RU2675540C1 - Method for preparing a system for modification of polydienes, modified polydienes, rubber mixtures based on modified polydienes - Google Patents

Abstract

FIELD: technological processes.SUBSTANCE: invention relates to the production of synthetic rubbers used in the manufacture of tires, rubber products, electrical and other fields, and specifically to a method for producing a system for modifying polydienes. Method for producing a system for modifying polydienes is described, including the interaction of a compound selected from the group of amines and at least one compound containing at least two maleic fragments. Also described are a system for modifying polydienes, a method for producing modified polydienes, a modified polydiene, and rubber compounds.EFFECT: highly effective system for modifying polydienes has been proposed, providing rubber based on the obtained polydiene with increased wear resistance, physicomechanical properties, as well as improved elastic-hysteresis properties.20 cl, 3 tbl, 18 ex

Description

FIELD OF THE INVENTION

The invention relates to the production of synthetic rubbers used in the manufacture of tires, rubber products, in the electrical and other fields. Namely, the present invention relates to a method for producing a system for modifying polydienes by reacting a compound selected from the group of amines and at least one compound containing at least two maleic fragments and a modified polydiene obtained in a medium organic solvent on a catalytic system comprising lanthanide, an organoaluminum compound and a halogen-containing component, followed by the interaction of the obtained polymer and the system to obtain modi polycyene diene. Also, the present invention relates to rubber mixtures obtained on the basis of modified polydienes.

State of the art

Today, the main consumers of synthetic polymers are tire companies, as a result of which increased demands are made primarily on such polymer characteristics as wear resistance, wet and icy grip, low rolling resistance, which, in turn, leads to lower fuel consumption. One of the directions for solving these problems is the introduction of functional groups in the composition of polymer molecules. The most common method of introducing functional groups is post-polymerization processing of reactive polymers - modification at the ends of chains. The presence of functional groups in the polymer structure helps to reduce the number of free ends of the polymer chains, improves interaction with fillers, prevents the agglomeration of their particles and, as a result, provides increased wear resistance of tread rubbers and reduced hysteresis losses (F. Kuperman. New rubbers for tires. Priority requirements Evaluation Methods, Scientific and Technical Center NIISHP, Moscow, 2005, p. 329).

It should be borne in mind that various modifying agents manifest themselves in different ways. The choice of the optimal modifier depends on the catalytic system used, on the nature of the reactive polymer chains and on the final polymer properties to be obtained.

A known method of postpolymerization and polymerization modification of neodymium 1,4-cis-polybutadiene by introducing maleic fragments. At the same time, the author notes a change in the molecular parameters and plasto-elastic obtained properties of polybutadiene (V. Zolotarev. On the mechanism of the post-polymerisation modification of neodymium 1,4-cis-polybutadiene. Industrial production and use of elastomers, No. 3, 2015, p. 3-5).

In RU2425845, a modified polymer is prepared by polymerizing a conjugated diene compound in the presence of a catalyst containing a lanthanide rare earth compound in an organic solvent, followed by modifying the resulting polymer containing an active organometallic center with a modifier. Moreover, the modifier has at least one functional group selected from the group consisting of an azacyclopropane group, ketone groups, carboxyl groups, thiocarboxyl groups, carbonates, carboxylic anhydrides, metal salts of carboxylic acids, acid halide, urea groups, thiourea groups, amido groups, thioamido groups, isocyanate groups, thioisocyanate groups, haloisocyanogroups, epoxy groups, thioepoxy groups, imino groups, and the MZ bond (where M-Sn, Si, Ge or P, and Z is a halogen atom) and contains neither an active proton nor o ievuyu salt that deactivates the active organometallic center.

As modifiers in the patents RU 2425845 and RU 2431644 it is proposed to use a wide range of compounds, and the patents say that the modifiers can be used individually or as a mixture of two or more components. In this case, one of the essential components of the catalytic system is methylaluminoxane. Despite a number of advantages, it is known that alumoxanes have poor storage stability and contribute to an increase in polymer ash content, as well as being expensive compounds.

In US Pat. No. 8,017,695, functionalized cis-1,4-polydienes are prepared by a process comprising the following steps: (1) preparation of a reactive polymer by polymerization of a conjugated diene monomer with a lanthanide catalyst in the presence of less than 20 wt. % organic solvent based on the total weight of the monomer, organic solvent and the resulting polymer, wherein the lanthanide catalyst is a combination or reaction product of (a) a lanthanide compound, (b) aluminoxane, (c) an organoaluminum compound other than aluminoxane, and ( d) a halogen-containing compound; (2) the interaction of a reactive polymer with a functionalizing agent. According to this method, the functionalizing agent is a compound selected from the group consisting of ketones, quinones, aldehydes, amides, esters, isocyanates, isothiocyanates, epoxides, imines, aminoketones, aminothioketones, acid anhydrides, metal halides, metalloid halides, metal ethers alkoxysilanes, alkoxystannanes and mixtures thereof.

However, this method requires the use of aluminoxanes, which, as mentioned above, have several disadvantages.

The disadvantage of this method is the high dosage used functionalizing agent. This leads to an increase in the cost of the resulting product. Also, under industrial production conditions, an excess of the functionalizing agent accumulates in the circulation solvent and, when this solvent is reused, inhibits the polymerization process.

Many scientific research and development in the field of synthetic polymers are aimed at the introduction of several functional groups. So, for example, patent RU2481361 describes a method for producing a modified conjugated diene polymer, comprising a modification step (A), in which the conjugated diene polymer is subjected to a modification reaction with the introduction of an alkoxysilane compound containing two or more reaction groups, including an alkoxysilyl group and at least , one functional group selected from an epoxy group and an isocyanate group, at the active end of the conjugated diene polymer chain, and a condensation step (B) in which the residue is alk the xisilane compound introduced at the active end of the polymer chain is subjected to a condensation reaction in the presence of a condensation catalyst.

US Pat. No. 7,022,306 discloses a method for producing a modified conjugated diene polymer. The method includes the step of modifying the active end of the conjugated diene polymer with an alkoxysilane compound containing at least one functional group selected from the group consisting of (a) an epoxy group, (b) an isocyanate group and (c) a carboxyl group and the step of adding a condensation accelerator to conduct condensation reactions of alkoxysilane compounds (residue) in an aqueous solution.

