1.8 mmol per 100 g of monomers. A mixture of electron-donating additives includes ditetrahydrofurylpropane in the form of a solution in nephras with a concentration of 0.32 M from the calculation of DTGFP / lithium = 0.35 mol / mol and a solution of potassium amylate in nephras with a concentration of 0.30 M from the calculation of AK / lithium = 0.1 mol / mol. The copolymerization process is carried out at a temperature of 55 ^o C. As an antioxidant use agidol-2 in an amount of 0.5% of the mass ..

The resulting product is characterized by the following characteristics: styrene content - 21% of the mass .; the content of 1,2-butadiene units per polybutadiene - 67% of the mass .; glass transition temperature - -20 ^о С; Mn = 152000; polydispersity - 1.6; Mooney viscosity - 55 units.

Example 10

200 ml of absolute toluene and 20 ml of sec- butyl lithium are placed in a 500 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel 3.0 ml of 1,3-diisopropenylbenzene and 1.0 ml THF. Then, 5.0 ml of 4-diphenylphosphine styrene is also added via a dropping funnel. Upon completion of the addition of monomers, the reaction mixture was warmed to room temperature and stirred for another 30 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.35 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a glass reactor with a volume of 1 liter, equipped with devices for measuring temperature and pressure, loading and unloading, a stirrer and a jacket, a charge is introduced, consisting of 350 g of nephras, previously dried and deoxygenated and 68 g of isoprene. The flow temperature of the charge in the reactor minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of a dilithium initiator prepared above mixture electron additives. The mixture of electron-donor additives includes ethylene glycol ethyl tert-butyl ether (ETBEG) in the form of a solution in nephras of a concentration of 0.0912 M based on ETBEG / Lithium = 0.5 mol / mol and a solution of potassium tetrahydrofurfurylate (THFK) in a concentration of 0.05 M based on THFK / Lithium = 0.2 mol / mol. The dilithium initiator is fed to the reactor at the rate of 1.3 mmol per 100 g of monomers.

The copolymerization process is carried out at a temperature of 50 ° C to a conversion of 100%. Upon conversion, the polymerization mixture is mixed with a solution of antioxidant in nephras. As an antioxidant use agidol-2 in an amount of 0.5% of the mass.

The resulting product contains 65% - 3,4-isoprene units, glass transition temperature -18 ^о С, Мn = 186000, polydispersity - 1.5, Mooney viscosity - 61 units.

Example 11

200 ml of absolute toluene and 15 ml of n- butyllithium (1.6 M) are placed in a 500 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel 3.0 ml of 1,3-diisopropenylbenzene and 1,5 ml THF. Next, 6.0 ml of dimethylaminomethyl methyl styrene is also added via a dropping funnel. Then 20 ml of 1,3-heptadiene are added to the reaction solution. Upon completion of the addition of monomers, the reaction mixture was warmed to room temperature and stirred for another 40 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.40 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a 1 liter glass reactor equipped with devices for measuring temperature and pressure, loading and unloading, a stirrer and a jacket, a charge is introduced consisting of 350 g of nephras previously dried and deoxygenated, 46 g of butadiene and 12 g of isoprene (mass ratio of monomers to reaction medium 80:20). The flow temperature of the charge in the reactor minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of a dilithium initiator prepared above and the mixture of the electron donor additives. The mixture of electron-donating additives includes sodium tetrahydrofurfurylate in the form of a solution in toluene with a concentration of 0.075 M from the calculation of THFN / Lithium = 0.1 mol / mol and tetramethylethylenediamine in the form of a solution in nephras with a concentration of 0.066 M from the calculation of TMEDA / Lithium = 1.0 mol / mol . The dilithium initiator is fed to the reactor at the rate of 1.2 mmol per 100 g of monomers.

The copolymerization process is carried out at a temperature of 60 ° C to a conversion of 100%. Upon conversion, the polymerization mixture is mixed with a solution of antioxidant in nephras. As an antioxidant use agidol-2 in an amount of 0.5% of the mass ..

