WO2018088919A1 - Procédé de production de polydiènes modifiés, polydiènes modifiés produits par ce procédé, et mélanges de caoutchoucs à base des polydiènes modifiés produits - Google Patents

Procédé de production de polydiènes modifiés, polydiènes modifiés produits par ce procédé, et mélanges de caoutchoucs à base des polydiènes modifiés produits Download PDF

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WO2018088919A1
WO2018088919A1 PCT/RU2016/000763 RU2016000763W WO2018088919A1 WO 2018088919 A1 WO2018088919 A1 WO 2018088919A1 RU 2016000763 W RU2016000763 W RU 2016000763W WO 2018088919 A1 WO2018088919 A1 WO 2018088919A1
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hydride
iso
neodymium
butylaluminum
butadiene
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PCT/RU2016/000763
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English (en)
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Svetlana Alekseevna LAGUNOVA
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Public Joint Stock Company "Sibur Holding"
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Priority to RU2019117617A priority Critical patent/RU2727714C1/ru
Priority to PCT/RU2016/000763 priority patent/WO2018088919A1/fr
Publication of WO2018088919A1 publication Critical patent/WO2018088919A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/20—Incorporating sulfur atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups

Definitions

  • the invention relates to the industry of synthetic rubbers used in the manufacture of tires, industrial rubber goods, in the electrical engineering and other fields.
  • the present invention relates to a method for producing modified polydienes in an organic solvent on a catalyst system comprising a lanthanide compound, an organoaluminum compound, and a halogen-containing component, followed by terminal modification of the produced "pseudo-living" polymer with at least one compound selected from the group of heterocyclic nitrogen-containing compounds.
  • the present invention also relates to modified polydienes produced by this method.
  • the invention relates to rubber mixtures based on the produced polydienes .
  • the produced modified polydiene is characterized by a high modification degree (less than 90%) , a high content of 1 , -cis-units , and a narrow molecular-weight distribution, and an improved processability at the step of rubber mixing; rubbers based on the polymer according to the invention have an increased wear-resistance and improved physical and mechanical properties, as well as improved elastic-hysteresis properties (rolling resistance, wet-tire traction) .
  • the main field of application of conjugated diene- based polymers is the tire industry.
  • One of the requirements to the modern tires is wear-resistance, tire traction on wet and icy roads, and low rolling resistance that leads to a reduction in fuel consumption.
  • One of the solutions to the above problems is the introduction of functional groups in a rubber molecule, i.e. modification.
  • the presence of functional groups in the structure of a polymer can reduce the number of free polymer chain ends, an improved interaction with fillers, prevents agglomeration of their particles, and, as a consequence, increases the wear-resistance of tread rubbers and reduces hysteresis loss (Kuperman F.E., Novye kauchuki dlya shin.
  • modified polymers The most common method for producing modified polymers is post-polymerization treatment of reactive polymers - terminal modification. This approach is commonly used in the industry and is disclosed in detail in scientific literature and in Russian and foreign patents.
  • Patent RU2425845 discloses a modified polymer produced by polymerization of a conjugated diene in the presence of a catalyst comprising a lanthanide rare-earth element compound in an organic solvent, followed by modification of the produced polymer comprising an active organic metal site, with a modifier that comprises a functional group capable of entering into substitution or addition reactions with the active organic metal site of the polymer.
  • the used 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, carboxylic acid metal salts, acid halides, urea groups, thiourea groups, amido groups, thioamido groups, isocyanate groups, thioisocyanate groups, haloisocyano groups, epoxy groups, thioepoxy groups, imino groups, and a M-Z bond (where M is Sn, Si, Ge, or P, and Z is a halogen atom) , and contains neither active proton nor onium salt that deactivates the active organic metal site.
  • a M-Z bond where M is Sn, Si, Ge, or P, and Z is a halogen atom
  • a disadvantage of the method is its high-energy consumption.
  • it is proposed to carry out polymerization at (-78) to 25°C, but since the method is exothermic, the polymerization in this temperature range requires removal of heat.
  • aluminoxanes proposed as an alkylating agent increase the ash content in the rubber and makes the final product expensive.
  • Patent US7642322 discloses a method for preparing functionalized 1 , 4 -cis-polybutadienes .
  • the method comprises the following steps: 1) preparing a pseudo-living polymer by polymerizing conjugated diene monomer with a lanthanide- based catalyst; and 2) reacting the pseudo- living polymer with at least one functionalizing agent defined by the formula :
  • R 1 is a divalent bond or divalent organic group comprising from 0 to about 20 carbon atoms
  • A is a substituent that will undergo an addition reaction with a pseudo- living polymer
  • Z is a substituent that will react with silica or carbon black reinforcing fillers, with the proviso that A, R 1 , and Z are substituents that will not protonate a pseudo- living polymer.
  • Said substituent A in the above formula is a compound selected from the group of ketones, aldehydes, amides, esters, and imidazolidines , as well isocyanates and isothiocyanates . These groups include amide isocyanurate groups.
  • the catalyst system comprises aluminoxanes or a mixture of aluminoxane with trialkylaluminum or dialkylaluminum hydride .
  • the use of this catalyst system makes the product very expensive.
  • Another disadvantage of the method is a high dose of the functionalizing agent, which also leads to a high cost of the product. In industrial production, an excess of the functionalizing agent may accumulate in the circulating solvent, and the reuse of this solvent will inhibit the polymerization process.
  • Patent RU2486209 discloses a method for preparing functionalized polymers, in particular, describes variants of the method for preparing a functionalized polymer, comprising the following steps: (a) polymerizing a conjugated diene monomer optionally together with monomers copolymerizable with conjugated diene, in the presence of a coordination catalyst to form a polymer; (b) inhibiting said polymerization step with a Lewis base; and (c) reacting the polymer with a functionalizing agent different from the Lewis base used at step (b) .
  • the technical result of the method is to inhibit the polymerization without deleteriously impacting the ability of the reactive polymer to react with a functionalizing agent, to reduce a risk of uncontrolled polymerization, and to reduce the fouling of equipment.
  • patent RU249 114 provides modifying agents selected from heterocyclic nitrile compounds; in patent US8268933, the modification is carried out with polyimine compounds; in patent RU2516519, polymers are modified with imide compounds; and in application US 2015329655, there is used a protected oxyme containing cyano groups.
  • different modifying agents have different effects on the properties of a polymer, and not each functional group introduced in a polymer reduces hysteresis loss.
  • Patent US8207275 discloses functionalized polymers and vulcanizates prepared therefrom.