From patent RU 2464280 a method for producing a modified conjugated diene polymer is known. The method includes carrying out a reaction between a modifier that includes a particular compound and a conjugated diene polymer. The modifier includes at least one compound selected from the group consisting of a number of components, wherein one of the components is an alkoxysilane compound, which in the molecular structure has at least one group selected from the group consisting of an epoxy group and isocyanate groups, and groups of compounds represented by different chemical formulas.

However, in order to maintain sufficient catalytic activity during polymerization and to obtain a polymer with a narrow molecular weight distribution, it is necessary to use a large amount of methylaluminoxane compared to a catalytic system comprising organoaluminum compounds. This leads to an increase in the ash content of the polymer. In addition, compared with organoaluminum compounds, alumoxane is an expensive component of the catalytic system, which also has poor storage stability. Also, the use of glycidyloxypropyltrimethoxysilane can lead to polymer crosslinking and gel formation.

In patent EP 1022291, a modified diene elastomer is proposed to be obtained by polymerizing a diolefin compound containing a conjugated double bond in the liquid phase in the presence of a cobalt compound, an organic aluminum compound containing a halogen atom, and water to obtain a solution containing a diene elastomer; and then the interaction of the diene elastomer with an elastomer-modifying compound. The elastomer modifying compound is an organic silicon compound having an amino group and an alkoxy group selected from the group consisting of 3-aminopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane and 3- (2-aminoethylpropyl) trimethoxysilane.

According to patent EP 2604632, it is proposed to obtain a modified conjugated diene polymer by a method comprising 1) polymerizing a conjugated diene polymer, 2) reacting the obtained polymer with a first modifier, and 3) reacting a polymer with a second modifier. According to the patent, the first modifier has the chemical formula XR ₁ -Si (R ₂ ) ₃ , where X is a functional group selected from the group consisting of an epoxypropoxy group, an isocyanate group and a 2- (3,4-epoxycyclohexyl group), R ₁ represents an alkyl group with 2-3 carbon atoms, R ₂ represents an alkyl group with 2-3 carbon atoms or an alkoxy group with 1-3 carbon atoms; the second modifier has the chemical formula R ₃ -S ₁ (R ₄ ) ₃ , where R _{3 is} selected from the group consisting of an alkyl group, an alkoxy group, an aromatic group, an aryloxy group and a cycloalkyl group with 1-12 carbon atoms, R _{4 is} selected from the group consisting of from an alkyl group, an alkoxy group, an aryloxy group and a cycloalkyl group with 1-12 carbon atoms.

RU 2599633 proposes a method for producing a functionalized polymer, comprising the steps of: (i) polymerizing a conjugated diene monomer using an anionic initiator to produce a reactive polymer; and (ii) reacting the reactive polymer with a carboxylic or thiocarboxylic acid ester containing a silylated amino group, wherein the silylated amino group is directly attached to a moiety selected from the group consisting of acyclic moieties, heterocyclic moieties and non-aromatic cyclic moieties.

From the application US 4304886 a method for producing a modified polymer is known, comprising reacting a living lithium-terminated polymer with two combining agents that provide different degrees of functionality, so that it is possible to control the degree of modification of the polymer.

The closest in technical essence and the achieved result is a method for producing a functionalized polymer disclosed in US 7671136, comprising the step of producing a pseudo-living polymer by polymerizing a conjugated diene monomer with a lanthanide catalyst and reacting the pseudo-living polymer with at least one functionalizing agent represented by the formula (I) or (II):

Where Z is a substituent that will react or interact with organic or inorganic fillers; R ¹ represents a single bond or a divalent organic group; R ² represents a monovalent organic group or a divalent organic group, which forms a cyclic organic group with R ¹³ or R ¹⁴ ; R ³ represents a single bond, a divalent organic group or a trivalent organic group, which forms a cyclic organic group with R ⁴ or R ⁵ ; R ¹³ represents a single bond, a divalent organic group or a trivalent organic group, which forms a cyclic organic group with R ² or R ¹⁴ ; R ⁴ represents a monovalent organic group or a divalent organic group, which forms a cyclic organic group with R ³ or R ⁵ ; R ¹⁴ represents a monovalent organic group or a divalent organic group, which forms a cyclic organic group with R ² or R ¹³ ; and R ⁵ represents a monovalent organic group or a divalent organic group that forms a cyclic organic group with R ³ or R ⁴ ; provided that each group attached to iminocarbon is attached via a carbon atom and R ¹ , R ² R ³ , R ⁴ , R ⁵ , R ¹³ , R ¹⁴ and Z are substituents that will not protonate the pseudo-living polymer. It is also said that functionalized polymers are prepared by contacting one or more functionalizing agents, including mixtures thereof, with a pseudo-living polymer.

The resulting polymers are characterized by a very narrow molecular weight distribution, which negatively affects the processability, namely, inevitable problems with the selection and drying.

Disclosure of Invention

The objective of the present invention was to improve the plasto-elastic properties of the polymer while maintaining the molecular weight characteristics at the required level, to improve the interaction of the polymer with various fillers at the rubber mixing stage, to improve the elastic-hysteresis properties of polydienes.

The task is achieved by obtaining a system for modifying polydienes by reacting a compound selected from the group of amines and at least one compound containing at least two maleic fragments; obtaining modified polydienes using the above system and obtaining rubber compounds based on the modified polydiene obtained according to the invention.

The method of obtaining modified polydienes includes the following stages:

i) preparation of a catalytic system consisting of (A) a lanthanide, (B) an organoaluminum compound, (C) a conjugated diene, and (D) a halogen-containing component taken in a molar ratio of (A) :( B) :( C) :( D) equal to 1: (8-30) :( 5-30) :( 1.5-3.0);

ii) carrying out the polymerization of the conjugated diene in an organic solvent medium in the presence of the catalyst system obtained in stage i);

iii) introducing into the polymer the inventive system for modification.

EFFECT: obtaining a highly effective system for modifying polydienes, which retains its activity unchanged for at least 60 hours. Also the technical result of the present invention is the receipt of a modified polydiene having improved adaptability at the stage of rubber mixing; rubbers based on the obtained polydiene have increased wear resistance, physical and mechanical properties, as well as improved elastic-hysteresis properties (rolling resistance, wet grip).

According to the present invention, dimethylamine, methylamine, trimethylamine, ethylamine, diethylamine, methylethylamine, n-propylamine, isopropylamine, n-butylamine, dibutylamine, iso-butylamine, phenylamine can be used to prepare a system for modification as a compound selected from the group of amines. , diphenylamine, methylphenylamine, 2,2-diphenylethylamine, 3,3-diphenylpropylamine, butylmethylamine, 1-benzyl-2,2-diphenylethylamine, methylpropylamine, methylbutylamine, ethylbutylamine, ethylpropylamine, etc.

