RU2707102C1 - Method of producing modified rubber by solution anionic polymerisation, a rubber composition containing such rubber and use thereof - Google Patents

Abstract

FIELD: chemical or physical processes; method of production.SUBSTANCE: invention relates to production of modified rubber by anionic solution polymerisation. Disclosed is a method of producing rubber by anionic solution polymerisation of a conjugated diene or by copolymerisation of a conjugated diene and a vinyl aromatic compound in an organic solvent medium in the presence of a lithium-organic N, N-disubstituted aminomethylstyrol oligomer initiator, a special N, N-disubstituted aminomethylstyrene monomer and a terminal functionalising agent of general formula (CH)HalSi, where Hal is a halogen atom. Disclosed also is rubber for making a rubber composition obtained by the disclosed method, a rubber composition for making tires, comprising said rubber, and use thereof for making a tread of car tires.EFFECT: technical result is complex modification of rubber at stage of polymerisation enables to obtain rubber compositions with its use, suitable for production of tires with reduced rolling resistance and improved adhesion with wet road.17 cl, 5 tbl, 12 ex

Description

FIELD OF THE INVENTION

The present invention relates to the field of production of modified rubbers by the solution of anionic polymerization method, as well as to the production, on their basis, of rubbers, rubber products and tires characterized by an improved complex of hysteresis properties. In particular, the invention relates to a method for producing modified rubber in the presence of an organolithium N, N-disubstituted aminomethylstyrene oligomeric initiator, a special N, N-disubstituted aminomethylstyrene monomer and a terminal functionalizing agent with the general formula (CH ₃ ) ₂ Hal ₂ Si, where Hal is an atom halogen. In this way, 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 (Mn) of 50,000 to 400,000 g / mol, a polydispersity coefficient of 1 to 3, and a content of 1,2-butadiene units of 40 to 100% by weight. on the polydiene part of rubber, and from 0 to 50% of the mass. on rubber vinylaromatic links. Modified rubbers with these properties have increased compatibility with carbon black and precipitated colloidal silicic acid (silica, OKN), which allows the production of rubbers with improved hysteresis characteristics, which are used in the tire industry for the manufacture of car tire treads.

State of the art

The performance properties of rubbers for tire tread, such as rolling resistance, grip and others, are largely determined by the nature of the rubber used and, in particular, the presence of functional groups in the rubber molecule.

The functionalization of rubber leads to an improvement in the hysteresis properties of rubbers obtained from rubber data. In particular, functionalization is widely used at the polymerization stage, and various initiators containing functional groups and special monomers are used. In addition, functionalization at the ends of the chain using functionalizing, combining or branching agents is used.

The use of functionalized initiators is described, for example, in patent US7405262, where preliminary mixing of cinnamylhexamethyleneimine and organolithium compounds give an initiator of the general formula:

where A is alkyl, dialkyl, cycloalkyl or dicycloamine or a cyclic amine; R _1-6 are independently selected from the group consisting of alkyl, cycloalkyl and aryl hydrocarbons having from 1 to 12 carbon atoms. This initiator is used in the solution (co) polymerization of conjugated dienes and / or vinyl aromatic compounds. Obtained using this initiator polymer has a Mooney viscosity (ML1 + 4 at ¹⁰⁰ ° C) from 1 to 150, a number average molecular weight of from 50,000 to 1,000,000 and a molecular weight distribution of less than 2.

US Pat. No. 5,393,721 describes a functionalized initiator of the general formula ALi (SOL) _y , where A is an alkyl, dialkyl, cycloalkyl or dicycloamine or cyclic amine, SOL is a solubilizing component selected from the group of hydrocarbons, ethers, amines, or a mixture thereof, which allows to obtain initiators soluble in nonpolar organic solvents. The initiator is obtained by pre-mixing hexamethyleneimine and an organolithium compound and is used in the solution (co) polymerization of conjugated dienes. According to the authors of US 5393721, the resulting polymer has a narrow range of molecular weights: from 20,000 to 250,000.

From the prior art (see, for example, US6630552, US6790921, US20100152364 and US6803462) it is known to use special monomers in polymerization processes in order to give products the required performance characteristics. The use of special monomers of the general formula is disclosed:

where R represents an alkyl group containing from 1 to 10 carbon atoms or a hydrogen atom, R ₁ and R ₂ may be the same or different and represent hydrogen atoms or groups of structural formulas:

where R _{3 is the} same or different alkyl groups containing from 1 to 4 carbon atoms, or hydrogen atoms, R ₄ is an alkyl group containing from 1 to 10 carbon atoms, an aryl or allyl group, Z is a nitrogen-containing heterocycle, n and x are integer numbers from 1 to 10, provided that R ₁ and R ₂ cannot be both hydrogen atoms. Most often receive rubber containing from 0.2 to 10% of the mass. special monomers. So, according to one example of the invention according to patent US6630552, rubber based on a copolymer of butadiene, styrene and 1% of the mass. 1 - [(4-vinylphenyl) methyl] pyrrolidine as a special monomer has a rolling resistance of 38.7% less compared to unmodified styrene butadiene rubber.

From US20100099810 and US20130303683 known the joint use of the above special monomers and crosslinking agents based on silicon. A method for producing a pneumatic tire having good wet grip and abrasion resistance is described. Special monomers have the general formula:

,

,

where R ₁ and R _{2 are the} same or different groups of general formulas

,

,

where R ₃ is an aliphatic hydrocarbon containing from 1 to 4 carbon atoms, Z is a divalent hydrocarbon saturated radical, optionally containing nitrogen, oxygen or sulfur, R ₄ - R _{7 is an} aliphatic hydrocarbon containing from 1 to 30 carbon atoms, an acyclic hydrocarbon containing from 3 to 30 carbon atoms, an aromatic hydrocarbon containing from 5 to 30 carbon atoms, or a hydrogen atom. A crosslinking agent is characterized by the general formula:

,

,

in which R ₂₁ represents a group —OR ₂₅ —O) _t —R ₂₆ , where R ₂₅ are the same or different branched or linear divalent hydrocarbon groups C ₁ -C _30, R ₂₆ is a branched or linear C ₁ -C ₃₀ alkyl or an unbranched C ₂ -C ₃₀ alkenyl or C ₆ -C ₃₀ aryl or C ₇ -C ₃₀ arylalkyl hydrocarbon radical; t is an integer from 1 to 30; R ₂₂ and R ₂₃ are the same or different aliphatic and / or aromatic branched or linear hydrocarbon radicals containing up to 30 carbon atoms. Thus, at the moment, the prior art does not know the combined use of a functionalized initiator, special monomers and terminal functionalizing agents in the production of modified rubber by the solution polymerization method, which would allow obtaining modified rubber, the rubber on the basis of which will have an improved complex of hysteresis properties.

