KR20220119102A - Branched polydiene, rubber composition based thereon - Google Patents

Abstract

The present invention relates to the production of synthetic polymers used in the manufacture of tire and rubber technical products, in the electrical industry and in other fields. In particular, the present invention relates to a method for preparing a branched polydiene by polymerization of a conjugated diene, comprising the steps of: preparing a catalyst composite comprising a lanthanide compound, an organoaluminum compound, a conjugated diene, and a halogen-containing component to do; polymerizing the conjugated diene in the presence of the catalyst complex; performing post-polymerization modification with at least one branching agent selected from halogen-containing compounds, phosphorus-nitrogen compounds, or mixtures thereof; end stage; introducing into the polymer a plasticizer, which is a low molecular weight polymer having a molecular weight of 1500 g/mol to 50,000 g/mol; and degassing and drying the polymer. In another aspect, the present invention relates to a method for producing a rubber composition based on the branched polydiene. The technical result of the present invention is a branched type characterized by a branching index characterized by a Mooney viscosity of about 40 to about 49 Mooney units (MU), and a mechanical loss angular tangent tgδ (1200%) of about 4.7 to about 5.3. production of polydiene. The polydiene prepared according to the present invention has improved processability, improved distribution of fillers in the polymer matrix, and a rubber composition based on it has improved elastic-hysteresis properties (i.e. Mooney viscosity ML (1) +4) (unit: MU), Payne effect Δ(G'1%-G'50%) (unit: kPa), Tanδ 60 °C (at 10% strain)).

Description

Branched polydiene, rubber composition based thereon

The present invention relates to the production of synthetic polymers used in the manufacture of tire and rubber technical products in the electrical industry and other fields.

In particular, the present invention relates to a method for preparing a branched polydiene by polymerization of a conjugated diene, comprising the following steps: a catalyst complex comprising a lanthanide compound, an organoaluminum compound, a conjugated diene, and a halogen-containing component; manufacturing; polymerizing the conjugated diene in the presence of the catalyst complex; performing post-polymerization modification using at least one branching agent selected from halogen-containing compounds, phosphorus-nitrogen compounds, or mixtures thereof; termination; introducing a plasticizer into the polymer, wherein the plasticizer is a low molecular weight polymer having a molecular weight of 1500 g/mol to 50,000 g/mol; and degassing and drying the polymer. In another aspect, the present invention relates to a method for producing a rubber composition based on the branched polydiene.

The branched polydiene prepared according to the present invention has a Mooney viscosity index of 40 to 49 Mooney Units (MU), a polydispersity index ranging from 2.16 to 2.60, and a mechanical loss angular tangent tgδ (1200) of about 4.7 to about 5.3. %), and a content of 1,4-cis units from 96.0% to 98.0%. The prepared polydiene-based rubber composition is characterized by low Mooney viscosity of the rubber composition, and exhibits excellent elastic-hysteresis properties.

Today, in order to increase competitiveness, it is very important for rubber producers to take advantage of the properties considered in the environmental labeling of tires. To achieve this goal, the rolling resistance index, which accounts for 20% to 30% of fuel consumption by motor vehicles, must be optimized. The reduction in rolling resistance not only reduces fuel consumption, but also leads to reduced carbon dioxide emissions.

Various low-molecular-weight polymers, so-called liquid rubbers, have appeared on the market, allowing non-studded tires for winter with improved grip in winter conditions. Some companies are already using liquid rubber as a reinforcing additive in tread compounds. In tests, the tread thus obtained exhibits high plasticity, maintains flexibility even at low temperatures, and also exhibits improved ice grip.

Patent RU 2,394,692 (SUMITOMO RABBER INDASTRIES, LTD (JP), 07.20.2010) describes the preparation of a rubber composition for side walls of pneumatic tires containing: 30% by mass to 70% by mass of natural rubber and epoxidized natural rubber 100 parts by mass of a first rubber component consisting of 70% by mass to 30% by mass; 20 parts by mass to 60 parts by mass of silica; and 3 parts by mass to 60 parts by mass of a second rubber component consisting of a liquid rubber and a vulcanizing agent. This provides an “ecological” pneumatic tire with improved durability (improved heat resistance, anti-crack properties, ozone resistance).

However, introducing the liquid rubber in the step of mixing the rubber does not ensure its uniform distribution in the polymer matrix, and also requires additional energy consumption. Also, according to this patent, only liquid polyisoprene rubber (natural rubber) was used.

The use of liquid polydiene as part of rubber compositions is well known. Patent EP 2082899 (CONTINENTAL AG(DE), 18.05.2011) describes a process for the preparation of a rubber composition consisting of 5 to 50 parts by mass of a liquid low-viscosity polymer. The mixture so obtained exhibits improved elasticity at low temperatures and improved tensile modulus at 300% elongation.

Also liquid rubber is introduced in the rubber mixing step, and the improvement of the physical and mechanical properties and elastic hysteresis properties of the rubber mixture is not mentioned in this patent.

A method for improving the abrasion resistance of rubber compositions for the manufacture of tire treads using functionalized liquid polybutadiene is disclosed in US Pat. No. 8,975,324 (RANDALL AMY M (US), AGARWAL SHEEL P (US), HERGENROTHER WILLIAM L (US), BRIDGESTONE CORP (JP)) , 10.03.2015). The rubber composition according to the present invention comprises: a conjugated diene polymer or copolymer; at least one filler; 2 to 10 phr of liquid polybutadiene functionalized with an unsaturated carboxylic acid anhydride; Zinc oxide 0.2 to 5 phr; and 1 to 100 phr of process oil. In this patent, liquid rubber is introduced in the step of mixing rubber, and through comparison of a rubber composition having liquid rubber and a rubber composition based on oil-filled polymers, the former Mooney viscosity (Mooney viscosity) is 10% to 28% higher than the latter (which indicates poor processability), and also demonstrates that the rate of vulcanization of rubber compositions with liquid rubber is 1.5 to 2 times lower. did.