In a preferred embodiment, butylamine, phenylamine are used as compounds from the amine group.

Most preferably, the amines are selected from silicon-containing or sulfur-containing amines.

As a compound selected from sulfur-containing amines, 2-aminoethylthioethyl- (triacetoxy) silane, 3-aminopropylthioethyl (triethoxy) silane, 6- (3-triethoxysilylpropyl) amino-1,3,5-triazine-2,4- can be used dithiol, 2,2-thiobis (ethylamine).

In the most preferred embodiment, 2-aminoethylthioethyl- (triacetoxy) silane, 3-aminopropylthioethyl (triethoxy) silane, 2,2-thiobis (ethylamine) are used as compounds from the group of sulfur-containing amines.

As the compound selected from silicon-containing amines, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane is used

N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane,

N, N-bis (trimethylsilyl) aminopropyltriethoxysilane,

N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane,

N, N-bis (trimethylsilyl) aminoethyltrimethoxysilane,

N, N-bis (trimethylsilyl) aminoethyltriethoxysilane,

N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane,

N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane,

N, N-bis (triethylsilyl) aminopropylmethyldimethoxysilane,

N, N-bis (triethylsilyl) aminopropyltrimethoxysilane,

N, N-bis (triethylsilyl) aminopropyltriethoxysilane,

N, N-bis (triethylsilyl) aminopropylmethyldiethoxysilane,

N, N-bis (triethylsilyl) aminoethyltrimethoxysilane,

N, N-bis (triethylsilyl) aminoethyltriethoxysilane,

N, N-bis (triethylsilyl) aminoethylmethyldimethoxysilane,

N, N-bis (triethylsilyl) aminoethylmethyldiethoxysilane,

N, N ', N'-Tris (trimethylsilyl) -N- (2-aminoethyl) -3aminopropyltriethoxysilane,

N, N ', N'-Tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane,

N, N ', N'-Tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,

N, N ', N'-Tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane,

3-dimethylaminopropyltrimethoxysilane,

3-diethylaminopropyltrimethoxysilane,

3-dimethylaminopropyltriethoxysilane,

3-diethylaminopropyltriethoxysilane,

3-ethylmethylaminopropyltrimethoxysilane,

3-ethylmethylaminopropyltriethoxysilane,

3-dimethylaminopropiomethyldimethoxysilane,

3-diethylaminopropylmethyldimethoxysilane,

3-dimethylaminopropylethyldimethoxysilane,

3-diethylaminopropylethyldimethoxysilane,

3-dimethylaminopropyl dimethylmethoxysilane,

3-dimethylaminopropylethylmethoxysilane,

3-diethylaminopropyl dimethylmethoxysilane,

3-diethylaminopropyl diethylmethoxysilane,

3-ethylmethylaminopropylmethyldimethoxysilane,

3-methyl-3-ethylaminopropylethyldimethoxysilane,

3-dimethylaminopropylmethyldiethoxysilane,

3-diethylaminopropylmethyldiethoxysilane,

3-dimethylaminopropylethyldiethoxysilane,

3-diethylaminopropylethyldiethoxysilane,

3-dimethylaminopropyl dimethylethoxysilane,

3-dimethylaminopropyl diethylethoxysilane,

3-diethylaminopropyl dimethylethyl ethoxysilane,

3-diethylaminopropyl diethylethoxysilane,

3-ethylmethylaminopropylmethyldiethoxysilane,

3-ethylmethylaminopropylethyldiethoxysilane,

3-di (methoxymethyl) aminopropyltrimethoxysilane,

3-di (methoxyethyl) aminopropyltrimethoxysilane,

3-di (methoxymethyl) aminopropyltriethoxysilane,

3-di (methoxyethyl) aminopropyltriethoxysilane,

3-di (ethoxyethyl) aminopropyltrimethoxysilane,

3-di (ethoxymethyl) aminopropyltrimethoxysilane,

3-di (ethoxyethyl) aminopropyltriethoxysilane,

3-di (ethoxymethyl) aminopropyltriethoxysilane,

3-di (trimethylsilyl) aminopropyltrimethoxysilane,

3-di (trimethylsilyl) aminopropyltriethoxysilane,

3-di (tert-butyldimethylsilyl) aminopropyltrimethoxysilane,

3-di (tert-butyldimethylsilyl) aminopropyltriethoxysilane,

3-di (trimethylsilyl) aminopropylmethyldimethoxysilane,

3-di (trimethylsilyl) aminopropylmethyldiethoxysilane,

3-di (tert-butyldimethylsilyl) aminopropylmethyldimethoxysilane,

3-di (tert-butyldimethylsilyl) aminopropylmethyldiethoxysilane,

3-di (trimethylsilyl) aminopropyl dimethylmethoxysilane,

3-di (trimethylsilyl) aminopropyl dimethylethoxysilane,

3-di (tert-butyldimethylsilyl) aminopropyl dimethylmethoxysilane,

3-di (tert-butyldimethylsilyl) aminopropyl dimethylethoxysilane

N, N-bis (triethylsilyl) aminopropylmethyldimethoxysilane,

N, N-bis (trimethylsilyl) aminopropylaethyl dimethoxysilane,

N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane,

N, N-bis (trimethylsilyl) aminopropyltriethoxysilane,

3-dimethylaminopropyltrimethoxysilane,

3-diethylaminopropyltrimethoxysilane,

3-dimethylaminopropyltriethoxysilane,

3-diethylaminopropyltriethoxysilane.

Most preferably, silicon-containing amines include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminophenyltrimethoxysilane, aminophenyltriethoxysilane, 3- (N-methylamino) propyltrimethoxysilane,

3- (N-methylamino) propyltriethoxysilane,

N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,

2- (6-aminohexyl) aminopropyltrimethoxysilane.

In accordance with the present invention, an amine or a mixture of amines, preferably silicon and sulfur-containing amines, is used to prepare a system for modification. The use of these compounds as a component of the system is preferable to other various compounds, since the combination of the functional groups present in them - an amino group and a silicon atom / sulfur atom, in the case of using silicon and sulfur-containing amines provides improved interaction with silicic acid fillers and carbon black at the stage of rubber mixing, as a result, the resulting rubbers have consistently high consumer (mainly elastic-hysteretic) properties (US patent 775 0087).