Object of the present invention is the development of an industrial method for producing modified rubber by solution polymerization in the presence of organolithium N, N-disubstituted aminomethylstyrene oligomeric initiator of the general formula (I)

(I),

(I)

special N, N-disubstituted aminomethylstyrene monomer with the general formula (II)

(II)

(Ii)

and a terminal functionalizing agent with the general formula (CH ₃ ) ₂ Hal ₂ Si.

The technical result of the present invention is to improve the hysteretic characteristics of rubbers based on rubbers obtained by the claimed method, which provides a reduction in the hysteretic rubbing in rubbers operating in dynamic conditions. This is expressed in a decrease in the tangent of the angle of mechanical loss at 60 ° C (rolling resistance) by 14-19% and in an increase in the tangent of the angle of mechanical loss at 0 ° C (improved grip on wet roads) by 9-10%. The specified technical result is achieved due to the complex modification of rubber at the polymerization stage, namely as a result of the use of a functionalized initiator, a special monomer and a terminal functionalizing agent.

DESCRIPTION OF THE INVENTION A method for producing the modified rubber of the present invention is to carry out a solution of anionic (co) polymerization of a conjugated diene and / or vinyl aromatic compound in an organic solvent in the presence of an organolithium N, N-disubstituted aminomethylstyrene oligomeric initiator, a special N, N-disubstituted aminomethylmethylmethylene functionalizing agent with the General formula (CH ₃ ) ₂ Hal ₂ Si, where Hal is a halogen atom, as shown in the diagram below me:

,

,

where f-SM is a special monomer, f-InLi- N, N-disubstituted aminomethylstyrene oligomeric initiator, f-In-N, N-disubstituted aminomethylstyrene functional group.

As starting monomers for the production of rubbers, conjugated dienes and vinyl aromatic compounds are used. Examples of conjugated dienes are conjugated dienes 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 (C ₁ -C ₅ 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 are selected from styrene, α-methyl styrene, ortho-, meta- and para-methyl styrene, 3-vinyl toluene, ethyl vinyl benzene, 4-cyclohexyl styrene, para-tert-butyl styrene, methoxy styrene, vinyl mesitylene, divinylbenzene, 1-vinyl 6-trimethylstyrene. Styrene or α-methylstyrene are preferably used.

As special N, N-disubstituted aminomethylstyrenes or α-aminomethylstyrenes, compounds of the general formula (II) are used:

(II)

(Ii)

where x = 1, y = 0 or x = 0, y = 1;

R represents a —CH ₂ N (R ₁ ) (R ₂ ) group in which R ₁ and R ₂ may be the same or different and independently represent alkyl or cycloalkyl optionally substituted with one or more substituents selected from a hydroxy group, a dialkylamino group , alkoxy groups, aryloxy groups, alkylsulfanyl groups, arylsulfanyl groups, aryl;

or aryl optionally substituted with one or more substituents selected from halogen, alkyl, dialkylamino, alkoxy, aryloxy, alkylsulfanyl, arylsulfanyl, aryl;

or heteroaryl containing one or more nitrogen atoms, wherein the heteroaryl is optionally substituted with one or more substituents selected from a halogen, alkyl, dialkylamino group, alkoxy group, aryloxy group, alkylsulfanyl group, arylsulfanyl group, aryl;

or R ₁ and R ₂ taken together with nitrogen form a 5-6 membered heterocyclic or 5 membered heteroaromatic ring, optionally containing one or more additional heteroatoms selected from nitrogen, oxygen or sulfur.

Examples of such compounds are, but are not limited to 1 - [(4-vinylphenyl) methyl] pyrrolidine, 4- (3-ethenylbenzyl) morpholine.

The inventors of the present invention have found that the best result is achieved by using as a special monomer compounds where R ₁ and R ₂ taken together with nitrogen form a 6-membered heterocyclic ring containing one additional heteroatom, the most preferred compounds where the heteroatom is oxygen. An example of such a monomer is 4- (3,4-ethenylbenzyl) morpholine.

Special monomers are added in an amount of from 0 to 40% by weight, preferably from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight. based on the weight of the polymer.

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.

Polymerization solvents are selected from the groups of saturated hydrocarbons, for example, pentane, hexane, heptane, cyclic hydrocarbons, for example, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, p-xylene, including mixtures thereof in various ratio with a purity of 99% or more. It is preferable to use solvents containing from 3 to 12 carbon atoms. An oil solvent (nefras) is also used, for example, nephras of the 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.

According to the present invention, the functionalized initiator in most cases is the oligomer of the selected special monomer, or the so-called macromonomer. Using an initiator with a controlled long oligomeric chain allows you to adjust the properties of the resulting rubber. In particular, the functionalized initiator is an anionic polymerization initiator containing an amine functional group, which is obtained by reacting said organolithium compound and a secondary amine in situ , i.e. in a polymerization medium, or previously, i.e. before being introduced into the polymerization medium. As the organolithium compound, substances of the general formula R'Li 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, preferably radicals containing 1-4 carbon atoms, most preferred are n-butyl, sec-butyl. Examples of the aryl radical include, but are not limited to: phenyl, 2-benzyl, 3-benzyl, 4-benzyl, 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-tetramethylphenyl; 2,3,4,6-tetramethylphenyl. Aryl radicals containing 6-12 carbon atoms are preferred, a phenyl radical is most preferred.