A rubber composition prepared as disclosed in US 6,472,461 (BRIDGESTONE CORP (JP), 29.10.2002) consists of: 1) a rubber composition, comprising: a) at least one natural or synthetic diene rubber, and b) based on the molecular weight of polystyrene A low molecular weight polybutadiene having an average molecular weight of 5,000 to 30,000 and a content of 1,4-cis structure of 60% to 98% as measured by gel permeation chromatography, and a low molecular weight polybutadiene in an amount of 6% or more based on the rubber component A rubber composition comprising; 2) polyethylene short fibers having an average length of 10 mm or less; and 3) blowing agents. This invention relates to a method of manufacturing a pneumatic tire that exhibits improved braking capability on ice.

The inventors of this invention do not provide data on indices that are very important to tire manufacturers (wear, elastic hysteresis properties at 60° C., and strength properties of rubber).

RU 2,429,252 (BRIDGESTONE CORP (JP), 20.09.2011) also describes a method of introducing a low molecular weight polymer in the step of mixing the rubber. Here, the rubber mixture is a low molecular weight conjugated diene-based polymer (B) having a weight average molecular weight of greater than 30,000 and not more than 200,000 measured by gel permeation chromatography converted into polystyrene, and a rubber component (A) mixed with (B) 100 parts by weight It is prepared by mixing with (A) in an amount of 1 to 60 parts by weight. The rubber component (A) comprises natural rubber and/or polyisoprene rubber, and optionally, at least one rubber selected from the group consisting of styrene-butadiene copolymer rubber, polybutadiene rubber and isobutylene isoprene rubber. do. The composition according to the invention has good workability and heat resistance during production, high storage elastic modulus and low loss tangent (tg δ).

However, the introduction of liquid rubber in the rubber mixing step does not guarantee its uniform distribution in the polymer matrix.

Changes in molecular parameters and plasto-elastic properties of polybutadiene after the active center (the growing macromolecule) interacts with the carbonyl group after polymerization with maleic fragments and during polymerization modification is known to follow. In addition, a new phenomenon was discovered. In particular, when introducing a modifier directly into the finished catalyst complex (polymerization modification), the modifier not only interferes with the polymerization process, but also provides a result close to post-polymerization modification (V.L. Zolotarev). , On the mechanism of the process of post-polymerization modification of neodymium 1,4-cis-polybutadiene, J. "Vysokomolekulyarnye soedineniya" [High Molecular Compounds], No. 3, p.3-5, 2015).

However, the use of maleinized polybutadiene alone for modification does not impart optimal performance properties to the rubber, regardless of the timing of its introduction.

A promising direction is post-polymerization modification of 1,4-cis polybutadiene and low molecular weight polymers that affect the properties of rubber compositions based on them.

The process for preparing polybutadiene disclosed in US 7,112,632 (POLIMERI EUROPA SPA(IT), 26.09.2006) is closest to the essence of the present invention. According to this method, the process for preparing polybutadiene comprises the following steps: (a) polymerization of butadiene; (b) treating the polymer solution obtained upon completion of step (a) with a coupling agent, the coupling agent being (i) unsaturated natural oil, (ii) butadiene and/or isoprene oligomers, (iii) butadiene and/or a copolymer of isoprene with a vinylarene monomer, wherein the unsaturation present in compounds (i) to (iii) may be at least partially substituted with a group selected from epoxides, anhydrides and esters; and (c) recovering low branch content polybutadiene obtained upon completion of step (b). According to this patent, the polymer obtained has a low branching content.

However, it is known that excellent processability of a rubber compound is secured by using a branched polymer. This patent contains no information on the uniformity of the distribution of the filler in the polymer matrix, nor on the improvement of the wear and processability of the obtained polymer.

It is an object of the present invention to improve the processability of polymers in the rubber mixing step.

This object is solved by developing a process for the preparation of branched polydiene by polymerization of a conjugated diene, the process comprising: a catalyst complex comprising a lanthanide compound, an organoaluminum compound, a conjugated diene and a halogen-containing component ( preparing a catalyst complex); polymerizing the conjugated diene in the presence of the catalyst complex; performing post-polymerization modification with at least one branching agent selected from halogen-containing compounds, phosphorus-nitrogen compounds, or mixtures thereof; termination step; introducing a plasticizer into the polymer, wherein the plasticizer is a low molecular weight polymer having a molecular weight of 1,500 g/mol to 50,000 g/mol; and degassing, isolating, and drying the polymer.

The technical result of the present invention is a Mooney viscosity of about 40 to about 49 Mooney Units (MU), and a mechanical loss angle tangent tgδ (1200%) of about 4.7 to about 5.3. Preparation of branched polydiene characterized by a branching index expressed. The polydienes produced according to the invention have improved processability, improved distribution of fillers in the polymer matrix, and rubber compositions based on them have improved elastic-hysteresis properties (e.g. , Mooney viscosity ML(1+4) (unit: MU), Payne effect Δ(G'1%-G'50%) (unit: kPa), tgδ 60 °C (10% strain) (in deformation)) is characterized.