  • the produced functionalized polymers correspond to the formula -R 1 -a, where ⁇ is a polymer chain, R 1 is a bond or a divalent organic group, and a is a sulfur-containing heterocycle selected from ethylene sulfide, propylene sulfide, tetrahydrothiophene, thiazoline, dihydrothiophene , thiadiazine, thioxanthene, thianthrene, phenoxyethanol , dihydroisothiazole , and thienofuran groups or substituted forms thereof .
  • a disadvantage of the method is that the use of the above-indicated compounds is characteristic of anionic polymerization.
  • the method has a number of disadvantages, in particular, a low content of 1, 4-cis-units, resulting in impaired viscoelastic properties, gel formation, low consumer properties (elastic hysteresis properties) .
  • Application US2014187711 discloses a method for preparing a functionalized polymer, comprising the steps of: (I) polymerizing monomer to form a reactive polymer, and (II) reacting the reactive polymer with an unsaturated heterocycle containing an azolinyl group.
  • the technical result is to reduce hysteresis loss.
  • the use of aluminoxanes as an alkylating agent increases the cost of the final product.
  • the method provides the use of aluminoxane in toluene, which is totally unacceptable in the case of using aliphatic solvents due to polymer chain transfer to toluene. Toluene accumulates in the aliphatic solvent.
  • the catalyst system according to the invention is unstable and could be used immediately after preparation since its reactivity is inversely proportional to the storage time. This aspect is an essential disadvantage since it leads to instability of the process as a whole.
  • the method for producing a functionalized polymer from a conjugated diene is closest in view of the technical essence and the achieved result.
  • the resulting polymer has at least 50% terminal modification, a molecular weight (Mn) of 1.3 to 5, a weight average molecular weight (Mw) of 100,000 to 1,000,000, and a cis- 1,4 -bond content of at least 70%.
  • this method has a number of disadvantages: an increased consumption of an organoaluminum compound in the catalyst complex, resulting in an increased ash content in the polymer; the preparation of the complex takes a long time due to the use of preferably linear carboxylic acids; instability of the catalyst complex and, as a consequence, a necessity to use thereof immediately after the preparation; a low monomer conversion; an increased consumption of the modifying agent, including due to a large amount of the organoaluminum compound.
  • an increased consumption of several components of the method increases the cost of the final product.
  • the object of the present invention is to reduce the economic cost of the process of producing modified polydienes, to improve polymer- filler interaction in the production of rubber mixtures, and to increase elastic hysteresis properties of polydienes.
  • the object has been addressed by a developed method for producing modified polydienes by polymerization of a conjugated diene in an organic solvent in the presence of a catalyst system comprising (A) a lanthanide rare-earth element, (B) an organoaluminum compound, (C) a conjugated diene, and (D) a halogen-containing component in a molar ratio of (A) : (B) : (C) : (D) equal to 1: (8-30) : (5-30) : (1.5- 3.0), up to at least 95% conversion of the conjugated diene to produce a living polymer, followed by modification of the terminal groups of the living polymer with at least one modifying agent selected from the group of nitrogen- containing heterocycles .
  • a catalyst system comprising (A) a lanthanide rare-earth element, (B) an organoaluminum compound, (C) a conjugated diene, and (D) a halogen-containing component in a
  • an organoaluminum compound comprising at least one hydrogen atom may be additionally added to the charge, which is a mixture of a conjugated diene monomer and an organic solvent, at a molar ratio of (A) : (B) equal to 1: (3.0-6.0).
  • the sum amount of the total organoaluminum compound used in the synthesis process does not exceed the above-indicated molar ratio of (A) : (B) , i.e. 1: (8-30) .
  • the produced modified polydiene has the modification degree of not less than 90% and is characterized by an improved processability at the step of rubber mixing.
  • the rubbers produced from the polymer according to the invention are characterized by increased wear resistance and improved physical and chemical properties, as well as by improved elastic hysteresis properties (rolling resistance, wet-tire traction) .
  • Lanthanide-based catalyst systems including organoaluminum compounds are commonly used catalysts for polymerization of conjugated dienes (Toube R. Metalorganic Catalyst for Synthesis and Polymerization. Ed. By Kaminsky . Berlin; Heidelberg, New Jork: Springer, Verlag, 1999, p. 531) .
  • Stereospecific polymerization of dienes under the action of the catalyst system based on rare-earth element carboxylates and organoaluminum compounds allows the production of polymers with a high content of 1,4-cis units .
  • Coordination catalysts initiate polymerization of a monomer according to the mechanism that comprises, before the introduction of the monomer in a growing polymer chain, coordination or complexing of the monomer on the metal - containing active site.
  • One of the most advantageous features of coordination catalysts is their ability to provide a stereochemical control of the polymerization reaction and, thus, the production of stereoregular polymers.
  • Coordination catalysts can be one-, two-, three-, or multicomponent systems. Coordination catalysts can be produced by various methods .
  • the components of a catalyst are pre-mixed outside the polymerization system in the absence or in the presence of a small amount of a monomer.
  • the resulting catalyst system may be optionally subjected to maturation and after that added to the monomer.
  • These catalyst systems provide the production of 1 , 4 -cis-polydienes that, before deactivation of the active sites, have reactive terminal groups and may be considered as pseudo- living polymers.
  • the catalyst system may include a lanthanide compound, an alkylating agent, and a halogen-containing compound that comprises one or more labile halogen atoms.
  • the alkylating agent may include one or more organoaluminum compounds that are introduced in the catalyst complex simultaneously or separately.
  • organoaluminum compounds may be used as regulators of the degree of polymerization in chain transfer to alkylaluminum . Such chains are in a rest state and are not able to attach to a monomer. Chains containing a neodymium atom are active. Chain transfer to a monomer molecule is also possible, and, in such a case, the molecule becomes incapable of further growth and modification.
  • the ability of the modifying agent to interact with polymer produced on a coordination catalyst system is often unobvious.
  • the reactivity of the polymer depends on some factors: on the number of active sites, competing reactions running in a polymerization mixture, for example, monomer polymerization reactions.
  • the rate of the reaction between the modifying agent and polymer produced on the coordination catalyst system may be very low, and the modifying agent is not completely reacted with the polymer chain.
  • the use of at least one compound selected from the group of nitrogen- containing heterocycles, as a modifying agent in the catalyst system used in the method according to the invention provides a high rate of modification (within a half hour) and a polydiene with a high degree of modification (not less than 90%) .
  • the method according to the present invention is carried out in the presence of a catalyst system comprising (A) a lanthanide rare-earth element, (B) an organoaluminum compound, (C) a conjugated diene, and (D) a halogen- containing component in a molar ratio of (A) : (B) : (C) : (D) equal to 1: (8-30): (5-30) .-(1.5-3.0).
