WO2016108715A1

WO2016108715A1 - Dilithium initiator for anionic polymerization

Info

Publication number: WO2016108715A1
Application number: PCT/RU2014/001010
Authority: WO
Inventors: Anna Viktorovna BUDEEVA; Kirill Nikolaevich SHIRIN
Original assignee: Public Joint Stock Company "Sibur Holding"
Priority date: 2014-12-30
Filing date: 2014-12-30
Publication date: 2016-07-07
Also published as: RU2667061C1

Abstract

The invention relates to a dilithium initiator for anionic polymerization having functional groups, a method for preparing thereof, and a process for preparing diene rubbers based thereof. The present invention further relates to an effective process for preparing functionalized diene (со-)polymer rubbers characterized by a random distribution of their monomer units, a high content of vinyl units such as 1,2-butadiene and/or 3,4-isoprene units (more than 60%), and a narrow molecular weight distribution (1.4-1.7), using said dilithium initiator for anionic polymerization. Vulcanizates produced from the rubbers prepared according to the process are characterized with an optimal combination of properties, in particular an improved combination of physico-mechanical and elastic-hysteresis properties.

Description

DILITHIUM INITIATOR FOR ANIONIC POLYMERIZATION, A METHOD FOR PREPARING THEREOF, AND A PROCESS FOR PREPARING DIENE

RUBBERS BASED THEREOF

Technical field

The invention relates to the field of production of synthetic rubbers, in particular diene rubbers, such as polybutadiene , polyisoprene and styrene-butadiene rubber (SBR) , and styrene- isoprene-butadiene rubber (SIBR) , which can be used in the production of tires and rubber technical goods, modification of bitumen, in the electrical engineering and other fields. In particular, the invention relates to a functional group-containing dilithium initiator for anionic (co) polymerization, and a method for preparing thereof, as well as to a process for preparing functionalized diene (co) polymers by using said initiator.

Background

Performance characteristics of rubbers, such as rolling resistance, road grip, and the like, depend on both properties of a rubber and how the rubber interacts with and to what extent it is compatible with a silica filler. An increase in thermodynamic affinity of a rubber for silica fillers promotes a reduction in energy consumption during mixing these components and a significant improvement of basic properties of the rubber. Silica fillers contribute to an increase in rolling resistance, road grip, while reducing hydroplaning risk. A main drawback of silica fillers is in their poor thermodynamic affinity for general-purpose rubbers, which, in turn, affects physicochemical properties of the vulcanizates (rubbers) prepared by using thereof.

An improvement of thermodynamic affinity of a rubber for silica fillers is achieved through modification of the rubber with polar groups. In the art it is known that the existence of functional groups, for example, tin-, silicon- or nitrogen-containing groups allows an improved distribution of reinforcing fillers in the rubber matrix, which, in turn, provides a decrease in hysteresis losses and an improvement of wear resistance and wet grip properties of rubber-based vulcanizate mixtures.

Modification of a rubber with polar groups is possible in several ways:

- use of functionalizing agents (such as Michler's ketone, N-methylpyrrolidone, etc.), i.e. compounds capable of being incorporated into the macromolecules of an obtained rubber, the compounds comprising a heteroatom- containing functional group. The functionalizing agents are generally introduced into a rubber polymerizate at 95-100% conversion of initial monomers to ensure chain-end- functionalization of the macromolecules of the rubber;

use of monolithium, dilithium and multilithium initiators containing functional groups;

- a combined method (use of an organolithium initiator containing functional groups, followed by a reaction between living chains of a rubber and functionalizing agents) ; and

- use of functional group-containing monomers (such as aminostyrene and the like), i.e. compounds capable of entering into a polymerization process (i.e. capable of being incorporated into the macromolecule of an obtained rubber) , which compounds comprise a heteroatom-containing functional group. The functional group-containing monomers are generally introduced into a polymerization system either together with initial monomers or up to 50% conversion of initial monomers to ensure functionalization of the macromolecules of a rubber along the chains (in- chain-functionalization) , or at 95-100% conversion of initial monomers to ensure, just as for the use of a functionalizing agent, functionalization of the ends of the macromolecules of a rubber (end-chain-functionalization)

[1. V. R.-S. Quiteria , C.A. Sierra , J. M. Gomez-Fatou, C. Galan , L.M. Fraga. Tin-coupled styrene-butadiene rubbers (SBRs) . Relationship between coupling type and properties //Macromolecular Materials and Engineering, 1999. - 246. - 2025-2032 p. 2. C.A. Uraneck, J.N. Short. Solution- polymerized rubbers with superior breakdown properties //J. Appl.Polym. Sci, 2003. - 14. - 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, Kenj i 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, Kenj i Ohnuma, Akira Hirao, and Seiichi Nakahama. Anionic polymerization of monomers containing functional groups. 8. Anionic living polymerization of 4-cyano-a- methylstyrene //Macromolecules, 1997. - No.30. - pp.757- 763] .

Patent US 8362164 discloses multifunctional aminolithium initiators containing at least two aminolithium groups, and a method for preparing polymers by using such initiators.

The document discloses a method for preparing an aminodilithium initiator of the following general formula:

wherein Q is a methylene group, oxygen or sulphur; Rl and R2 can be the same or different and represent an alkyl group, a cycloalkyl group, or an aryl group, each of which comprises from 1 to 20 carbon atoms;

The initiator disclosed in US 8362164 is prepared in situ, i.e. directly in a reactor by a reaction of an amino- containing compound with butyllithium . The synthesis of butadiene -styrene rubber is conducted in a hydrocarbon solvent at temperature of 50°C. The electron donor used in said method is 2-bis (2 ' -tetrahydrofuranyl) propane or Ν,Ν,Ν' ,Ν' - tetramethylethylenediamine (TMEDA) . The end- modifier used in the discussed method is cyclohexanecarboxaldehyde homopiperidyhydrazone (CyAHPH) .

The method for preparing an anionic polymer initiator according to US 8362164 comprises steps of providing at least one conjugated diene monomer (i) ; obtaining an initiator in situ, i.e. directly in a reactor, through reaction between an amino-containing compound and butyllithium (ii) , and contacting the monomer with the initiator (iii) .

Disadvantages of the method for preparing an initiator according to US 8362164 include a low polymerization rate since the bond N-Li is less active in anionic (co) olymerization processes than C-Li. The process rate can be increased by raising temperature of the synthesis and, respectively, by increasing the amount of an electron- donor compound (to obtain a desired microstructure) , which, in turn, makes the process more expensive.

The known prior art discloses another bifunctional organolithium initiator containing functional groups:

(see patent EP 2336137 A2) . This document is considered as the closest prior art (prototype) of the present invention.

An advantage of said initiator is its long-term stability and homogenicity of its solutions. A disadvantage is in that said initiator is dissolved only in polar solvents or in aromatic solvents with polar additives (such as TMEDA) that are used in the synthesis of rubbers as electron donors, thus making it impossible to control the microstructure of rubbers .

Another disadvantage consists in a low processability, in particular multistaged nature of the method, and its long duration. This makes the initiator several times more expensive. And yet another disadvantage is in a high probability of the formation of a mixture of various products: along with di- forms, mono-, tri- or tetra-forms of the initiator can also exist, thus complicating the process of controlling the properties of rubbers.

The synthesis of a butadiene-styrene rubber is conducted in the presence of the above-described initiator in a hydrocarbon solvent at temperature of 50 °C. The concentration of monomers in a batch is 14% (by weight) in the following ratio thereof: 20% (by weight) of styrene and 80% (by weight) of butadiene. The dose of the initiator is 2.3 mmol per 100 g of monomers.

Vulcanizate mixtures based on the butadiene-styrene rubbers prepared by using the described initiator show improved physico-mechanical properties, but their elastic- hysteresis properties are deteriorated.