According to the invention, the modification is carried out by using at least one branching agent selected from halogen-containing compounds, phosphorus-nitrogen compounds or mixtures thereof.

Compounds used as branched halogen containing compounds include thionyl chloride, diphenyltin dichloride, phenyltin trichloride, triphenyltin chloride, dibutyltin dichloride, butyltin trichloride, tin tetrachloride, and silicon tetrachloride. include

The phosphorus-nitrogen compound is a compound having a chemical structure based on repeating units of (-P=N-) _n , where n is an integer from 3 to 24.

The branching agent interacts with the polymer at the active ends of its polymer chain. The branching agent affects changes in the molecular weight properties of the polymer, such as Mooney viscosity and branching index, number average molecular weight Mn, weight average molecular weight Mw, polydispersity Mw/Mn, and the like.

Plasticizers (emollients) are substances that, when incorporated into a polymer, facilitate processing. In this case, the plasticizer does not chemically interact with the polymer; Only physical mixing takes place. Plasticizers are, in principle, added at the stage of mixing the rubber. The presence of classical liquid plasticizers in the formulation of rubber mixtures in the rubber mixing step allows, to some extent, homogenization of the rubber mixture; In most cases, a significant amount (average 15 parts by weight) adversely affects the complex of physicochemical properties of the vulcanizates produced.

A distinguishing feature of the present invention is the introduction of the plasticizer in the form of a solution in an inert organic solvent in the polymer preparation step. This technique allows the use of a low amount of plasticizer (at least 6 times less than the amount introduced in the rubber mixing step) and, compared to a polymer that has undergone only post-polymerization modification without the addition of plasticizer, the processability is at least It can be increased by 6% to 10%.

According to the invention, a plasticizer is used in the polymer preparation step, wherein the plasticizer is a low molecular weight polymer having a molecular weight of 1,500 g/mol to 50,000 g/mol. Nonfunctionalized low molecular weight polybutadiene, polybutadiene functionalized with maleic anhydride or triethoxysilane, as well as nonfunctionalized low molecular weight polyisoprene and polyisoprene functionalized with maleic anhydride are preferred as such plasticizers. used

Unfunctionalized low molecular weight polybutadiene and polybutadiene functionalized with maleic anhydride or triethoxysilane are most preferred as plasticizers because they have the same microstructure as neodymium polybutadiene.

Exemplary commercially available plasticizers are: isoprene homopolymer (eg, LIR-30, LIR-50 produced by Kuraray Co., Ltd.), polyisoprene modified with maleic anhydride (eg, , MIP-004 Kuraray Co., Ltd.), nonfunctionalized low molecular weight (“liquid”) polybutadiene (eg, Polyvest 130 from Evonik), polybutadiene functionalized with maleic anhydride (eg, Evonik) Polyvest 75MA from Cray Valley, Ricon 130 МА 8, Ricon 130 МА 10, Ricon 130 МА 13, Ricobond 1031, Ricobond 1731, Ricobond 2031, Ricobond 1756) or triethoxysilane (e.g., Polyvest EP ST- from Evonik) E 60, Polyves t EP ST-E 80, Polyvest EP ST-E 100). Table 2 shows the properties of the plasticizers (liquid rubbers) used according to the present invention.

The amount of the plasticizer used according to the present invention is 0.5 mass% to 5.0 mass%, preferably 0.7 mass% to 2.0 mass%, and the most preferred amount of the plasticizer according to the present invention is 0.8 mass% to 1.5 mass%, based on the polymer. mass %. The amount of plasticizer used in excess of the defined range significantly reduces the Mooney viscosity of the polymer and reduces the conditional tensile strength in rubber compositions. An amount of less than 0.5% by mass does not lead to improvement of the properties of polymers and rubber compositions based thereon.

The catalyst complex used according to the present invention comprises a lanthanide compound, an organoaluminum compound and a halogen-containing component. Compounds used as lanthanide compounds include compounds containing at least one lanthanide atom of neodymium, lanthanum, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. include Neodymium is preferred.

Compounds containing lanthanides include, but are not limited to, carboxylates, organophosphates (especially alkyl phosphates and aryl phosphates), organophosphonates (especially alkyl phosphonates and aryl phosphonates), organophosphinates (especially alkyl phosphites). nates and aryl phosphinates), carbamates, lanthanide xanthates, β-diketonates, halides, oxyhalides, alcoholates.

Neodymium carboxylate includes neodymium formate, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, 2-ethylhexanoate, neodymium neodecanoate, 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)phosphate, neodymium bis(2-ethylhexyl)phosphate. didecyl phosphate, neodymium didodecyl phosphate, neodymium dioctadecyl phosphate, neodymium bis(n-nonylphenyl)phosphate, neodymium butyl(2-ethylhexyl)phosphate, neodymium(1-methylphenyl)(2-ethylhexyl)phosphate, and Neodymium (2-ethylhexyl) (n-nonylphenyl) phosphate.