  • a catalyst system comprising (A) a lanthanide rare-earth element, (B) an organoaluminum compound, (C) a conjugated diene, and (D) a halogen- containing component in a molar ratio of (A) : (B) : (C) : (D) equal to 1: (8-30): (5-30) .-(1.5-3.0).
  • the lanthanide rare-earth element is a compound that comprises at least one atom of lanthanum, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium.
  • the compounds comprising lanthanide atoms may have various oxidation degrees: 0, +2, +3, and +4.
  • Trivalent lanthanides with an oxidation degree of +3 are preferred. It is preferable to use neodymium compounds.
  • Compounds comprising lanthanides include, but are not limited to, carboxylates , organophosphates , organophosphonates , organophosphinates , carbamates, dithiocarbamates , lanthanide xanthogenates , ⁇ -diketones, halides, oxyhalides, and alcoholates.
  • Neodymium carboxylates include neodymium formate, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2- ethylhexanoate , neodymium neodecanoate (brand name neodymium versatate) , neodymium naphthenate , neodymium stearate, neodymium oleate, neodymium benzoate, neodymium picolinate, neodymium dibutyl phosphate, neodymium diphenyl phosphate, neody
  • Neodymium organophosphonates include neodymium butylphosphonate , neodymium pentylphosphonate , neodymium hexylphosphonate , neodymium heptylphosphonate, neodymium octylphosphonate, neodymium (l-methylheptyl)phosphonate, neodymium (2-ethylhexyl) phosphonate, neodymium decylphosphonate, neodymium dodecylphosphonate, neodymium octadecylphosphonate, neodymium oleylphosphonate , neodymium phenylphosphonate , neodymium (n-nonylphenyl) phosphonate , neodymium butyl (butylphosphonate) , neodymium pen
  • Neodymium organophosphinates include neodymium butylphosphinate , neodymium pentylphosphinate , neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, neodymium (1-methylheptyl) phosphinate, neodymium (2-ethylhexyl) phosphinate, neodymium decylphosphinate , neodymium dodecylphosphinate , neodymium octadecylphosphinate, neodymium oleylphosphinate, neodymium phenylphosphinate , neodymium (n-nonylphenyl) phosphinate, neodymium dibutylphosphin
  • Neo acids comprise a moiety of trialkylcarboxylic acid (branched a, a' -carboxylic acid).
  • Derivatives of neo acids more soluble in hydrocarbon solvents are alkylated more quickly and more completely to form more active catalyst compounds.
  • Neodymium carboxylates are preferred, and neodymium neodecanoate is most preferred.
  • the organoaluminum compound used in the catalyst system is selected from trialkylaluminum, triphenylaluminum, or dialkylaluminum hydrids .
  • Alkylaluminum dihydride is selected from the group including trimethylaluminum, triethylaluminum, tri-n- propylaluminum, tri- iso-propylaluminum, tri-n- butylaluminum, tri-iso-butylaluminum, tri-tert- butylaluminum, triphenylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, di-iso-butylaluminum hydride, dihexylaluminum hydride, di-iso-hexylaluminum hydride, dioctylaluminum hydride, di-iso-octylaluminum hydride, phenylethylaluminum hydride, phen
  • Alkylaluminum or alkylaluminum hydride, or a mixture thereof is preferred.
  • Triethylaluminum, tri-isobutylaluminum, di- isobutylaluminum hydride, or a mixture thereof is most preferred.
  • the conjugated dienes used in the catalyst system include 1 , 3 -butadiene , isoprene, 2, 3 -dimethyl -1, 3- butadiene, piperylene, 2 -methyl -3 -ethyl -1, 3 -butadiene, 3- methyl-1, 3-pentadiene, 2 -methyl- 3 -ethyl -1, 3-pentadiene, 3- methyl-1 , 3-pentadiene, 1 , 3 -hexadiene , 2 -methyl- 1 , 3 - hexadiene, 1, 3 -heptadiene , 3 -methyl- 1, 3 -heptadiene , 1,3- octadiene, 3 -butyl -1, 3-octadiene, 3 , 4 -dimethyl- 1, 3- hexadiene, 4 , 5-diethyl-l, 3-octadiene, phenyl- 1 , 3 -
  • the halogen- containing compound used in the catalyst system is dimethylaluminum chloride, diethylaluminum chloride, di-iso-butylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, di-iso-butylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, di-iso-butylaluminum fluoride, dimethylaluminum iodide, diethylaluminum iodide, di-iso-butylaluminum iodide, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquich
  • Ethylaluminum sesquichloride, ethylaluminum dichloride, or diethylaluminum chloride is preferred as a halogen- containing compound.
  • the polymerization process is carried out in the presence of the catalyst system in which the molar ratio of components (A) : (B) : (C) : (D) is 1: (8-30) : (5-30) : (1.5-3.0) .
  • the molar ratio of the components of the catalyst system of (A) : (B) : (C) : (D) 1: (8-20) : (5-20) : (1.8-2.8) is preferred.
  • the molar ratio of the components of the catalyst system Of (A) : (B) : (C) : (D) 1 : ( 10 - 15 ) : ( 10 - 15 ) : (2.1-2.5 ) is most preferred.
  • an organoaluminum compound comprising at least one hydrogen atom is additionally added to the charge, which is a mixture of a conjugated diene monomer and an organic solvent, at a molar ratio of (A) : (B) equal to 1: (3.0-6.0).
  • the sum amount of the total organoaluminum compound used in the synthesis i.e. the amount of the organoaluminum compound used both in the charge and in the catalyst system, does not exceed a molar ratio of (A) : (B) equal to 1: (8:30) .
  • the amount of the additionally added organoaluminum compound is 3.5 to 5.0 mol based on the component (A) of the catalyst system.
  • the living polymer resulted from the polymerization of a conjugated diene is modified in the terminal groups with at least one modifying agent selected from the group of nitrogen-containing heterocycles .
  • Such heterocycles include N-substituted aminothioaldehydes , N-substituted aminothioketones , N- substituted aminothioaldehydes;
  • N-substituted aminoketones such as 4-N,N- dimethylaminoacetophenone , 4-N,N-diethylaminoacetophenone,
  • N-substituted aminoaldehydes for example, 4- N, N-dimethylaminobenzaldehyde , 4-N,N- diphenylaminobenzaldehyde, and 4-N,N- divinylaminobenzaldehyde ; N-substituted lactams, such as N- phenyl ⁇ -propiolactam, N-methyl ⁇ -propiolactam, N-methyl-2- pyrrolidone, N-phenyl -2 -pyrrolidone, N-tert-butyl-2- pyrrolidone, N-phenyl -5 -methyl-2 -pyrrolidone, N-methyl-2- pyrrolidone, N-phenyl- 2 -piperidine, N-methyl ⁇ -caprolactam, N-phen
  • the preferred compounds as a modifying agent of the method according to the invention include N-Methyl-2- pyrrolidone, N-phenyl-2-pyrrolidone, N-tert-butyl-2- pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1 , 3 -diethyl-2 imidazolidone, 1, 3-di-n-propyl-2-imidazolidone, 1,3-di-iso- propyl-2-imidazolidone, 2-methyl-2-thiazoline, 2-ethyl-2- thiazoline, 2-n-propyl-2-thiazoline, and 2 -benzothiazolyl - diethyl -dithiocarbamate, or a mixture thereof.