The resulting product contains 50% - 1,2-butadiene units, 48% - 3,4-isoprene units, glass transition temperature -21 ^о С, Мn = 175000, polydispersity - 1.6, Mooney viscosity - 63 units.

Example 12

200 ml of absolute toluene and 20 ml of n- butyllithium (1.6 M) are placed in a 500 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel 3.0 ml of 1,3-diisopropenylbenzene and 2,0 ml THF. Next, 8.0 ml of 4-triphenyltin stirol is also added via a dropping funnel. Then 20 ml of 1,3-octadiene are added to the reaction solution. Upon completion of the addition of monomers, the reaction mixture was warmed to room temperature and stirred for another 15 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.42 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a glass reactor with a volume of 1 liter, equipped with devices for measuring temperature and pressure, loading and unloading, a stirrer and a jacket, a charge is introduced, consisting of 350 g of nephras, previously dried and deoxygenated, 46 g of butadiene and 12 g of isoprene and 8 g of styrene. The flow temperature of the charge in the reactor minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of a dilithium initiator prepared above and the mixture of the electron donor additives. The mixture of electron-donor additives includes tetramethylethylenediamine in the form of a solution in nephras with a concentration of 0.066 M based on the calculation of TMEDA / Lithium = 0.4 mol / mol and a solution of ethylene glycol di-tert-butyl ether in nephras with a concentration of 0.05 M based on DTBEG / Lithium = 0 5 mol / mol. The dilithium initiator is fed into the reactor at the rate of 1.5 mmol per 100 g of monomers.

The copolymerization process is carried out at a temperature of 50 ° C to a conversion of 100%. Upon conversion, the polymerization mixture is mixed with a solution of antioxidant in nephras. As an antioxidant use agidol-2 in an amount of 0.5% of the mass ..

The resulting product is characterized by the following characteristics: styrene content - 14% of the mass .; the content of 1,2-butadiene units per polybutadiene - 65% of the mass .; the content of 3,4-isoprene units on polyisoprene - 73%; glass transition temperature - -11 ^о С; Mn = 166,000; polydispersity - 1.6; Mooney viscosity - 57 units.

Example 13

Carry out, as described in example 1. Additionally carry out the functionalization of the ends of the polymer chain. Upon reaching a conversion of 95-100%, the functionalizing agent N, N-dimethylaminopropyl acrylamide is supplied in the form of a solution with a concentration of 0.037 M in a molar ratio to Li = 0.8; the reaction is continued for another 30 minutes at the same temperature.

Example 14

Carry out, as described in example 1. Additionally carry out the functionalization of the ends of the polymer chain. Upon reaching a conversion of 95-100%, the functionalizing agent N, N-dimethylaminopropyl methacrylamide is supplied in the form of a solution with a concentration of 0.047 M in a molar ratio to Li = 0.1; the reaction is continued for another 15 minutes at a temperature of 60 ^about C.

Example 15

Carry out, as described in example 1. Additionally carry out the functionalization of the ends of the polymer chain. Upon reaching a conversion of 95-100%, the functionalizing agent N-vinyl-2-pyrrolidone is supplied in the form of a solution with a concentration of 0.030 M at a molar ratio to Li = 0.5; the reaction is continued for another 30 minutes at a temperature of 60 ^about C.

Example 16

Carry out, as described in example 1. Additionally carry out the functionalization of the ends of the polymer chain. Upon reaching a conversion of 95-100%, the functionalizing agent 1,3-dimethylethylene urea is supplied in the form of a solution with a concentration of 0.035 M at a molar ratio to Li = 0.01; the reaction is continued for another 45 minutes at a temperature of 70 ^about C.

Example 17

Carry out, as described in example 1. Additionally carry out the functionalization of the ends of the polymer chain. Upon reaching a conversion of 95-100%, the functionalizing agent N, N'-bis- (diethylamino) benzophenone is fed in the form of a solution with a concentration of 0.037 M in a molar ratio to Li = 1.0; the reaction is continued for another 45 minutes at a temperature of 60 ^about C.

