Method for obtaining butadiene polymers and butadiene copolymers with styrene

FIELD: chemistry.

SUBSTANCE: invention claims method of obtaining polybutadiene or butadiene copolymers with styrene by polymerisation of respective monomers in hydrocarbon solvent medium in the presence of initiating system, where initiating system is a complex of lithium organic compound and modifying additive obtained by reaction of alkali metal lapramolate and tetrahydrofurfurylic alcohol, metal magnesium and sodium (potassium) at molar ratio of 1 : 2-4 : 1-2 : 0-2 respectively. Polybutadiene and butadiene copolymers with styrene with 1,2-link content in diene part adjustable from 9 to 75 wt %, reduced rate of macromolecules with mass over 106 g/mol (up to 5 wt %), is obtained at temperatures over 60°C.

EFFECT: improved method of obtaining polybutadiene or butadiene copolymers with styrene.

5 cl, 5 tbl, 14 ex

 



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention concerns process of obtaining polymerisate by anion polymerisation involving conjugated dienes and vinyl aromatic compounds. It describes obtaining of statistic polymerisates by anion polymerisation involving conjugated dienes and vinyl aromatic compounds, in inert medium, in the presence of at least one lithium-organic compound; at least one dialkyl ester represented by the formula: R1-O-CH2-CH(R3)-O-R2 (where R1 and R2 independently denote alkyl residues from methyl, ethyl, n- and isopropyl group, as well n-, iso-, di- and tributyl group, with different number of carbon atoms, while total amount of carbon atoms in both alkyl residues R1 and R2 comprises 5 to 7, and R3 stands for hydrogen, methyl or ethyl group); and at least one organic alkali compound at the ratio of more that 0.5 mol for one mol of lithium in organic lithium compound. As an organic alkali compound alkali metal alkoholate of formula M-OR is taken, where R is an alkyl group with 1-10 carbon atoms, and M is sodium.

EFFECT: production of vinyl order rubber with high styrol content with sufficient monomer randomisation.

13 cl, 1 tbl, 10 ex

FIELD: rubber industry.

SUBSTANCE: invention relates to process of manufacturing synthetic rubber, in particular solution butadiene-styrene rubber suitable in manufacture of tires with high performance characteristics, resistance to high wheel rolling and providing long lifetime, good maneuverability, adhesion to wet pavement, and low consumption of fuel. Butadiene-styrene rubber is obtained via copolymerization of butadiene with styrene in hydrocarbon solvent and in presence of organolithium catalyst and modifying additive at catalyst-to-additive molar ratio 1:(0.2-1.0). Process comprises mixing monomers with solvent, deactivation of catalyst to stabilize polymer, degassing, and drying of rubber. As modifying additive, alkali metal alcoholates originated from hydroxyalkylated secondary amines.

EFFECT: enabled manufacture of butadiene-styrene rubber with middle and predominant content of 1,2-units in butadiene portion of copolymer.

2 tbl, 22 ex

FIELD: polymerization of conjugated dienes and copolymerization with vinyl aromatic copolymers by interaction in hydrocarbon solvent medium.

SUBSTANCE: proposed method is used for copolymerization with vinyl aromatic solvent of lithium alkyl and organic amine; used as organic amine is compound of the following formula:

, where R1 and R2 are similar or different; C1-C4 are alkyl or allylic radicals; R3 is vinyl or phenyl radical. Process is performed at temperature of 20-35°C at equimolar ratio of lithium alkyl: organic amine and concentration of lithium alkyl in solution from 0.1 to 1.0 mole/l; then, diene or vinyl aromatic monomer or their mixture is fed to reaction zone continuously or in batches to mole ratio of conjugated monomer: starting lithium alkyl no less than 3 at concentration maintained at 0.05 to 0.20 mole/l. Invention is also useful to nitrogen-containing initiating agent of the following formula:

.

EFFECT: enhanced ecological safety with no change in polymerization of structure and composition of (co)polymers of conjugated dienes.

3 cl, 1 tbl, 8 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention describes a method for preparing polymers. Method involves anionic polymerization reaction of vinylaromatic monomers and coupled dienes or by their copolymerization reaction in medium of hydrocarbon solvent in the presence of lithium-organic initiating agent followed by functioning ends of polymeric chains. Method involves using monofunction amine-containing lithium-organic initiating agent as a lithium-organic initiating agent wherein active lithium is stabilized with vinyl or phenyl radical of the general formula: wherein R1 and R2 are similar or different alkyl or allyl radicals; R3 means vinyl or phenyl radical. The functioning ends of polymeric chains is carried out by treatment of "living" macromolecules with a coupling agent or by the functioning break, and (co)polymerization reaction is carried out in the presence of alkaline metal alkoxides or phenolates. Invention provides preparing polymer showing reduced hysteresis losses and high mechanical strength, and improved ecological indices.