  • 1, 3 -Dimethyl- 2 -imidazolidone, 2-ethyl-2-thiazoline, and 2 -benzothiazolyl -diethyl -dithiocarbamate or mixtures thereof are most preferred as a modifying agent.
  • the amount of the modifying agent used for the production of a modified polydiene in the method according to the invention may vary from 0.1 to 15 mol per 1 mol of rare-earth element, preferably from 0.25 to 10 mol, and most preferably from 0.5 to 5 mol.
  • An excess of the modifying agent does not enter into reaction with the active site of a polymer chain and remains free in the polymerizate, which leads to extra expenses for purification of the polymer and solvent and, thus, to a higher cost of rubber.
  • the use of more than 15 mol of the modifying agent per 1 mol of rare-earth element is not expedient.
  • the method for producing a modified polydiene is carried out in a batch or continuous mode in a hydrocarbon solvent by feeding hydrocarbon charge to a reactor/autoclave, wherein the hydrocarbon charge is a mixture of a conjugated diene monomer and the hydrocarbon solvent pre-mixed with the solvent of a catalyst system consisting of a rare-earth element compound, an organoaluminum compound, the conjugated diene, and a halogen-containing organic compound.
  • the concentration of the monomer in the solvent is as a rule 7 to 12 wt.%, preferably 9 to 10%.
  • the concentration of lower than 7% leads to a reduction in the energy efficiency of the process, and the concentration of more than 12% leads to an increase in the polymerizate viscosity and, as a consequence, to an increased energy consumption for isolation and drying processes.
  • the conjugated dienes used in the production of modified polydienes include 1, 3 -butadiene, isoprene, 2,3- dimethyl-1, 3 -butadiene, piperylene, 2 -methyl-3 -ethyl-1, 3- butadiene, 3 -methyl- 1, 3 -pentadiene , 2 -methyl-3 -ethyl-1, 3- pentadiene, 3 -methyl-1, 3-pentadiene, 1 , 3 -hexadiene , 2- methyl-1, 3-hexadiene, 1 , 3 -heptadiene, 3 -methyl-1, 3- heptadiene, 1 , 3 -octadiene , 3 -butyl- 1, 3-octadiene, 3,4- dimethy1-1, 3-hexadiene, 4, 5-diethyl-l, 3-octadiene, phenyl- 1, 3 -butadiene, 2 , 3 -dieth
  • the solvent for polymerization is an inert organic solvent that may be an individual compound or a mixture of aliphatic hydrocarbons, in particular, such as butane, pentane, hexane, heptane; alicyclic hydrocarbons, in particular, cyclopentane, cyclohexane ; mono-olefins , such as 1-butene, 2-butene, or a mixture thereof; aromatic hydrocarbons, in particular, such as benzene, toluene, xylene; and halogenated hydrocarbons, in particular, such as methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene , 1 , 2 -dichloroethane .
  • aliphatic hydrocarbons in particular, such as butane, pentane, hexane, heptane
  • alicyclic hydrocarbons in particular, cyclopentane,
  • the hydrocarbon solvent which is a mixture of cyclohexane : hexane or cyclohexane : nefras (commercial hexane-heptane fraction of paraffin hydrocarbons of dearomatized gasolines from catalytic reforming with a boiling point of 65 to 75°C) in a ratio of (30-55) ⁇ (70-45) , is most preferred as a solvent in the method according to the invention.
  • the catalyst system (CS) is prepared by adding an organoaluminum compound and a rare-earth element compound to a solution of a conjugated diene in an aliphatic solvent, keeping the prepared mixture for from 2 to 20 hours at temperature of 23 ⁇ 2°C, followed by the addition of a halogen-containing compound at a molar rate of the components of the catalyst complex: (A) a lanthanide rare earth element, (B) an organoaluminum compound, (C) a conjugated diene, and (D) a halogen-containing component, (A) : (B) : (C) : (D) equal to 1: (8-30) : (5-30) : (1.5-3.0) .
  • the charge and the solution of the catalyst complex are fed to a reactor/autoclave equipped with a mixer and a thermal control system.
  • an organoaluminum compound comprising at least one hydrogen atom is additionally added to the charge, i.e. to the conjugated diene in an organic solvent, at an amount of 3.0 to 6.0 mol based on 1 mol of rare-earth element, to control the molecular weight of the polymer.
  • the sum amount of the total organoaluminum compound used in the process of synthesis of the organoaluminum compound does not exceed the above-indicated ratio of from 8 to 30 mol.
  • the preferred molar ratio of (A) : (B) is 1: (3.5-5.0), the ratio of 1: (4.0-4.5) is most preferred.
  • Polymerization of conjugated dienes is performed until the conversion of dienes reaches 95-99% for from 1.5 to 2 hours.
  • a solution of a modifier is added to the polymerizate at a molar ratio of 0.1 to 15 mol of the modifier per 1 mol of rare-earth element.
  • Interaction between the modifier and polymerizate occurs under stirring for from 30 min to 2 hours at a temperature of 62 to 80 °C.
  • the modification is performed at the temperature to which the reaction mixture is heated during the polymerization. There is no need for special heating or cooling of the polymerizate in order to carry out the modification process.
  • the polymerizate is stopped by softened water or ethyl or isopropyl alcohol and is stabilized with a solution of an antioxidant taken in an amount of 0.2 to 0.4% based on polymer.
  • the modified polydiene (rubber) produced by the claimed method has a Mooney viscosity value of 37 to 45 Mooney relative units (RU) before the modification and of 41 to 50 Mooney RU after the modification; the polydispersity index of the produced polydienes corresponds to the range of 2.49 to 2.63; and the content of 1,4-cis- units is more than 96 wt . % .
  • the modified polymers produced by the present method are used in the manufacture of rubber mixtures.
  • Rubber mixtures are prepared according to standard formulations that may comprise, along with polymers, other optional additives well known to a skilled person, for example, such as fillers, activators, vulcanization accelerators, vulcanizing agents, various plastisizers, and other processing additives.
  • Suitable fillers include, for example, carbon black, oxides of silicon, titanium, zinc, and the like.