Example 18

Carry out, as described in example 1. Additionally carry out the functionalization of the ends of the polymer chain. Upon reaching a conversion of 95-100%, a monomer is fed containing the functional groups N, N'-bis- (trimethylsilyl) aminomethylstyrene in the form of a solution with a concentration of 0.046 M in an amount of 0.01% per polymer; the reaction is continued for another 15 minutes at the same temperature.

Example 19

Carry out, as described in example 1. Additionally carry out the functionalization of the ends of the polymer chain. Upon reaching a conversion of 95-100%, a monomer is fed containing functional groups 4-trimethylsilyl styrene in the form of a solution with a concentration of 0.052 M in an amount of 30% per polymer; the reaction is continued for another 30 minutes at the same temperature.

Example 20

Carry out, as described in example 1. Additionally carry out the functionalization of the ends of the polymer chain. Upon reaching a conversion of 95-100%, a monomer is fed containing 4-diphenylphosphine styrene functional groups in the form of a solution with a concentration of 0.030 M in an amount of 5.0% per polymer; the reaction is continued for another 45 minutes at the same temperature.

Example 21

Carry out, as described in example 1. Additionally carry out the functionalization of the ends of the polymer chain. Upon reaching a conversion of 95-100%, a monomer is fed containing functional groups of 4-triphenyltin stirol in the form of a solution with a concentration of 0.058 M in an amount of 1.5% per polymer; the reaction is continued for another 30 minutes at the same temperature.

Example 22

Carry out, as described in example 1. Additionally carry out the functionalization of the ends of the polymer chain. Upon reaching a conversion of 95-100%, a monomer is fed containing dimethylaminomethylstyrene functional groups in the form of a solution with a concentration of 0.060 M in an amount of 13.0% per polymer; the reaction is continued for another 30 minutes at the same temperature.

Example 23

Carry out, as described in example 1. Additionally carry out the functionalization of the ends of the polymer chain. Upon reaching a conversion of 95-100%, a monomer is fed containing functional groups diethylaminomethylstyrene in the form of a solution with a concentration of 0.075 M in an amount of 15% per polymer; the reaction is continued for another 15 minutes at the same temperature.

Example 24

50 ml of absolute cyclohexane and 10 ml of n- butyllithium (1.6 M) are placed in a 250 ml glass reactor. The reactor is cooled to minus 10 ^° C. Then 1.5 ml of p-2-propenylstyrene and 10 ml of THF are fed via a dropping funnel. Then dimethylaminomethyl methyl styrene is also added via a dropping funnel. Then 1,1 ', 4,4'-tetraphenylbutadiene is added to the reaction solution, then 2-dimethylaminopropylbutadiene is fed at a ratio of p-2-propenylstyrene: (dimethylaminomethylstyrene + 2-dimethylaminopropylbutadiene): 1,1', 4,4'-tetraphenylbutadiene 1 : 15: 20 respectively. Upon completion of the addition of monomers, the reaction mixture was heated to 60 ° C and stirred for another 20 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.45 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a 1 liter glass reactor equipped with devices for measuring temperature and pressure, loading and unloading, an agitator and a jacket, a charge consisting of 350 g of nephras, previously dried and deoxygenated, 46 g of butadiene and 12 g of styrene (mass ratio of monomers to reaction medium 79:21). The flow temperature of the charge in the reactor minus 10 ^{° C,} for achieving the reactors 20 ° C is introduced catalytic system consisting of a dilithium initiator prepared above, and the electron donor additive. Electron donor additive includes triethylamine (TEA) as a solution in 0.040 M nefras based TEA / Li = 5 mol / mol. The dilithium initiator is fed into the reactor in the form of a solution in toluene (concentration of 0.45 M ) at the rate of 1.6 mmol per 100 g of monomers. The copolymerization process is carried out at a temperature of 40 ° C. Upon reaching a conversion of 95-98%, a monomer is fed containing functional groups diethylaminomethylstyrene in the form of a solution with a concentration of 0.090 M in an amount of 70% per polymer; the reaction is continued for another 15 minutes at a temperature of 30 ° C. Upon reaching 100% conversion, an antioxidant is added. As an antioxidant use agidol-2 in an amount of 0.5% of the mass.