Neodymium organophosphonates include neodymium butylphosphonate, neodymium pentylphosphonate, neodymium hexylphosphonate, heptylphosphonate neodymium, neodymium octylphosphonate, neodymium (1-methylheptyl)phosphonate, neodymium (2 -Ethylhexyl) phosphonate, neodymium decyl phosphonate, neodymium dodecyl phosphonate, neodymium octadecyl phosphonate, neodymium oleyl phosphonate, neodymium phenyl phosphonate, neodymium (n-nonylphenyl) phosphonate Nate, neodymium butyl (butylphosphonate), neodymium pentyl (pentylphosphate), neodymium hexyl (hexylphosphonate), neodymium heptyl (heptylphosphonate), neodymium octyl (octylphosphonate), neodymium (1-methyl Heptyl) ((1-methylheptyl) phosphonate), neodymium (2-ethylhexyl) ((2-ethylhexyl) phosphonate), neodymium decyl (decyl phosphonate), neodymium dodecyl (dodecyl phosphonate) nate), neodymium octadecyl (octadecyl phosphonate), neodymium oleyl (oleyl phosphonate), neodymium phenyl (phenyl phosphonate), neodymium (n-nonylphenyl) ((n-nonylphenyl) phosphonate nate), neodymium butyl ((2-ethylhexyl) phosphonate), neodymium (2-ethylhexyl) (butyl phosphonate), neodymium (1-methylheptyl) ((2-ethylhexyl) phosphonate), Neodymium (2-ethylhexyl)((1-methylheptyl)phosphonate), neodymium (2-ethylhexyl)((n-nonylphenyl)phosphonate), and neodymium (p-nonylphenyl)((2- ethylhexyl) phosphonate).

Neodymium organophosphinate is neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, neodymium (1-methylheptyl) phosphinate, (2- Ethylhexyl) phosphinate, neodymium decyl phosphinate, neodymium dodecyl phosphinate, neodymium octadecyl phosphinate, neodymium oleyl phosphinate, neodymium phenyl phosphinate, neodymium (n-nonylphenyl) phosphinate , Neodymium dibutylphosphinate, neodymium dipentylphosphinate, neodymium dihexylphosphinate, neodymium diheptylphosphinate, neodymium dioctylphosphinate, neodymium bis(1-methylheptyl)phosphinate, neodymium bis (2-ethylhexyl)phosphinate, tris-[bis(2-ethylhexyl)phosphinate]neodymium, neodymium didecylphosphinate, neodymium didodecylphosphinate, neodymium dioctadecylphosphinate, neodymium diol Rail phosphinate, neodymium diphenylphosphinate, neodymium bis (n-nonylphenyl) phosphinate, neodymium butyl (2-ethylhexyl) phosphinate, neodymium (1-methylheptyl) (2-ethylhexyl) phosphinate phinate, and neodymium (2-ethylhexyl)(n-nonylphenyl)phosphinate.

The carboxylate of neo acid is most preferred due to the faster and more complete alkylation, which results in more active catalyst compounds.

Preference is given to using neodymium carboxylate and organophosphinate, of which neodymium neodecanoate and tris-[bis(2-ethylhexyl)phosphate]neodymium or mixtures thereof are most preferred.

Compounds suitably used as organoaluminum compounds according to the present invention are trialkylaluminum compounds, triphenyl aluminum or dialkylaluminum hydrides, alkyl aluminum dihydrides, in particular trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum , triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-tert-butyl aluminum, triphenyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, diethyl aluminum hydride, di- n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, di-isohexyl aluminum hydride, dioctyl aluminum hydride, di-isooctyl aluminum hydride , phenylethyl aluminum hydride, phenyl-n-propyl aluminum hydride, phenyl isopropyl aluminum hydride, phenyl-n-butyl aluminum hydride, phenyl isobutyl aluminum hydride, benzyl ethyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzyl isobutyl aluminum hydride, benzyl isopropyl aluminum hydride, and the like.

Preference is given to the use of alkyl aluminum or alkyl aluminum hydride, or mixtures thereof. Most preferred are triethyl aluminum, triisobutyl aluminum, diisobutyl aluminum hydride or mixtures thereof.

The compounds used as the conjugated diene according to the present invention are 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-hexa Diene, 4,5-diethyl-1,3-octadiene, phenyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3 -butadiene, and 2-methyl-3-isopropyl-1,3-butadiene.

The most preferred conjugated dienes are 1,3-butadiene and isoprene.

Compounds used as halogen-containing components in the catalyst complex are halogen organic compounds of aluminum and tin, in particular, for example, dimethyl aluminum chloride, diethyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum bromide, diisobutyl aluminum bromide, dimethyl aluminum fluoride, diethyl aluminum fluoride, diisobutyl aluminum fluoride, dimethyl aluminum iodide, diethyl aluminum iodide, diisobutyl aluminum iodide, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, methyl aluminum difluoride, ethyl aluminum difluoride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isobutyl aluminum sesquichloride or mixtures thereof , as well as trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di-tert-butyltin dichloride, di-tert-butyltin dibromide, dibutyltin dichloride, dibutyltin dibromide , tributyltin chloride and tributyltin bromide, and the like, or mixtures thereof.

Preferred halogen-containing components are ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum chloride or mixtures thereof.

The polymerization solvent is an inert organic solvent, for example, aliphatic hydrocarbons, in particular, for example, butane, pentane, hexane, heptane; alicyclic hydrocarbons, especially cyclopentane, cyclohexane; mono-olefins such as 1-butene, 2-butene, or mixtures thereof; aromatic hydrocarbons, in particular, for example, benzene, toluene, xylene; these may be used individually or as a mixture with one another.

According to the proposed method, the most preferred hydrocarbon solvent is a mixture of cyclohexane and hexane, or cyclohexane and nefras (with a boiling point of 65°C to 75°C), paraffin of dearomatic gasoline obtained by a catalytic reforming process. It is a solvent with a mixture (mixing ratio = (30 to 55) : (70 to 45)) of commercial grade hexane-heptane fractions of hydrocarbons.