In view of the above, the object of the present invention is to develop an effective method for preparing functionalized diene (co) polymers characterized by a random distribution of their monomer units, a high content of vinyl units, such as 1, 2 -butadiene and/or 3,4-isoprene units (more than 60%), and a narrow molecular weight distribution (1.4-1.7), and having an optimal combination of properties, in particular an improved physicomechanical and elastic-hysteresis characteristics.

Summary of the invention

The object is solved and a desirable technical result is achieved by the present invention according to which a rubber is prepared in a hydrocarbon solvent in the presence of a dilithium initiator for anionic (co) polymerization, wherein said initiator is a compound of general formula:

Li-X-Li;

wherein X is 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- ,

wherein "A" is a unit formed by a branched or linear

C₄-C₂odiene monomer; "B" is a unit formed by a branched or linear C₄-C₂odiene monomer or alkylstyrene , each of which comprises a heteroatom selected from Si, N, P, and Sn; "C" is a unit formed by Ci₀ - C₄oalkenylstyrene ; and "D" is a unit formed by a divinyl monomer containing a functional group.

Said initiator can be synthesized in a mixed organic solvent (an aliphatic or aromatic solvent in combination with a polar solvent) by a reaction between an organolithium compound with an alkenylstyrene (forming unit C) or divinyl monomer (forming unit D) containing a functional group, and, thereafter, a monomer forming unit A and/or a monomer forming unit B may be added when necessary. The present invention also relates to a method for preparing functionalized diene (co) polymers by polymerization of dienes or their copolymerization with each other and/or with alpha-olefins in a hydrocarbon solvent in the presence of an organolithium initiator for anionic (co) polymerization and an electron-donor additive, wherein said organolithium initiator for anionic (co) polymerization is the aforesaid organolithium initiator .

Detailed description of the invention

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

Li-X-Li;

wherein X is 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- , wherein "A" is a unit formed by a branched or linear C₄- C₂odiene monomer; B is a unit formed by a branched or linear C₄-C₂odiene monomer or alkylstyrene , each of which comprises a heteroatom selected from Si, N, P, and Sn; "C" is a unit formed by Ci₀-C₄₀alkenylstyrene; and "D" is a unit formed by a divinyl monomer containing a functional group.

The branched or linear C₄-C₂odiene monomer (unit A) can be a compound selected from the group including 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 , 4¹ - tetraphenyl- 1 , 3 -butadien, 3 -methyl -1 , 3 -heptadiene , 1 , 3 -octadiene , 3- butyl-1, 3-octadiene, 3 , 4 -dimethyl- 1 , 3 -hexadiene , 3-n- propy1-1, 3 -butadiene, 4 , 5-diethyl-l, 3-octadiene, 2,3- diethyl-1, 3 -butadiene, 2-methyl-3-isopropyl-l, 3 -butadiene, or a mixture thereof .

The branched or linear C₄-C₂odiene monomer or alkylstyrene , each of which comprises a heteroatom, in particular Si, and/or N, and/or P, and/or Sn, (unit B) can be a compound selected from the group comprising a silicon- containing compound, a compound phosphorus-containing, a silicon-nitrogen-containing compound, a nitrogen-containing compound, or a tin-containing compound, in particular, such as, for example, 2 -dimethylaminopropyl-1, 3 -butadiene, 2- triethylsilylpropyl-1, 3-butadiene or dimethylaminomethyl styrene, trimethylsilyl styrene, Ν,Ν'- bis (trimethylsilyl) aminomethyl styrene, 4-diphenylphosphine styrene, 4 -triphenyltin styrene, or a mixture thereof.

The Cio-Cjoalkenylstyrene (unit C) can be a compound selected from the group including divinylbenzene , diisopropenylbenzene , p-2-propenylstyrene, p-2 -butenyl- - methylstyrene , p-2-propenyl- -methylstyrene, p-2-methyl-2- propenylstyrene , p-2-butenylstyrene, p-2 -methyl-2 -propenyl- a-methylstyrene, 8- (p-vinylphenyl) -1-octene, and 2 -methyl- 7- (p-vinylphenyl) -1-heptene .

The divinyl monomer containing a functional group (unit D) can be a compound selected from the group including alkylalkenylamine , in particular methyldialkenylamine and butyldialkenylamine ; alkylallylsilane, in particular diethyldiallylsilane , dipropyldiallylsilane , and methyltriallylsilane .

The dilithium initiator according to the present invention is prepared in a mixed organic solvent (an aliphatic or aromatic solvent in combination with a polar solvent) by a reaction between an organolithium compound with an alkenylstyrene or divinyl monomer containing a functional group, followed when necessary by adding a monomer forming unit A and/or a monomer forming unit B. Each monomer is added separately, by dropping, to a reaction medium consisting of a mixed solvent and an organolithium compound. At the end of the synthesis, the solvent is distilled under vacuum.

The aliphatic solvent used herein is a compound selected from the group including linear or branched saturated acyclic and cyclic hydrocarbons. The aromatic solvent used herein is a compound selected from the group including benzene, toluene, xylene, and ethylbenzene . The polar solvent used herein is a compound selected from the group including diethyl ether, tetrahydrofuran, trimethylamine , etc.

The organolithium compound used herein can be, in particular, an alkyllithium compound, preferably C₄-C₆- alkyllithium, more preferably n-butyllithium, sec- butyllithium, tert-butyllithium, or isopropyllithium.

In one embodiment of the method according to present invention, when X is -B-C-B-, a ratio of C:B can be 1:30; 1 : 20 or 1 : 10.

In another embodiment of the method according to present invention, when X is -A-D-A-, a ratio of D:A can be 1:30; 1:20 or 1:10.

In yet another embodiment of the method according to present invention, when X is -A-B-C-B-A-, a ratio of A:B:C can be 20:15:1, or 15:10:1, or 10:4:1.

In yet another embodiment of the method according to present invention, when X is -B-A-D-A-B-, a ratio of A : B : D can be 20:15:1, or 15:10:1, or 10:4:1.

In yet another embodiment of the method according to present invention, when X is -B-A-B-C-B-A-B- , a ratio of A : B : C can be 20:15:1, or 15:10:1, or 10:4:1.

The reaction an organolithium compound with an alkenylstyrene or divinyl monomer containing a functional group, followed when necessary by adding a monomer forming unit A and/or a monomer forming unit B, in a mixed organic solvent is generally conducted at temperature of from -20 to 80°C, preferably from -10 to 60°C, more preferably from 0 to 20°C.

The reaction generally lasts not more than 5 hours, preferably from 60 to 300 minutes, more preferably from 120 to 180 minutes.

Polymerization of dienes or their copolymerization with each other and/or with alpha-olefins according to the present invention is carried out in a hydrocarbon solvent in the presence of the above-described dilithium initiator and an electron-donor additive. The dienes used herein are preferably conjugated dienes, in particular, C₄ - Ci₂dienes , such as butadiene, isoprene, piperylene, 2 , 3 -dimethyl- 1 , 3 - butadiene, 2-methyl-3-ethyl-l, 3-butadiene, 3-methyl-l, 3- pentadiene, 2-methyl-3-ethyl-l, 3 -pentadiene , 3-methyl-l, 3- pentadiene, 1 , 3 -hexadiene , 2 -methyl- 1, 3-hexadiene, 1,3- heptadiene, 2 -phenyl -1, 3-butadiene, 3-methyl-l, 3- heptadiene, 1, 3-octadiene, 3-butyl-l, 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.

The alpha-olefin can be a C₈-C₄₀arylvinyl compound, for example, such as, vinylbenzenes , in particular styrene and alpha-methylstyrene ; vinylbiphenyls , in particular vinyldiphenyl ; vinylnaphthalenes , in particular 1- vinylnaphthalene , and 1 -methylvinylnaphthalene ; and vinylanthracenes , in particular, 9-vinylanthracene .

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

The organolithium initiator used herein is a dilithium initiator for anionic (co) olymerization according to the present invention of general formula

Li-X-Li, wherein X is as defined above.

