RU2709530C1 - Method of producing caoutchouc, a rubber composition containing caoutchouc obtained using said method, as well as use of a rubber composition - Google Patents

Abstract

FIELD: manufacturing technology.

SUBSTANCE: present invention relates to production of caoutchouc, as well as rubber based thereon. Described is a method of producing caoutchouc by anionic polymerisation of a conjugated diene and/or copolymerisation of a conjugated diene and a vinyl aromatic compound in an organic solvent medium in the presence of an electron donor and lithium organozincate of general formula R₄ZnLi₂ as an initiator. Electron donor used is 2,2-bis(2-oxolanyl)propane (ditetrahydrofurylpropane, DTHFP) in a hydrocarbon solvent and an inert medium. Invention also relates to rubber obtained using said method and to rubber compositions containing said caoutchouc.

EFFECT: improved hysteresis characteristics of caoutchouc based rubbers.

13 cl, 2 dwg, 4 tbl, 7 ex

Description

FIELD OF THE INVENTION

The present invention relates to the field of production of rubbers, as well as rubber based on them, characterized by an improved complex of hysteresis properties. In particular, the invention relates to a method for producing (co) butadiene polymers by solution anionic polymerization in the presence of lithium organozincate by the general formula (I) R₄Znli₂where R is the same or different aliphatic and / or aromatic hydrocarbon radicals, as the initiator, and 2,2-bis (2-oxolanyl) propane (ditetrahydrofurylpropane, DTGFP) as the electron donor. Using this method, you can get butadiene, butadiene-styrene or butadiene-styrene-isoprene rubbers.

The rubbers obtained by the claimed method are characterized by a number average molecular weight of 50,000 to 400,000 g / mol, a polydispersity coefficient of 1 to 3, and the amount of vinylalkyl (1,2- and / or 3,4 units) butadiene equal to more than 60% of the mass. on the butadiene part of the rubber and the number of vinyl aromatic units from 0 to 40% of the mass. rubber, and are used in the tire industry for the manufacture of tread rubber, characterized by an improved set of elastic-hysteresis characteristics, in particular, improved grip on wet and icy roads.

State of the art

The performance properties of rubber for the tire tread, in particular, such as rolling resistance, traction, are largely determined by the structure of the rubber. One of the main factors is the ratio of monomers in the rubber molecule, for example styrene, butadiene and special monomers (if any) having functional groups, as well as the isomeric composition of the monomers, and, in particular, the number of vinylalkyl units. Tires made of rubber with a high content of vinylalkyl units, above all, have good grip.

Currently, the main industrially feasible method for the production of rubbers, mainly styrene-butadiene, with a high content of vinyl alkyl and / or vinyl aromatic units is anionic solution polymerization. Organolithium compounds are traditionally used as a polymerization initiator. However, lithium organozincates are becoming increasingly popular, which are slightly inferior in activity to organolithium initiators, but are more stable and, therefore, more convenient to use, including in industry, and also less sensitive to pollutants.

Thus, in patent US3716495, as the initiator of anionic polymerization, a composition obtained by reacting organolithium R (Li) _x and organometallic R _n M compounds is used, where M is selected from 2a, 2b or 3a of the Periodic Table and R represents a hydrocarbon radical containing up to 20 carbon atoms. The solvent for preparing the initiator is selected from polar compounds, for example, ethers, thioethers or tertiary amines. The obtained initiator is used for (co) polymerization of such monomers as conjugated dienes containing from 4 to 12 carbon atoms, vinyl aromatic hydrocarbons containing up to 20 carbon atoms. The authors of US3716495 do not exclude the possibility of using special monomers capable of entering into the polymerization process (i.e., capable of incorporating into the macromolecule of the resulting rubber and incorporating functional groups). It was also noted that the introduction of polar compounds, for example, tetrahydrofuran (THF) or diethyl ether, into the polymerization reactor does not affect the microstructural characteristics of the rubber, including the content of vinylalkyl units. The disadvantage of this method is the low content of vinylalkyl units. So, in the case of polybutadiene, their amount is at the level of 10% of the mass.

JP2010209271 describes an initiator of the general formula tert-BuR ₃ ZnM, where R - are alkyl or aryl hydrocarbon radicals, M is an alkali metal, including lithium. The initiator is used in the anionic polymerization of conjugated dienes, and, above all, in the copolymerization of 1,3-butadiene and styrene. The technical result consists in obtaining rubber with a content of vinylalkyl units of 17.1% of the mass. and with a styrene content of 10.2% of the mass. In the patent application JP2010209273 the same initiator is described, but the styrene content is increased up to 21-23% of the mass. and vinylalkyl units up to 53-61% of the mass. through the use of electron donors described by the formulas R ₂ NRNR ₂ , for example, N, N, N ', N'-tetramethylethylenediamine (TMEDA), and ROROR. Moreover, to achieve the desired technical result, it is necessary to apply a seven-fold excess of TMEDA in relation to the initiator. However, the use of this initiator in industry is difficult due to the need for mandatory use of tert-butyl lithium, which is a pyrophoric substance capable of self-igniting upon contact with air. Furthermore, the presence of tert-butyllithium requires temperatures well below 0 ° ^C. It is also claimed a styrene content in the polymer in both methods, it indicates incomplete conversion during the polymerization, since a 100% conversion of the styrene content in the rubber must be 25 wt% .

JP2010209273 discloses the use of organozincate lithium initiators in the presence of an electron donor compound other than the electron donor compound of the present invention, which results in rubber having a low amount of vinyl alkyl units and low styrene conversion. Patent EP0594107 discloses the use of organolithium initiators in combination with an excess of tetrahydrofuran or 2,2-bis (2-oxolanyl) propane (ditetrahydrofurylpropane, DTGFP) as electron donors, which leads to the production of rubber with no more than 40% by weight of vinylalkyl units.

A common disadvantage of the known methods is also the low styrene conversion, the low content of vinylalkyl units in the resulting rubber, as well as the technological difficulties associated with the use of low temperatures and self-igniting tert-butyl lithium.