  • Activators and vulcanization accelerators may include, for example, oxides of lead, zinc, and magnesium, acetanilide, stearic acid, sulfenamides , diphenylguanidine , and the like.
  • the vulcanizing agents include, for example, sulfur, organic peroxides, polyhalogen derivatives, alkylphenol- formaldehyde resins, oligoether acrylates, and other unsaturated compounds .
  • Plastisizers and processing additives include, for example, naphthene oils, stearic and oleic acids, paraffins, rosins, and the others.
  • the produced rubber mixture is characterized by an increased processability at the step of rubber mixing, an increased wear resistance and improved physical and vechanical properties, as well as by improved elastic hysteresis properties (rolling resistance, wet- tire traction) .
  • the microstructure of polymer chains was determined by IR spectroscopy developed in-house using a multiple frustrated total internal reflection (MFTIR) device with a ZnSe crystal; the IR- spectrum of a sample was registered within a range of 4000 to 600 cm “1 with a resolution of 4 cm “1 , and a scan-number of 32.
  • MFTIR multiple frustrated total internal reflection
  • the IR- spectrometer was calibrated using industrial reference samples of the microctructure of polydiene, in which the fraction of isomeric units was determined by 1 H and 13 C NMR spectra.
  • the content of a residual modifier in polymer was determined by pre-extraction of the modifier with ethyl alcohol, followed by analysis on a chromatograph with a flame ionization detector.
  • the residual modifier was calculated by an in-house reference method.
  • X is a modification degree
  • m f is the weight of a fed modifying agent
  • m r is the weight of a residual modifying agent.
  • Plasto-elastic properties of rubbers were determined according to GOST 19920.17 and GOST 19920.18 on a GT7060SA compression plastometer with a thermostat.
  • the elastic component of the complex dynamic modulus G' (KPa) to determine the distribution of the filler in rubber mixtures and silanization of the filler was measured on an RPA-2000 rubber process analyzer (Alpha Technologies) at 0.1 Hz and 100°C in a deformation range of from 1 to 450%.
  • the heat build-up was determined by an increase in the temperature of a sample after multiple compressions under certain conditions on an RH-2000 dynamic flexometer. Test conditions: statistical deformation: 10%; dynamic deformation: 25%; dynamic deformation frequency: 30 Hz.
  • volume loss of rubber mixtures in the Shopper- Schlobach abrasion test determined by the volume loss of a sample due to the friction between the sample and an abrasive surface, was measured according to GOST 23509 on a device for testing rubber resistance to abrasion-wearing of GIBITRE INSTRUMENTS SRL company.
  • Hysteresis properties of rubber mixtures were analyzed on a NETZSCH DMA 242 E Artemis device. Test conditions: dual cantilever bending: 2x5; sample dimensions: 10.00x6.40x1.60 mm; amplitude: 40 ⁇ , frequency: 10 Hz; load: 7 N; range of test temperature: - 40°C to 60°C; rate of temperature rise: 2.50°C/min. The hysteresis properties were also measured on the RPA-2000 evice in the mode of shear deformation at a frequency of 0 Hz, 60° C, and a deformation of 1%.
  • a catalyst complex was prepared by adding 1.67 g f 8.6% solution of neodymium versatate in an aliphatic olvent and 40 mL of 0.93 mol/L di-iso-butylaluminum hydride (DIBAH) to a butadiene solution and stirring for 15 minutes. Then, a solution of tri-butylphosphine (TBP) (10 mL, 0.5 mol/L) was added to the CC and stirred for 10 min.
  • DIBAH di-iso-butylaluminum hydride
  • a 20L autoclave was filled with 1008 g of butadiene dissolved in 13 L of a cyclohexane/nefras mixture, the prepared solution of the CC, and ethylaluminum sesquichloride (EASC) (3.8 mL, 0.65 mol/L), and heated to 60 °C.
  • the molar ratio of neodymium versatate : TBP : DIBAH : EASC was 1:5:37:2.5.
  • Polymerization was carried out for 3 hours at 60 to 65 °C, and the conversion of butadiene was 84%. 2 kg of the polymerizate was sampled from the apparatus to use them for the analytical control of the molecular weight and plasto-elastic properties of the polymer before modification.
  • the resulting polymer had a Mooney viscosity value of 37, a polydispersity index of 2.6, and a 1,4 -unit content of 96.4%.
  • a catalyst complex was prepared by mixing a 1.4 mmol solution of Nd versatate in cyclohexane, a 14 mmol solution of TIBA in hexane, and a 14 mmol solution of butadiene in cyclohexane in a cyclohexane/nefras solvent, the resulting mixture was kept for 10 hours at 25°C. Then, a 2.8 mmol solution of DIBAH in hexane and a 3.36 mmol solution of EASC in hexane were added to the complex. The molar ratio of the components :
  • neodymium versatate butadiene :TIBA:DIBAH: EASC was 1:10:10:2:2.4.
  • a 20L autoclave under nitrogen was filed with 13 L of a cyclohexane/nefras solvent, 1002 g of butadiene, and the prepared catalyst complex.
  • a solution of DIBAH was additionally added to the charge before the addition of the catalyst complex, at a molar ratio of DIBAH/Nd versatate of 3.2 : 1 to control the molecular weight of the polymer.
  • the polymer produced using this catalyst system had a Mooney viscosity value of 44, a polydispersity index of 2.6, and a 1,4 -unit content of 96.4%.
  • a catalyst complex was prepared by mixing a 1.4 mmol solution of Nd versatate in cyclohexane, a 14 mmol solution of TIBA in hexane, and a 14 mmol solution of butadiene in cyclohexane in a cyclohexane/nefras solvent, the resulting mixture was kept for 10 hours at 25 °C. Then, a 2.8 mmol solution of DIBAH in hexane and a 3.36 mmol solution of EASC in hexane were added to the complex.
  • the molar ratio of the components in the prepared catalyst system :
  • neodymium versatate butadiene :TIBA: DIBAH: EASC was 1 : 12 : 10 : 2 : 2.4.
  • a 20L autoclave under nitrogen was filed with 13 L of a cyclohexane/nefras solvent, 1002 g of butadiene, and the prepared catalyst system.
  • a solution of DIBAH was additionally added to the charge before the addition of the catalyst complex, at a molar ratio of DIBAH/Nd versatate of 3.5:1 to control the molecular weight of the polymer.
  • a modifying agent which was a solution of N-methylpyrrolidone (N-MP) in cyclohexane, was added to the prepared polymerizate at a molar ratio of N-MP/Nd of 0.5. Modification was carried out under continuous stirring at 75 °C for 30 min. Upon the completion of modification, an Irganox 1520L antioxidant was added to the polymerizate, the polymer was isolated by water- steam degassing and dried on drying rolls at 110 °C.