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

In particular, the compound comprising at least one heteroatom can be compounds represented by one of the following formulas:

wherein n is from 1 to 20; R and R' are CH₃, C₂H₅, n-

C₃H₇, i.-C₃H₇, n-C Hg, S-C₄H₉, t-C Hg, I-C₄H₉, C5H11, 0βΗΐ3 , C₇Hi₅ ,

C₈H₁₇, C₉H₁₉, C₁₀H₂₁, C₆H₅, o-C₆H₄CH₃, m-C₆H₄CH₃, p-C₆H₄CH₃, o- C₅H₄C₂H₅, ffl-C₆H₄CH_3i or p-C₆H₄CH₃, and

νΐβΌ—X X—O-Mc^' O \CH/_n wherein n is from 1 to 20; m is from 1 to 4; Me is Li,

Na, and K; X is -CH₂-, -C₂H₄-, -C₃H₆-, -C₄H₈-, -C₅H₁₀-, -C₆Hi₂- , -C₇H₁₄-, or -C₈H₁₆-_; R is CH₃, C₂H₅, n-C₃H₇, i-C₃H₇, r!-C₄H₉, S-C₄H₉, t-C₄H9, 2-C₄H₉, C₅H₁₁, CgHi₃ , C₇Hi₅ , CeHi-7, C₉H₁₉, CioH₂i, C₆H₅, o-C₆H₄CH₃, m-C₆H₄CH₃, p-C₆H₄CH₃, o-C₆H₄C₂H5, m-C₆H₄CH_3i or p-C₆H₄CH₃. The electron-donor additive also can be a compound, such as Ν,Ν,Ν' ,Ν' -tetramethylethylenediamine , trimethylamine , sodium or potassium tetrahydrofurfurylate, calcium butilate, ethylene glycol ethyl- tert-butyl ether, ditetrahydrofurylpropane, ethylene glycol di- tert-butyl ether, or a mixture thereof.

A molar ratio of the organolithium initiator to the compound comprising at least one heteroatom can generally be 1 : (0.1-20.0) , and a molar ratio of the organolithium initiator to alkoxide of an alkali and/or alkaline metal is 1 : (0.1-20.0) . The indicated ranges of molar ratios are determined by the need to obtain a given amount of vinyl groups (not more than 50 wt.%) in the butadiene part of a polymer chain, control a degree of statistical distribution (microblockiness) of alpha-olefins in a rubber, for example, styrene or derivatives thereof when they are used as comonomers of diene.

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

After synthesis, the catalyst is deactivated, and the rubber is stabilized by addition of a solution of an antioxidant, for example, 2, 2¹ -methylenebis [6- (1, 1- dimethylethyl) -4 -methyl-phenol (agidol-2) or another type to the polymerizate in an amount of 0.2 to 0.6%. Then, the rubber is isolated by known methods, such as water-steam degassing and drying on rollers.

The properties of the prepared rubber can be additionally improved by further functionalization. The additional functionalization is carried out after reaching 95-100% conversion by addition of functionalizing agents to the polymerization system. The functionalizing agents are used for end-chain functionalization of the macromolecules of the rubber. In another embodiment, the functionalization is carried out by addition of functional group-containing monomers to the polymerization system, wherein the monomers are added simultaneously with initial monomers or during the polymerization reaction up to 50% conversion of the initial monomers, and, in some cases, in 95-100% conversion of the initial monomers. The functional group-containing monomers are used for in-chain functionalization and, some cases, end-chain functionalization of the macromolecules of the rubber.

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

The functional group-containing monomer used herein is a compound selected from the group including a silicon- containing compound, a phosphorus-containing compound, a silicon-nitrogen-containing compound, a nitrogen-containing compound, and a tin-containing compound, in particular, such as N, -dimethylaminomethyl styrene and N,N- diethylaminoethyl styrene, 2 -dimethylaminopropyl ~ 1 , 3 - butadiene, 2-triethylsilylpropyl-l, 3 -butadiene or dimethylaminomethyl styrene, trimethylsilylstyrene , Ν,Ν'- bis (trimethylsilyl) aminomethyl styrene, 4 -diphenylphosphine styrene, 4 -triphenyltin styrene, or a mixture thereof. The functional group-containing monomer is added in an amount of from 0.01 to 70.0%, preferably from 1 to 60%, more preferably from 20 to 40% based on weight of polymer. The functionalization is preferably conducted at temperature of from 30 to 100°C, preferably from 40 to 80°C or from 60 to 80°C, more preferably from 50 to 70°C, for 15-60 minutes.

The use of the claimed method allows the preparation of functionalized diene (co) polymers having statistical distribution of monomer units, narrow molecular weight distribution (MMD) , and a high content of vinyl units (1,2- butadiene and/or 3,4-isoprene units (more than 50%)), as well as an improved combination of properties, in particular, physicochemical and elastic-hysteresis characteristics .

Examples

Example 1

A 250 ml glass reactor was filled with 50 ml of dehydrated cyclohexane and 10 ml of n-butyllithium (1.6 M) . The reactor was cooled to 0°C. Then, 1.5 ml of 1,3- diisopropenylbenzene and 6 ml of tetrahydrofuran (THF) were added to the reactor through a drop funnel. After that, dimethylaminomethyl styrene was added also through the drop funnel in an amount of 1.5 ml. Then 5 ml of isoprene were filled to the reaction mixture. When addition of the monomers was complete, the reaction mixture was heated to room temperature and mixed for additional 30 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.35 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium, as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 46 g of butadiene, and 12 g of styrene (in a weight ratio of monomers in the reaction medium of 79:21) . The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and an electron-donor additive was added thereto. The electron-donor additive included ditetrahydrofurylpropane (DTHFP) in the form of a 0.054 M solution in nefras, based on a ratio of DTHFP : lithium of 0.2 mol/mol. The dilithium initiator was fed to the reactor in the form of a solution in nefras (0.35 M) in an amount of 1.4 mmol of the initiator per 100 g of monomers. The process of copolymerization was conducted at 50°C to 100% conversion. When the conversion was complete, an antioxidant was added. The antioxidant used herein was agidol-2 taken in an amount of 0.5 wt . % .

The resulting product had the following characteristics: the amount of sterene - 21 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 66 wt.%; glass- transition point - minus 21°C; Mn = 146,000; polydispersity - 1.4; and Mooney viscosity - 50 units.

Vulcanizates based on the obtained rubber show an improved complex of properties, in particular, physico- mechanical and elastic-hysteresis characteristics. Example 2

A 250 ml glass reactor was filled with 50 ml of dehydrated cyclohexane and 10 ml of n-butyllithium (1.6 M) . The reactor was cooled to 0°C. Then, 1.5 ml of 1,3- diisopropenylbenzene and 6 ml of THF were added to the reactor through a drop funnel. After that, dimethylaminomethyl styrene was added also through the drop funnel in an amount of 1.5 ml. When addition of the monomers was complete, the reaction mixture was heated to room temperature and mixed for additional 30 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.45 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium, as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, and 54 g of butadiene. The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and an electron-donor additive was added thereto. The electron- donor additive included sodium tetrahydrofurfurylate (STHF) in the form of a 0.60 M solution in toluene, based on a ratio of STHF: lithium of 0.2 mol/mol. The dilithium initiator was fed to the reactor in an amount of 1.6 mmol of the initiator per 100 g of monomers. The process of copolymerization was conducted at 55°C to 100% conversion. When the conversion was complete, the polymerization mixture was mixed with an antioxidant solution in nefras. The antioxidant used herein was agidol-2 taken in an amount of 0.5 wt.%.

The resulting product contained 50% of 1, 2-butadiene units, glass transition temperature was minus 25 °C, Mn = 155,000, polydispersity was 1.6, and Mooney viscosity was 50 units.