The resulting product is characterized by the following characteristics: styrene content - 20% of the mass .; the content of 1,2-butadiene units per polybutadiene - 70% of the mass .; glass transition temperature - minus 19 ^о С; Mn = 138000; polydispersity - 1.5; Mooney viscosity - 46 units.

Example 25

50 ml of absolute toluene and 20 ml of n- butyllithium (1.6 M) are placed in a 250 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel methyldiallylamine 5 ml and 15 ml THF. Then 3-methyl-1,3-pentadiene is also added via a dropping funnel, then diethylaminomethylstyrene is added at a ratio of methyldiallylamine: (3-methyl-1,3-pentadiene: diethylaminomethylstyrene 1:20:15 respectively. After the monomers are added, the reaction mixture is heated to 80 ° C and stirred for another 5 minutes, then, under reduced pressure, tetrahydrofuran was removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution was measured by titration with an alcohol-toluene solution in the presence of o - phenanthroline. The concentration of active lithium in the solution is 0.50 mol / L. The initiator stability is measured at 25 ° C by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a glass reactor with a volume of 1 liter, equipped with devices for measuring temperature and pressure, loading and unloading, a stirrer and a jacket, a charge is introduced, consisting of 350 g of nephras, previously dried and deoxygenated, 17 g of styrene, 20 g of butadiene and 20 g of isoprene. Low feed batch reactors minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of the dilithium initiator and the above electron donor additive. The electron-donor additive is a solution of ditetrahydrofurylpropane (DTGFP) in nephras with a concentration of 0.030 M based on the calculation of DTGFP / lithium = 0.60 mol / mol. The dilithium initiator is fed to the reactor at the rate of 1.2 mmol per 100 g of monomers. The copolymerization process is carried out at a temperature of 38.5 ^o C. Upon reaching a conversion of 50% serves a monomer containing functional groups diethylaminomethylstyrene in an amount of 10% per polymer. The reaction is continued until the conversion is 100% at a temperature of 100 ^o C. Then add the antioxidant agidol-2 in an amount of 0.5% of the mass.

The resulting product is characterized by the following characteristics: styrene content - 27% of the mass .; the content of diethylaminomethylstyrene is 8% wt., 1,2-butadiene units per polybutadiene - 40% wt .; the content of 3,4-isoprene units on polyisoprene - 50%; glass transition temperature - minus 18 ^{° C;} Mn = 200000; polydispersity - 1.8; Mooney viscosity - 71 units.

Example 26

50 ml of absolute cyclohexane and 10 ml of n- butyllithium (1.6 M) are placed in a 250 ml glass reactor. The reactor is cooled to minus 10 ^° C. Then 1.5 ml of p-2-propenylstyrene and 10 ml of THF are fed via a dropping funnel. Then dimethylaminomethyl methyl styrene is also added via a dropping funnel. Then 1,1 ', 4,4'-tetraphenylbutadiene is added to the reaction solution, then 2-dimethylaminopropylbutadiene is fed at a ratio of p-2-propenylstyrene: (dimethylaminomethylstyrene + 2-dimethylaminopropylbutadiene): 1,1', 4,4'-tetraphenylbutadiene 1 : 4: 10 respectively. Upon completion of the addition of monomers, the reaction mixture was heated to 60 ° C and stirred for another 20 minutes. Then, under reduced pressure, tetrahydrofuran is removed from the reaction mixture by vacuum distillation. The concentration of active lithium in the resulting solution is measured by titration with an alcohol-toluene solution in the presence of o- phenanthroline. The concentration of active lithium in the solution is 0.45 mol / L. The initiator stability is measured at 25 ° C. by the concentration of active lithium as a parameter. As a result, the concentration of active lithium remains unchanged for 1 month.