N, N-disubstituted aminomethylstyrene compounds are selected from those previously described as special monomers of the compounds.

Upon receipt of the initiator using the same solvents as in the polymerization process. The reaction is carried out in an inert atmosphere, for example, in an atmosphere of nitrogen or argon.

Synthesis of the initiator is carried out under constant stirring at room temperature (15 to 30 ° ^C) or under heating ^to 100 ° C, preferably ^to 50 ° C, most preferably up to ^about 38 C. The duration of the reaction depends on the starting materials varies from a few minutes to a few hours.

The amount of initiator used is determined by the required molecular weight of the rubber and the presence of impurities in the starting components. Preferably, the amount of initiator used ranges from 1 to 50 mol / t of rubber, more preferably from 2 to 25 mol / t of rubber, most preferably from 3 to 10 mol / t of rubber.

Also, in the polymerization process, electron donors are used to increase the number of 1,2- or 3,4-units. As the electron donors in the polymerization reactions, any donor known in the art is used, for example: bis (2-oxolanyl) methane, 1,1-bis (2-oxolanyl) ethane, 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, dialkyl ethers of mono and oligoalkylene glycols, for example, ethylene glycol dimethyl ether, dibutyl ether ethylene glycol, tertiary amines, for example, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetraethylethylenediamine. Preferably, tetramethylenediamine, tetrahydrofuran, 2,2-bis (2-oxolanyl) propane are used.

The molar ratio of the amount of electron donor to initiator is from 0.5 to 4, preferably from 0.8 to 2, more preferably from 1 to 1.5.

The temperature regime of the polymerization process is determined by the thermal effect of the exothermic reaction of the (co) polymerization of the conjugated diene and / or vinyl aromatic compound. The polymerization temperature is from -30 ° C to + 120 ° C, preferably from 0 ° C to 100 ° C, more preferably from 15 ° C to 80 ° C. The process is carried out in an inert atmosphere at a pressure of from 0 to 10 atmospheres, preferably from 0.5 to 5 atmospheres, more preferably from 1 to 3 atmospheres.

In accordance with the inventive method, the duration of the polymerization process, depending on temperature, is from 10 minutes to 120 minutes, preferably from 20 minutes to 80 minutes, more preferably from 30 minutes to 50 minutes.

Preferably, the polymerization process is carried out to a degree of monomer conversion of at least 95%.

The starting monomer feed, solvent, electron donor can be introduced into the reactor in any sequence, proceeding from technological convenience. The components are introduced into the reactor as follows: first, the solvent, monomers without solvent or in the form of a charge in the solvent used, an electron donor, initiator are introduced, after which continuous or batch addition of monomer or monomers is continued until the polymerization reaction is completed. The addition of monomer or monomers may be single when the conversion reaches 90-100%. Preferably, the components are introduced in the following sequence: solvent, starting monomer feed and electron donor. In this case, the previously obtained initiator or components for receiving the initiator in situ are introduced last.

The polymerization process is carried out in any batch or continuous equipment known in the art for carrying out the anionic polymerization process.

Upon reaching the degree of monomer conversion of not less than 95%, a modification process is carried out — the interaction of the “living” polymer with the terminal functionalizing agent by introducing a solution of this agent into the polymerization reactor.

Scheme 1 presents, but is not limited to, the stage of interaction of the living polymer with a terminal functionalizing agent, which is used as a compound of the general formula (CH ₃ ) ₂ Hal ₂ Si, preferably dimethyldichlorosilane (SiMe ₂ Cl ₂ ):

Scheme 1

where f-SM is a special monomer, f-In is N, an N-disubstituted aminomethylstyrene functional group, f-polymer is a functionalized polymer.

The process of interaction of the living polymer with the terminal functionalizing agent is carried out at a temperature of from 20 ° C to 120 ° C, preferably from 40 ° C to 100 ° C, more preferably from 60 ° C to 80 ° C, in an inert atmosphere at a pressure of from 0 up to 10 atm, preferably from 0.5 to 5 atm, more preferably from 1 to 3 atm, with effective stirring.

The duration of the process varies from 5 to 100 minutes, preferably from 20 to 60 minutes, more preferably from 30 to 40 minutes. The modification time is determined by the modification temperature: the higher the temperature, the less time is required for the modification.

The inventive method allows to obtain rubber with a number average molecular weight of from 50,000 to 500,000, preferably from 100,000 to 450,000, more preferably from 200,000 to 400,000 g / mol, with a polydispersity coefficient of from 1 to 3, with a content of 1.2- (or 3.4- depending on the type of diene monomer selected) units equal to from 40 to 100% of the mass. per polybutadiene part of the rubber, preferably from 50 to 80 wt. -%, more preferably from 60 to 70 wt. % The content of vinyl aromatic units in the rubber according to this invention is from 0 to 60% by weight, preferably from 10 to 45% by weight, more preferably from 15 to 40% by weight. on rubber.

At the end of the process, the polymerizate is mixed with an antioxidant, if necessary, filled with oil-filler, then subjected to degassing, rubber is isolated and dried.

Phenolic or amine compounds and any other antioxidants, including mixed ones recommended for rubber stabilization, are used as rubber antioxidants. Examples of phenolic antioxidants are 2,6-di-tert-butyl-4-methylphenol (ionol, Agidol 1, alkofen, Antioxidant 264); 2,2-di- (4-methyl-6-tert-butylphenol) methane (antioxidant 2246, Agidol 2, Bisalkofen), 2-methyl-4,6-bis (octylsulfanylmethyl) phenol (IRGANOX 1520L); pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (IRGANOX 1010); benzenepropanoic acid ester of 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy-C ₇ -C ₉ branched alkyl (IRGANOX 1135); 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 (IRGANOX 1076). 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), N, N'-diphenyl -p-phenylenediamine (DFFD), mixed antioxidants of the Santoflex ™ 134PD type, which are a 1: 2 mixture of 6PPD and 7PPD products. Antioxidants are introduced into the polymerizate in an amount of from 0.2 to 3.0% of the mass. by weight of the rubber obtained. The most effective and appropriate dosage of the antioxidant is 0.3-1.5% of the mass. on rubber.