  • N-MP N-methylpyrrolidone
  • the produced modified polymer had a Mooney viscosity value of 49, a 1,4 -unit content of 96.6%, Mw/Mn of 2.6, and a modification degree of 100%.
  • a catalyst system was prepared according to Example 1, except the use of diethylaluminum chloride (DEAC) instead of EASC, and isoprene instead of butadiene.
  • DEAC diethylaluminum chloride
  • isoprene instead of butadiene.
  • DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 6.0:1 to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1, and the molar ratio of N-MP/Nd was 1.
  • the produced modified polymer had a Mooney viscosity value of 46, a 1,4 -unit content of 96.7%, Mw/Mn of 2.7, and a modification degree of 100%.
  • a catalyst system was prepared according to Example 1, except the use of ethylaluminum dichloride (EADC) instead of EASC, and piperylene instead of butadiene.
  • the molar ratio of the components of the catalyst system: neodymium versatate:piperylene:TIBA:DIBAH:EADC was 1:10:8:2:2.1.
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 5:1 to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1, and the molar ratio of N-MP/Nd was 3.3.
  • the produced modified polymer had a Mooney viscosity value of 49, a 1,4- unit content of 96.3%, Mw/Mn of 2.6, and the modification degree of 100%.
  • a catalyst system was prepared by adding neodymium versatate in an aliphatic solvent and di-iso-butylaluminum hydride (DIBAH) to a solution of butadiene and stirring the mixture for 60 min. Then, a solution of EASC was added to the CC and stirred for 10 min.
  • DIBAH di-iso-butylaluminum hydride
  • neodymium versatate butadiene: DIBAH: EASC was
  • Modification was carried out according to Example 1, and the molar ratio of N-MP/Nd was 5.
  • the produced modified polymer had a Mooney viscosity value of 49, a 1,4 -unit content of 96.3%, Mw/Mn of 2.6, and a modification degree of 90%.
  • a catalyst system was prepared according to Example 1, except the use of neodymium 2 -ethylhexanoate instead of neodymium versatate, and dimethylaluminum chloride (DMAC) instead of EASC.
  • DMAC dimethylaluminum chloride
  • neodymium 2 -ethylhexanoate : butadiene : TIBA: DIBAH : DMAC was 1:15:5.2:2:2.2.
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 6:1 to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1, using 1 , 3 -dimethylimidazolidone (1,3-DMI) instead of N- methylpyrrolidone at a molar ratio of 1,3-DMI/Nd of 0.5.
  • the produced modified polymer had a Mooney viscosity value of 40, a 1,4 -unit content of 96.1%, Mw/Mn of 2.7, and a modification degree of 100%.
  • a catalyst system was prepared according to Example 1, except the use of diethylaluminum chloride (DEAC) instead of EASC, and isoprene instead of butadiene.
  • DEAC diethylaluminum chloride
  • isoprene instead of butadiene.
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 5.5:1 to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1, using 1 , 3 -dimethylimidazolidone (1,3-DMI) instead of N- methylpyrrolidone at a molar ratio of 1,3-DMI/Nd of 1.
  • the produced modified polymer had a Mooney viscosity value of 47, a 1,4 -unit content of 96.6%, Mw/Mn of 2.5, and a modification degree of 100%.
  • a catalyst system was prepared according to Example 1, except the use of ethylaluminum dichloride (EADC) instead of EASC.
  • EASC ethylaluminum dichloride
  • neodymium versatate : butadiene : TIBA: DIBAH : EADC was
  • DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 6:1 to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1, using 1 , 3 -dimethylimidazolidone (1,3-DMI) instead of N- methylpyrrolidone at a molar ratio of 1,3-DMI/Nd of 5.
  • the produced modified polymer had a Mooney viscosity value of 40, a 1,4 -unit content of 96.3%, Mw/Mn of 2.6, and a modification degree of 92%.
  • a catalyst system was prepared according to Example 1, except the use of tri-ethylaluminum (TEA) instead of TIBA and diethylaluminum chloride (DEAC) instead of EASC.
  • TEA tri-ethylaluminum
  • DEAC diethylaluminum chloride
  • neodymium versatate butadiene: TEA: DIBAH: DEAC was
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 6:1 to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1, using 2 -methylthiozoline (2-MT) instead of N- methylpyrrolidone at a molar ratio of 2-MT/Nd of 0.1.
  • the produced modified polymer had a Mooney viscosity value of 48, a 1,4-unit content of 96.6%, Mw/Mn of 2.8, and a modification degree of 100%.
  • a catalyst system was prepared according to Example 1, except the use of tri-ethylaluminum (TEA) instead of TIBA, diethylaluminum chloride (DEAC) instead of EASC, and 1,3- hexadiene instead of butadiene.
  • TEA tri-ethylaluminum
  • DEAC diethylaluminum chloride
  • 1,3- hexadiene 1,3- hexadiene
  • DIBAH neodymium versatate : 1 , 3 -hexadiene : TEA: DIBAH : DEAC was 1.3:30:8:2:2.3.
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 4.5:1, to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1, using 2 -methylthiozoline (2-MT) instead of N- methylpyrrolidone at a molar ratio of 2-MT/Nd of 0.25.
  • the produced modified polymer had a Mooney viscosity value of 43, a 1,4-unit content of 96.4%, Mw/Mn of 2.6, and a modification degree of 100%.
  • a catalyst system was prepared according to Example 1, except the use of neodymium naphthenate instead of neodymium versatate, silicon tetrachloride (STC) instead of EASC, and piperylene instead of butadiene.
  • STC silicon tetrachloride
  • piperylene instead of butadiene.
  • neodymium naphthenate piperylene :TIBA: DIBAH: STC was 1:10:9:2:3.0.
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 3.9:1 to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1, using 2 -methylthiozoline (2-MT) instead of N- methylpyrrolidone at a molar ratio of 2-MT/Nd of 1.
  • the produced modified polymer had a Mooney viscosity value of 47, a 1,4-unit content of 97.4%, Mw/Mn of 2.8, and a modification degree of 100%.
  • a catalyst system was prepared according to Example 4, except the use of neodymium tris- [bis- (2- ethylhexyl) phosphate] instead of neodymium versatate, DEAC instead of EASC, and isoprene instead of butadiene.
  • the molar ratio of the components: neodymium tris- [bis- (2- ethylhexyl ) hosphate] : isoprene: DIBAH :DEAC was 1:15:12:1.6.
  • a catalyst system was prepared according to Example 1, except the use of isobutylaluminum dihydride (IBADH) instead of DIBAH.
  • IBADH isobutylaluminum dihydride
  • neodymium versatate : butadiene : TIBA: IBADH : EASC was 1:7:10:2:2.4.