EFFECT: improved preparing method.

2 cl, 5 tbl, 11 ex

The invention relates to the field of production of rubber for the manufacture of tyres, rubber, bitumen modification

The invention relates to the production of rubbers for the production of tires with high performance

The invention relates to a method of obtaining new undescribed in the literature polylithium derivatives karbosilanovykh compounds (PLCS), which can find application in the chemical industry as intermediates for various materials organiseorganised

The invention relates to techniques for the polymerization of butadiene-1,3 and can be used in the synthetic rubber industry, and the resulting product is the basis for the manufacture of anti-corrosion and insulating coatings, as a plasticizing additive in the production of tires and rubber products

The invention relates to the technology of high molecular weight polybutadiene with a predominant content of vinyl units and can be used in the synthetic rubber industry, and the obtained product is in the tire, rubber, abrasive and other industries

The invention relates to the production of /over/of polymers of isoprene, which has a higher content of vinyl units and high cohesive strength, designed to get rubbers with good damping characteristics

FIELD: chemistry.

SUBSTANCE: invention pertains to vinyl-cis-polybutadiene rubber, obtained by simultaneous bonding of 1,2-polybutadiene, characterised by melting point of 170°C or higher, and polyisoprene , characterised by a low melting point, and their dispersion in a matrix of cis-polybutadiene rubber. The invention also relates to butadiene rubber mixture based on vinyl cis-polybutadiene rubber. In the vinyl cis-butadiene rubber 1,2-polybutadiene and polyisoprene are dispersed in adsorbed form such that, polyisoprene becomes insoluble in boiling n-hexane, in cis-polybutadiene rubber, which acts as a matrix component, where content of isoprene ranges from 0.01 to 50 wt % on the overall quantity of crystalline fibre of 1,2-polybutadiene and cis-polybutadiene rubber.

EFFECT: formation of a rubber mixture, characterised by low die swell and excellent processing properties and manufacturability in the extrusion method when making outer covers, and which after vulcanisation has excellent bursting strength, abrasion resistance and crack resistance and very hard.

18 cl, 7 tbl, 12 ex, 8 dwg

FIELD: polymerization catalysts.

SUBSTANCE: proposed catalytic system used for production of polybutadienes is based on at least one conjugated diene monomer; organophosphorus acid salt of one or several rare-earth metals, said salt being suspended in at least one inert aliphatic or alicyclic saturated hydrocarbon solvent; alkylation agent selected from trialkylaluminum and dialkylaluminum hydride, wherein molar ratio of alkylation agent to rare-earth metal salt(s) exceeds 5:1; and hydrogen donor selected from alkylaluminum halides excepting alkylaluminum sesquihalides. Catalytic system is characterized by that concentration of rare-earth metal(s) is at least 0.005 mole/L. Polybutadienes obtained according to invention have polydispersity index below 2.1 and Mooney viscosity ML (1+4) at 100°C below 40.

EFFECT: improved physicochemical characteristics of polybutadienes.

14 cl, 2 tbl, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for processing 1,3-buradiene-containing mixtures of C4-hydrocarbons to yield polymers or copolymers of 1,3-butadiene. Method for processing 1,3-butadiene-containing mixture of C4-hydrocarbons involves incomplete poly- and/or (co)polymerization of 1,3-butadiene in the (co)polymerization zone, isolation of C4-hydrocarbons from its flow and the following isolation the fraction with enhanced concentration of 1,3-butadiene recirculating to the (co)polymerization zone. Method involves processing the parent mixture of C4-hydrocarbons with the concentration of 1,3-butadiene 25-99.7 wt.-% comprising as minimum n-butane and 2-butenes wherein in the (co)polymerization zone 60-95% of 1,3-buradiene is converted and the concentration of n-butane or the total concentration of n-butane and 2-butenes is maintained in outlet at the level 0.35-70 wt.-% relatively to it (their) sun with 1,3-butadiene. After the (co)polymerization step part of n-butane is separated by rectification from C4-hydrocarbon flow with the mass ratio of n-butane and 1,3-butadiene in distillate from 1:8 to 1:25 or in the mass ratio of n-butane and 1.3-butadiene in indicated flow of C4-hydrocarbons after (co)polymerization above 1:8, and part of n-butane is separated by rectification as a component of vat flow, possibly, with 2-butenes. Method provides processing a mixture of C4-hydrocarbons with broad range of concentration of 1,3-butadiene comprising as minimum n-butane and 2-butenes by a method wherein in the (co)polymerization system the accumulation of n-butane and 2-butenes is limited being without excessive loss of 1,3-butadiene by rectification and without using special separating agents.