The objective of the present invention is to develop an industrial method for producing rubbers, preferably styrene-butadiene rubbers, with vinylalkyl content of more than 60 wt.%, And in the case of styrene-butadiene rubbers with vinylaromatic content of up to 40 wt.%, By solution (co) polymerization dienes and / or vinylaromatic compounds in the presence of lithium organotsinkatov general formula (I) R ₄ ZnLi ₂ wherein R - identical or different aliphatic and / or aromatic hydrocarbon radicals as nitsiatora and 2,2-bis (2-oxolanyl) propane (ditetragidrofurilpropan, DTGFP) as an electron donor in a hydrocarbon solvent and an inert atmosphere.

Technical result the claimed invention consists in improving the hysteretic characteristics of rubbers based on rubbers obtained by the claimed method, and, in particular, improving the adhesion of tread rubbers to the road due to the content of vinylalkyl units in the rubber of more than 60% of the mass.

DESCRIPTION OF FIGURES

Figure 1, illustrating the present invention, shows differential curves of molecular weight distribution of rubber for a reference sample; figure 2 shows the differential curves of molecular weight distribution of rubber for the sample obtained in accordance with example 3 of the present invention.

DESCRIPTION OF THE INVENTION

The task and technical result are achieved by obtaining rubber anionic (co) polymerization of diene and / or vinyl aromatic compounds in an organic solvent in the presence of lithium organozincate with the general formula (I) R ₄ ZnLi ₂ as the initiator and 2,2 bis (2 -oxolanyl) propane (ditetrahydrofurylpropane, DTGFP) as an electron donor.

In addition, the authors of the present invention in the synthesis of styrene-butadiene rubbers found that the claimed technical result is provided by a combination of organozincate lithium initiators with 2,2-bis (2-oxolanyl) propane (ditetrahydrofurylpropane, DTGFP) as an electron donor.

The method for producing conjugated diene rubber comprises two stages: a stage for producing an initiator and a stage for anionic polymerization.

Getting the initiator is shown in scheme 1:

Scheme 1

The starting components are zinc-containing substances and organolithium compounds.

As zinc-containing components, zinc halides of the general formula ZnHal _{2 are used} , where Hal hal is chlorine, bromine or iodine, or compounds of the general formula R ₂ Zn, where R are the same or different aliphatic or aromatic hydrocarbon radicals. For example, dimethylzinc, diethylzinc, diisopropylzinc and di-tert-butylzinc can be used as compounds of the general formula R ₂ Zn.

As the organolithium compound, compounds of the general formula RLi are used, where R is an alkyl or aryl hydrocarbon radical. Examples of the alkyl radical include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, 2-ethylhexyl, heptyl , n-nonyl, n-decyl, n-undecyl, radicals containing 1-4 carbon atoms are preferred, n-butyl, sec-butyl are most preferred. Examples of the aryl radical include, but are not limited to, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3.4 xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2 , 3,4,5-tetramethyl, 2,3,4,6-tetramethylphenyl, aryl radicals containing 6-12 carbon atoms are preferred, the phenyl group is most preferred.

The molar ratio of the used zinc-containing and organolithium compounds is 1: 4 in the case of ZnHal ₂ : RLi and 1: 2 in the case of R ₂ Zn: RLi.

The synthesis of the initiator is carried out with constant stirring and a temperature of from -78 ^° C to 80 ^° C, preferably from -30 ^° C to 60 ^° C, most preferably from 20 ^° C to 40 ^° C. The reaction time depends on the starting materials and varies from several minutes to several hours.

The solvents for the synthesis of the catalyst are selected from the group of anhydrous ethers, including, for example, tetrahydrofuran (THF), diethyl ether, dipropyl ether. The reaction is carried out in an inert atmosphere, for example, in an atmosphere of nitrogen or argon.

The concentration of lithium organozincate after the reaction is determined by Knochel titration, as described in A. Krasovskiy, P. Knochel. Convenient Titration Method for Organometallic Zinc, Magnesium, and Lanthanide Reagents. Synthesis, 2006, 890-891.

Any electron donor known in the art can be used as electron donors in polymerization reactions, in particular, bis (2-oxolanyl) methane, 1,1-bis (2-oxolanyl) ethane, 2,2-bis (2-oxolanyl) propane ( ditetrahydrofurylpropane, DTGFP), 2,2-bis (2-oxolanyl) butane, 2,2-bis (5-methyl-2-oxolanyl) propane, 2,2-bis (3,4,5-trimethyl-2-oxolanyl ) propane, tetrahydrofuran, mono and oligoalkylene glycol dialkyl ethers, for example, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, tertiary amines, for example N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetraethyl Iamine.

According to the present invention, the initiator: electron donor molar ratio is from 0.1 to 100, preferably from 0.5 to 50, and most preferably from 1 to 3.

As conjugated dienes, conjugated dienes are used with the number of carbon atoms from 4 to 12, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-ethyl-1,3-butadiene, 2,3 -di (C1-C5 alkyl) -1,3-butadiene such as 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1 , 3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 2-methyl-pentadiene, 4-methyl-pentadiene . Preferably, 1,3-butadiene or isoprene is used.

Vinyl aromatic compounds can be selected from styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, 3-vinyltoluene, ethylvinylbenzene, 4-cyclohexylstyrene, para-tert-butylstyrene, methoxystyrenes, vinylmesitylene, divinylbenzene, 1-vinylbenzene, 1 4,6-trimethylstyrene. Styrene or α-methylstyrene are preferably used.

The present invention allows the addition of special monomers that contain functional groups and are usually introduced into the system either together with the starting monomers at the beginning of polymerization, or in the process up to the conversion of the starting monomer 50%, which allows functionalization of rubber macromolecules along the chain; or at the end, when the conversion of the starting monomer is 95-100%, which allows the rubber to functionalize at the ends of the macromolecules. Thus, monomers containing functional groups are used to functionalize the rubber macromolecules both along the chain (random or microblock), and, in some cases , at the ends of the chain.