Example 3

A 200 ml glass reactor was filled with 50 ml of dehydrated cyclohexane and 10 ml of sec-butyllithium. The reactor was cooled to 0°C. Then, 3 ml of methyldialkenylamine and 6 ml of THF were added to the reactor through a drop funnel. When addition of the monomer was complete, the reaction mixture was heated to room temperature and mixed for additional 30 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.25 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium, as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 54 g of isoprene, and 16 styrene. The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15°C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and an electron-donor additive was added thereto. The electron- donor additive included calcium butylate in the form of a 0.056 solution in toluene, based on a ratio of calcium butylate : lithium of 0.8 mol/mol. The dilithium initiator was fed to the reactor in an amount of 1.5 mmol of the initiator per 100 g of monomers. The process of copolymerization was conducted at 50 °C to 100% conversion. When the conversion was complete, the polymerization mixture was mixed with an antioxidant solution in nefras. The antioxidant used herein was agidol-2 taken in an amount of 0.5 wt . % .

The resulting product contained 50% of 3,4-isoprene units; glass transition temperature was -25°C; Mn 168,000, polydispersity was 1.7, and Mooney viscosity was 59 units.

Example 4

A 250 ml glass reactor was filled with 50 ml of dehydrated cyclohexane and 5 ml of tert-butyllithium . The reactor was cooled to 0°C. Then, 2.0 ml dimethyldiallylsilane and 3 ml of diethyl ether were added to the reactor through a drop funnel. Then 2 -phenyl -1, 3- butadiene was added to the reaction mixture in an amount of 10 ml. When addition of the monomers was complete, the reaction mixture was heated to room temperature and mixed for additional 30 minutes. Then, diethyl ether was removed from the reaction mixture under reduced pressure 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 was 0.45 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium, as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A 5 L metal reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 2273 g of nefras previously dried and deoxygenated, 348 g of butadiene, and 92 styrene. The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and a mixture of electron-donor additives was added thereto, wherein the dilithium initiator was added in an amount of 1.6 mol of the initiator per 100 g of monomers. The mixture of electron donor additives included tetramethylethylenediamine (TMEDA) in the form of a 0.36 M solution in nefras, based on a ration of TMEDA/lithium of 0.5 mol/mol, and a 0.30 M solution of potassium amylate in nefras, based on a ratio of PA/lithium of 0.1 mol/mol. The process of copolymerization was conducted at temperature of 50 °C. The antioxidant used herein was agidol-2 taken in an amount of 0.5 wt . % .

The resulting product had the following characteristics: the amount of styrene - 20 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 67 wt.%; glass- transition point - minus 20°C; Mn = 160,000; polydispersity was 1.6; and Mooney viscosity was 53 units.

Example 5

A 250 ml glass reactor was filled with 50 ml of dehydrated cyclohexane and 10 ml of sec-butyllithium. The reactor was cooled to 0°C. Then, 1.5 ml of 1,3- divinylbenzene and 2 ml of THF were added to the reactor through a drop funnel. After that, 4 ml of 4 - trimethylsilyl styrene were added also through the drop funnel . When addition of the monomers was complete, the reaction mixture was heated to room temperature and mixed for additional 30 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.50 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium, as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 17 g of styrene, and 20 g of butadiene, and 20 g of isoprene. The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15°C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and a mixture of electron-donor additives was added thereto. The mixture of electron donor additives included tetramethylethylenediamine in the form of a 0.066 M solution in nefras, based on a ratio of TMEDA/lithium of 0.25 mol/mol, and a 0.07 M solution of sodium tetrahydrofurfurylate in toluene, based on a ratio of STHF/lithium of 0.1 mol/mol. The dilithium initiator was fed to the reactor in an amount of 1.4 mmol of the initiator per 100 g of monomers. The process of copolymerization was conducted at temperature of 60 °C. The antioxidant used herein was agidol-2 taken in an amount of 0.5 wt . % . The resulting product had the following characteristics: the amount of styrene - 30 wt.%; the amount of 1, 2 -butadiene units per polybutadiene - 48 wt.%; the amount of 3,4-isoprene units per polyisoprene - 53%; glass- transition point - minus 20°C; Mn = 186,000; polydispersity was 1.7; and Mooney viscosity was 66 units.

Example 6

A 250 ml glass reactor was filled with 50 ml of dehydrated toluene and 10 ml of n-butyllithium (1.6 ) . The reactor was cooled to 0°C. Then, 1.5 ml of 1,3- divinylbenzene and 10 ml of THF were added to the reactor through a drop funnel. After that, 6.0 ml of Ν,Ν'- bis (trimethylsilyl) aminomethyl styrene were added also through the drop funnel. Then 10 ml of butadiene was added to the reaction mixture. When addition of the monomers was complete, the reaction mixture was heated to room temperature and mixed for additional 30 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.55 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium, as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer and, a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 46 g of butadiene, and 12 g of styrene (in a weight ratio of monomers in the reaction medium of 79:21) . The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and an electron-donor additive was added thereto. The electron-donor additive included tetramethylethylenediamine in the form of a 0.066 M solution in nefras, based on a ratio of TMEDA: lithium of 1.0 mol/mol. The dilithium initiator was fed to the reactor in an amount of 1.0 mmol of the initiator per 100 g of monomers. The process of copolymerization was conducted at 55°C to 100% conversion. When the conversion was complete, an antioxidant was added. The antioxidant used herein was agidol-2 taken in an amount of 0.5 wt . % .

The resulting product had the following characteristics: the amount of styrene - 21 wt.%; the amount of 1, 2 -butadiene units per polybutadiene - 64 wt.%; glass- transition point - minus 23 °C; Mn = 230,000; polydispersity was 1.7; and Mooney viscosity - 76 units.

Vulcanizate mixtures based on the obtained rubber show an improved complex of properties, in particular, physicochemical and elastic-hysteresis characteristics.

Example 7

A 250 ml glass reactor was filled with 50 ml of dehydrated toluene and 11 ml of sec-butyllithium. The reactor was cooled to minus 20°C. Then, 4.0 ml of dimethyldiallylsilane and 3 ml of THF were added to the reactor through a drop funnel. After that, piperylene was added also through the drop funnel in an amount of 8 ml. When addition of the monomers was complete, the reaction mixture was heated to room temperature and mixed for additional 30 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.65 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 54 g of butadiene, and 4 g of isoprene. The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and an electron-donor additive was added thereto. The electron donor additive was triethylamine in the form of a 0.045 solution in toluene, based on a ratio of triethylamine/lithium ratio of 20 mol/mol. The dilithium initiator was fed to the reactor in an amount of 1.7 mmol of the initiator per 100 g of monomers. The process of copolymerization was conducted at 20°C to 100% conversion. When the conversion was complete, an antioxidant was added. The antioxidant used herein was agidol-2 taken in an amount of 0.5 wt.

The obtained product had an isoprene/butadiene ratio of 7/93, and contained 55% of 3,4-isoprene units, 60% of 1 , 2 -butadiene units, glass transition temperature was minus 19°C, Mn = 169000, polydispersity was 1.7, and Mooney viscosity was 56 units.

Example 8

A 250 ml glass reactor was filled with 50 ml of dehydrated toluene and 15 ml of n-butyllithium (1.6 M) . The reactor was cooled to 0°C. Then, 3.5 ml of ethyldiallylamine and 5 ml of THF were added to the reactor through a drop funnel. After that, 3 -methyl-1 , 3 -pentadiene was added also through the drop funnel in an amount of 8.0 ml. When addition of the monomers was complete, the reaction mixture was heated to room temperature and mixed for additional 30 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.70 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 17 g of styrene, 20 g of butadiene, and 20 g of isoprene. The temperature of delivering the batch to the reactor was minus 10°C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and an electron-donor additive was added thereto. The electron-donor additive was a 0.050 M solution tetrahydrofurylpropane in nefras, based on a ratio of DTHFP/lithium of 0.40 mol/mol. The dilithium initiator was fed to the reactor in an amount of 1.5 mmol of the initiator per 100 g of monomers. The process of copolymerization was conducted at temperature of 80 °C. The antioxidant used herein was agidol-2 taken in an amount of 0.5 wt . % .