To obtain a system for modifying polydienes in accordance with the invention, it is also necessary to use at least one compound containing at least two maleic fragments. One maleic fragment gives a lower degree of branching and therefore, in the future, the processability of rubber compounds will be worse in comparison with a polymer modified using two or more maleic fragments.

Thanks to the reaction of the addition of the amino group to maleic fragments, a stable complex is obtained containing nitrogen and oxygen atoms, which has a positive effect on the elastic-hysteresis properties of the rubber compounds. And when using silicon / sulfur-containing amines, functionalized rubbers have a high affinity for silicic fillers and carbon blacks.

As a compound containing maleic fragments, maleized polybutadiene (MPB) containing from 4 to 20 wt.% Can be used. maleic anhydride, and having a molecular weight of from 1200 to 8000 g / mol.

In the most preferred embodiment, as the compound containing maleic fragments, maleated polybutadiene containing from 5 to 13% wt. maleic anhydride, with a molecular weight of from 2500 to 5000 g / mol.

The molar ratio of the modifiers used according to the invention in the system for modifying polydienes calculated as neodymium is (0.1-10): 1. This ratio allows you to get polydiene with optimal plasto-elastic properties and a high content of 1,4-cis units - at least 96% of the mass.

The preferred molar ratio of the system for modification is from 0.5 to 5.0 per 1 mol of neodymium.

Most preferably, 0.5 to 2.0 mol of the system is used for modification.

The molar ratio of maleized polybutadiene to amine is (0.5-1.0): 1. It is most preferable to use a system for modifying polydienes with a molar ratio of components of 1: 1.

An increase in the molar dosage of the amine above the range proposed by the invention does not lead to a significant change in the properties of rubber, on the contrary, a deterioration of such an indicator as elastic recovery can be observed. With a decrease in the molar dosage of the amine, the positive effect of using the system for modification also decreases.

A system for modification is obtained by mixing a compound selected from the group of amines and at least one compound containing at least two maleic fragments within 3 to 150 minutes. A longer mixing time is not necessary, since the indicated time is sufficient for the interaction between the components of the system and the formation of a stable complex. The mixing is carried out at a temperature of from 20 to 60 ° C. Pressure control is also not required.

The system for modification can be prepared in advance, immediately before polymerization, simultaneously or after polymerization, since this does not affect the final properties of the system.

It was found that the system for modifying polydienes retains its properties unchanged for more than 3 days. During the experiments, a system obtained at different time periods was used. Supporting data are shown in table 1.

The method of producing modified polydienes includes three stages, namely: preparation of a catalytic complex, polymerization using the above complex, adding a system for modification according to the invention to the obtained polymer.

To obtain the catalytic complex according to the invention, lanthanides are used compounds which include at least one atom of lanthanide, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium . Preferred are neodymium compounds.

Compounds containing lanthanides include, but are not limited to such compounds as: carboxylates, organophosphates, organophosphonates, organophosphinates, carbamates, dithiocarbamates, lanthanides xanthates, β-diketonates, halides, oxyhalides, alcoholates.

Neodymium carboxylates include neodymium formate, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate neodymium, neodymium neodymium (trade name, versatate) neodymium naphthenate, neodymium stearate, neodymium oleate, neodymium benzoate and neodymium picolinate.

Neodymium organophosphates include neodymium dibutyl phosphate, neodymium diphenyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis (1-methylheptyl) neodymium bis (2-ethylhexyl) neodymium bis (2-ethylhexyl) neodymium didecyl phosphate , dioctadecyl neodymium phosphate, bis (n-phenylphenyl) neodymium phosphate, butyl (2-ethylhexyl) neodymium phosphate, (1-methylphenyl) (2-ethylhexyl) neodymium phosphate and (2-ethylhexyl) (n-nonylphenyl) neodymium phosphate.

Neodymium organophosphonates include neodymium butylphosphonate, neodymium pentylphosphonate, neodymium hexylphosphonate, neodymium heptylphosphonate, neodymium octylphosphonate, (1-methylheptyl) neodymium phosphonate, neodymium phosphate, neodymiumphosphonate phosphonate, neodylphosphonate phosphonate n-nonylphenyl) neodymium phosphonate, butyl (butylphosphonate) neodymium, pentyl (pentylphosphonate) neodymium, hexyl (hexylphosphonate) neodymium, heptyl (heptylphosphonate) neodymium, octyl (octylphosphonate) neodymium, (1 (methylheptyl) 1-methylheptyl) phosphonate) neodymium, (2-ethylhexyl) ((2-ethylhexyl) phosphonate) neodymium, decyl (decylphosphonate) neodymium, dodecyl (dodecylphosphonate) neodymium, octadecyl (octadecylphosphonate) neodymium, phenyl phenylatefonate (oleyl) ) neodymium, (n-nonylphenyl) ((n-nonylphenyl) phosphonate) neodymium, butyl ((2-ethylhexyl) phosphonate) neodymium, (2-ethylhexyl) (butylphosphonate) neodymium, (1-methylheptyl) ((2-ethylhexyl) phosphonate) neodymium, (2-ethylhexyl) ((1-methylheptyl) phosphonate) neodymium, (2-ethylhexyl) ((n-nonylphenyl) phosphonate) neodymium and (p-nonylphenyl) ((2-ethylhexyl) phosphonate) neodymium but.

Neodymium organophosphinates include neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, (1-methylheptyl) neodymium phosphinate, neodymium phosphate, neodymium phosphate phosphate, neodymium phosphate phosphate, neodymium phosphate phosphate, neodymium phosphate phosphate n-nonylphenyl) neodymium phosphate, neodymium dibutyl phosphinate, neodymium dipentyl phosphinate, neodymium dihexyl phosphinate, neodymium diheptyl phosphinate, neodymium dioctyl phosphinate, neodymium bis (1-methylheptyl) nephosphate, bis- ( 2-ethylhexyl) neodymium phosphate, tris- [bis- (2-ethylhexyl) phosphate] neodymium, neodymium didecylphosphinate, neodymium diddecylphosphinate, neodymium dioctadecylphosphinate; neodymium dioleylphosphinate, neodymium diphenylphosphinate, neodymium bis- (n-nonylphenyl) neodymium phosphate, neodymium butyl (2-ethylhexyl) neodymium phosphate, (1-methylheptyl) (2-ethylhexyl) neodymium phosphate and (2-ethylhexyl) (n-nonylphenyl phosphine) .

Most preferably, the use of carboxylates of neo acids. Structurally, non-acids contain a fragment of a trialkylcarboxylic acid (branched α, α'-carboxylic acid). Derivatives of more soluble in hydrocarbon solvents of non-acids are faster and more fully alkylated, which leads to the production of more active catalytic compounds.