In a 1 liter glass reactor equipped with devices for measuring temperature and pressure, loading and unloading, an agitator and a jacket, a charge consisting of 350 g of nephras, previously dried and deoxygenated, 46 g of butadiene and 12 g of styrene (mass ratio of monomers to reaction medium 79:21). The flow temperature of the charge in the reactor minus 10 ^{° C,} for achieving the reactors 20 ° C is introduced catalytic system consisting of a dilithium initiator prepared above, and the electron donor additive. The electron donor additive includes triethylamine (TEA) in the form of a solution in nephras with a concentration of 0.040 M based on the calculation of TEA / Lithium = 5 mol / mol. The dilithium initiator is fed into the reactor in the form of a solution in toluene (concentration of 0.45 M) at the rate of 1.6 mmol per 100 g of monomers. The copolymerization process is carried out at a temperature of 40 ° C. Upon reaching a conversion of 95-98%, a monomer is fed containing functional groups diethylaminomethylstyrene in the form of a solution with a concentration of 0.090 M in an amount of 70% per polymer; the reaction is continued for another 15 minutes at a temperature of 30 ° C. Upon reaching 100% conversion, an antioxidant is added. As an antioxidant use agidol-2 in an amount of 0.5% of the mass.

The resulting product is characterized by the following characteristics: styrene content - 20% of the mass .; the content of 1,2-butadiene units per polybutadiene - 70% of the mass .; glass transition temperature - minus 19 ^о С; Mn = 138000; polydispersity - 1.5; Mooney viscosity - 46 units.

Example 27

50 ml of absolute toluene and 20 ml of n- butyllithium (1.6 M) are placed in a 250 ml glass reactor. The reactor was cooled ^to 0 ° C then fed via a dropping funnel methyldiallylamine 5 ml and 15 ml THF. Then 3-methyl-1,3-pentadiene is also added via a dropping funnel, then diethylaminomethylstyrene is added at a ratio of methyldiallylamine: (3-methyl-1,3-pentadiene: diethylaminomethylstyrene 1:15:10, respectively. After the monomers are added, the reaction mixture is heated to 80 ° C and stirred for a further 5 minutes then under reduced pressure, tetrahydrofuran was removed from the reaction mixture by vacuum distillation, concentration of active lithium in the resulting solution was measured by titration alcohol-toluene solution in the presence of.. - enantrolina. The concentration of active lithium in the solution is 0.50 mol / l. initiator Stability was measured at 25 ° C in the concentration of active lithium as a parameter. As a result, for 1 month concentration of the active lithium does not change.

In a glass reactor with a volume of 1 liter, equipped with devices for measuring temperature and pressure, loading and unloading, a stirrer and a jacket, a charge is introduced, consisting of 350 g of nephras, previously dried and deoxygenated, 17 g of styrene, 20 g of butadiene and 20 g of isoprene. Low feed batch reactors minus 10 ^{° C,} for achieving the reactors 15 ° C is introduced catalytic system consisting of the dilithium initiator and the above electron donor additive. The electron-donor additive is a solution of ditetrahydrofurylpropane (DTGFP) in nephras with a concentration of 0.030 M based on the calculation of DTGFP / lithium = 0.60 mol / mol. The dilithium initiator is fed to the reactor at the rate of 1.2 mmol per 100 g of monomers. The copolymerization process is carried out at a temperature of 38.5 ^o C. Upon reaching a conversion of 50% serves a monomer containing functional groups diethylaminomethylstyrene in an amount of 10% per polymer. The reaction is continued until the conversion is 100% at a temperature of 100 ^o C. Then add the antioxidant agidol-2 in an amount of 0.5% of the mass.

The resulting product is characterized by the following characteristics: styrene content - 27% of the mass .; the content of diethylaminomethylstyrene is 8% wt., 1,2-butadiene units per polybutadiene - 40% wt .; the content of 3,4-isoprene units on polyisoprene - 50%; glass transition temperature - minus 18 ^{° C;} Mn = 200000; polydispersity - 1.8; Mooney viscosity - 71 units.