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 1,3-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% by weight, more preferably 20-40% by weight. based on the weight of the polymer. Functionalization is carried out for 15-60 minutes at a temperature of 30-100 ° C, preferably at a temperature of 40-80 ^o C, more preferably at a temperature of 50-70 ° C.

To further improve the properties of the rubber obtained, additional terminal functionalization is carried out. Such functionalization is carried out upon reaching 95-100% conversion by introducing special functionalizing agents into the polymerization system. 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.

It is preferable to use conjugated dienes, vinyl aromatic compounds and special monomers with a purity of 99.5% or more and a moisture content of 50 ppm (ppm) or less.

As starting monomers, conjugated dienes and vinyl aromatic compounds are used in a weight ratio of from 0 to 1, preferably from 0.1 to 0.9, more preferably from 0.2 to 0.7.

The amount of initiator used is determined by the necessary molecular weight of the rubber and the presence of impurities in the starting components. The preferred amount of initiator is in the range of 1 to 50 mol / t of rubber, preferably 2 to 25 mol / t of rubber, more preferably 3 to 12 mol / t of rubber.

The polymerization process is carried out in any equipment of periodic or continuous operation, designed for the anionic polymerization process (see, for example, Reichsfeld V.O., Shein V.S. Ermakov V.I. Reaction equipment and machines of organic synthesis plants and synthetic rubber, p. 180).

Solvents for anionic polymerization are selected from saturated hydrocarbon groups, for example, pentane, hexane, heptane, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, p-xylene, and mixtures thereof in various ratios with a purity of 99% and more. It is preferable to use solvents containing 3-12 carbon atoms. Most preferred is a petroleum solvent (nefras), which is a mixture of solvents. For example, nefras hexane-heptane fraction P1-65 / 75. The mass ratio of solvent to the total amount of monomers is from 2 to 20, preferably from 4 to 12, more preferably from 6 to 8.

Anionic polymerization process is conducted at a temperature of from -80 ° C to + 150 ^{° C,} preferably from 0 ° C ^to 100 ° C, more preferably from 40 ° C to 80 ° ^C.

The duration of polymerization varies from 5 minutes to 48 hours, mainly from 30 minutes to 10 hours.

The starting monomer feed, solvent, electron donor can be introduced into the reactor in any sequence, proceeding from technological convenience. Preferably, the components are introduced in the following sequence: a solvent, a starting monomer feed and an electron donor, followed by the introduction of a pre-prepared initiator or components to obtain it in situ .

Antioxidants, reinforcing fillers, and other processing aids can be incorporated into the resulting polymer.

As rubber antioxidants, any compounds known from the prior art that are recommended for stabilizing rubbers, including phenolic or amine type antioxidants, can be used. Examples of phenolic antioxidants are: 2,6-di-tert-butyl-4-methylphenol (ionol, agidol-1, alkofen, butylhydroxytoluene, dibunol, 2,6-di-tert-butyl-p-cresol); 2,2-di- (4methyl-6-tert-butylphenol) methane (Antioxidant 2246, Agidol 2, Bisalkofen), pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (Irganox 1010, BASF); benzolpropanoic acid ester of 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy-C7-C9 branched alkyl (Irganox 1135, BASF); 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-yl-amino) phenol (BNX ™ 565, Mayzo. Inc); octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. Examples of amine type antioxidants are N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD, Vulcanox 4010), N (1,3-dimethyl-butyl) -N'-phenyl-p-phenylenediamine (Antioxidant 4020, 6PPD), N (1,3-dimethyl-phenyl) -N'-phenyl-p-phenylenediamine (7PPD), N-2-ethylhexyl-N'-phenyl-p-phenylenediamine (Novantox 8 PFDA, Antioxidant C789, Orgkhim OJSC) , N, N'-diphenyl-p-phenylenediamine (DFPD), Santoflex ™ 134PD type mixed antioxidants, which are a 1: 2 mixture of 6PPD and 7PPD.

The Mooney viscosity (ML1 + 4, 100 ° C) of the rubber obtained according to the claimed invention is preferably 30-150 units. and preferably 40-130 units. When the viscosity of the rubber is less than 30 units. the cohesive strength of rubber and rubber based on it, as a rule, is insufficient if the Mooney viscosity exceeds 150 units, the manufacturability of rubber both in synthesis and in processing is unsatisfactory: pumping the polymerizate, isolating and drying the rubber, and obtaining rubber compositions become problematic and require increased energy costs and / or special equipment. If the Mooney viscosity is in the range of 80-150 units, it is recommended to dilute the rubber with filler oil to improve its processing. The filler oils for rubbers can be oils of the types TDAE (purified distillate aromatic extract), TRAE (purified residual aromatic extract), MES (mild solvate), RAE (residual aromatic extract), naphthenic oils (NAP). The possibility of using oils of vegetable origin, for example, rapeseed, for filling rubbers is also not excluded. It is possible to use oils such as DAE (aromatic oils), but it is undesirable because of the high content of carcinogenic substances in their composition. The use of a mixture of various oils is also possible. Examples of TDAE oils: NORMAN 346 (OJSC Orgkhim), Vivatec 500 (Hansen & Rosental), Nytex 840 (Nynas). Examples of MES oils: Vivatec 200 (Hansen & Rosental), Nytex 832 (Nynas), NORMAN 132 (OJSC Orgkhim). Examples of DAE oils: PN-6 (OJSC "Orgkhim"). Examples of NAP oils: Nytex 4700 (Nynas), Octopus N317 (Petroyag, Turkey). Examples of TRAE oils: NORMAN 583 (OJSC "Orgkhim"). The filler oil may be supplied in an amount of 5-80 parts by weight per 100 parts by weight rubber, depending on what technological properties it is necessary to provide rubber. However, most often receive rubber with a content of 20-40 wt.h. oil per 100 parts by weight rubber.

The rubber obtained according to the present method contains from 40 to 100% vinylalkyl units per butadiene part of the rubber and the amount of vinyl aromatic units from 0 to 40% per rubber.

The rubber obtained according to this invention can be used in rubber for various purposes, however, it is preferable to use it as part of the tread of a car tire to increase its adhesion to the road.

General requirements for rubber composition are well known to those skilled in the art.