Preferred are carboxylates, neodymium phosphates, most preferably neodymium neodecanoate, tris [bis (2-ethylhexyl) phosphate] neodymium.

As the organoaluminum compound in the method according to the invention, trialkyl aluminum, triphenyl aluminum or dialkylaluminium hydrides, aluminum alkyl dihydrides in particular, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-iso-propylaluminum, tri-n-butylaluminum, tri-iso-aluminum are used tri-tert-butylaluminum, triphenylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, diethylaluminum hydride, di-n-propylaluminium hydride, di-n-butylaluminum hydride, di-iso-butylaluminum hydride, d , di-iso-hexylaluminium hydride, dioctylaluminium hydride, di-iso-actylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenyl-iso-propylaluminum hydride, phenyl-n-butylaluminum hydride, benzyl-ethyl-butyl-ethyl-benzyl-ethyl-butyl-ethyl-benzyl-ethyl-butyl-ethyl-butyl-ethyl-benzyl-ethyl-butyl-ethyl-butyl-ethyl-benzyl-ethyl-butyl-ethyl-benzyl-ethyl-butyl-ethyl-butyl-ethyl-benzyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-benzyl-ethyl-butyl-ethyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-benzyl-ethyl-butyl-ethyl-benzyl n-butylaluminum hydride, benzyl-iso-butylaluminum hydride, benzyl-iso-propylaluminum hydride and the like.

The use of aluminum alkyls or aluminum alkyl hydrides or mixtures thereof is preferred.

Most preferably, triethylaluminum, tri-iso-butylaluminum, di-iso-butylaluminum hydride or mixtures thereof are used.

1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, piperylene, 2-methyl-3-ethyl-1,3-butadiene, 3-methyl-1 are used as conjugated dienes according to the method according to the invention , 3-pentadiene, 2-methyl-3-ethyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene , 3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene , phenyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene .

Most preferably, 1,3-butadiene and isoprene are used as conjugated dienes.

As the halogen compound used dimethylaluminum chloride, diethylaluminum chloride, di-iso-butilalyuminiyhlorid, dimethylaluminum bromide, diethylaluminum bromide, di-iso-butilalyuminiybromid, dimetilalyuminiyftorid, dietilalyuminiyftorid, di-iso-butilalyuminiyftorid, dimetilalyuminiyiodid, dietilalyuminiyiodid, di-iso-butilalyuminiyiodid, methylaluminum dichloride, ethylaluminum dichloride, metilalyuminiydibromid , ethylaluminium dibromide, methylaluminium difluoride, ethylaluminium difluoride, methylaluminium sesquichloride, ethylaluminium sesquichlor d, iso-butilalyuminiyseskvihlorid and trimethyltin chloride, trimetilolovobromid, trietilolovohlorid, trietilolovobromid, di-tert-butilolovodihlorid, di-tert-butilolovodibromid, dibutilolovodihlorid, dibutilolovodibromid, tributyltin chloride and the like and tributilolovobromid

It is preferable to use ethyl aluminum sesquichloride, ethyl aluminum dichloride or diethyl aluminum chloride as a halogen-containing compound.

The polymerization solvent is an inert organic solvent, which can be used individually or in mixtures with each other aliphatic hydrocarbons, in particular such as butane, pentane, hexane, heptane; alicyclic hydrocarbons, namely cyclopentane, cyclohexane; monoolefins such as 1-butene, 2-butene, or mixtures thereof; aromatic hydrocarbons, in particular, such as benzene, toluene, xylene; as well as halogenated hydrocarbons, in particular, such as methylene chloride, chloroform, carbon tetrachloride, trichlorethylene, perchlorethylene, 1,2-dichloroethane.

According to the proposed method, it is most preferable to use a hydrocarbon solvent as a solvent, which is a mixture of cyclohexane: hexane or cyclohexane: nefras (industrial hexane-heptane fraction of paraffinic hydrocarbons of dearomatized catalytic reforming gasolines with a boiling point of 65-75 ° C) in the ratio (30-55 ) ÷ (70-45).

In accordance with the present invention, a catalytic system is used to carry out the polymerization, including (A) lanthanide, (B) an organoaluminum compound, (C) a conjugated diene, and (D) a halogen-containing component taken in molar ratio to each other (A) :( B): (B) :( D) equal to 1: (8-30) :( 5-30) :( 1.5-3.0).

The preferred molar ratio of the components of the catalytic system (A) :( B) :( C) :( D) = 1: (8-20) :( 5-20) :( 1.8-2.8).

The most preferred molar ratio of the components of the catalytic system (A) :( B) :( C) :( D) = 1: (10-15) :( 10-15) :( 2.1-2.5).

In one of the embodiments of the present invention, it is proposed, to regulate the molecular weight of the polymer, an organoaluminum compound containing at least one hydrogen atom taken in molar ratio (B) :( A) equal to 3.0-6.0. In this embodiment, the total amount of the organoaluminum compound used in the synthesis process does not exceed a range of ratios of 8 to 30 mol.

In this case, the preferred amount of additionally supplied organoaluminum compounds is 3.5-5.0 mol.

Most preferably, a further 4.0-4.5 mol of the organoaluminum compound is added.

The process of producing polydiene is carried out in a batch or continuous manner in a hydrocarbon solvent medium by feeding a hydrocarbon charge consisting of a monomer and a solvent and a catalyst complex pre-mixed with a solvent consisting of a lanthanide compound, an organoaluminum compound, a conjugated diene and a halogen-containing organic compound to the reactor / autoclave . The concentration of monomer in the solvent is typically 7-12% by weight, preferably 9-10%. A concentration below 7% leads to a decrease in the energy efficiency of the process, a concentration above 12% leads to an increase in the viscosity of the polymerizate, and, as a result, an increase in energy consumption during the isolation and drying of rubber.

The catalytic complex (CC) is prepared by introducing into the solution of a conjugated diene (most preferably 1,3-butadiene) in an aliphatic solvent an organoaluminum compound (most preferably triisobutylaluminum, triethylaluminum, diisobutylaluminum hydride or mixtures thereof), a lanthanide compound (most preferably carboxylate, in particular neodecano or neodymium phosphate) by holding the resulting mixture for 2 to 20 hours at a temperature of 23 ± 2 ° C followed by the addition of a halogen-containing compound (most preferably ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum chloride or mixtures thereof), with a molar ratio of the components of the catalytic complex: (A) lanthanide, (B) organoaluminum compound, (C) conjugated diene and (D) halogen-containing component in the ratio (A): (B): (B) :( D) equal to 1: (8-30) :( 5-30) :( 1.5-3.0).