Physico-mechanical and elastic-hysteresis characteristics of rubbers based on rubbers obtained according to some of the above examples are shown in table 1.

Table 1 - Comparative characteristics of vulcanizates obtained on the basis of rubbers given in the examples and vulcanizates obtained on the basis of rubbers given as an example of a prototype

Strength properties,% Wear resistance,% Elastic hysteresis properties wet grip rolling resistance Prototype one hundred one hundred one hundred one hundred Example 1 105 103 one hundred 112 Example 4 105 104 110 113 Example 6 110 110 105 114 Example 9 110 108 107 116 Example 13 110 107 110 117 Example 14 106 105 110 119 Example 15 103 106 110 118 Example 16 108 106 107 110 Example 17 108 107 105 105 Example 18 105 105 110 120 Example 19 105 106 110 115 Example 20 104 106 108 116 Example 21 107 110 108 119 Example 22 107 109 109 114 Example 23 110 108 110 114

Note: ≥ 100 - improvement, ≤ 100 - deterioration

As can be seen from table 1, the use of the initiators of the present invention for the synthesis of rubbers provides vulcanizates with substantially improved elastic-hysteresis properties, in particular rolling resistance, based on these rubbers, while maintaining or simultaneously improving characteristics such as strength properties and wear resistance.

Claims (44)