The resulting product had the following characteristics: the amount of styrene - 30 wt . % ; the amount of 1 , 2 -butadiene units per polybutadiene - 45 wt.%; the amount of 3,4-isoprene units per polyisoprene - 55%; glass- transition point - minus 20°C; Mn = 185,000; polydispersity was 1.7; and Mooney viscosity was 60 units.

Example 9

A 250 ml glass reactor was filled with 60 ml of dehydrated toluene and 15 ml of n-butyllithium (1.6 M) . The reactor was cooled to 0°C. Then, 4 ml of dimethyldiallylsilane and 3 ml of THF were added to the reactor through a drop funnel. When addition of the monomer was complete, the reaction mixture was heated to room temperature and mixed for additional 30 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.68 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A 5 L metal reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 2273 g of nefras previously dried and deoxygenated, 348 g of butadiene, and 92 styrene. The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and a mixture of electron-donor additives was added thereto, wherein the dilithium initiator was added in an amount of 1.8 mol of the initiator per 100 g of monomers. The mixture of electron donor additives included ditetrahydrofurylpropane (DTHFP) in the form of a 0.32 M solution in nefras, based on a ration of DTHFP/lithium of 0.35 mol/mol, and a 0.30 M solution of potassium amylate in nefras, based on a ratio of PA/lithium of 0.1 mol/mol. The process of copolymerization was conducted at temperature of 55°C. The antioxidant used herein was agidol-2 taken in an amount of 0.5 wt . % .

The resulting product had the following characteristics: the amount of styrene - 21 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 67 wt.%; glass- transition point - minus 20°C; Mn = 152,000; polydispersity was 1.6; and Mooney viscosity was 55 units.

Example 10

A 500 ml glass reactor was filled with 200 ml of dehydrated toluene and 20 ml of sec-butyllithium . The reactor was cooled to 0°C. Then, 3.0 ml of 1,3- diisopropenylbenzene and 1.0 ml of THF were added to the reactor through a drop funnel. After that, 5.0 ml of 4- diphenylphosphine styrene were added also through the drop funnel. When addition of the monomers was complete, the reaction mixture was heated to room temperature and mixed for additional 30 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.35 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, and 68 g of isoprene. The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and a mixture of electron-donor additives was added thereto. The mixture of electron donor additives included ethylene glycol ethyl- tert-butyl ether (EGETBE) in the form of a 0.0912 M solution in nefras, based on a ratio of EGETBE/lithium of 0.5 mol/mol, and a 0.05 M solution of potassium tetrahydrof rfurylate in toluene based on a ratio of PTHF/lithium of 0.2 mol/mol. The dilithium initiator was fed to the reactor in an amount of 1.3 mmol of the initiator per 100 g of monomers.

The process of copolymerization was conducted at 50°C to 100% conversion. When the conversion was completed, the polymerization mixture was mixed with an antioxidant solution in nefras. The antioxidant used herein was agidol- 2 taken in an amount of 0.5 wt . % .

The resulting product contained 65% of 3, 4 -isoprene units; glass transition temperature was -18°C; and Mn = 186,000, polydispersity was 1.5, and Mooney viscosity was 61 units.

Example 11

A 500 ml glass reactor was filled with 200 ml of dehydrated toluene and 15 ml of n-butyllithium (1.6 M) . The reactor was cooled to 0°C. Then, 3.0 ml of 1,3- diisopropenylbenzene and 1.5 ml of THF were added to the reactor through a drop funnel. After that, dimethylaminomethyl styrene was added also through the drop funnel in an amount of 6.0 ml. Then 20 ml of 1 , 3 -heptadiene were added to the reaction mixture. When addition of the monomers was complete, the reaction mixture was heated to room temperature and mixed for additional 40 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.40 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 46 g of butadiene, and 12 g of isoprene (in a weight ratio of monomers in the reaction medium of 80:20). The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and a mixture of electron-donor additives was added thereto. The mixture of electron donor additives included sodium tetrahydrofurylate in the form of a 0.075 M solution in toluene, based on a ratio of STHF/lithium of 0.1 mol/mol, and a 0.066 M solution of tetramethylethylenediamine in nefras, based on a ratio of T EDA/lithium of 1.0 mol/mol. The dilithium initiator was fed to the reactor in an amount of 1.2 mmol of the initiator per 100 g of monomers.

The process of copolymerization was conducted at 60 °C to 100% conversion. When the conversion was completed, the polymerization mixture was mixed with an antioxidant solution in nefras. The antioxidant used herein v/as agidol- 2 taken in an amount of 0.5 wt . % .

The resulting product contained 50% of 1 , 2-butadiene units, 48% of 3,4-isoprene units; glass transition temperature was minus 21°C; Mn = 175,000; polydispersity was 1.6, and Mooney viscosity was 63 units.

Example 12

A 500 ml glass reactor was filled with 200 ml of dehydrated toluene and 20 ml of n-butyllithium (1.6 M) . The reactor was cooled to 0°C. Then, 3.0 ml of 1,3- diisopropenylbenzene and 2.0 ml of THF were added to the reactor through a drop funnel. After that, 4 -triphenyltin styrene was added also through the drop funnel in an amount of 8.0 ml. Then, 20 ml of 1 , 3 -octadiene were added to the reaction mixture. When addition of the monomers was complete, the reaction mixture was heated to room temperature and mixed for additional 15 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.42 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 46 g of butadiene, 12 g of isoprene, and 8g of styrene. The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and a mixture of electron-donor additives was added thereto. The mixture of electron donor additives included tetramethylethylenediamine in the form of a O.066 M solution in nefras, based on a ratio of TMEDA/lithium of 0.4 mol/mol, and a 0.05 M solution of ethylene glycol di- tert-butyl ether in nefras, based on EGDTBE/ lithium of 0.5 mol/mol. The dilithium initiator was fed to the reactor in an amount of 1.5 mmol of the initiator per 100 g of monomers .

The process of copolymerization was conducted at 50 °C to 100% conversion. When the conversion was complete, the polymerization mixture was mixed with an antioxidant solution in nefras. The antioxidant used herein was agidol- 2 taken in an amount of 0.5 wt . % .

The resulting product had the following characteristics: the amount of styrene - 14 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 65 wt.%; the amount of 3,4-isoprene units per polyisoprene - 73%; glass-transition point was-ll°C; Mn = 166,000; polydispersity was 1.6; and Mooney viscosity was 57 units.

Example 13

The process was conducted as disclosed in Example 1, except for that the prepared polymer was further subjected to end-chain functionalization . When the conversion reached 95-100%, a functionalizing agent (N, N-dimethylaminopropyl acrylamide) was added in the form of a 0.037 M solution in a molar ratio to Li of 0.8; the reaction was continued for additional 30 minutes at the same temperature.

The resulting product had the following characteristics: the amount of styrene - 20 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 65 wt.%; glass-transition point was -20 °C; Mn = 140 000; polydispersity was 1.6; and Mooney viscosity was 48 units.

Example 14

The process was conducted as disclosed in Example 1, except that the prepared polymer was further subjected to end-chain functionalization . When the conversion reached 95-100%, a functionalizing agent (N, N-dimethylaminopropyl methacrylamide) was added in the form of a 0.047 M solution in a molar ratio to Li of 0.1; the reaction was continued for additional 15 minutes at temperature of 60 °C.

The resulting product had the following characteristics: the amount of styrene - 22 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 68 wt.%; glass-transition point was -19°C; Mn = 150 000; polydispersity was 1.5; and Mooney viscosity was 52 units.

Example 15

The process was conducted as disclosed in Example 1, except that the prepared polymer was further subjected to end-chain functionalization . When the conversion reached 95-100%, a functionalizing agent (N-vinyl-2-pyrrolidone) was added in the form of a 0.030 M solution in a molar ratio to Li of 0.5; the reaction was continued for additional 30 minutes at temperature of 60 °C.