The rubbers proposed in the present invention, differing from known compositions of a similar purpose in that they include rubbers obtained according to this invention.

The rubber compositions according to the invention may also include the following ingredients traditional for tire and, in particular, tread rubbers (parts by weight per 100 parts by weight of rubber), for example 0-150 parts. including silicon dioxide (silica); 0-150 mass. including carbon black; 0-30 mass. including silanizing agent;

vulcanizing group containing sulfur or sulfur donors, accelerators from among sulfenamides, thiurams, thiazoles, guanidines, phosphates, and combinations thereof, used to accelerate the vulcanization of rubbers and obtain the optimal structure of the vulcanization network, activators - metal oxides, amines, among which the most widely zinc oxide, scorch inhibitors are common, among which Santogard PVI is the most widespread;

technological additives that improve the dispersion of fillers and the processability of rubber compositions; plasticizers, softeners, petroleum products, vegetable, synthetic ether, processed products of the coal industry, synthetic oligomeric functionalized and non-functionalized; antioxidants / antiozonants / physical and chemical antagonists; other components that ensure the achievement of the necessary complex of technological, vulcanizing, physico-mechanical and operational characteristics, for example: modifiers; fillers, including fibrous, layered, polymer (such as crosslinked polymer gels); agents that prevent reversion during vulcanization and increase the heat resistance of rubbers; improving stickiness.

To produce rubbers, butadiene and isoprene rubbers obtained on various catalytic systems (by polymerization in solution in the presence of a polymerization initiator or catalyst) and containing 1,4-cis addition units of at least 90% mass can be used. The rubbers may also contain a styrene-butadiene copolymer obtained in an emulsion (aqueous phase) or solution (organic solvent), containing: styrene units from 10 to 50% wt., Most preferably from 15 to 40% wt., Units 1.2 -butadiene from 10 to 90% wt. per butadiene portion, most preferably from 20 to 70% by weight.

To obtain the rubber compositions that are the subject of the present invention, natural rubber of various manufacturers, grades and brands from RSS (Ribbed Smoked Sheet) to IRQPC (International Standards of Quality and Packing of Natural Rubber - International Quality Standards and Packaging of Natural Rubber) can be used.

The elastomeric part of the rubber composition may also include a triple copolymer of styrene isoprene and butadiene, obtained as emulsion (in the aqueous phase) and solution (organic solvents) polymerization, with a ratio of styrene: butadiene: isoprene (% wt.), Respectively, equal to 5- 70: 20-70: 20-70. It is desirable that the total content of 1,2-butadiene and 3,4-isoprene units is in the range from 20 to 90% of the mass. on the butadiene and isoprene part, most preferably from 40 to 70% of the mass. The preparation of such copolymers is disclosed, for example, in patents RU2058322 or RU2124529.

In addition, the rubber composition may also include oil-filled brands of rubbers, while the content of such rubbers in the rubber, as a rule, increases so that the total amount of all elastomers in the rubber, excluding the additives present in them, corresponds to 100 masses. hours

Each of the rubbers represented in the described rubbers may have a branched structure, for example, a star structure, of polymer chains. As reinforcing fillers for the rubber compositions according to the present invention, synthetic amorphous silicon dioxide (silica) is used, mainly precipitated silica, either alone or in combination with carbon black, or carbon black. It is allowed to use two-phase fillers, which are silica coated with carbon black on the surface, as well as silicon dioxide, the surface of which is impregnated with a combination agent or chemically modified. The use of silica obtained by the pyrogenetic method is allowed.

The amount of carbon black can vary from 0 to 150 mass. o'clock When the content of carbon black corresponds to 0 mass. including this suggests that the function of the main filler performs silicon dioxide. When the content of carbon black is above 150 mass. including the deteriorating technological and some operational properties of rubbers. The amount of silicon dioxide in the elastomeric composition is 0-150 mass. hours, preferably 10-110 mass. hours, and more preferably 30-95 mass. hours per 100 mass. including rubber. If the content of silicon dioxide corresponds to 0 mass. hours, carbon black acts as the main filler. When the content of silicon dioxide is above 150 mass. including the deteriorating technological and some operational properties of rubbers. The silica according to the present invention is characterized by BET surface in the range 40-600 m ² / g and an oil absorption (DBP) values in the range of 50-400 ^cm3 / 100g In a preferred embodiment, the silica has a BET surface area of 100- 250 m ² / g, a CTAB surface area of 100-250 m ² / g and an oil absorption (DBP) 150-250 cm ^3/100 g (see GOST 25699.2-90;. ER157703).

Various commercially available grades of silicon dioxide may be applicable for these purposes, for example Zeosil 1165MP, Zeosil 1165 GR, Hi-Sil 210, Hi-Sil 243, Ultrasil VN2, Ultrasil VN3, Ultrasil VN3 GR, as well as other grades of silica, mainly precipitated and used to strengthen elastomers.

Silicon-filled rubber compositions contain silanizing agents (silica-elastomer combination agents). The most commonly used coupling agents are bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxypropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptropropyltrimethoxysilane, 3-mercanthylpropyltrimethoxysilane , 2-mercaptoethyltriethoxysilane, 3-nitropropyltrimethoxysilane, 3-nitropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 2-chloropropyltriethoxysilane, 2-chloroethyltriethoxysilane, 3-trimethoxysilylpropyl-nitroethyl-tetraethyltropyl-nitroethyl-tetraethyl-tetraethyl-tetraethyl-tetraethyl-tetraethyl-tetraethyl-tetra-nitroethyl 3-trimethoxysilylpropylbenzothiazole tetrasulfide; 3-triethoxysilylpropylmethacrylate monosulfide. Most preferred are bis (3-triethoxysilylpropyl) tetrasulfide and 3-trimethoxysilyl-propylbenzothiazole tetrasulfide.

In addition, combination agents can be used, which are compositions of the above compounds and other compounds intended for these purposes, with a powdered carrier, for example, carbon black.

Allowed the use of other coupling agents designed to improve the compatibility of silicones and rubber, for example, such as NXT and NXT Z 100, manufactured by Momentive (US).