1. Dilithium initiator for anionic (co) polymerization, which is a compound of the general formula: Li-X-Li, where X is defined by one of the following formulas: -B-C-B-, -D-, -A-D-A-, -A-B-C-B-A-, -B-A-D-A-B- or -B-A-B-C-B-A-B-, where "A" is a block formed by a branched or unbranched C4-C20 diene monomer, "B" is a block formed by a branched or unbranched C4-C20 diene monomer or alkylstyrene containing a heteroatom selected from silicon, nitrogen, phosphorus, tin; “C” is a block formed by C10-C40 alkenylstyrene; "D" is a block formed by divinyl monomers containing a functional group, where the functional group of the divinyl monomer includes a heteroatom selected from nitrogen and silicon. 2. The dilithium initiator according to claim 1, characterized in that the branched or unbranched C4-C20 diene monomer (A) is a compound selected from the group consisting of: 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl- 1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-methyl-3-ethyl-1,3-pentadiene, 3-methyl-1, 3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 1,1 ', 4,4'-tetraphenyl-1, 3-butadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1, 3-butadiene, 4,5-diethyl-1,3-octadiene, 2,3-diethyl-1,3 -butadiene, 2-methyl-3-isopropyl-1,3-butadiene or a mixture thereof. 3. The dilithium initiator according to claim 1, characterized in that the branched or unbranched C4-C20 diene monomer or alkyl styrene containing heteroatom (B) in its composition is a compound selected from the group comprising silicon-containing, phosphorus-containing, silicon-nitrogen-containing, nitrogen-containing, tin-containing compounds, in particular, such as 2-dimethylaminopropyl-1,3-butadiene, 2-triethylsilylpropyl-1,3-butadiene or dimethylaminomethylstyrene, trimethylsilyl styrene, N, N'-bis- (trimethylsilyl) aminomethylstyrene, 4-diphenylphosphinerifenilolovostirol or a mixture thereof. 4. The dilithium initiator according to claim 1, characterized in that the alkenylstyrene C10-C40 (C) is a compound selected from the group consisting of: divinylbenzene, diisopropenylbenzene, p -2-propenylstyrene, p -2-butenyl-α-methylstyrene, p -2-propenyl-α-methylstyrene, p -2-methyl-2-propenylstyrene, p -2-butenylstyrene, p -2-methyl-2-propenyl-α-methylstyrene, 8- ( p- vinylphenyl) -1- octene, 2-methyl-7- ( p- vinylphenyl) -1-heptene. 5. The dilithium initiator according to claim 1, characterized in that the divinyl monomer containing a functional group (D) is a compound selected from the group consisting of: alkylalkenylamine, in particular methyldialkenylamine, butyl dialkylamine; alkylallylsilane, in particular diethyl diallyl silane, dipropyl diallyl silane, methyltriallyl silane. 6. A method of obtaining a dilithium initiator for anionic (co) polymerization containing functional groups, which is a compound of the general formula: Li-X-Li, where X is determined by one of the following formulas: -B-C-B-, -D-, -A-D-A-, -A-B-C-B-A-, -B-A-D-A-B-, -B-A-B-C-B-A-B-, where "A" is a block formed by a branched or unbranched C4-C20 diene monomer; "B" is a block formed by a branched or unbranched C4-C20 diene monomer or alkylstyrene containing a heteroatom selected from silicon, nitrogen, phosphorus, tin; “C” is a block formed by C10-C40 alkenylstyrene; "D" is a block formed by divinyl monomers containing a functional group, where the functional group of the divinyl monomer includes a heteroatom selected from nitrogen and silicon; which comprises reacting an organolithium compound with alkenylstyrene or a divinyl monomer containing a functional group in an organic solvent, optionally followed by the addition of a monomer forming a block "A" and / or a monomer forming a block "B". 7. The method according to p. 6, characterized in that the preparation of the dilithium initiator for anionic (co) polymerization containing functional groups is carried out at a temperature of -20 ÷ 80 ° C, preferably at a temperature of -10 ÷ 60 ° C, more preferably at 0 ÷ 20 ° С. 8. The method according to p. 6, characterized in that for X = -B-C-B- the ratio C: B has a value selected from the following: 1:30, 1:20 or 1:10. 9. The method according to p. 6, characterized in that for X = -A-D-A- the ratio D: A has a value selected from the following: 1:30, 1:20 or 1:10. 10. The method according to p. 6, characterized in that for X = -A-B-C-B-A- the ratio A: B: C has a value selected from the following: 20: 15: 1, 15: 10: 1 or 10: 4: 1. 11. The method according to p. 6, characterized in that for X = -B-A-D-A-B- the ratio A: B: D has a value selected from the following: 20: 15: 1, 15: 10: 1 or 10: 4: 1. 12. The method according to p. 6, characterized in that for X = -B-A-B-C-B-A-B- the ratio A: B: C has a value selected from the following: 20: 15: 1, 15: 10: 1 or 10: 4: 1. 