The catalyst complex used in the polymerization process according to the present invention comprises a lanthanide compound (A), a conjugated diene (B), an organoaluminum compound (C), and a halogen-containing component (D) 1: (5 to 30): (8) to 30):(1.5 to 3.0) in a molar ratio of (A):(B):(C):(D).

A preferred molar ratio of the components (A):(B):(C):(D) of the catalyst composite is 1:(5-20):(8-20):(1.8-2.8).

The most preferred molar ratio of the components (A):(B):(C):(D) of the catalyst composite is 1:(10-15):(10-15):(2.1-2.5).

The process for producing a diene polymer is a batch or continuous process carried out in a hydrocarbon solvent by feeding the hydrocarbon mixture to a polymerization vessel (reactor/autoclave), where the hydrocarbon mixture is a catalyst complex premixed with monomer and solvent, and solvent. and the catalyst complex includes a lanthanide compound, a conjugated diene, an organoaluminum compound, and a halogen-containing component. The concentration of the monomer in the solvent is, in principle, from 7% by mass to 12% by mass, preferably from 9% by mass to 10% by mass. When the concentration is less than 7%, the energy efficiency of the process is lowered, and when the concentration exceeds 12%, the viscosity of the polymerizate increases, and consequently, the energy consumption during isolation and drying of the rubber increases.

The catalyst complex (CC) is prepared by adding an organoaluminum compound (most preferably triisobutyl aluminum, triethyl aluminum, diisobutyl aluminum hydride) to a solution of a conjugated diene (most preferably 1,3-butadiene) in an aliphatic solvent. Ride or mixtures thereof), a lanthanide compound (most preferably a carboxylate, in particular neodecane or tris-[bis(2-ethylhexyl)neodymium phosphate); After aging the resulting mixture at a temperature of 23±2° C. for 2 to 20 hours, a halogen-containing component (most preferably ethyl aluminum sesquichloride, ethylaluminum dichloride, diethyl aluminum chloride or mixtures thereof) ), as a molar ratio of the components (A):(B):(C):(D) of the catalyst complex of 1:(5-30):(8-30):(1,5-3,0), adding; (A) is a lanthanide compound, (B) is a conjugated diene, (C) is an organoaluminum compound, (D) is a halogen-containing component. The amount of the catalyst complex used is calculated based on the monomer (hydrocarbon mixture), and the calculation for component (A) is based on the lanthanide (metal), that is, 1.0 to 3.0 moles of lanthanide per ton of monomer. do.

The polymerization time is from 1.5 hours to 3 hours. Monomer conversion ranges from 95% to 99%.

When the monomer conversion reaches at least 95%, 2 kg of polymer is discharged, and an antioxidant solution is added in an amount of 0.2% by mass to 0.4% by mass, based on the polymer, to stabilize the polymer, and at 75°C to 85°C It is degassed and dried on rollers at a temperature of The resulting product is used as an unmodified reference sample. The reference polymer has a Mooney viscosity of 30 MU to 39 MU and is characterized by a linear structure: its branching index, characterized by mechanical loss angular tangent tgδ (1200%), is 9 units to 7 units.

A branching agent selected from phosphorus-nitrogen containing compounds and/or halogen containing compounds is then fed to the remainder of the polymer. The branching process is carried out for 5 minutes to 3 hours, preferably 20 minutes to 1 hour with constant stirring at a temperature of 60°C to 90°C. After the branching process is completed, 2 kg of the polymer is discharged, an antioxidant solution is added to the polymer in an amount of 0.2 to 0.4 mass% based on the polymer, degassed on a roller at a temperature of 75° C. to 85° C., and dried.

If the modification temperature is less than 60° C., the polymer viscosity increases, which is undesirable because it increases the unavoidable difficulty in the isolation and processing of the polymer. At the same time, the end groups of the polymer chains tend to lose their activity at temperatures above 90° C. As a result, a high degree of branching of the polymer is not possible.

Compounds useful as branching agents (BA) according to the invention are phosphorus-nitrogen containing compounds and/or halogen containing compounds.

Suitable halogen-containing compounds are tin compounds, namely tin tetrachloride, methyltin trichloride, dimethyltin dichloride, ethyltin trichloride, diethyltin dichloride, n-butyltin trichloride, di-n-butyltin dichloride. chloride, phenyltin trichloride, diphenyltin dichloride, as well as silicone compounds such as silicon tetrafluoride, silicon tetrachloride, silicon tetrabromide, and silicon tetraiodide.

Tin tetrachloride, methyltin trichloride, ethyltin trichloride, butyltin trichloride, and silicone tetrachloride are preferred. In a most preferred embodiment, tin tetrachloride and silicone tetrachloride are used.

The amount of branching agent introduced depends on the desired properties of the final product, such as the Mooney viscosity of the polymer, with an increase in Mooney viscosity of the polymer after branching compared to the unbranched polymer (ΔML,%) is 30% to 40%, and at a frequency of 0.1 Hz and a temperature of 100 °C, the branching index (of the polymer) characterized by the mechanical loss angular tangent tgδ (1200%), measured in an RPA (Rubber Processing Analyzer) instrument. characteristic indicating the degree of branching) varies by 35% by mass to 50% by mass.

According to the present invention, the molar ratio of the halogen-containing compound selected as branching agent BA to lanthanide is between 1.0 and 20, preferably between 2 and 15, most preferably between 5.0 and 10.0. If the amount used is increased beyond 20.0 moles, the properties of the polymer are not improved, resulting in excessive consumption of BA. A molar dosage reduction of less than 1.0 per lanthanide does not change the properties of the polymer and rubber, respectively.