The monomer (1,3-butadiene), the solvent and the solution of the catalytic complex are fed into a reactor / autoclave equipped with a mixing device and a thermoregulation system.

The polymerization time is from 1.5 to 2 hours. Monomer conversion reaches 95-99%.

Upon reaching the above conversion, a system for modification is introduced into the polymer in an amount of 0.1 to 10.0 mol per 1 mol of neodymium and mix thoroughly for 15 minutes to 60 hours at a temperature of 60-90 ° C. If the system is used in an amount of more than 10 mol, a sharp jump in Mooney viscosity is observed, as a result, in addition to the deterioration of the plasto-elastic properties of the polymer, problems arise with its isolation and processing. The use of the system for modification in an amount of less than 0.1 mol per 1 mol of neodymium does not affect the properties of the obtained polymer. The preferred amount of system for modification is from 0.5 to 5.0 mol. Most preferably, 0.5-2.0 mol of the system.

The preparation of the system for modification is carried out as follows. A calculated amount of a compound containing at least two maleic fragments, an organic solvent, and then a compound selected from the group of amines is added to a vessel (flask, reactor, etc.). The resulting mixture is stirred for 3 to 150 minutes at a temperature of 20 to 60 ° C.

The resulting system for modifying polydienes containing functional groups interacts with the polymer at the active ends of its chains.

It is also possible to prepare a system for modifying polydiene in situ. For this, a calculated amount of a compound containing at least two maleic fragments, and then a compound selected from the group of amines, is supplied to the pseudo-living polymer. Thus, at first the reaction proceeds along the active ends of the polymer with maleic fragments, and after the amino group is attached to maleic fragments.

The modification time is preferably from 15 minutes to 5 hours, most preferably from 20 minutes to 1 hour. At temperatures from 60 ° C and below, the viscosity of the polymer will increase, which is undesirable, because difficulties in its isolation and processing are inevitable. At the same time, the end groups of the polymer chain tend to lose their activity at temperatures above 90 ° C, so it is impossible to achieve a high degree of polymer modification.

The system for modifying polydienes is a product of the interaction of an amine with maleated polybutadiene containing maleic fragments. A system for modifying polydienes interacts with a pseudo-living polymer at the ends of the polymer chains.

At the end of the modification, after 20-60 minutes in a preferred embodiment, the polymerizate is stopped with softened water or ethyl or isopropyl alcohol and stabilized with an antioxidant solution taken in an amount of from 0.2 to 0.4% per polymer.

The rubber obtained has a Mooney viscosity index of 37 to 45 conv. units Mooney before modification and from 41 to 66 srvc. units Mooney after modification, the polydispersity coefficient of the obtained polydienes corresponds to the range from 2.16 to 2.6, the content of 1,4-cis units is more than 96% wt.

The rubber compounds based on the obtained polydienes are prepared according to standard recipes (table 2) and are distinguished by improved processability at the stage of rubber mixing, increased wear resistance and physical and mechanical properties, as well as improved elastic-hysteresis properties (rolling resistance, wet grip).

The implementation of the invention

Next, embodiments of the present invention will be described. Specialists in this field will be clear that it is not limited to the presented examples and the same effect can be achieved in other embodiments, without going beyond the essence of the claimed invention.

The following describes the test methods used to evaluate the properties of the polymers obtained by the claimed method.

1. The percentage of conversion is determined by the method of deposition of the polymer from the polymerisate with ethyl alcohol and drying the selected polymer.

2. The microstructure of the polymer chains was determined by IR spectroscopy according to a proprietary method using an MNPVO attachment (multiple impaired total internal reflection) with a ZnSe crystal, registration of the IR spectrum of the sample in the range from 4000 to 600 cm-1 with a resolution of 4 cm-1, amount scans 32. The IR spectrometer was calibrated using industry standard samples of the polydiene microstructure, in which the mass fraction of isomeric units was determined by 1H and 13C NMR spectra.

3. The molecular weight characteristics of the rubbers were determined by gel permeation chromatography using a proprietary method using a Waters Breeze gel chromatograph with a refractometric detector. Rubber samples were dissolved in freshly distilled tetrahydrofuran, the mass concentration of the polymer in the solution was 2 mg / ml, universal calibration according to polystyrene standards. The calculation was carried out using the Mark-Kun-Hauwink constant for polydiene (K = 0.000457, α = 0.693). Definition conditions:

- a bank of 4 high-resolution columns (300 mm long, 7.8 mm in diameter) filled with styrene, HR3, HR4, HR5, HR6, which allows analyzing polymers with a molecular weight of 500 to 1 * 107 a.u. ;

- the solvent is tetrahydrofuran, the flow rate is 1 cm ³ / min;

- the temperature of the thermostat columns and refractometer - 300 ° C.

4. The determination of plasto-elastic indicators of rubbers (ductility, cold flow) was carried out according to GOST 19920.17 and GOST 19920.18 on a compressing plastometer with a thermostat model GT7060SA.

5. The Mooney viscosity was determined according to ASTM D 1646.

6. The vulcanization characteristics of the rubber compounds were determined on an MDR 2000 instrument (T = 160 ° C, vibration amplitude 0.50 °, vibration frequency 1.7 Hz, time 30 minutes) according to ASTM D 5289.

7. Physico-mechanical properties (FMF) of the vulcanizates were determined on a Zwick / Roell / Z005 tensile testing machine according to ASTM D 412-98.

8. The elastic component of the complex dynamic shear modulus G '(kPa), which allows to assess the distribution of the filler in rubber compounds and the silanization of the filler, was determined on a device by the Alpha Technologies RPA-2000 rubber processing analyzer at 0.1 Hz and 100 ° C in the range deformations from 1 to 450%. The difference between the accumulation moduli at a strain amplitude of 1% and 50% - ΔG '= (G' _1% - G _'43% ) is the Payne effect.

9. The hysteresis properties (tanδ 60 ° С - tangent of the angle of mechanical losses at 60 ° С) of rubber compounds were evaluated using a NETZSCH DMA 242 Е Artemis instrument. Test conditions: two-arm bend 2 × 5, sample dimensions 10.00 × 6.40 × 1.60 mm, amplitude 40 μm, frequency 10 Hz, load 7 N. Test temperature range - from minus 40 ° С to 60 ° С, the rate of temperature increase is 2.50 ° C / min, and also using the RPA-2000 device in shear deformation mode at a frequency of 10 Hz, T = 60 ° C and a strain of 1%.