The resulting product had the following characteristics: the amount of styrene - 21 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 64 wt.%; glass-transition point was -23°C; Mn = 159 000; polydispersity was 1.7; and Mooney viscosity was 55 units.

Example 16

The process was conducted as disclosed in Example 1, except that the prepared polymer was further subjected to end-chain functionalization . When the conversion reached 95-100%, a functionalizing agent ( 1 , 3 -dimethylethylene urea) was added in the form of a 0.035 M solution in a molar ratio to Li of 0.01; the reaction was continued for additional 45 minutes at temperature of 70 °C.

The resulting product had the following characteristics: the amount of styrene - 20 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 66 wt.%; glass-transition point was -21°C; Mn = 143 000; polydispersity was 1.4; and Mooney viscosity was 49 units.

Example 17

The process was conducted as disclosed in Example 1, except that the prepared polymer was further subjected to end-chain functionalization . When the conversion reached 95-100%, a functionalizing agent (Ν,Ν'- bis (diethylamino) benzophenone) was added in the form of a 0.037 M solution in a molar ratio to Li of 1.0; the reaction was continued for additional 45 minutes at temperature of 60 °C.

The resulting product had the following characteristics: the amount of styrene - 22 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 70 wt.%; glass-transition point was -18 °C; Mn = 160 000; polydispersity was 1.6; and Mooney viscosity was 57 units.

Example 18

The process was conducted as disclosed in Example 1, except that the prepared polymer was further subjected to end-chain functionalization . When the conversion reached 95-100%, a functional group-containing monomer (Ν,Ν'- bis ( trimethylsilyl) aminomethyl styrene) was added in the form of a 0.046 M solution in an amount of 0.01% based on polymer; the reaction was continued for additional 15 minutes at the same temperature.

The resulting product had the following characteristics: the amount of styrene - 21 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 66 wt.%; glass-transition point was -20 °C; Mn = 140 000; polydispersity was 1.5; and Mooney viscosity was 50 units.

Example 19

The process was conducted as disclosed in Example 1, except that the prepared polymer was further subjected to end-chain functionalization . When the conversion reached 95-100%, a functional group-containing monomer (4- trimethylsilylstyrene) was added in the form of a 0.052 M solution in an amount of 30% based on polymer; the reaction was continued for additional 30 minutes at the same temperature .

The resulting product had the following characteristics: the amount of styrene - 19 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 63 wt.%; glass-transition point was -24 °C; Mn = 158 000; polydispersity was 1.6; and Mooney viscosity was 53 units.

Example 20

The process was conducted as disclosed in Example 1, except that the prepared polymer was further subjected to end-chain functionalization. When the conversion reached 95-100%, a functional group-containing monomer (4- diphenylphosphine styrene) was added in the form of a 0.030 M solution in an amount of 5.0% based on polymer; the reaction was continued for additional 45 minutes at the same temperature .

The resulting product had the following characteristics: the amount of styrene - 19 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 66 wt.%; glass-transition point was -20 °C; Mn = 146 000; polydispersity was 1.5; and Mooney viscosity was 51 units.

Example 21

The process was conducted as disclosed in Example 1, except that the prepared polymer was further subjected to end-chain functionalization. When the conversion reached 95-100%, a functional group-containing monomer (4- triphenyltin styrene) was added in the form of a 0.058 M solution in an amount of 1.5% based on polymer; the reaction was continued for additional 30 minutes at the same temperature .

The resulting product had the following characteristics: the amount of styrene - 21 wt.%; the amount of 1, 2-butadiene units per polybutadiene - 65 wt.%; glass- transition point was -22 °C; n = 168 000; polydispersity was 1.5; and Mooney viscosity was 60 units.

Example 22

The process was conducted as disclosed in Example 1, except that the prepared polymer was further subjected to end-chain functionalization. When the conversion reached 95-100%, a functional group-containing monomer

(dimethylaminomethyl styrene) was added in the form of a 0.060 M solution in an amount of 13.0% based on polymer; the reaction was continued for additional 30 minutes at the same temperature .

The resulting product had the following characteristics: the amount of styrene - 20 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 68 wt.%; glass-transition point was -19°C; Mn = 138 000; polydispersity was 1.4; and Mooney viscosity was 46 units.

Example 23

The process was conducted as disclosed in Example 1, except that. The prepared polymer was further subjected to end-chain functionalization. When the conversion reached

95-100%, a functional group-containing monomer

(diethylaminomethyl styrene) was added in the form of a 0.075 M solution in an amount of 15% based on polymer; the reaction was continued for additional 15 minutes at the same temperature .

The resulting product had the following characteristics: the amount of styrene - 21 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 65 wt.%; glass- transition point was -21°C; Mn = 150 000; polydispersity was 1.6; and Mooney viscosity was 52 units.

Example 24

A 250 ml glass reactor was filled with 50 ml of dehydrated cyclohexane and 10 ml of n-butyllithium (1.6 M) . The reactor was cooled to 10 °C. Then, 1.5 ml of n-2- propenylstyrene and 10 ml of THF were added to the reactor through a drop funnel. After that, dimethylaminomethyl styrene was also added through the drop funnel. Then, 1 , 1 ' , 4 , 4 ' - tetraphenylbutadiene was added to the reaction mixture, after that 2-dimethylaminopropylbutadiene was filled in a ratio of n-2- propenylstyrene : (dimethylaminomethyl styrene + 2- dimethylaminopropylbutadiene ):1,1',4,4'- tetraphenylbutadiene of 1:15:20, respectively. When addition of the monomers was complete, the reaction mixture was heated to temperature of 60 °C and mixed for additional 20 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.45 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 46 g of butadiene, and 12 g of styrene (in a weight ratio of monomers in the reaction medium of 79:21). The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 20 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and an electron-donor additive was added thereto. The electron-donor additive included triethylamine (TEA) in the form of a 0.040 solution in nefras, based on a ratio of TEA: lithium of 5 mol/mol. The dilithium initiator was fed to the reactor in the form of a solution in nefras (0.45 M) in an amount of 1.6 mol of the initiator per 100 g of monomers. The process of copolymerization was conducted at temperature of 40 °C. When the conversion reached 95-98%, a functional group-containing monomer (diethylaminomethyl styrene) was added in the form of a 0.090 M solution in an amount of 70% based on polymer; the reaction was continued for additional 15 minutes at temperature of 30°C. When the conversion reached 100%, an antioxidant was added. The antioxidant used herein was agidol-2 taken in an amount of 0.5 wt . % .

The resulting product had the following characteristics: the amount of styrene - 20 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 70 wt.%; glass-transition point was -19°C; Mn = 138,000; polydispersity was 1.5; and Mooney viscosity was 46 units.

Example 25

A 250 ml glass reactor was filled with 50 ml of dehydrated toluene and 20 ml of n-butyllithium (1.6 M) . The reactor was cooled to 0°C. Then, 5 ml of methyldiallylamin and 15 ml of THF were added to the reactor through a drop funnel. Further, 3 -methyl - 1 , 3 -pentadiene was added also through the drop funnel, after that diethylaminomethyl styrene was filled in a ratio of methyldiallylamin: 3 - methyl-1, 3 -pentadiene: diethylaminomethyl styrene of 1:15:20, respectively. When addition of the monomers was complete, the reaction mixture was heated to temperature of 80°C and mixed for additional 5 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.50 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium, as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 17 g of styrene, 20 g of butadiene, and 20 g of isoprene. The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and an electron-donor additive was added thereto. The electron-donor additive was a solution of ditetrahydrofurylpropane (DTHFP) in the form of a 0.030 M solution in nefras, based on a ratio of DTHFP : lithium of 0.60 mol/mol. The dilithium initiator was fed to the reactor in an amount of 1.2 mmol of the initiator per 100 g of monomers. The process of copolymerization was conducted at temperature of 38.5°C. When the conversion reached 50%, a functional group-containing monomer (diethylaminomethyl styrene) was added in an amount of 10% based on polymer. The reaction was continued to 100% conversion at temperature of 100 °C. After that, an antionxidant , namely agidol-2, was added in an amount of 0.5 wt . % .