According to the present invention, the phosphorus-nitrogen compound is a compound having a chemical structure based on (-P=N-) _n repeating units, where n is an integer from 3 to 24. Exemplary compounds used as phosphorus-nitrogen compounds include, but are not limited to:

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine;

2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene;

1,1-diphenyl-3,3,5,5-tetramethylaminotriphosphoronitrile;

2,2,4,4-tetrachloro-6,6-dimethylmercaptocyclotriphosphazatriene;

ethyloxypentafluorocyclotriphosphazene;

trifluoroethoxy)pentachlorocyclotriphosphazene;

hexafluorocyclotriphosphazene;

4,4,6,6-tetrachloro-1,3,5-triaza-2,4,6-triphosphocyclohexa-1,3,5-triene-2,2-diamine;

2,4,6-trichloro-2,4,6-trifluoro-1,3,5-triaza-2λ5,4λ5,6λ5-triphosphacyclohexa-1,3,5-triene;

2,4,6-trichloro-2,4,6-tri(phenoxy)-1,3,5-triphosphorine;

trichloride trinitride diamide tetrachloride;

octachlorocyclotetraphosphazene;

1,1-dimethyl-3,3,5,5-tetrachlorocyclotriphosphazene;

2,2,4,4-tetrachloro-6-isopropyl-2λ5,4λ5,6λ5-[1,3,5,2,4,6]triaza triphosphinine;

1-methyl-1,3,3,5,5-pentachlorocyclotriphosphazene;

1,3,5,2,4,6-triazatriphosphorine, 2,4,6-tribromo-2,4,6-trifluoropolymer dialdehyde;

4,6-difluoro-2-N,N-2,2-N'2-N',4-N,4-N,N-6,6-N-octemethyl-1,3,5- triaza-2λ5,4λ5,6λ5-triphospha-cyclohexa-1,3,5-triene-2,2,4,6-tetraamine;

2,2,4,4,6,6-hexahydro-2,2,4,4,6,6-hexapropoxy-propoxy-1,2,3,4,5,6-triazatriphos porin;

1,1-diphenyl-3,3,5,5-tetramethylamino-triphosphoronitrile and others.

In a preferred embodiment, chlorine-containing phosphorus-nitrogen compounds containing 2 to 6 chlorine atoms are used.

The compounds used in the most preferred embodiment are: 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine; 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene; 2,2,4,4-tetrachloro-6,6-dimethylmercaptocyclotriphosphazatriene, 4,4,6,6-tetrachloro-1,3,5-triaza-2,4,6 -triphosphocyclohexa-1,3,5-triene-2,2-diamine or mixtures thereof.

According to the present invention, the amount of the phosphorus-nitrogen compound selected as BA is 0.5 to 15.0 moles per mole of lanthanide. Based on the lanthanide, increasing the molar dosage of more than 15.0 molar does not lead to an improvement in the properties of the polymer and rubber, but results in excessive consumption of the modifier. Based on the lanthanide, a reduction in molar usage of less than 0.5 moles does not improve the properties of polymers and rubbers, respectively.

The most preferred amount of the chlorine-containing phosphorus-nitrogen compound used is 1.0 to 5.0 moles per mole of lanthanide, since this amount of modifier consumes relatively little modifier while providing the optimum properties of polymers and rubbers based thereon. because it makes it achievable.

The resulting branched polymer is characterized by a branching index, characterized by a Mooney viscosity of 44 MU to 53 MU, and a mechanical loss angular tangent tgδ (1200%) of 4.0 to 5.0. Also, compared to the unmodified reference sample, the increase in Mooney viscosity of the branched polymer is in the range of 30% to 50%.

The viscosity increase (%) is calculated by the following formula.

ΔML _2/1 =(ML ₂ -ML ₁ )/ML ₁ *100,

where ΔML _2/1 is the increase in Mooney viscosity of the branched polymer relative to the linear polymer;

ML ₂ is the Mooney viscosity of the branched polymer;

ML ₁ is the Mooney viscosity of the linear polymer;

The change in polymer branching (%) is calculated with the following formula:

Δtgδ 1200% _2/1 = (tgδ 1200% ₂ - tgδ 1200% ₁ )/tgδ 1200% ₁ *100,

where Δtgδ 1200% _2/1 is the change in branching of the polymer relative to the linear polymer.

tgδ 1200% ₂ is the branching index of the branched polymer, expressed as the mechanical loss angular tangent determined at a variable amplitude from 0 to 1200%, a frequency of 0.1 Hz, and a temperature of 100° C.;

tgδ 1200% ₁ is the branching index of a linear polymer, expressed as the mechanical loss angular tangent determined at a variable amplitude from 0 to 1200%, a frequency of 0.1 Hz, and a temperature of 100°C.

Also, a solution of antioxidant in an amount of 0.2% by mass to 0.4% by mass, based on the polymer, and a plasticizer that is a low molecular weight polymer having a molecular weight of 1500 g/mol to 5000 g/mol (usage: 0.5 based on polymer) mass % to 5.0 mass %) is introduced into the residual polymer, stirred for 5 minutes to 10 minutes, degassed and dried on rollers at a temperature of 75° C. to 85° C.

The amount of the plasticizer used is calculated so that the drop in the polymer viscosity does not exceed 10% and the change in the branching index does not exceed 10% after the plasticizer is added. Otherwise, the conditional tensile strength is lowered.