The filler oils for rubbers can be oils of the types TDAE (purified distillate aromatic extract), TRAE (purified residual aromatic extract), MES (mild solvate), 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. The most typical rubber filler oils are TDAE oils. 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 is served in an amount of from 5 to 80 mass. hours per 100 parts by weight rubber, depending on what technological properties it is necessary to provide rubber. However, most often receive rubber with an oil content of from 25 to 30% of the mass. in the composition, which corresponds to 34 ÷ 44 parts by weight oil per 100 parts by weight rubber.

The rubber obtained according to the present invention can be used in rubbers for various purposes, providing them with lower hysteresis losses under dynamic operating conditions, including as part of the tread of a car tire to increase traction and reduce rolling losses.

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

The rubber proposed in the present invention, differ from the known compositions for a similar purpose in that they include rubbers obtained according to the claimed method.

In accordance with the invention, rubbers can be obtained on the basis of a mixture of several rubbers, mainly two or three, selected from the group of styrene-butadiene (A), butadiene (B) and isoprene (C), styrene-butadiene-isoprene (D) or other rubbers that can be used to produce rubbers for a given purpose. In this case, one or more rubbers belonging to group A, B or D and synthesized in the environment of a hydrocarbon solvent by anionic polymerization are 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):

a) 0-150 mass. including precipitated colloidal silicic acid (silica, OKN);

b) 0-150 mass. including carbon black;

c) 0-30 mass. including silanizing agent;

d) a vulcanizing system containing: sulfur or sulfur donors, accelerators from among sulfenamides, thiurams, thiazoles, guanidines, phosphates and their combinations, used to accelerate the process of vulcanization of rubbers and obtain the optimal structure of the vulcanization network, activators - metal oxides, amines, among which the most widely distributed zinc oxide, vulcanization inhibitors, among which the most widely distributed Santogard PVI.

d) technological additives that improve the dispersion of fillers and the processability of rubber compositions;

f) plasticizers, softeners: oil products, vegetable, synthetic, essential, products of the processing of the coal industry, synthetic oligomeric functionalized and non-functionalized;

g) antioxidants / antiozonants / anti-fatigue physical and chemical;

h) other components ensuring 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 can be used, obtained on various catalytic systems by solution polymerization in the presence of a polymerization initiator or catalyst and containing 1,4-cis units of at least 90% by weight. The rubbers may also contain styrene-butadiene copolymers obtained in an emulsion (aqueous phase) or solution (organic solvent).

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

The elastomeric part of the rubber compositions may also include a triple copolymer of styrene isoprene and butadiene, obtained both in emulsion and in solution, with the ratio of styrene: butadiene: isoprene units (% wt.), Respectively 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.

It is also possible to use other elastomers and copolymers applicable for the production of tire and other rubbers, for example, isoprene-butadiene copolymer, polybutadiene with a high content of 1,2-butadiene units, polyisoprene with a high content of 3,4-isoprene units.

The composition of the rubber composition may also include oil-filled brands of rubbers, for example, from among emulsion and solution styrene-butadiene or butadiene.

Each of the rubbers represented in the described rubbers may have a branched structure, for example, a star structure of polymer chains. Branching can be achieved, in particular, by using, at the polymerization stage, such known branching agents as SiCl ₄ , SnCl ₄ , divinylbenzene.

As the main reinforcing filler for rubber compositions according to the present invention, colloidal silicic acid (silica, OKN), mainly precipitated, and / or carbon black is used. It is possible to use biphasic fillers, which are silica coated with carbon black, silica, the surface of which is impregnated with a combination agent or chemically modified, as well as silica obtained by the pyrogenetic method.

The amount of carbon black can vary from 0 to 150 mass. hours per 100 mass. including rubber. When the content of carbon black is above 150 mass. including the deteriorating technological and operational properties of rubbers. The amount of silica present in the elastomeric composition is from 0 to 150 mass. hours per 100 mass. including rubber, preferably from 10 to 110 mass. hours, more preferably from 30 to 95 mass. h .. When the content of silica is above 150 mass. including the deteriorating technological and some operational properties of rubbers. Silica, in accordance with the present invention is characterized by BET surface ranging from 40 to 600 ^m2 / g and oil absorption (DBP) values in the range of from 50 to 400 ^cm3 / 100g In a preferred embodiment, the silica has a BET surface area of from 100 to 250 m ² / g, a CTAB surface area of 100 to 250 m ² / g and an oil absorption (DBP) of 150 to 250 cm ^3/100 g

Various commercially available grades of colloidal silicic acid 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 brands, mainly precipitated colloidal silicic acid (silica, OKN), used to strengthen elastomers.

Silica-filled rubber compositions contain silanizing agents (combination agents of precipitated silicic fillers and elastomers). The most commonly used coupling agents are compounds: bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxypropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane 2-mercanthyl -mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-nitropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane-2-chloroethyltriethoxysilethyltrimethyloethyl-ethyltrimethyloethyl-ethyltrimethylsilethyltriethyl-ethyltrimethylsilyl-3- rasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide. Of the above components, bis (3-triethoxysilylpropyl) tetrasulfide and 3-trimethoxysilylpropylbenzothiazoletetrasulfide are preferred.

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.

Other combination agents may be used to improve the compatibility of precipitated silicic fillers and rubber, such as, for example, NXT and NXT Z 100, manufactured by Momentive (USA).

The content of silanizing agents in the rubber is determined so 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 to 30 wt. -%, most preferably from 5 to 25% of the mass.

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, etc. Elemental or polymer sulfur is most widely used in the tire industry. As is known in the art, the dosage of vulcanizing agents in rubber is most often in the range from 0.5 to 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, Ca), metals together with fatty acids, accelerators (sulfenamides, thiazoles, thiurams, guanidines, urea derivatives) and moderators vulcanization (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. 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. In particular, products based on fatty acid derivatives known under the trademarks Struktol E44, Struktol GTI and Actiplast ST can be used.