The content of silanizing agents in rubber is determined in such a way that the amount of the main active substance, excluding the carrier in the case of composite silanizing agents, with respect to silicone is in the range from 1-30% by weight, most preferably 5-25% by weight.

Rubber vulcanization is carried out using vulcanizing agents known in the art, for example elemental sulfur, sulfur donors, for example N, N'-dimorpholyl disulfide, polymer polysulfides. Most widely used in the tire industry is elemental or polymer sulfur. As is known in the art, the dosage of vulcanizing agents in rubber is most often in the range of 0.5-4.0 mass. hours, sometimes it can reach up to 10 mass. hours. Traditionally, together with sulfur, such ingredients as vulcanization activators are used: oxides and hydroxides of alkaline-earth metals (Zn, Mg, Pb, Ca), metals together with fatty acids, accelerators (sulfenamides, thiazoles, thiurams, guanidines, urea derivatives) and vulcanization inhibitors (phthalic anhydride, N-nitrosodiphenylamine, cyclohexylthiophthalimide). Their content depends on the amount of vulcanizing agent and the requirements for the kinetics of vulcanization and the structure of the vulcanization network.

Silicon-filled rubber compositions typically also contain processing aids that improve the dispersion of the fillers and the processability of the rubber compositions. Silicon-filled rubber compositions typically also contain processing aids that improve the dispersion of the fillers and the processability of the rubber compositions. These ingredients most often include derivatives of fatty acids (zinc salts and esters, as well as mixtures thereof), which improve the dispersion of fillers and reduce the viscosity of the composition. As an example, fatty acid derived products known under the trademarks Struktol E44, Struktol GTI and Actiplast ST can be mentioned.

Plasticizers and softeners commonly used in the rubber industry, which are oil products, vegetable, synthetic ethers, coal products, synthetic oligomeric functionalized and non-functionalized, can also be components of the rubbers of the present invention.

The composition of rubber compositions for tires, as a rule, includes antioxidants, antiozonants, anti-fatigue agents and other components that ensure the achievement of the necessary complex of technological, vulcanizing, physico-mechanical and operational characteristics, for example: modifiers; fillers, including fibrous, layered, polymer (such as crosslinked polymer gels); agents that prevent reversion during vulcanization and increase the heat resistance of rubbers; stickiness enhancers. The nature of such a compound and their content in rubber depend on the required level of properties of rubber compositions and rubbers and are well known to those skilled in the art.

Compositions are prepared by methods known in the art, disclosed, for example, in J. C. Dick, Rubber Technology: Formulation and Testing. p. 606-616, preferably using closed rubber mixers, such as Banbury or Intermix. The mixing process can be carried out in two or three stages, and the second or third stages are designed to add components of the vulcanizing group to the mixture. The vulcanization temperature is 130-180 ° C., Preferably 140-170 ° C. The rubber compositions thus obtained are used as compositions for manufacturing a tire tread, and are characterized by an improved complex of elastic-hysteresis characteristics, namely, better grip on wet and icy roads.

The implementation of the present invention is illustrated by the following experimental examples.

Examples of carrying out the invention

Initiator Synthesis (n-Bu) ₄ Znli ₂

Into a 250 ml flask was placed 0.954 g of anhydrous zinc chloride, 120 ml of THF were added, stirred until complete dissolution, and then, at a temperature of 20 ° C, 11.2 ml of n-BuLi (2.5 M) was added dropwise so that the temperature did not exceed 50 ^about C, and stirred for 60 minutes. After that, the resulting initiator solution was titrated according to Knohel; for this, 0.025 g of iodine was weighed in a flask, 0.5 ml of THF was added, then, after dissolution, titrated with a solution of the obtained initiator until the solution bleached. The spent volume of the initiator solution determines the concentration, which, in this case, is 0.2 M.

Comparative example. Obtaining styrene-butadiene rubber using n-butyllithium and DTGFP

The process for producing styrene-butadiene rubbers is carried out in a Buchi reactor with a metal bowl having a working volume of 2 l, equipped with a stirrer, a jacket for thermostating, fittings and special removable metal batchers for supplying reagents.

Nephras (987 g), butadiene (47.13 g), styrene (13.68 g) and 1, are fed into a reactor cooled to -20 ° С (± 2 ° С) in a nitrogen stream at a stirrer speed of 50 rpm 91 ml of a solution of 2,2-bis (2-oxolanyl) propane (ditetrahydrofurylpropane, DTGFP) in nephras (0.32 M solution). Then, the stirrer rotational speed is set at 300 rpm, the temperature of the reaction mixture begins to increase to 55 ° C with a heating rate of 7 ° / min, at a temperature of 15 ° C, 1.62 ml of a solution of n-butyllithium in nephras (0.32 M solution) is supplied. To achieve the necessary degree of conversion of monomers (100%), the polymer is poured into a glass and seasoned with an antioxidant - Novantox 8 PFDA (0.4% by weight per 100 g of polymer). Next, rubber is degassed in an oil bath at a temperature of 150 ° C. The resulting degassed rubber is dried on rollers at a temperature of 85 ^about C.

The properties of the rubber obtained are presented in table 1. The hysteresis properties of the rubbers obtained using this rubber are shown in tables 3.4. The rubber obtained in this example is unbranched and non-functional.

Example 1. Obtaining styrene-butadiene rubber using (n-Bu) ₄ Znli ₂  without DTGFP.

The process for producing styrene-butadiene rubbers is carried out in a Buchi reactor with a glass bowl having a working volume of 1 liter, equipped with a stirrer, a jacket for temperature control, fittings and special removable metal batchers for supplying reagents.

Nephras (412.2 g), butadiene (48.05 g), styrene (12.01 g) are fed into a reactor cooled to -20 ° C (± 2 ° C) in a nitrogen stream at a stirrer speed of 50 rpm. Then, the stirrer rotational speed is set at 300 rpm, the temperature of the reaction mixture is increased to 55 ° C with a heating rate of 7 ° / min, and when the temperature reaches 15 ° C, 3.6 ml of a lithium organozincate solution in THF (0.2 M solution) is supplied. After 10 hours of synthesis from the start of the initiator addition, a 100% degree of monomer conversion is achieved. Next, the polymer is poured into a glass and seasoned with an antioxidant - Novantox 8 PFDA (0.4% by weight per 100 g of polymer). Then, rubber is degassed in an oil bath at a temperature of 150 ° C. The resulting rubber containing water is dried on rollers at a temperature of 85 ^about C.