The resulting product had the following characteristics: the amount of styrene - 27 wt.%; the amount of diethylaminomethyl styrene - 8 wt.%, the amount of 1 , 2 -butadiene units per polybutadiene - 40 wt.%; the amount of 3,4-isoprene units per polyisoprene - 50%; glass- transition point was -18°C; Mn = 200,000; polydispersity was 1.8; and Mooney viscosity was- 71 units.

Example 26

A 250 ml reactor was filled with 50 ml of dehydrated cyclohexane and 10 ml of n-butyllithium (1.6 M) . The reactor was cooled to 10°C. Then, 1.5 ml of n-2- propenylstyrene and 10 ml of THF were added to the reactor through a drop funnel. After that, dimethylaminomethyl styrene was added also through the drop funnel. Further, 1 , 1 ', 4 , 4 ' -tetraphenylbutadiene was added to the reaction mixture, after that 2 -dimethylaminopropylbutadiene was filled in a ratio of n-2- propenylstyrene : (dimethylaminomethyl styrene + 2- dimethylaminopropylbutadiene) : 1 , 1 ' , 4 , 4 ' - tetraphenylbutadiene of 1:4:10, respectively. When addition of the monomers was complete, the reaction mixture was heated to temperature of 60 °C and mixed for additional 20 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.45 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 46 g of butadiene, and 12 g of styrene (in a weight ratio of monomers in the reaction medium of 79:21) . The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 20°C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and an electron-donor additive was added thereto. The electron-donor additive included triethylamine (TEA) in the form of a 0.040 M solution in nefras, based on a ratio of TEA: lithium of 5 mol/mol. The dilithium initiator was fed to the reactor in the form of a solution in nefras (0.45 M) in an amount of 1.6 mol of the initiator per 100 g of monomers. The process of copolymerization was conducted at temperature of 40 °C. When the conversion reached 95-98%, a functional group- containing monomer (diethylaminomethyl styrene) was added in the . form of a 0.090 M solution in an amount of 70% based on polymer; the reaction was continued for additional 15 minutes at temperature of 30°C. When the conversion reached 100%, an antioxidant was added. The antioxidant used herein was agidol-2 taken in an amount of 0.5 wt . % .

The resulting product had the following characteristics: the amount of styrene - 20 wt.%; the amount of 1 , 2 -butadiene units per polybutadiene - 70 wt . % ; glass- transition point was -19C; Mn = 138,000; polydispersity was 1.5; and Mooney viscosity was 46 units. Example 27

A 250 ml glass reactor was filled with 50 ml of dehydrated toluene and 20 ml of /i-butyllithium (1.6 M) . The reactor was cooled to 0°C. Then, 5 ml of methyldiallylamin and 15 ml of THF were added to the reactor through a drop funnel. Further, 3 -methyl- 1 , 3 -pentadiene was also added through the drop funnel, after that diethylaminomethyl styrene was filled in a ratio of methyldiallylamin: 3 - methyl-1, 3 -pentadiene: diethylaminomethyl styrene of 1:10:15, respectively. When addition of the monomers was complete, the reaction mixture was heated to temperature of 80 °C and mixed for additional 5 minutes. Then, tetrahydrofuran was removed from the reaction mixture under reduced pressure 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 was 0.50 mol/1. Stability of the initiator was measured at 25 °C based on the concentration of active lithium as a parameter. As a result, the concentration of active lithium did not change for 1 month.

A I L glass reactor equipped with temperature and pressure sensors, a loading unit and a discharger, a mixer, and a jacket was loaded with a batch consisting of 350 g of nefras previously dried and deoxygenated, 17 g of styrene, 20 g of butadiene and, 20 g of isoprene. The temperature of delivering the batch to the reactor was minus 10 °C. When the temperature in the reactor reached 15 °C, a catalytic system consisting of the dilithium initiator prepared as disclosed above and an electron-donor additive was added thereto. The electron-donor additive was a solution of ditetrahydrofurylpropane (DTHFP) in the form of a 0.030 M solution in nefras, based on a ratio of DTHFP : lithium of 0.60 mol/mol. The dilithium initiator was fed to the reactor in an amount of 1.2 mmol of the initiator per 100 g of monomers. The process of copolymerization was conducted at temperature of 38.5°C. When the conversion reached 50%, a functional group-containing monomer (diethylaminomethyl styrene) was added in an amount of 10% based on polymer. The reaction was continued to 100% conversion at temperature of 100 °C. After that, an antionxidant , namely agidol-2, was added in an amount of 0.5 wt . % .

The resulting product had the following characteristics: the amount of styrene - 27 wt.%; the amount of diethylaminomethyl styrene - 8 wt.%, the amount of 1 , 2 -butadiene units per polybutadiene - 40 wt.%; the amount of 3, 4 -isoprene units per polyisoprene - 50%; glass- transition point was -18°C; Mn = 200,000; polydispersity was 1.8; and Mooney viscosity was 71 units.

Physico-mechanical and elastic-hysteresis characteristics of vulcanizates obtained based on the rubbers prepared according to some of the above examples are given in Table 1.

Table 1. Comparative characteristic of the vulcanizates produced from the rubbers described in the examples with vulcanizates produced from the rubbers disclosed in the prototype

Stress- Wear Elastic -hi steresis strain resistance, % properties properties , Wet Rolling grip resistance

Prototype 100 100 100 100

Example 1 105 103 100 112

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 1108 116

Example 21 107 110 108 119

Example 22 107 109 109 114

Example 23 110 108 110 114

Note: ≥ 100 means improvement, 100 means deterioration .

As can be seen from Table 1, the use of the initiators according to the present invention in the synthesis of rubbers provides obtaining of vulcanizates based on said rubbers with substantially enhanced elastic-hysteresis properties, in particular rolling resistance, while maintaining or improving such characteristics such as stress strain properties and wear resistance.

Claims

1. A dilithium initiator for anionic (co) polymerization, wherein said initiator is a compound of the general formula:

Li-X-Li;

wherein 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- ,

wherein "A" is a unit formed by a branched or linear C4-C20 diene monomer;

"B" is a unit formed by a branched or linear C₄-C₂o diene monomer or alkylstyrene , each of which comprises a heteroatom selected from Si, N, P, and Sn;

"C" is a unit formed by C10-C40 alkenylstyrene; and "D" is a unit formed by a divinyl monomer containing a functional group.

2. The dilithium initiator of claim 1, characterized in that the branched or linear C₄-C₂₀ diene monomer (A) is a compound selected from the group including: 1 , 3 -butadiene , isoprene, piperylene, 2, 3-dimethyl-l, 3-butadiene, 2-methyl- 3 -ethyl-1, 3 -butadiene, 3-methyl-l, 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, 1¹ , 4 , 4 ' -tetraphenyl-1, 3-butadien, 3-methyl-l, 3 -heptadiene, 1, 3-octadiene, 3-butyl-l,3- octadiene, 3 , 4 -dimethyl- 1, 3 -hexadiene, 3-n-propyl-l, 3- butadiene, 4 , 5-d.iethyl-l, 3-octadiene, 2 , 3 -diethyl- 1 , 3 - butadiene, 2-methyl-3 -isopropyl-1, 3-butadiene, or a mixture thereof .

3. The dilithium initiator of claim 1, characterized in that the branched or linear C₄-C₂o diene monomer or alkylstyrene, each of which comprises a heteroatom, (B) , is a compound selected from the group including a silicon- containing compound, a phosphorus-containing compound, a silicon-nitrogen-containing compound, a nitrogen-containing compound, and tin-containing compound, in particular, such as 2 -dimethylaminopropyl-1, 3 -butadiene, 2- triethylsilylpropyl-1, 3-butadiene or dimethylaminomethyl styrene, trimethylsilyl styrene, Ν,Ν'- bis (trimethylsilyl) aminomethyl styrene, 4 -diphenylphosphine styrene, 4 -triphenyltin styrene, or a mixture thereof.