EFFECT: improved processing method.

12 cl, 4 dwg, 6 tbl, 10 ex

FIELD: polymer production.

SUBSTANCE: crystalline 1,2-polybutadiene with high crystallinity level is obtained via polymerization of 1,3-butadiene in hydrocarbon solvent using catalytic system containing (i)cobalt salt, (ii) phosphine compound having one branched aliphatic group with 3 or more carbon atoms or one alicyclic group with 3 or more carbon atoms and diphenyl and (iii) methylalumoxane or compound obtained when trialkylaluminum is brought into contact with water.

EFFECT: enabled preparation of 1,2-polybutadiene with high level of vinyl bond and controlled molecule mass.

9 cl, 1 dwg, 3 tbl, 7 ex

FIELD: polymers, rubber industry, in particular production of stereoblock polymers of conjugated dienes, such as cis-1,4-polyisoprene.

SUBSTANCE: modified cis-1,4-polyisoprene is obtained by polymerization pf isoprene in isopentane medium in presence of Ziegler-Natta catalyst. Then catalyst is deactivated; polymer is stabilized and modified with nitrogen-containing compound; polymer in isolated and dried. As nitrogen-containing compound reaction product of maleic anhydride and N-alkyl-N'-phenyl-n-phenylenediamine in amount of 0.5-2 % based on polymer is used.

EFFECT: simplified method for production of polymers having heat oxidative stability.

1 tbl, 1 ex

FIELD: chemistry of polymers, chemical technology, catalysts.

SUBSTANCE: invention relates to a method for preparing a catalyst used in polymerization of butadiene and copolymerization of butadiene with coupled dines. Method involves interaction of components comprising the compound of rare-earth element, diisobutyl aluminum hydride, triisobutyl aluminum, alkyl aluminum halide and coupled diene. Firstly, method involves mixing rare-earth element and coupled diene solutions with diisobutyl aluminum hydride solution, and the mixture is kept for 10-30 min at stirring, and then triisobutyl aluminum and alkyl aluminum halide solutions are added. After mixing all components the mixture is kept for 10-15 h in the following mole ratio of components: rare-earth element : diisobutyl aluminum hydride : triisobutyl aluminum : alkyl aluminum halide : coupled diene = 1:(3-12):(6-12):(1.5-3):(2-20), respectively, wherein rare-earth element carboxylate or alcoholate is used as a source of rare-earth element. Invention provides preparing the high-effective catalyst allowing preparing highly stereoregular polybutadiene and butadiene copolymer with the couples diene with simultaneous reducing the range of molecular-mass disposition by 3-3.5 times.

EFFECT: improved preparing method.

5 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalyst preparation involves interaction of rare-earth element compound, conjugated diene, and diisobutylaluminum hydride followed by ageing of reaction mixture for 10-30 min, adding tetraisobutyl-dialumoxane and alkylaluminum hydroxide at molar ratio 1:(2-20):(3-12):(6-12):(1.5-3), respectively, and ageing resulting mixture for 10-15 h. Diene utilized is in the process is pyperilene or isoprene and rare-earth element compound is rare-earth element carboxylate or alcoholate. Catalyst can, in particular, find use in production of cis-1,4-polydienes.

EFFECT: achieved preparation of high-efficiency catalyst enabling production of highly stereospecific polybutadiene or butadiene/isoprene or butadiene/pyperilene copolymers at narrower molecular mass distribution.

4 ex

FIELD: polymers, chemical technology.

SUBSTANCE: invention relates to oil-filled 1,2-polybutadiene that can be used as different molded articles, to a method for its preparing, its composition and molded article, shoes footing material. Oil-filled 1,2-polybutadiene is prepared by addition of the definite amount of oily filling agent to 1,2-polybutadiene solution wherein polymerization process is terminated followed by stirring in the polymerization solution containing organic solvent and removing the solvent at the second stage of the method. The composition of oil-filled 1,2-polybutadiene for making molded article comprises abovementioned oil-filled 1,2-polybutadiene and one component taken among the group involving a foaming agent, functional compound for rubber or plastics and at least one component taken among the group consisting of thermoplastic resin, thermoplastic elastomer, natural rubber and synthetic rubber. The molded article is prepared by molding the oil-filled 1,2-polybutadiene. Material for shoes footing is prepared by foaming the composition of oil-filled 1,2-polybutadiene or by cross-linking and molding. Oil-filled 1,2-polybutadiene or composition based on thereof show excellent functions by abrasion resistance, fluidity, technological effectiveness, capacity for coloring, high image precision, flexibility and attachment capacity. Also, oil-filled 1,2-polybutadiene and compositions based on thereof can be used for different types of foodstuffs, material for shoes footing with high exploitation indices.