The properties of the rubber obtained are presented in table 1.

Example 2. Obtaining styrene-butadiene rubber using (n-Bu) ₄ Znli ₂  and DTGFP

The process for producing styrene-butadiene rubbers is carried out in a Buchi reactor with a glass bowl having a working volume of 1 liter, equipped with a stirrer, a jacket for temperature control, fittings and special removable metal batchers for supplying reagents.

Nephras (412.2 g), butadiene (50.69 g), styrene (14.72 g) are fed to a reactor cooled to -20 ° C (± 2 ° C) in a nitrogen stream at a mixer speed of 50 rpm 0.75 ml of a solution of 2,2-bis (2-oxolanyl) propane (ditetrahydrofurylpropane, DTGFP) in nephras (0.2 M). Then, the stirrer rotational speed is set at 300 rpm, the temperature of the reaction mixture begins to increase to 55 ° C with a heating rate of 7 ° / min, and when the temperature reaches 15 ° C, 2.26 ml of a lithium organozincate solution in THF (0.2 M solution) are supplied. After 3 hours of synthesis from the start of initiator addition, a 100% degree of monomer conversion is achieved. Next, the polymer is poured into a glass and seasoned with an antioxidant - Novantox 8 PFDA (0.4% by weight per 100 g of polymer). Then, rubber is degassed in an oil bath at a temperature of 150 ° C. The resulting rubber containing water is dried on rollers at a temperature of 85 ^about C.

The properties of the rubber obtained are presented in table 1.

Example 3. Obtaining styrene-butadiene rubber using (n-Bu) ₄ Znli ₂  and DTGFP

The process for producing styrene-butadiene rubbers is carried out in a Buchi reactor with a glass bowl having a working volume of 1 liter, equipped with a stirrer, a jacket for temperature control, fittings and special removable metal batchers for supplying reagents.

Nephras (412.2 g), butadiene (56.74 g), styrene (17.43 g) are fed into a reactor cooled to -20 ° C (± 2 ° C) in a nitrogen stream at a stirrer speed of 50 rpm 2.4 ml of a solution of 2,2-bis (2-oxolanyl) propane (ditetrahydrofurylpropane, DTGFP) in nephras (0.2 M). Then, the stirrer rotational speed is set at 300 rpm, the temperature of the reaction mass is increased to 55 ° C with a heating rate of 7 ° / min, and when the temperature reaches 15 ° C, 1.80 ml of a lithium organozincate solution in THF (0.2 M solution) is supplied. After 2 hours of synthesis from the start of the initiator addition, a 100% degree of monomer conversion is achieved. Next, the polymer is poured into a glass and seasoned with an antioxidant - Novantox 8 PFDA (0.4% by weight per 100 g of polymer). Then, rubber is degassed in an oil bath at a temperature of 150 ° C. The resulting rubber containing water is dried on rollers at a temperature of 85 ^about C.

The properties of the rubber obtained are presented in table 1. The hysteresis properties of the rubbers obtained using this rubber are shown in tables 3.4.

Example 4. Obtaining styrene-butadiene rubber using (n-Bu) ₄ Znli ₂  and DTGFP

The process for producing styrene-butadiene rubbers is carried out in a Buchi reactor with a glass bowl having a working volume of 1 liter, equipped with a stirrer, a jacket for temperature control, fittings and special removable metal batchers for supplying reagents.

Nephras (412.2 g), butadiene (54.59 g), styrene (16.12 g) are fed to a reactor cooled to -20 ° C (± 2 ° C) in a nitrogen stream at a mixer speed of 50 rpm 2.4 ml of a solution of 2,2-bis (2-oxolanyl) propane (ditetrahydrofurylpropane, DTGFP) in nephras (0.2 M). Then, the stirrer rotational speed is set at 300 rpm, the temperature of the reaction mixture begins to increase to 55 ° C with a heating rate of 7 ° / min, and when the temperature reaches 15 ° C, 0.90 ml of a lithium organozincate solution in THF (0.2 M solution) is supplied. After 2 hours of synthesis from the start of the initiator addition, a 100% degree of monomer conversion is achieved. Next, the polymer is poured into a glass and seasoned with an antioxidant - Novantox 8 PFDA (0.4% by weight per 100 g of polymer). Then rubber is degassed in an oil bath at a temperature of 150 ° C. The resulting rubber containing water is dried on rollers at a temperature of 85 ^about C.

The properties of the rubber obtained are presented in table 1.

Example 5 (comparative). Commercially Available Rubber

The properties of the competitor rubber, which is branched and functionalized, are presented in Table 1. The hysteresis properties of the rubbers obtained using this rubber are shown in tables 3.4.

Example 6. Obtaining butadiene rubber using (n-Bu) ₄ Znli ₂

The process for producing butadiene rubber is carried out in a Buchi reactor with a glass bowl having a working volume of 1 liter, equipped with a stirrer, a jacket for temperature control, fittings and special removable metal batchers for supplying reagents.

Nephras (412.2 g), butadiene (53.99 g) are fed into a reactor cooled to -20 ° C (± 2 ° C) in a stream of nitrogen at a stirrer speed of 50 rpm. Then, the stirrer rotational speed is set at 300 rpm, the temperature of the reaction mixture begins to increase to 55 ° C with a heating rate of 7 ° / min, when the temperature reaches 15 ° C, 2.4 ml of a lithium organozincate solution in THF (0.2 M solution) is supplied. After 2 hours of synthesis from the start of the initiator addition, a 100% degree of monomer conversion is achieved. Next, the polymer is poured into a glass and seasoned with an antioxidant - Novantox 8 PFDA (0.4% by weight per 100 g of polymer). Then, rubber is degassed in an oil bath at a temperature of 150 ° C. The resulting rubber containing water is dried on rollers at a temperature of 85 ^about C.