4. The dilithium initiator of claim 1, characterized in that the C10-C40 alkenylstyrene (C) is a compound selected from the group including divinylbenzene , diisopropenylbenzene , p-2-propenylstyrene, p-2-butenyl-a- methylstyrene , p-2-propenyl-a-methylstyrene, p-2-methyl-2- propenylstyrene, p-2 -butenylstyrene , p-2 -methyl-2 -propenyl- a-methylstyrene, 8- (p-vinylphenyl) -1-octene, 2-methyl-7- (p- vinylphenyl) -1-heptene.

5. The dilithium initiator of claim 1, characterized in that the divinyl monomer containing a functional group (D) is a compound selected from the group including: alkylalkenylamine , in particular, methyldialkenylamine and butyldialkenylamine ; alkylallylsilane , in particular diethyldiallylsilane , dipropyldiallylsilane , and methyltriallylsilane .

6. A method for preparing a functional group- containing dilithium initiator for anionic (co-) polymerization, the initiator being a compound of general formula

Li-X-Li;

wherein 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-, wherein "A" is a unit formed by a branched or linear C4-C₂₀ diene monomer; "B" is a unit formed by a branched or linear C₄-C₂o diene monomer or alkylstyrene , each of which comprises a heteroatom selected from Si, N, P, and Sn; "C" is a unit formed by C10-C40 alkenylstyrene ; and "D" is a unit formed by a divinyl monomer containing a functional group,

wherein the method comprises reacting of an organolithium compound with the alkenylstyrene or divinyl monomer containing a functional group, in an organic solvent, followed when necessary by adding a monomer forming unit A and/or a monomer forming unit B.

7. The method of claim 6, characterized in that the functional group-containing dilithium initiator for anionic (co- ) olymerization is prepared at the temperature of from -20 to 80°C, preferably from -10 to 60°C, more preferably from 0 to 20 °C.

8. The method of claim 6, characterized in that for X

- B-C-B a ratio of C:B is 1:30, 1:20 or 1:10.

9. The method of claim 6, characterized in that for X = A-D-A a ratio of D : A is 1:30, 1:20 or 1:10.

10. The method of claim 6, characterized in that for X = A-B-C-B-A a ratio Of A:B:C is 20:15:1, 15:10:1 or 10:4:1.

11. The method of claim 6, characterized in that for X = B-A-D-A-B a ratio Of A: B : D is 20:15:1, 15:10:1 or 10:4:1.

12. The method of claim 6, characterized in that for X = B-A-B-C-B-A-B a ratio of A:B:C is 20:15:1, 15:10:1 or 10:4:1.

13. The method of claim 6, characterized in that the reaction of an organolithium compound with the alkenylstyrene or divinyl monomer containing a functional group followed when necessary by adding a monomer forming unit A and/or a monomer forming unit B is conducted for not more than 5 hours .

14. A process for preparing a functionalized diene (co-) polymer by polymerization of dienes or copolymerization thereof with each other and/or with alpha- olefins in a hydrocarbon solvent in the presence of an organolithium initiator and an electron-donor additive, characterized in that the organolithium initiator used is a compound of general formula

Li-X-Li;

wherein "A" is a unit formed by a branched or linear

C4-C20 diene monomer;

"C" is a unit formed by C10-C40 alkenylstyrene ; and

"D" is a unit formed by a divinyl monomer containing a functional group.

15. The process of claim 14, characterized in that the functionalized diene (co-) polymer is prepared at the temperature of 0 to 80°C, preferably 20 to 70°C, more preferably 40 to 60°C.

16. The process of claim 14, characterized in that the diene is 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 -penradiene , 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-l, 3-octadiene, 3 , 4 -dimethyl- 1 , 3 - hexadiene, 3-n-propyl-l, 3-butadiene, 4 , 5-diethyl-l, 3- octadiene, 2 , 3 -diethyl- 1 , 3 -butadiene , 2-methyl-3-isopropyl- 1 , 3 -butadiene , or a mixture thereof.

17. The process of claim 14, characterized in that the alpha-olefin is a C8-C40 arylvinyl compound.

18. The process of claim 17, characterized in that the C₈-C₄oa-rylvinyl compound is a compound selected from: vinylbenzenes , in particular styrene and alpha- methylstyrene ; vinylbiphenyls , in particular vinyldiphenyl ; vinylnaphthalenes , in particular 1-vinylnaphthalene and 1- methylvinylnaphthalene ; and vinylanthracenes , in particular 9 -vinylanthracene .

19. The process of claim 14, characterized in that a ratio of the alpha-olefin to the diene is of from 5:95 to

10:90, or from 15:85 to 20:80, or from 20:80 to 24:76.

20. The process of claim 14, characterized in that as the electron-donor additive a compound comprising at least one heteroatom or a mixture thereof with alkoxides of alkali or earth-alkaline metals is used.

21. The process of claim 20, characterized in that the compound comprising at least one heteroatom is Ν,Ν,Ν',Ν'- tetramethylethylenediamine , trimethylamine , sodium or potassium tetrahydrofurfurylate , calcium butilate, ethylene glycol ethyl- tert-butyl ether, di-tetrahydrofuryl propane, ethylene glycol di- tert-butyl ether, or a mixture thereof.

22. The process of claim 14, characterized in that a molar ratio of the organolithium initiator to the alkoxide of alkali and/or earth alkaline metal is 1 : (0.1÷20.0) , and a molar ratio of the organolithium initiator to the compound comprising at least one heteroatom is 1 : (0.1÷20.0) .

23. The process of claim 14, characterized in that the prepared polymer chain is subjected to additional functionalization with a functionalizing agent and/or a functional group-containing monomer.

24. The process of claim 23, characterized in that the additional functionalization of the polymer chain is carried out with the functionalizing agent and/or the functional group-containing monomer at the temperature of from 30 to 100°C, preferably from 40 to 80°C, more preferably from 50 to 70°C.

25. The process of claim 23, characterized in that the functionalizing agent is a compound selected from the group including: N, N-di-substituted aminoalkylacrylamides and N, N-di-substituted aminoalkylmethacrylamides, in particular N, -dimethylaminopropyl acrylamide and N,N- dimethylaminopropyl methacrylamide ; N-substituted cyclic amides, N-methyl-2 -pyrrolidon, N-vinyl-2 -pyrollidon, N- phenyl - 2 -pyrrolidon, and N-methyl-epsilon-caprolactam; N- substituted cyclic ureas, such as 1 , 3 -dimethylethylene urea and 1 , 3 -diethyl-2 - imidazolidinone ; and N-substituted aminoketones , in particular such as N,N- bis (dimethylamino) benzophenone (Michler's ketone), Ν,Ν'- bis (diethylamino) benzophenone , or a mixture thereof.

26. The process of claim 23, characterized in that the functionalizing agent is used in a molar ratio to the dilithium initiator of from 0.01 to 2.0, preferably from 0.1 to 1.5, more preferably from 0.5 to 1.0.

27. The process of claim 23, characterized in that, as the functional group-containing monomer, a compound is used selected from the group including: a silicon-containing compound, a phosphorus-containing compound, a silicon- nitrogen-containing compound, a nitrogen-containing compound, and tin-containing compound, in particular such as N, N-dimethylaminoethyl styrene, N, -diethylaminoethyl styrene, 2 -dimethylaminopropyl- 1 , 3 -butadiene , 2- triethylsilylpropyl-1, 3-butadiene or dimethylaminomethyl styrene, trimethylsilyl styrene, Ν,Ν'- bis (trimethylsilyl) aminomethyl styrene, 4 -diphenylphosphine styrene, 4 -triphenyltin styrene, or a mixture thereof.

28. The process of claim 23, characterized in that the functional group- containing monomer is added in an amount of from 0.01 to 70% by weight based on the polymer, preferably from 1 to 60% by weight based on the polymer, more preferably from 20 to 40% by weight based on the polymer .