EFFECT: improved preparing method, improved and valuable properties of composition and article.

13 cl, 17 tbl, 43 ex

FIELD: organic chemistry, chemical technology, rubber industry.

SUBSTANCE: invention relates to technology used in preparing diene rubber by effect of Ziegler-Natt's catalytic system. Preparing of cis-1,4-diene rubber is carried out by (co)polymerization of diene monomer(s) in hydrocarbon solvent medium in battery of in-line of at least three in-line connected reactors and by using Ziegler-Natt's catalyst based on compounds of rare-earth elements from lanthanides order followed by stopping, washing out, degassing and dehydration of polymer. Butadiene, isoprene or their mixture are used as diene monomer(s), and diene monomer or mixture of diene monomers is fed in common or separately by fractional dosing. The catalyst is fed into the first reactor only and 1-99 wt.-% of the total amount of diene monomer(s) is fed firstly into the first reactor as a charge dissolved in hydrocarbon solvent and then 1-99 wt.-% of remain diene monomer or a mixture of diene monomers of the total amount of charged monomers is fed into next second and third reactors. These monomers are fed either simultaneously into both second and third reactors or successively into the second and third reactors separately. Also possibly that the solution of trialkyl aluminum or dialkyl aluminum hydride, or tetraisobutyldialumoxane or their mixture are fed simultaneously with diene monomer(s) adding into the first, second or third reactor. Also, possible that a hydrocarbon solvent with temperature from -25°C to +140°C is fed simultaneously but separately from a monomer adding into the third or the next reactors. Proposed method provides preparing cis-1,4-diene rubbers showing narrow molecular-mass distribution and high physical-mechanical indices of vulcanized rubber. Invention can be used in industry of synthetic rubber and synthesized polymer - in rubber and tire branches of industry.

EFFECT: improved preparing method.

3 cl, 2 tbl, 27 ex

FIELD: polymer production and polymer production catalysts.

SUBSTANCE: invention relates to synthesis of catalysts for production of cis-polybutadiene and butadiene/isoprene cis-copolymer, which can be employed in synthetic rubber industry. Task of invention resides in providing a novel method for synthesis of high-activity catalytic component, in particular neodymium neodecanoate, by reaction of neodymium oxide with neodecanoic acid in presence of metal chloride catalysts characterized by low acidity enabling conduction of process in stainless steal apparatuses and so making it possible to exactly controlling molar ratio of neodymium neodecanoate to free neodecanoic acid and water. Catalytic complex is formed by mixing neodymium neodecanoate-based catalytic component with butadiene, triisobutylaluninum, and diisobutylaluninum hydride in hydrocarbon solvent. Polymerization of butadiene or copolymerization of butadiene with isoprene is carried out in presence of thus formed catalytic complex in hydrocarbon solvent.

EFFECT: increased percentage of cis-1,4 units in polybutadiene or butadiene/isoprene copolymer and narrowed polymer or copolymer molecular weight distribution.

11 cl, 1 tbl, 45 ex

FIELD: chemistry.

SUBSTANCE: invention concerns process of obtaining polymerisate by anion polymerisation involving conjugated dienes and vinyl aromatic compounds. It describes obtaining of statistic polymerisates by anion polymerisation involving conjugated dienes and vinyl aromatic compounds, in inert medium, in the presence of at least one lithium-organic compound; at least one dialkyl ester represented by the formula: R1-O-CH2-CH(R3)-O-R2 (where R1 and R2 independently denote alkyl residues from methyl, ethyl, n- and isopropyl group, as well n-, iso-, di- and tributyl group, with different number of carbon atoms, while total amount of carbon atoms in both alkyl residues R1 and R2 comprises 5 to 7, and R3 stands for hydrogen, methyl or ethyl group); and at least one organic alkali compound at the ratio of more that 0.5 mol for one mol of lithium in organic lithium compound. As an organic alkali compound alkali metal alkoholate of formula M-OR is taken, where R is an alkyl group with 1-10 carbon atoms, and M is sodium.

EFFECT: production of vinyl order rubber with high styrol content with sufficient monomer randomisation.

13 cl, 1 tbl, 10 ex

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