  • a 20L autoclave under nitrogen was filed with 13 L of a cyclohexane/nefras solvent, 951 g of butadiene, 50 g of isoprene, and the prepared catalyst complex.
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 4.5:1 to control the molecular weight of the polymer.
  • a catalyst system was prepared according to Example 1. The molar ratio of the components :
  • neodymium versatate : butadiene : TIBA: DIBAH : EADC was
  • a catalyst system was prepared according to Example 1, except the use of diethylaluminum chloride (DEAC) instead of EASC and diethylaluminum hydride (DEAH) instead of DIBAH.
  • DEAC diethylaluminum chloride
  • DEH diethylaluminum hydride
  • neodymium versatate : butadiene : TIBA: DIBAH : DEAC was
  • a solution of DEAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 5:1 to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1 at a molar ratio of N-MP/Nd of 10.
  • the produced modified polymer had a Mooney viscosity value of 46, a 1,4-unit content of 96.9%, Mw/Mn of 2.6, and a modification degree of 95%.
  • a catalyst system was prepared according to Example 4, except the use of dimethylaluminum chloride (DMAC) instead of EASC and piperylene instead of butadiene.
  • DMAC dimethylaluminum chloride
  • neodymium versatate piperylene : DIBAH : DMAC was
  • Modification was carried out according to Example 1 at a molar ratio of N-MP/Nd of 16.
  • the produced modified polymer had a Mooney viscosity value of 47, a 1,4 -unit content of 96.7%, Mw/Mn of 2.7, and a modification degree of 88%.
  • a catalyst system was prepared according to Example 1, except the use of isobutylaluminum dichloride (IBADC) instead of EASC.
  • IBADC isobutylaluminum dichloride
  • neodymium versatate : butadiene : TIBA: DIBAH : IBADC was 1:25:6:2:2.6.
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 6:1 to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1, using 2-methylthiozoline (2-MT) instead of N- methylpyrrolidone at a molar ratio of 2-MT/Nd of 8.
  • the produced modified polymer had a Mooney viscosity value of 47, a 1,4 -unit content of 97.1%, Mw/Mn of 2.6, and a modification degree of 93%.
  • a catalyst system was prepared according to Example 1, except the use of diethylaluminum iodide (DEAI) instead of EASC.
  • DEAI diethylaluminum iodide
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 4:1 to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1, using 2-methylthiozoline (2-MT) instead of N- methylpyrrolidone at a molar ratio of 2-MT/Nd of 12.
  • the produced modified polymer had a Mooney viscosity value of 48, a 1,4 -unit content of 96.9%, Mw/Mn of 2.6, and a modification degree of 95%.
  • a catalyst system was prepared according to Example 1, except the use of trimethylylaluminum (TMA) instead of TIBA.
  • TMA trimethylylaluminum
  • neodymium versatate butadiene: TMA :DIBAH:EASC was 1:12:10:2:2.4.
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 3.7:1 to control the molecular weight of the polymer.
  • Modification was carried out according to Example 1, using 1, 3-dimethylimidazolidone (1,3-DMI) instead of N- methylpyrrolidone at a molar ratio of 1,3-DMI/Nd of 8.
  • the produced modified polymer had a Mooney viscosity value of 45, a 1,4 -unit content of 96.6%, Mw/Mn of 2.7, and a modification degree of 90%.
  • a catalyst system was prepared according to Example 1, except the use of trihexylaluminum (THA) instead of TIBA.
  • TAA trihexylaluminum
  • neodymium versatate butadiene: THA: DIBAH :EASC was 1:10:12:2:2.4.
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 4.5:1 to control the molecular weight of the polymer.
  • Example 20 Modification was carried out according to Example 1, using 1, 3-dimethylimidazolidone (1,3-DMI) instead of N- methylpyrrolidone at a molar ratio of 1,3-DMI/Nd of 15.
  • the produced modified polymer had a Mooney viscosity value of 47, a 1,4 -unit content of 97.0%, Mw/Mn of 2.7, and a modification degree of 92%.
  • Example 20 1, 3-dimethylimidazolidone (1,3-DMI) instead of N- methylpyrrolidone at a molar ratio of 1,3-DMI/Nd of 15.
  • the produced modified polymer had a Mooney viscosity value of 47, a 1,4 -unit content of 97.0%, Mw/Mn of 2.7, and a modification degree of 92%.
  • Example 20 Example 20
  • a catalyst system was prepared according to Example 1, except the use of trioctylaluminum (TOA) instead of TIBA.
  • TOA trioctylaluminum
  • neodymium versatate butadiene: TOA :DIBAH:EASC was
  • a solution of DIBAH was additionally added to the charge at a molar ratio of DIBAH/Nd versatate of 4.5:1 to control the molecular weight of the polymer.
  • Rubber mixtures are prepared by vulcanization of polymer-based compositions.
  • the choice of a polymer and a composition of a rubber mixture is determined by the purpose, working conditions and technical specification of an article, technology of production, and other parameters.
  • the technology of rubber production comprises mixing raw rubber with ingredients in specific mixers or roll mills, cutting and tailoring a rubber half -finished product (shape and size depend on further planned use of the produced rubber, in particular, on a planned test method) , and vulcanizing the produced half -finished products in special apparatuses (press machines, autoclaves, shaper- vulcanizers, and the like) .
  • rubber mixtures were prepared according to modes and formulations set forth in standard ASTM D 3189 (Table 2) . Rubber mixing was carried out in two steps in an internal rubber mixer.
  • the initial mixing step in the internal mixer was carried out at a temperature allowing reaching discharge conditions and at an angular velocity of 8.0 rad/s.
  • the mixer was charged with half of polymer, the whole zinc oxide, carbon black, oil, and stearic acid, and then with the remaining polymer.
  • the mixture was stirred until a temperature of 170 °C or for the total mixing time of 6 min, whichever was sooner.
  • the mixture was discharged and passed over a roll mill at a temperature of 40 ⁇ 5°C and a gap between rolls of 6.0 mm. Then, the mixture was kept for 1-24 hours at room temperature.
  • the final mixing step in the internal rubber mixer was carried out at a temperature of 40 ⁇ 5°C, disconnecting the steam supply and including the cooling water supply to the rotors, at a velocity of 8.0 rad/s.
  • the whole sulfur and sulfenamide was wrapped to half of a masterbatch (the mixture resulting from the initial mixing step) and loaded to the rubber mixer, and then the remainder of the masterbatch was added.
  • the mixture was stirred until a temperature of 110 ⁇ 5°C or for the total mixing time of 3 min, whichever was sooner.