As plasticizers and softeners, petroleum products, vegetable, synthetic, ethereal, and products of the processing of the coal industry are used.

The composition of rubber for tires includes ingredients of the following purpose, well known to a person skilled in the art: antioxidants, antiozonants, anti-fatigue agents and other components ensuring the achievement of the required 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 the reversion of vulcanization and increase the heat resistance of rubbers; tackifiers.

Rubber compositions are prepared by methods known in the art, disclosed, for example, in J.S. 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 a material for tread tires and are characterized by an improved set of elastic-hysteresis characteristics, namely, better grip on wet and icy roads.

Examples of the Invention

Synthesis of initiator based on DEAMS (diethylaminomethylstyrene)

In a 250 ml round bottom flask at 0 ° C, 100 ml of solvent (cyclohexane (70% wt.) + Nephras (30% wt.)) And 18.8 ml (0.03 mol) of n-butyllithium (1.6 M in hexane), at a temperature of 0 ° C with stirring, 5.679 g (0.03 mol) of DEAMS are added over 30 minutes. Then the solution was allowed to warm to room temperature with stirring for 1 hour. The resulting solution is homogeneous, transparent, has a red color. An aliquot of the resulting mixture was titrated with a solution of isopropanol in toluene. The resulting stopped solution is washed with 50 ml of water. The solvent was evaporated from the organic layer, the residue was dried in a vacuum oven and analyzed by gel permeation chromatography (GPC). The results are presented in Table 1. The calculated concentration of active lithium in the final solution is 0.22 mol / L. The actual concentration of 0.20 mol / L.

Synthesis of initiator based on DIPAMS (diisopropylaminomethylstyrene)

In a 250 ml round bottom flask at 0 ° C, 100 ml of solvent (cyclohexane (70% wt.) + Nephras (30% wt.)) And 18.8 ml (0.03 mol) of n-butyllithium (1.6 M in hexane), at a temperature of 0 ° C, with stirring over 30 minutes, add 6.52 g (0.03 mol) of DIPAMS. After adding the entire amount of DIPAMS, the solution was allowed to warm and stirred for 60 minutes. During mixing, the solution turns red. An aliquot of the resulting mixture was titrated with a solution of isopropanol in toluene. The resulting stopped solution is washed with 50 ml of water. The solvent was evaporated from the organic layer, the residue was dried in a vacuum oven and analyzed by gel permeation chromatography (GPC). The results are presented in Table 1. The calculated concentration of active lithium in the final solution is 0.22 mol / L. The actual concentration of 0.20 mol / L. The color of the solution at the end of the synthesis is less saturated than that of the initiator based on DEAMS.

Table 1. Molecular Weight Characteristics of Stopped Oligomeric Initiators

Initiator Mp, g / mol Mn, g / mol Mw, g / mol Mz, g / mol Mz + 1, g / mol Mv, g / mol PD Number of mon links DEAMS-Li 1817 1361 1918 2565 3259 2466 1,409 7 DIPAMS-Li 3551 2353 4160 6535 9244 6169 1,768 12

Example 1. Polymerization in the presence of n-butyllithium (n-BuLi)

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 (984 g), butadiene (92.62 g), styrene (30.98 g) and 6, are fed into a reactor cooled to -20 ° C (± 2 ° C) in a nitrogen stream at a mixer speed of 50 rpm 18 ml of a solution of DTGFP (ditetrahydrofurylpropane or 2,2-bis (2-oxolanyl) propane) in nephras (0.2 M solution). Next, the rotation speed of the mixer is set at 300 rpm, the temperature of the reaction mixture is increased to 55 ° C with a heating rate of 7 ° / min; when the temperature reaches 15 ° C, 4.94 ml of a solution of n-butyllithium in nephras (0.2 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, water 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 ° C.

The properties of the rubber obtained are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Tables 4-5.

Example 2. Polymerization in the presence of n-butyllithium and SiMe ₂ Cl ₂

The process for producing styrene-butadiene rubbers is carried out according to the procedure described in Example 1, except that upon reaching a 100% degree of conversion, a solution of SiMe ₂ Cl ₂ (0.2 M) is added in an amount of 0.5 of the molar amount of initiator taken . Modification of SiMe ₂ Cl _{2 is} carried out at 60 ° C for 30 minutes.

The amount of reagents in the synthesis of rubber and the properties of the rubber obtained are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Tables 4-5.

Example 3. Polymerization in the presence of n-butyllithium and a special monomer - MMS (morpholylmethyl styrene)

The process for producing styrene-butadiene rubbers is carried out according to the procedure described in Example 1, except that before introducing the initiator into the charge, a special monomer, MMS, is added in the amount of 2.6% by weight. on rubber.

The amount of reagents in the synthesis of rubber and the properties of the rubber obtained are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Tables 4-5.

Example 4. Polymerization in the presence of n-butyllithium, MMS and SiMe ₂ Cl ₂

The process for producing styrene-butadiene rubbers is carried out according to the procedure described in Example 1, except that before introducing the initiator into the charge, a special monomer, MMS, is added in the amount of 2.6% by weight. on rubber and upon reaching a 100% degree of conversion add a solution of SiMe ₂ Cl ₂ (0.2 M) in an amount of 0.5 of the molar amount of the taken initiator. Modification of SiMe ₂ Cl _{2 is} carried out at 60 ° C for 30 minutes.

The amount of reagents in the synthesis of rubber and the properties of the rubber obtained are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Tables 4-5.

Example 5. Polymerization in the presence of an oligomeric initiator based on DEAMS-Li

The process for producing styrene-butadiene rubbers is carried out according to the procedure described in Example 1, except that an oligomeric initiator obtained on the basis of DEAMS is used as an initiator instead of n-butyllithium.

The amount of reagents in the synthesis of rubber and the properties of the rubber obtained are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Tables 4-5.