Prototype Example

The catalyst was prepared by mixing 0.45 g of butadiene in hexane, 0.28 mmol of neodymium neodecanoate in hexane, 27.5 mmol of methylaluminoxane in toluene and 5.77 mmol of DIBAG in hexane. After 2 minutes of mixing, ethyl aluminum sesquichloride (EASC) was added. The mixture was kept for 18 minutes. 611 g of 1,3-polybutadiene and hexane 3464 were fed into the reactor. Polymerization was carried out, then a functionalizing agent, N- (3-triethoxysilylpropyl 4,5-dihydroimidazole (TEOSI), which contains an imine group and a silicon group, was introduced. polymer 180 min., the amount of modifier 50 mol / Nd. The Mooney viscosity of the rubber mixture is 63.0, the polydispersity is 2.0.

Example 1 (comparative)

The polymerization of butadiene (BD) was carried out in a hydrocarbon solvent in the presence of a catalytic complex prepared on the basis of neodymium versatate (Nd), followed by the addition of an alkylating agent diisobutylaluminium hydride (DIBAG) and a halogen donor (EACC). The ratio of the components in the catalytic complex was BD: Nd: DIBAG: EAX = 10: 1: 10: 2.5. The ripening time of the complex is 22 hours at a temperature of 25 ° C. The polymerization was carried out in a 10 liter reactor equipped with a stirrer and a jacket for heat removal. The polymerization reaction temperature was 60 ° C.

Upon reaching 95% conversion of the monomer, 2 kg of polymerizate were selected in order to analyze and compare the data obtained with the modified polymer. An antioxidant was introduced into the selected polymerizate, degassed and dried on rollers. Then determined its physical and mechanical properties and molecular weight characteristics.

In the remaining part of the polymerizate, a modifier — an amine-containing compound — 3-aminopropyltriethoxysilane (AMEO) was fed through a dispenser. The specified modifier is a 2% solution in nefras, the dosage of the modifier was 0.8 mol in relation to neodymium. The modification process was carried out with constant stirring for 60 min at a temperature of 60 ° C. Then, a non-staining phenolic type antioxidant was administered. Mass fraction of antioxidant was 0.2-0.4%. The polymer was degassed and dried on rollers, and the physical and mechanical properties and molecular weight characteristics were determined (table No. 1).

Example 2 (comparative)

Similar to example 1, with the difference that the introduced modifier was a low molecular weight maleinized polybutadiene (MPB) with a content of maleic anhydride of 8% and a molecular weight of 2700 g / mol. The molar ratio of modifier to neodymium is 0.8.

Examples of the invention

Example 3

Similar to example 1, with the difference that a modification system was used — the product of the interaction of low molecular weight maleated polybutadiene with a content of maleic anhydride of 8% with 3-aminopropyltriethoxysilane (AMEO). The interaction time of the components of the system with each other was 15 minutes, the molar ratio of the components of the mixture and neodymium (MPB: AMEO: Nd) was 0.25: 0.5: 1.

Example 4

Similar to example 3, with the difference that the system was prepared for modification in situ — the components were administered separately, sequentially with a difference of 15 minutes — first, MPB, then AMEO were introduced.

Example 5

Similar to example 3, with the difference, the interaction time between the components of the system components for modification was 60 minutes, the molar ratio of the components of the mixture and neodymium (MPB: AMEO: Nd) was 0.8: 0.8: 1.

Example 6

Similar to example 3, with the difference, the interaction time between the components of the system components for modification was 60 minutes, the molar ratio of the components of the mixture and neodymium (MPB: AMEO: Nd) was 0.6: 1.2: 1.

Example 7

Similar to example 5, with the difference that the catalytic complex was prepared on the basis of neodymium phosphate (Nd), the interaction time of the components of the system for modification with each other was 60 min, the molar ratio of the components of the mixture and neodymium (MPB: AMEO: Nd) was 0, 4: 0.8: 1.

Example 8

Similar to example 4, with the difference that the interaction time between the components of the system components for modification was 60 minutes, the molar ratio of the components of the mixture and neodymium (MPB: AMEO: Nd) was 2.0: 1.0: 1.

Example 9

Similar to example 3, with the difference that butylamine was used as the amine-containing compound, and MPB with 13% maleic anhydride and a molecular weight of 3100 g / mol. The interaction time between the components of the system components for modification was 3600 min; the molar ratio of the components of the mixture to neodymium (MPB: AMS: Nd) was 0.4: 0.8: 1 mol.

Example 10

Similar to example 3, with the difference that phenylamine was used as the amine-containing compound, and MPB with a content of maleic anhydride of 17% and a molecular weight of 5400 g / mol. The interaction time of the components of the system for modification with each other was 120 min; the molar ratio of the components of the mixture and neodymium (MPB: AMS: Nd) was 1.5: 6.0: 1.

Example 11

Similar to example 3, with the difference that methylpropylamine was used as the amine-containing compound, and MPB with 5% maleic anhydride and a molecular weight of 4700 g / mol. The interaction time between the components of the system components for modification was 120 min; the molar ratio of the components of the mixture to neodymium MnB: AMC: Nd was 2.5: 2.5: 1.

Example 12

Similar to example 3, with the difference that N-cycloamino) propylmethyldimethoxysilane (PMDMS) was used as the amine-containing compound, and MPB with 17% maleic anhydride and a molecular weight of 15,000 g / mol. The interaction time of the components of the system for modification with each other was 180 min; the molar ratio of the components of the mixture and the neodymium of MPB: PMDMS: Nd was 0.8: 0.4: 1.0.

Example 13

Similar to example 3, with the difference that 3- (2-aminoethyl) aminopropyltrimethoxysilane (APTMS) was used as the amine-containing compound, and MPB with maleic anhydride content of 17% and a molecular weight of 8000 g / mol. The interaction time of the components of the system for modification with each other was 360 min; the molar ratio of the components of the mixture and neodymium of MPB: APTMS: Nd was 5: 10: 1.0.

Example 14

Similar to example 3, with the difference that MPB was used with a content of maleic anhydride of 17% and a molecular weight of 4400 g / mol. The interaction time between the components of the system components for modification was 3600 min; the molar ratio of the components of the mixture and neodymium MPB: AMEO: Nd was 6.5: 6.5: 1.0 mol.