The drop in viscosity ML _3/2 is calculated by the formula:

ΔML _3/2 = (ML ₂ - ML ₃ )/ML ₂ *100,

where ΔML _3/2 is the drop in the Mooney viscosity of the polymer;

ML ₂ is the Mooney viscosity of the branched polymer;

ML ₃ is the Mooney viscosity of the branched and plasticizer-modified polymer.

The change (%) of branching of the polymer is calculated by the following formula.

Δtgδ 1200% _3/2 = (tgδ 1200% ₃ - tgδ 1200% ₂ )/ tgδ 1200% ₂ *100,

where Δtgδ 1200% _3/2 is the change in branching of the polymer;

tgδ 1200% ₂ is the branching index of the branched polymer, expressed in terms of the mechanical loss angular tangent, determined at a variable amplitude of 0% to 1200%, a frequency of 0.1 Hz, and a temperature of 100 °C;

tgδ 1200% ₃ is the branching index of the branched and modified polymer, expressed as the mechanical loss angular tangent, determined at a variable amplitude from 0% to 1200%, a frequency of 0.1 Hz, and a temperature of 100°C.

The rubber composition is processed on a roller after mixing, wherein the preparation of the rubber composition for vulcanization, and vulcanization and preparation of the test samples are performed according to ASTM D 3182 and ASTM D 3189. ASTM D 3189 formulations are shown in Table 1.

The branched polydiene prepared according to the present invention was characterized by a Mooney viscosity index of 40 MU to 49 MU, a polydispersity index ranging from 2.16 to 2.60, and a mechanical loss angular tangent tgδ (1200%) of 4.7 to 5.3. It has a branching index, wherein the content of 1,4-cis units is between 96.0% and 98.0%. The rubber mixtures obtained based on the prepared polydiene have low Mooney viscosity, good dispersion of fillers in the polymer matrix, and good elastic-hysteresis properties (e.g., ML(1+4) (unit : MU), Payne effect Δ(G'1%-G'50%) (unit: kPa), tgδ 60 °C (at 10% deformation)).

The use of BA and a plasticizer according to the invention provides a branched polydiene, wherein the branched polydiene, in the test of the rubber composition, compared to the unmodified polymer, with only one BA or mixtures thereof Compared to the modified polymer (without plasticizer), as well as compared to the polymer prepared using only the plasticizer, it shows better results in processability and elastic-hysteresis properties.

Table 1 - Formulations of rubber mixtures (ASTM 3189)

ingredient parts by weight butadiene rubber 100.0 Carbon Black N330 (IRB 8) 60.0 Zinc Oxide Paint 3.0 commercial grade stearic acid 2.0 naphthenic oil 15.0 gas sulfur 1.5 Sulfenamide T 0.9 Sum: 182.40

In the following, embodiments of the present invention are disclosed. A person skilled in the art will understand that the present invention is not limited only to the embodiments shown, and the same effect can be achieved in other embodiments without departing from the purpose of the claimed invention.

Test methods used to evaluate the properties of polymers prepared by the claimed method are disclosed below.

1. The percent conversion was determined gravimetrically by precipitating the polymer from the polymer with ethyl alcohol, drying the isolated polymer and calculating the weight fraction of the polymer in the polymer.

2. The molecular weight properties of rubber were measured using gel permeation chromatography according to the method provided by the present inventors, using a gel chromatograph (Waters Breeze System) equipped with a refractive index detector. A rubber sample was dissolved in freshly distilled tetrahydrofuran, and the weight concentration of polymer in the solution was 2 mg/ml; Universal calibration was performed with polystyrene standards. Calculations were made using the Kuhn-Mark-Houwink constant for polydiene (K = 0.00041, α = 0.693). Exam conditions:

- a bank of 4 high-resolution columns (300 mm long, 7.8 mm diameter) filled with Styragel (HR3, HR4, HR5, HR6) capable of analyzing polymers with a molecular weight of 500 amu to 1 x 10 ⁷ amu;

- tetrahydrofuran solvent with a flow rate of 1 cm ³ /min;

- Temperature of thermostat columns and refractometer: 3000 °C.

3. Mooney viscosity was measured according to ASTM D 1646.

4. The elastic component of the complex dynamic shear modulus G' (kPa) for evaluation of dispersion of fillers in rubber compositions and silanization of fillers, in a deformation range of 1% to 450% at 0.1 Hz and 100 °C , measured on an RPA-2000 rubber processing analyzer (Alpha Technologies). The difference between the measured storage moduli at strain amplitudes of 1% and 50% was the Payne effect, CG' = (G'1% - G'43%).

5. The branching index, characterized by mechanical loss angular tangent tgδ (1200%), was measured on an RPA-2000 rubber processability analyzer (Alpha Technologies) using the following test mode: tgδ Changes were evaluated at variable shear amplitudes, in the amplitude range of 10% to 1200%, at a frequency of 0.1 Hz and a temperature of 100 °C.