Example 6. Polymerization in the presence of an oligomeric initiator based on DEAMS-Li and SiMe ₂ Cl ₂

The process for producing styrene-butadiene rubbers is carried out according to the procedure described in Example 1, except that instead of n-butyllithium, an oligomeric initiator obtained on the basis of DEAMS is used as an initiator, and when a 100% conversion is achieved, a SiMe ₂ Cl ₂ solution is added (0.2 M) in an amount of 0.5 of the molar amount of initiator taken. Rubber modification of SiMe ₂ Cl _{2 is} carried out at 60 ° C for 30 minutes.

The amount of reagents in the synthesis of rubber and the properties of the rubber obtained are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Tables 4-5.

Example 7. Polymerization in the presence of an oligomeric initiator based on DEAMS-Li and a special MMS monomer.

The process for producing styrene-butadiene rubbers is carried out according to the procedure described in Example 1, except that before introducing the initiator into the charge, a special monomer, MMS, is added in the amount of 2.6% by weight. on rubber and as an initiator, instead of n-butyl lithium, an oligomeric initiator obtained on the basis of DEAMS is used.

The amount of reagents in the synthesis of rubber and the properties of the rubber obtained are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Tables 4-5.

Example 8. Polymerization in the presence of an oligomeric initiator based on DEAMS-Li, a special monomer MMS and SiMe ₂ Cl ₂

The process for producing styrene-butadiene rubbers is carried out according to the procedure described in Example 1, except that before introducing the initiator into the charge, a special monomer, MMS, is added in the amount of 2.6% by weight. on the rubber and as an initiator, instead of n-butyl lithium, an oligomeric initiator obtained on the basis of DEAMS is used, and upon reaching 100% conversion, a solution of SiMe ₂ Cl ₂ (0.2 M) is added in an amount of 0.5 of the molar amount taken initiator. Rubber modification of SiMe ₂ Cl _{2 is} carried out at 60 ° C for 30 minutes.

The amount of reagents in the synthesis of rubber and the properties of the rubber obtained are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Tables 4-5.

Example 9. Polymerization in the presence of an oligomeric initiator based on DIPAMS-Li

The process for producing styrene-butadiene rubbers is carried out according to the procedure described in Example 1, except that an oligomeric initiator obtained on the basis of DIPAMS is used instead of n-butyllithium as an initiator.

The amount of reagents in the synthesis of rubber and the properties of the rubber obtained are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Table 4.

Example 10. Polymerization in the presence of an oligomeric initiator based on DIPAMS-Li and a special monomer MMS

The process for producing styrene-butadiene rubbers is carried out according to the procedure described in Example 1, except that before introducing the initiator into the charge, a special monomer, MMS, is added in the amount of 2.6% by weight. on rubber and as an initiator, instead of n-butyl lithium, an oligomeric initiator obtained on the basis of DIPAMS is used.

The amount of reagents in the synthesis of rubber and the properties of the rubber obtained are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Table 4.

Example 11. Polymerization in the presence of an oligomeric initiator based on DIPAMS-Li, a special monomer MMS and SiMe ₂ Cl ₂

The process for producing styrene-butadiene rubbers is carried out according to the procedure described in Example 1, except that before introducing the initiator into the charge, a special monomer, MMS, is added in the amount of 2.6% by weight. on rubber and as an initiator, instead of n-butyllithium, an oligomeric initiator obtained on the basis of DIPAMS is used, and upon reaching 100% conversion, a solution of SiMe ₂ Cl ₂ (0.2 M) is added in an amount of 0.5 of the molar amount taken initiator. Rubber modification of SiMe ₂ Cl _{2 is} carried out at 60 ° C for 30 minutes.

The amount of reagents in the synthesis of rubber and the properties of the rubber obtained are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Table 4.

Example 12 (comparative). Commercially Available Rubber

The properties of commercially available rubber, which is branched and functionalized, are presented in Table 2. The properties of the rubbers obtained using this rubber are shown in Table 4-5.

The rubbers obtained according to examples 1-12, including comparative and commercially available samples, were tested in the composition of the rubber composition for the tread of passenger cars (Recipe 1) and standard rubber composition (GOST ISO 2322-2013, Example A) 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 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 rpm;

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 rpm;

Stage 3 - introduction to the rubber composition of the vulcanizing group; the initial temperature of the chamber walls is 80 ° C, the maximum is not more than 110 ° C, the rotor speed is 40 rpm. 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, Example A.

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 rubber compositions obtained by Recipe 1: 160 ° C for 20 min to assess the deformation-strength properties and within 30 min to assess abrasion. The vulcanization modes of rubber compositions obtained according to Recipe 2 are given in GOST ISO 2322-2013. Vulcanization properties (t _s1 - time to start vulcanization, t ₅₀ - time to reach 50% degree of vulcanization, t ₉₀ - optimal vulcanization time, M _H - maximum torque, M _L - minimum torque, R _V - vulcanization rate) was evaluated on the device RPA 2000, 160 ° C × 30 min, according to ASTM ASTM D 5289-07. Evaluation of the main indicators of vulcanizates in tension ( f ₃₀₀ - conditional stress at 300% elongation, f _p - conditional tensile strength _, ε _rel - relative elongation at break) was carried out according to ASTM D 412-98. Abrasion according to Shopper-Schlobach (ABR) (Method B) was evaluated according to GOST 23509-79. The hysteresis properties (the tangent of the angle of mechanical losses tanδ) 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 -60 ° C up to + 60 ° С, rate of temperature increase - 2 ° / min.