The properties of the rubber obtained are presented in table 1.

Example 7. Obtaining butadiene rubber using (n-Bu) ₄ Znli ₂  and DTGFP

The process for producing butadiene rubber is carried out in a Buchi reactor with a glass bowl having a working volume of 1 liter, equipped with a stirrer, a jacket for temperature control, fittings and special removable metal batchers for supplying reagents.

Nephras (412.2 g), butadiene (52.15 g), and 6.27 ml of solution 2 are fed into a reactor cooled to -20 ° C (± 2 ° C) in a nitrogen stream at a stirrer speed of 50 rpm 2-bis (2-oxolanyl) propane (ditetrahydrofurylpropane, DTGFP) in nephras (0.2 M). Then, the stirrer rotational speed is set at 300 rpm, the temperature of the reaction mixture begins to increase to 55 ° C with a heating rate of 7 ° / min, at a temperature of 15 ° C, 2.35 ml of a lithium organozincate solution in THF (0.2 M solution) is supplied. After 2 hours of synthesis from the start of the initiator addition, a 100% degree of monomer conversion is achieved. Next, the polymer is poured into a glass and seasoned with an antioxidant - Novantox 8 PFDA (0.4% by weight per 100 g of polymer). Then, rubber is degassed in an oil bath at a temperature of 150 ° C. The resulting rubber containing water is dried on rollers at a temperature of 85 ^about C.

The properties of the rubber obtained are presented in table 1.

The rubbers obtained according to Example 3, a comparative example and a competitive, commercially available rubber were tested as part of a rubber composition for tread of passenger tires (recipe 1) and a standard rubber composition (GOST ISO 2322-2013) filled with carbon black (recipe 2) . The rubber compositions are listed in Table 3. The rubber compositions were prepared on a Plastograph EC Plus, Model 2008 plastikorder company "Brabender" (Germany). The free volume of the mixing chamber with cam rotors of type N 50 EHT was 80 cm ³ . The preparation of the rubber composition according to the recipe 1 was carried out in three stages:

Stage 1 - the mixing of all ingredients except the vulcanizing group, i.e. sulfur, MBT, DFG, SAC, the initial temperature of the chamber walls is 130 ° C, the maximum in the chamber during mixing is not more than 165 ° C, the rotor speed is 40-60 r ^-1 ;

Stage 2 - dispersing mixing of a mixture of stage 1 without adding additional ingredients, the initial temperature of the chamber walls is 80 ° C, the maximum is not more than 130 ° C, the rotor speed is 60 r ^-1 ;

Stage 3 - the introduction of a vulcanizing group into the rubber composition, the initial temperature of the chamber walls is 80 ° C, the maximum is not more than 110 ° C, the rotor speed is 40 r ^-1 . The preparation of rubber compositions according to recipe 2 was carried out in a closed mixer in one stage according to GOST ISO 2322-2013.

Table 1. The structure and properties of rubbers

Example No. n-Bu ₄ ZnLi ₂ , mmol /
100 g C (DTGFP), mmol /
100 g Microstructural Characteristics (IR Analysis) Molecular weight characteristics T _article , ^about With Mooney Viscosity St
% wt. 1,2-Bd,
% wt. 1,4-Bd,
% wt. M _n * 10 ^-3 M _w * 10 ^-3 M _w / M _n Srav n-buli
0.85 1,0 22.5 62.32 37.68 162 201 1.24 -22.1 49 1 1,2 - 19.9 39.8 60,2 109 157 1.44 -47.4 22 2 0.75 0.25 22.4 54.5 45.5 156 216 1.39 -31.6 43 3 0.6 0.8 23,4 62.7 37.3 169 220 1.30 -20.3 54 4 0.3 0.8 22.6 65.8 34.2 312 384 1.23 -15.7 102 5 No data No data 19.3 63.3 36.7 133 240 1.80 -22.0 58 6 0.9 - - 42,2 57.8 166 248 1.49 -73.5 56 7 0.9 2,4 - 76.0 24.0 112 139 1.23 -31.0
-0.7 eleven

The rubber of example 3, the reference sample and competitive rubber were tested in rubbers.

Table 2. The composition of the rubber compositions

Name of ingredients Content, parts by weight per 100 parts by weight rubber Recipe 1 Recipe 2 Natural rubber TSR RSS-1 30,0 - Mortar-styrene butadiene rubber according to examples 1-5 70.0 100.0 Carbon black N 339 (Yaroslavl plant of carbon black) 13.0 50,0 Silica Zeosil 1165 MP (Solvay) 86.0 - Plasticizer Vivatec 200 (Hansen & Rosental) 50,0 - Plasticizer rapeseed oil technical (LLC "Profet") 8.0 - Antioxidant 6PPD (Eastman Santoflex) 2.5 - Antioxidant TMQ (Chemtura) 2.0 - Antilux 111 Protective Wax (RheinChemie) 2.0 - Zinc oxide (Empils LLC) 2.0 3.0 Stearic acid (OJSC Nefis Cosmetics) 1,0 1,0 Techniplast Actiplast ST (RheinChemie) 4.0 - Silanizing agent Si-69 (Evonic) 8.0 - Mercaptobenzthiazole (MBT-2) (Stair, China) 0.1 - Diphenylguanidine (DFG) (RheinChemie) 2.0 - Sulfenamide C (SAC) (Lanxess) 2.0 1,0 Technical ground sulfur 9998 (NK LUKOIL) 1.7 1.75

Table 3. Hysteresis properties of rubbers (change in indicators relative to a comparative example,%)

Indicator Silicon dioxide as the main filler (recipe 1) Carbon black as the main filler (recipe 2) Comparative example Example 3 Comparative example Example 3 tgδ (-20 ° C) 100 107 100 128 tgδ (0 ° C) 100 104 100 107 tgδ (60 ° C) 100 103 100 99

Values of more than 100 indicate an improvement in the indicator, values of less than 100 indicate deterioration.