Example 15

Similar to Example 7, with the difference that 3- (2,2-aminoethyl) aminoethylaminopropyltrimethoxysilane (AEAPTMS) was used as the amine-containing compound, and MPB was used with a molecular weight of 2500 g / mol. The interaction time of the components of the system for modification with each other was 100 min; the molar ratio of the components of the mixture and the neodymium of MPB: AEAPTMS: Nd was 4.1: 8.2: 1.

Example 16

Similar to example 7, with the difference that aminopropylethyldiethoxysilane (APEDES) was used as an amine-containing compound, and MPB was used with a maleic anhydride content of 20% and a molecular weight of 5600 g / mol. The interaction time of the components of the system for modification with each other was 7200 min, the molar ratio of the components of the mixture and the neodymium of MPB: APEDES: Nd is 0.25: 0.8: 1.

Example 17

Similar to Example 7, with the difference that N-butyl-3-aminopropyltrimethoxysilane (BAPTMS) was used as the amine-containing compound, and MPB with 4% maleic anhydride and a molecular weight of 1800 g / mol. The interaction time between the components of the system for modification was 4320 min, the molar ratio of the components of the mixture and neodymium MPB: BAPTMS: Nd is 2: 10: 1.

Example 18

Similar to example 3, with the difference that aminopropylmethyldimethoxysilane (APMDS) was used as the amine-containing compound, and MPB with 4% maleic anhydride and a molecular weight of 1200 g / mol. The interaction time of the components of the system for modification with each other was 7200 min; the molar ratio of the components of the mixture and the neodymium of MPB: APMDS: Nd is 5: 10: 1.

The resulting polymers were tested in rubber mixtures according to the formulation shown in table 2, the test results are presented in table 3.

List of abbreviations shown in table 1

SM - system for modification

AMEO - 3-aminopropyltriethoxysilane

PMDMS - (N-cycloamino) propylmethyldimethoxysilane

APTMS - 3- (2-aminoethyl) aminopropyltrimethoxysilane

AEAPTMS - 3- (2,2-aminoethyl) aminoethylaminopropyltrimethoxysilane

BAPTMS - N-butyl-3aminopropyltrimethoxysilane

APMDS - aminopropylmethyldimethoxysilane

APEDES - aminopropylethyldiethoxysilane

* - numbering of examples corresponds to the numbering of table 1.

As can be seen from the experimental data in the tables, the introduction of only one modifier (examples 1 and 2) - an amine-containing compound or maleated polybutadiene - does not significantly affect the properties of the polymer and rubbers. At the same time, the introduction of a system for the modification of polydienes, consisting of amines or mixtures thereof, and at least one compound containing at least two maleic fragments, both prepared in advance and obtained in situ , positively affects the properties of the polymer (reduction of cold flow, reduction of ductility while maintaining a high content of 1,4-cis units and narrow polydispersity) and significantly improves the properties of rubbers, in particular physicomechanical, elastic-hysteresis properties a (tan δ 60 ° С) and processability (Payne effect).

In addition, the system for modification obtained by the method according to the invention demonstrates stably persisting activity for at least 3 days from the moment of its preparation (Table 1).

Claims (23)

1. A method of obtaining a system for modifying polydienes, comprising reacting a compound selected from the group of amines and at least one compound containing at least two maleic fragments. 2. The method according to p. 1, characterized in that the molar ratio of amine to compound containing maleic fragments is (0.25-1): 1. 3. The method according to p. 1, characterized in that the preferred molar ratio of amine to compound containing maleic fragments is 1: 1. 4. The method according to p. 1, characterized in that a mixture of amines is used. 5. The method according to p. 1, characterized in that preferably the amines are selected from silicon-containing or sulfur-containing amines. 6. The method according to p. 5, characterized in that it is most preferable to use 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminophenyltrimethoxysilane, aminophenyltriethoxysilane, 3- (N-methylamino) propyltrimethoxysilane, 3- (N-methylanethylamino) 2-aminoethyl) -3-aminopropyltrimethoxysilane, 2- (6-aminohexyl) aminopropyltrimethoxysilane, 2-aminoethylthioethyl- (triacetoxy) silane, 3-aminopropylthioethyl (triethoxy) silane, 2,2-thiobis (ethylamine). 7. The method according to p. 1, characterized in that the compound containing maleic fragments is maleated polybutadiene. 8. The method according to p. 7, characterized in that the maleized polybutadiene contains from 4 to 20 wt. % maleic anhydride and has a molecular weight of from 1200 to 8000 g / mol. 9. The method according to p. 7, characterized in that in the most preferred embodiment, maleated polybutadiene contains from 5 to 13 wt. % maleic anhydride and has a molecular weight of from 2500 to 5000 g / mol. 10. The method according to p. 1, characterized in that the system for modification is obtained by mixing the components for from 3 to 150 minutes. 11. The method according to p. 1, characterized in that in the most preferred embodiment, as the compound containing maleic fragments, low molecular weight maleated polybutadiene with a molecular weight of 2500-2700 g / mol is used. 12. The method according to p. 1, characterized in that the system for modification is obtained in situ. 13. A system for modifying polydienes obtained according to any one of paragraphs. 1-12. 14. A method of obtaining modified polydienes, comprising the following stages: i) preparation of a catalytic system consisting of (A) lanthanide, (B) an organoaluminum compound, (C) a conjugated diene, and (D) a halogen-containing organic compound taken in a molar ratio of (A) :( B) :( C) :( G ) equal to 1: (8-30) :( 5-30) :( 1.5-3.0); ii) carrying out the polymerization of the conjugated diene in an organic solvent medium in the presence of the catalyst system obtained in stage i); iii) introducing into the polymer obtained in step ii) a system for modification obtained according to the method of claim 1. 15. The method according to p. 14, characterized in that the most preferred molar ratio of the components of the catalytic system (A) :( B) :( C) :( D) = 1: (10-15) :( 10-15) :( 2.1-2.5). 16. The method according to p. 14, characterized in that before the polymerization, an organoaluminum compound, taken in a molar ratio (B) :( A) of 3.0-6.0, is additionally fed into the monomer solution. 17. The method according to p. 16, characterized in that it is most preferable to additionally serve 4.0-4.5 mol of an organoaluminum compound. 18. Modified polydiene obtained by the method according to any one of paragraphs. 14-17. 19. The modified polydiene according to claim 18, characterized in that it is mainly a polymer of 1,3-butadiene or isoprene. 20. Rubber compounds obtained on the basis of polydienes according to any one of paragraphs. 18, 19.