Table 2. The structure and properties of the rubbers described in Examples 1-12

No. Initiator dosage, mmol / 100 g Dosage of DTGFP, mmol / 100g Dose special monomer% wt. Dose SiMe ₂ Cl ₂ mmol / 100g Molecular weight characteristics Microstructural characteristics (1H NMR) T _article , ^about With Viscosity
by mooney Note M _n *
10 ^-3 M _w *
10 ^-3 M _w / M _n St
% of the mass. 1,2-Bt,
% of the mass.
(100% Bd) 1.4,
% of the mass. (100% Bd) ASt,
% mass one 0.8 one - - 241 296 1,2 22.4 69.3 30.8 0 -sixteen 90 Buli
Sample Comparison 2 0.8 one - 0.40 211 256 1,2 22.2 69.8 30,2 0 -eighteen 68 BuLi + SiMe ₂ Cl ₂ 3 0.9 1,1 2.6 - 219 310 1.4 21.5 67.6 32,5 2,51 -eighteen 71 BuLi + MMS 4 1,0 1.3 2.6 0.5 225 284 1.3 22.5 67.7 32,3 2,56 -17 83 BuLi + SiMe ₂ Cl ₂ + MMS 5 1,1 1.4 - - 224 333 1,5 23.8 70.8 29.2 0 -14 82 DEAMSLi 6 1,1 1.4 - 0.55 209 291 1.4 22.6 70.3 29.7 0 -14 112 DEAMS Li + SiMe ₂ Cl ₂ 7 1,2 1,5 2.6 - 209 392 1.9 21.7 69.8 30,2 2,57 -17 one hundred DEAMSLi + MMS 8 1,1 1,5 2.7 0.55 233 480 2.1 22.2 68,4 31.6 2,56 -eighteen 120 DEAMS Li ++ MMS + SiMe ₂ Cl ₂ nine 1,1 1.4 - - 216 276 1.3 23.9 70,2 29, 8 0 -sixteen 72 DIPAMS Li 10 1,2 1,5 2.6 - 197 268 1.4 22.4 68.6 31,4 2,58 -sixteen 78 DIPAMS Li + MMS eleven 1,2 1,5 2.6 0.6 231 476 2.1 22.3 70,2 29.8 2,56 -fifteen 101 DIPAMS Li + MMS + SiMe ₂ Cl ₂ 12 (compare) n / a n / a n / a n / a 133 240 1.8 19.3 63.3 36.7 n / a -22 55 Commercially Available Rubber

Table 3. The composition of the rubber compositions

Name of ingredients, manufacturer Content, parts by weight per 100 parts by weight rubber Recipe 1 Recipe 2 Natural rubber TSR RSS-1 30,0 - Solution styrene butadiene rubber according to examples 1-5 70.0 50,0 Rubber mortar butadiene-styrene rubber DSSK-2560 - 50,0 Carbon black N 339 (Yaroslavl plant of carbon black) 13.0 50,0 Precipitated Silica Fillers 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 - Mercaptobenzothiazole (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 4. Properties of standard rubbers (Recipe 2)

Index Example 12 one 2 3 5 6 7 8 nine 10 eleven Commercially Available Rubber Sample Comparison BuLi + SiMe ₂ Cl ₂ BuLi +
MMS DEAMSLi DEAMS Li + SiMe ₂ Cl ₂ DEAMSLi + MMS DEAMS Li + MMS + SiMe ₂ Cl ₂ DIPAMS Li DIPAMS Li + MMS DIPAMS Li + MMS + SiMe ₂ Cl ₂ Vulcanization characteristics, RPA 2000, 160 ° C × 30 min t _s1 , min 2.6 2,5 2.7 2.7 2.6 2.2 1.9 2.2 2,3 2,3 2,4 t ₅₀ min 8.9 10.1 8.1 9.3 8.1 6.2 4.8 5.5 7.9 6.4 6.7 t ₉₀ min 17.6 18.8 17.6 17.9 17.6 15,5 16,0 15.8 17.3 16,0 16.3 M _H -M _L , dNm 30.5 30.8 27.8 29.8 29.5 28.8 27.1 27.3 29.5 27.1 26.3 Properties of vulcanizates f ₃₀₀ , MPa 13.9 13.9 13.6 15.3 15.3 14.6 14.8 16,2 15,2 14,4 14.6 f _p , MPa 21.3 22.4 22.9 22.6 24.8 24.1 22.7 22.4 22.4 22.6 22.3 ε _rel ,% 430 440 460 420 450 460 420 410 410 430 420 Hysteresis properties (DMA 242 C, 1%, 10 Hz) tgδ (-20 ° C) 0,300 0.214 0.190 0.187 0.152 0.136 0.175 0.162 0.159 0.174 0.164 tgδ (0 ° C) 0.674 0.797 0.810 0.839 0.891 0.864 0.883 0.872 0.877 0.861 0.871 tgδ (60 ° C) 0.208 0.214 0.210 0,207 0.199 0.197 0.192 0.180 0.196 0.190 0.183 Relative change in hysteretic properties and abrasion Δ tgδ (-20 ° C),% one hundred 129 137 138 149 155 142 146 147 142 145 Δ tgδ (0 ° C),% one hundred 118 120 125 132 128 131 129 130 128 129 Δ tgδ (60 ° C),% one hundred 97 99 one hundred 104 105 108 113 106 109 112 Δ tgδ (-20 ° C),% one hundred 111 113 129 136 118 124 126 119 123 Δ tgδ (0 ° C),% one hundred 102 105 112 108 111 109 110 108 109 Δ tgδ (60 ° C),% one hundred 102 103 107 108 112 116 113 111 114

As the results of testing rubber compositions filled with carbon black (Table 4, Recipe 1) show, rubbers with triple functionalization (Examples 8 and 11) obtained according to the present invention provide rubbers with the lowest hysteresis losses (tanδ _{60 ° C} ) at a temperature of 60 ° C superior to non-functionalized rubber (Example 1), rubbers with functionalization by one of the modifying agents (Examples 2, 3, 5, 9) and with double functionalization (Examples 6, 7, 10). The tanδ value of _{60 ° C} characterizes the amount of rolling losses during tire operation. In terms of tanδ _{0 ° C} , which characterizes wet grip, rubbers with triple functionalization (Examples 8 and 11) are at the level of other modified rubbers described in Examples 2,3,5,9,6,7,10. Vulcanization parameters and physicomechanical properties of vulcanizates do not undergo significant changes when using rubbers with triple functionalization in the rubber composition (Examples 8 and 11), which limit the scope of application of rubbers.