Table 4. Hysteresis properties of rubbers (change in indicators relative to a competitive sample,%)

Indicator  Silicon dioxide as the main filler (recipe 1) Carbon black as the main filler (recipe 2) Competitor Example 3 Competitor Example 3 tgδ (-20 ° C) 100 102 100 128 tgδ (0 ° C) 100 106 100 110 tgδ (60 ° C) 100 102 100 99

Values of more than 100 indicate an improvement in the indicator, values of less than 100 indicate deterioration.

The preparation of rubber compositions for vulcanization, vulcanization and preparation of test specimens was carried out according to ASTM D 3182. The vulcanization modes of the rubber obtained by recipe 1 (table 2): 160 ° C for 20 minutes to assess the deformation-strength properties and for 30 minutes to assess hardness and abrasion. Modes of vulcanization of rubber obtained by recipe 2 (table. 2) are given in GOST ISO 2322-2013. Assessment of the main indicators of vulcanizates in tension ( f ₃₀₀ , f _p, ε _rel ,) was carried out according to ASTM D 412-98. Schopper-Schlobach abrasion (method B) was evaluated according to GOST 23509-79. Hysteresis properties were determined using DMA 242 C instruments (NETZSCH). Test conditions for DMA 242 C: two-arm bend, sample dimensions 10.00 × 6.50 × 2.0 mm, amplitude 40 μm (1%), frequency 10 Hz, load 7 N. Test temperature range - from minus 60 ° C up to plus 60 ° С, the rate of temperature increase is 2 ° С / min.

Table 3 and 4 show the hysteresis properties of rubber based rubber described in example 3, a comparative example and a competitive sample.

From the data of tables 3 and 4 it is seen that rubbers obtained using lithium organozincates can improve the hysteretic properties of rubbers at temperatures of -20 ° C (tgδ _{-20 ° C} ), which is equivalent to improved grip on icy roads, and hysteretic properties at 0 ° C, which indicates an improvement in wet grip. Moreover, the positive effects are more significant in the case of rubber filled with carbon black, which allows us to recommend the use of rubbers obtained according to the present invention, not only in tires for passenger cars of premium class, but also for tires of trucks, light trucks and cars not belonging to the category A and AA, whose tread mainly uses tread rubber filled with carbon black. The observed positive effect is ensured both due to the necessary microstructure of rubber, and the nature of the molecular weight distribution. So, rubbers synthesized using lithium organozincates as an initiator and 2,2-bis (2-oxolanyl) propane (ditetrahydrofurylpropane, DTGFP) as an electron donor have a monomodal distribution curve (Fig. 2, example 3), while the comparative the sample (see figure 1) has a bimodal distribution. This indicates that the use of organozincates affects the structure and activity of the initiating complex, the speed and the peculiarity of the addition of monomers in the polymerization process. When comparing with a competitive sample (example 5), a narrower molecular weight distribution of rubbers (see table 1, examples 3 and 4) obtained by the claimed method can be noted, which also helps to reduce hysteresis losses.

Claims (13)

1. A method of producing rubber by anionic polymerization of a diene and / or copolymerization of a diene and a vinyl aromatic compound in an organic solvent in the presence of an electron donor and lithium organozincate of the general formula R ₄ ZnLi ₂ as an initiator, where R is the same or different aliphatic and / or aromatic hydrocarbon radicals, characterized in that 2,2-bis (2-oxolanyl) propane (ditetrahydrofurylpropane, DTGFP) is used as an electron donor in a hydrocarbon solvent and an inert medium. 2. The method of producing rubber according to claim 1, where R is the same aliphatic radicals, preferably containing 1-4 carbon atoms, most preferably n-butyl or sec-butyl. 3. The method for producing rubber according to claim 1, wherein said dienes contain from 4 to 12 carbon atoms, and are preferably 1,3-butadiene and / or isoprene. 4. The method of producing rubber according to claim 1, wherein the vinyl aromatic compounds are selected from the group consisting of styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, 3-vinyltoluene, ethylvinylbenzene, 4-cyclohexylstyrene, para-tert-butylstyrene , methoxystyrenes, vinyl mesitylene, divinylbenzene, 1-vinylnaphthalene, 2,4,6-trimethylstyrene, preferably styrene or α-methylstyrene. 5. The method of producing rubber according to claim 1, where the mass ratio of the starting dienes and vinyl aromatic compounds is from 0 to 1, preferably from 0.1 to 0.9, more preferably from 0.2 to 0.7. 6. The method of producing rubber according to claim 1, wherein the initiator: electron donor molar ratio is from 0.1 to 100, preferably from 0.5 to 50, and most preferably from 1 to 3. 7. A method for producing rubber as claimed in claim. 1, where the polymerization is carried out at a temperature of from -80 ° C to ¹⁵⁰ ° C, preferably from 0 ° C ^to 100 ° C, more preferably from 40 ° C to 80 ° ^C. 8. The method for producing rubber according to claim 1, wherein the initiator content varies in the range from 1 to 50 mol / t of rubber, preferably from 2 to 25 mol / t of rubber, more preferably from 3 to 12 mol / t of rubber. 9. The method of producing rubber according to claim 1, where the solvents are selected from the groups of saturated hydrocarbons, preferably containing 3-12 carbon atoms, or mixtures thereof. 10. Rubber for the manufacture of rubbers based on polymers of conjugated dienes and / or copolymers of conjugated dienes and vinyl aromatic compounds, obtained by the method according to paragraphs. 1-9. 11. A rubber composition comprising rubber according to claim 10. 12. The rubber composition according to claim 11, further comprising components selected from the group consisting of natural rubber, silicon dioxide; carbon black; silanizing agent; vulcanizer; and traditional processing aids, such as those that improve the dispersion of fillers and the processability of rubber compositions; plasticizers, antioxidants / anitozonants / physical and chemical anti-haze agents; modifiers fillers, including fibrous, layered, polymer; agents that prevent reversion during vulcanization and increase the heat resistance of rubbers. 13. The use of the rubber composition according to paragraphs. 11, 12 for the manufacture of a tire tread.

Images