13. The method according to p. 6, characterized in that the interaction of the organolithium compounds with alkenylstyrene or divinyl monomers containing a functional group, if necessary, followed by the addition of the monomer forming the block "A" and / or the monomer forming the block "B", carry out for no more than 5 hours 14. A method of obtaining functionalized diene (co) polymers by polymerizing dienes or copolymerizing them with each other and / or with alpha-olefins in a hydrocarbon solvent in the presence of an organolithium initiator and electron-donor additive, characterized in that a compound of the general formula is used as an organolithium initiator: Li-X-Li, where X is defined by one of the following formulas: -B-C-B-, D-, -A-D-A-, -A-B-C-B-A-, -B-A-D-A-B-, B-A-B-C-B-A-B-, where "A" is a block formed by a branched or unbranched C4-C20 diene monomer; "B" is a block formed by a branched or unbranched C4-C20 diene monomer or alkylstyrene containing a heteroatom selected from silicon, nitrogen, phosphorus, tin; “C” is a block formed by C10-C40 alkenylstyrene; "D" is a block formed by divinyl monomers containing functional groups, where the functional group of the divinyl monomer includes a heteroatom selected from nitrogen and silicon. 15. The method according to p. 14, characterized in that the production of functionalized diene (co) polymers is carried out at a temperature of 0 ÷ 80 ° C, preferably at a temperature of 20 ÷ 70 ° C, more preferably at a temperature of 40 ÷ 60 ° C. 16. The method according to p. 14, characterized in that as the diene using a compound selected from the group including: butadiene, isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 2-methyl-3-ethyl- 1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3- heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-butadiene, 4,5-diethyl-1,3-octadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, or mixtures thereof. 17. The method according to p. 14, characterized in that C8-C40 aryl vinyl compounds are used as the alpha olefin. 18. The method according to p. 17, wherein the C8-C40 aryl vinyl compounds are selected from the following: vinylbenzenes, in particular styrene, alpha-methylstyrene; vinyl biphenyls, in particular vinyl diphenyl; vinylnaphthalenes, in particular 1-vinylnaphthalene, 1-methyl-vinyl-naphthalene; vinylanthracenes, in particular 9-vinyl-anthracene. 19. The method according to p. 14, characterized in that the ratio of alpha olefin to diene is from 5:95 to 10:90, or from 15:85 to 20:80, or from 20:80 to 24:76. 20. The method according to p. 14, characterized in that as electron-donating additives use a compound containing at least one heteroatom or its mixture with alkoxides of alkali or alkaline-earth metals. 21. The method according to p. 20, characterized in that the compound containing at least one heteroatom is N, N, N ', N'-tetramethylethylenediamine, trimethylamine, sodium or potassium tetrahydrofurfurylate, calcium butylate, ethyl tert ethylene glycol-butyl ether, ditetrahydrofurylpropane, ethylene glycol di-tert-butyl ether or a mixture thereof. 22. The method according to p. 20, characterized in that the molar ratio of organolithium initiator: alkali and / or alkaline earth metal alkoxide is 1: (0.1 ÷ 20.0), and the molar ratio of organolithium initiator: a compound containing at least at least one heteroatom is 1: (0.1 ÷ 20.0). 23. The method according to p. 14, characterized in that they carry out additional functionalization of the resulting polymer chain functionalizing agent and / or monomer containing functional groups. 24. The method according to p. 23, characterized in that the additional functionalization of the polymer chain functionalizing agent and / or monomer containing functional groups is carried out at a temperature of 30-100 ° C, preferably at a temperature of 40-80 ° C, more preferably at a temperature of 50 -70 ° C. 25. The method according to p. 23, characterized in that as a functionalizing agent using a compound selected from the group including: N, N-disubstituted aminoalkylacrylamides and N, N-disubstituted aminoalkylmethacrylamides, in particular, such as N, N-dimethylaminopropylacrylamide and N, N-dimethylaminopropylmethacrylamide; N-substituted cyclic amides, in particular, such as N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-methyl-epsilon-caprolactam; N-substituted cyclic ureas, in particular, such as 1,3-dimethylethylene urea and 1,3-diethyl-2-imidazolidinone; as well as N-substituted aminoketones, in particular, such as N, N'-bis- (dimethylamino) benzophenone (Michler's ketone) and N, N'-bis- (diethylamino) benzophenone or a mixture thereof. 26. The method according to p. 23, wherein the functionalizing agent is used in a molar ratio to the dilithium initiator of 0.01 ÷ 2.0, preferably 0.1 ÷ 1.5, more preferably 0.5 ÷ 1.0. 27. The method according to p. 23, characterized in that as a monomer containing a functional group, use is made of a compound selected from the group comprising silicon-containing, phosphorus-containing, silicon-nitrogen-containing, nitrogen-containing, tin-containing compounds, in particular, such as N, N-dimethylaminoethyl styrene , N, N-diethylaminoethyl styrene, 2-dimethylaminopropyl-1,3-butadiene, 2-triethylsilylpropyl-1,3-butadiene or dimethylaminomethylstyrene), trimethylsilyl styrene, N, N'-bis- (trimethylsilyl) aminomethylstyrene, 4-di - triphenyltinostyrene or their the mixture. 28. The method according to p. 23, characterized in that the monomer containing a functional group is added in an amount of 0.01-70% of the mass. per polymer, preferably 1-60 wt. % per polymer, more preferably in an amount of 20-40 mass. % per polymer.