  • the mixture was discharged and then passed as a roll over rolls perpendicularly to the surface of the rolls at a gap between rolls of 0.8 mm and a temperature of the surface of the rolls of 40 ⁇ 5°C. After that, the gap was set so as to obtain the thick of the mixture of not less than 6 mm, and the mixture was passed over the rolls, each time folding it double.
  • Samples which were sufficient to determine the viscosity of the mixture, its processability according to GOST P 54552, and vulcanization characteristics according to GOST P 54547, were cut from the prepared rubber mixture.
  • test sheets were prepared and vulcanized according to GOST P 54554.
  • the recommended standard vulcanization time for mixtures prepared by methods A, B, and C is 25, 35, and 50 minutes at 145°C.
  • the recommended standard vulcanization time for the mixture prepared in an internal mixer is 35 minutes at 145°C.
  • the vulcanized sheets were conditioned for 16-96 hours at 23 ⁇ 2°C.
  • the modified polydienes produced by the method according to the invention are characterized by a degree of modification of at least 90%, a reduced value of the Payne effect, and, as a consequence, by an improved distribution of filler particles in the rubber matrix.
  • the rubbers produced from the obtained polydiens are characterized by an increased wear resistance index and reduced elastic-hysteresis values compared to non-modified polydiene.
  • the use of polymers prepared by the method according to the invention in the manufacture of tires has a positive impact on their performance properties and fuel efficiency .

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Abstract

L'invention concerne l'industrie des caoutchoucs synthétiques utilisés dans la fabrication des pneumatiques, des produits de caoutchouc industriels, en électrotechnique et dans d'autres domaines. En particulier, la présente invention concerne un procédé de production de polydiènes modifiés dans un solvant organique sur un système catalyseur comprenant un composé lanthanide, un composé organoaluminique et un constituant halogéné, suivie d'une modification terminale du polymère "pseudo-vivant" produit avec au moins un composé choisi dans le groupe des composés hétérocycliques azotés. La présente invention concerne aussi des polydiènes modifiés produits par ce procédé. En outre, l'invention concerne des mélanges de caoutchoucs à base des polydiènes produits. Le polydiène modifié résultant est caractérisé par un degré élevé de modification (non inférieur à 90 %), une teneur élevée en unités 1,4-cis, par une distribution étroite du poids moléculaire, et une aptitude au traitement améliorée à l'étape de mélange de caoutchouc ; les caoutchoucs produits à partir des polydiènes modifiés sont caractérisés par une résistance à l'usure accrue et des propriétés physiques et chimiques améliorées, ainsi que par des propriétés d'hystérésis élastique améliorées (résistance au roulement, traction de pneu humide).
PCT/RU2016/000763 2016-11-10 2016-11-10 Procédé de production de polydiènes modifiés, polydiènes modifiés produits par ce procédé, et mélanges de caoutchoucs à base des polydiènes modifiés produits WO2018088919A1 (fr)

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RU2019117617A RU2727714C1 (ru) 2016-11-10 2016-11-10 Способ получения модифицированных полидиенов, модифицированные полидиены, полученные данным способом, и резиновые смеси на основе полученных полидиенов
PCT/RU2016/000763 WO2018088919A1 (fr) 2016-11-10 2016-11-10 Procédé de production de polydiènes modifiés, polydiènes modifiés produits par ce procédé, et mélanges de caoutchoucs à base des polydiènes modifiés produits

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CN112442151A (zh) * 2019-09-03 2021-03-05 中国石油化工股份有限公司 催化共聚制聚(丁二烯-异戊二烯)
WO2021154113A1 (fr) * 2020-01-29 2021-08-05 Публичное Акционерное Общество "Сибур Холдинг" (Пао "Сибур Холдинг") Procédé de production de polydiènes modifiés (variantes)
CN113896819A (zh) * 2021-11-11 2022-01-07 中国科学院长春应用化学研究所 一种酮类化合物改性聚丁二烯橡胶及其制备方法和硫化橡胶
CN113929803A (zh) * 2021-11-11 2022-01-14 中国科学院长春应用化学研究所 一种高强度航空轮胎胎面仿生橡胶及其制备方法、应用
JP2022525070A (ja) * 2019-03-10 2022-05-11 株式会社ブリヂストン 変性高シスポリジエンポリマー、関連する方法及びゴム組成物
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CN115304698A (zh) * 2022-07-20 2022-11-08 中国科学院大连化学物理研究所 一类官能化共轭二烯烃橡胶、复合材料及其制备方法
EP4077409A4 (fr) * 2019-12-20 2023-08-23 Public Joint Stock Company "Sibur Holding" (PJSC "Sibur Holding") Polymère diène modifié et procédé pour sa préparation
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JP2022525070A (ja) * 2019-03-10 2022-05-11 株式会社ブリヂストン 変性高シスポリジエンポリマー、関連する方法及びゴム組成物
CN112194748B (zh) * 2019-07-08 2022-07-12 中国石油化工股份有限公司 聚异戊二烯及其制备方法
CN112194748A (zh) * 2019-07-08 2021-01-08 中国石油化工股份有限公司 聚异戊二烯及其制备方法
CN112442151A (zh) * 2019-09-03 2021-03-05 中国石油化工股份有限公司 催化共聚制聚(丁二烯-异戊二烯)
CN112442151B (zh) * 2019-09-03 2023-07-21 中国石油化工股份有限公司 催化共聚制聚(丁二烯-异戊二烯)
EP4077410A4 (fr) * 2019-12-20 2023-12-06 Public Joint Stock Company "Sibur Holding" (PJSC "Sibur Holding") Polydiènes ramifiés et compositions de caoutchouc à base de ceux-ci
EP4077409A4 (fr) * 2019-12-20 2023-08-23 Public Joint Stock Company "Sibur Holding" (PJSC "Sibur Holding") Polymère diène modifié et procédé pour sa préparation
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RU2802970C1 (ru) * 2020-01-29 2023-09-05 Публичное Акционерное Общество "Сибур Холдинг" (Пао "Сибур Холдинг") Способ получения модифицированных полидиенов (варианты)
EP4098666A4 (fr) * 2020-01-29 2023-11-08 Public Joint Stock Company "Sibur Holding" (PJSC "Sibur Holding") Procédé de production de polydiènes modifiés (variantes)
WO2021154113A1 (fr) * 2020-01-29 2021-08-05 Публичное Акционерное Общество "Сибур Холдинг" (Пао "Сибур Холдинг") Procédé de production de polydiènes modifiés (variantes)
EP4126983A4 (fr) * 2020-03-31 2024-04-24 Bridgestone Americas Tire Operations, LLC Catalyseur à base de métal pour la production de polydiènes
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CN115304698A (zh) * 2022-07-20 2022-11-08 中国科学院大连化学物理研究所 一类官能化共轭二烯烃橡胶、复合材料及其制备方法

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