In the case of tread rubber (Table 5), in which the main filler is precipitated colloidal silicic acid, the use of rubber with triple functionalization (Example 8) also has a positive effect on tanδ of _{60 ° C} , when compared with non-functionalized rubber (Example 1), and with functionalized rubbers, including commercially available rubber (Examples 2,3,4,5,6,11,12). The remaining properties of the vulcanizates do not undergo significant changes.

Table 5. Properties of tread rubber (Recipe 1)

Index Sample Code 12 one 2 3 4 5 6 7 8 Commercially Available Sample Sample Comparison BuLi + SiMe ₂ Cl ₂ BuLi + MMS BuLi + MMS + SiMe ₂ Cl ₂ DEAMSLi DEAMS Li + SiMe ₂ Cl ₂ DEAMSLi + MMS DEAMS Li + MMS + SiMe ₂ Cl ₂ Properties of vulcanizates f ₃₀₀ , MPa 9.6 9.6 9,4 10.8 10.1 9.9 11.5 10.5 10.7 f _p , MPa 16.3 15.6 16,0 16.5 17.1 17.5 17.8 17.6 18.2 ε _rel ,% 480 460 460 440 480 490 430 460 470 Abrasion resistance ABR, mm ³ 136 142 141 144 146 144 144 143 139 Hysteresis properties (DMA 242 C, 1%, 10 Hz) tgδ (0 ° C) 0,358 0.329 0.361 0.331 0.382 0.407 0.440 0.407 0.394 tgδ (60 ° C) 0.182 0.183 0.162 0.176 0.157 0.163 0.159 0.157 0.147 Relative change in hysteretic properties and abrasion Δtgδ (0 ° C),% one hundred 109 one hundred 115 122 118 122 118 Δtgδ (60 ° C),% one hundred 112 104 115 111 114 115 120 Δ ABR,% one hundred one hundred 98 97 98 98 99 102

Claims (22)

1. A method for producing rubber by anionic solution polymerization of a conjugated diene or by copolymerization of a conjugated diene and a vinyl aromatic compound in an organic solvent in the presence of an organolithium N, N-disubstituted aminomethylstyrene oligomeric initiator, a special N, N-disubstituted aminomethylstyrene monomer and a terminal functionalizing CH ₃ ) ₂ Hal ₂ Si, where Hal is a halogen atom. 2. The method of producing rubber according to claim 1, where a special N, N-disubstituted aminomethylstyrene monomer is represented by the formula (II)

(Ii) where R ₃ represents a —CH ₂ —Hal group, R represents a —CH ₂ N (R ₁ ) (R ₂ ) group in which R ₁ and R ₂ may be the same or different and independently represent alkyl, cycloalkyl, aryl or heteroaryl or R ₁ and R ₂ taken together with nitrogen form a 5-6 membered heterocyclic or 5 membered heteroaromatic ring, optionally containing one or more additional heteroatoms selected from nitrogen, oxygen or sulfur, Hal is a halogen atom, x = 1, y = 0 or x = 0, y = 1. 3. The method of producing rubber according to claim 2, where the alkyl has one or more substituents selected from a hydroxy group, dialkylamino group, alkoxy group, aryloxy group, alkylsulfanyl group, arylsulfanyl group. 4. The method for producing rubber according to claim 2, wherein the aryl has one or more substituents selected from halogen, alkyl, dialkylamino group, alkoxy group, aryloxy group, alkylsulfanyl group, arylsulfanyl group, aryl. 5. The method of producing rubber according to claim 2, where heteroaryl has one or more substituents selected from halogen, alkyl, dialkylamino group, alkoxy group, aryloxy group, alkylsulfanyl group, arylsulfanyl group, aryl. 6. The method of producing rubber according to claim 1, where the organolithium N, N-disubstituted aminomethylstyrene oligomeric initiator is a reaction product of organolithium compounds and compounds according to any one of paragraphs. 2-5. 7. The method of producing rubber according to claim 1, where the terminal functionalizing agent is dimethyldichlorosilane. 8. The method of producing rubber according to claim 1, where the conjugated dienes contain from 4 to 12 carbon atoms, preferably 1,3-butadiene and / or isoprene. 9. The method of producing rubber according to claim 1, where 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 , methoxystyrene, vinyl mesitylene, divinylbenzene, 1-vinylnaphthalene, 2,4,6-trimethylstyrene, preferably styrene or α-methylstyrene. 10. The method of producing rubber according to claim 1, where the special monomers are added in an amount of from 0 to 40% wt., Preferably from 0.1 to 10% wt., More preferably from 0.5 to 5% wt. based on the weight of the polymer. 11. The method of producing rubber according to claim 1, where the polymerization is carried out at a temperature of from -30 ° C to 120 ° C, preferably from 0 ° C to 100 ° C, more preferably from 15 ° C to 80 ° C. 12. The method of producing rubber according to claim 1, where the molar ratio of initiator: rubber is from 1 to 50 mol / t of rubber, preferably from 2 to 25 mol / t of rubber, more preferably from 3 to 10 mol / t of rubber. 13. The method of producing rubber according to claim 1, where as the solvents of anionic polymerization using saturated hydrocarbons, preferably containing from 3 to 12 carbon atoms, or mixtures thereof. 14. Rubber for the manufacture of a rubber composition based on polymers of a conjugated diene or copolymers of a conjugated diene and a vinyl aromatic compound, obtained by the method according to any one of claims. 1-13. 15. A rubber composition for making tires containing rubber according to claim 14. 16. The rubber composition according to claim 15, further comprising components selected from the group consisting of natural rubber, colloidal silicic acid, carbon black, a silanizing agent, a vulcanizing agent, and traditional processing aids such as additives that improve the dispersion of fillers and the processability of rubber compositions, plasticizers , antioxidants / antiozonants / physical and chemical anti-haze agents, modifiers, fillers, including fibrous, layered, polymeric, anti-roaring agents A version during vulcanization and increasing the heat resistance of rubbers. 17. The use of the rubber composition according to paragraphs. 15-16 for the manufacture of treads for passenger tires.