Example 1 (according to the prototype)

After polymerization of butadiene (BD) in a hydrocarbon solvent in the presence of a catalyst complex prepared based on neodymium versatate (Nd), diisobutyl aluminum hydride (DIBAG) as an alkylating agent, diethyl aluminum chloride ( DEAC), neodymium versatate (NdV3), and diisobutyl aluminum hydride (DIBAH) were added. DIBAH was taken as an 8-fold molar excess over neodymium used, and DEAC was taken as a 3-fold molar excess. The amount of the catalyst complex used was 2.8 moles of neodymium per ton of butadiene (BD). Polymerization was carried out in a 20 liter reactor equipped with a mixing device and a jacket for heat removal. The polymerization process lasted for 90 minutes. At the end of polymerization, 2 liters of polymer were withdrawn from the reactor; The monomer conversion was 98%. To the selected aliquots a phenolic antioxidant (Irganox 1520) was added in an amount of 0.06% by mass. The solvent was removed, and rolling was performed at a temperature of 80 °C. The molecular weight properties (MMC) as determined by GPC and the branching index of the polymers were determined in selected aliquots; The prepared linear polymer had a Mooney viscosity of 35 MU. A solution of maleinized polybutadiene Ricon 130 MA 8 (solution concentration 0.15 mol/L) in a hexane mixture at an amount of 1.2 mol per Nd was fed into the polymer remaining in the reactor at a temperature of 90°C. After 10 minutes, primary (Irganox 565) and secondary (TNPP) antioxidants were added and the resulting modified polymer was drained. The modified polymer had a Mooney viscosity of 43 MU and its tgδ 1200% = 5.567, ie, the resulting polymer was branched.

Example 2 (Comparative Example)

Butadiene (BD) was mixed with the preformed catalyst complex (neodymium neodecanoate - butadiene (BD) - diisobutyl aluminum hydride (DIBAH) - ethyl aluminum sesquichloride (EASC); component molar ratio = 1:10:12: 2.5) in the presence of a hydrocarbon solvent. The aging time of the catalyst composite was 22 hours at a temperature of 23 °C. Polymerization was carried out in a 20 liter reactor. The dry residue was 11%. The amount of the catalyst complex used was 1.8 moles of neodymium per ton of butadiene (BD). After achieving a conversion of greater than 95% based on monomer, 2 kg of polymer was discharged, and a phenolic antioxidant solution was introduced in an amount of 0.3% by mass based on polymer to stabilize the polymer, 75° C. It was degassed and dried on a roller at a temperature of to 85°C. Then, physical and mechanical properties and molecular weight properties were measured (Table 3). 0.3% by mass of an antioxidant solution, based on the polymer, and 0.8% by mass (8 g per kg of polybutadiene) of low molecular weight polybutadiene Polyvest 130 were added to the residual polymer, stirred for 10 minutes, and at a temperature of 80° C. It was degassed and dried on a roller. Physical and mechanical properties, molecular weight properties, increase in polymer viscosity, change in branching index (mechanical loss angle tangent tgδ (1200%)) are shown in Table 3.

Example 3 (Comparative Example)

Butadiene (BD) was mixed with catalyst complex (neodymium neodecanoate - butadiene (BD) - diisobutyl aluminum hydride (DIBAH) - ethyl aluminum sesquichloride (EASC); component molar ratio = 1:10:11:2.5) was polymerized in a hydrocarbon solvent in the presence of The aging time of the catalyst composite was 20 hours at a temperature of 24 °C. The amount of the catalyst complex used was 1.7 moles of neodymium per ton of butadiene (BD).

After achieving greater than 95% conversion based on monomer, 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphos as branching agent Porin (HCF) was supplied in an amount of 1.0 mol based on neodymium. After continuing the reforming process for 60 minutes with constant stirring at a temperature of 80 ° C, 2 kg of the polymer was discharged, and an antioxidant solution was introduced in an amount of 0.4 mass % based on the polymer, and a roller at a temperature of 80 ° C. degassed and dried. The properties of the obtained polymers are shown in Table 3.

Example 4 (according to the invention)

Butadiene (BD), catalyst complex (neodymium neodecanoate - butadiene (BD) - diisobutyl aluminum hydride (DIBAH) - ethyl aluminum sesquichloride (EASC); component molar ratio = 1:10:13:2.5) Polymerization was carried out in a hydrocarbon solvent in the presence of The amount of the catalyst complex used was 1.7 moles of neodymium per ton of butadiene (BD). After achieving a conversion of greater than 95% based on monomer, 2 kg of polymer was discharged and a phenolic antioxidant solution was introduced in an amount of 0.3% by mass based on polymer to stabilize the polymer, 75° C. It was degassed and dried on a roller at a temperature of (HCF) was fed into the residual polymer at an amount of 1.3 moles per mole of neodymium, 2 kg of the polymer was discharged, and an antioxidant solution was introduced therein in an amount of 0.4% by mass based on the polymer, and a temperature of 80° C. degassed and dried on a roller in a (step 2). 0.4% by mass of an antioxidant solution, based on the polymer, and 1.5% by mass (15 g per kg of polybutadiene) of low molecular weight polybutadiene Polyvest 130 were added, stirred for 10 minutes, and degassed on a roller at a temperature of 80° C. and dried (step 3). Table 3 shows the physical and mechanical properties and molecular weight properties of the polymers obtained in various steps.

Example 5

Process similar to Example 4 except that 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene (THF) was used as the branching agent in an amount of 1.5 moles per mole of neodymium. this was used The reforming process was continued for 60 minutes with constant stirring at a temperature of 80 °C.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 6

Example 4 and 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene (THF) were used as a branching agent in an amount of 1.8 moles based on neodymium. A similar process was used (step 2). Polyvest EP-ST-E 60 was used as a plasticizer in an amount of 0.8% by mass (8 g per kg of polybutadiene) and stirred for 5 minutes.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 7

A process similar to Example 4 was used except that the catalyst complex was prepared based on gadolinium versatate (GdV3). The amount of branching agent (HCF) used was 1.5 moles per mole of gadolinium. Liquid polyisoprene LIR 50 was used as plasticizer in step 3 at an amount of 0.8% by mass (8 g per kg of polybutadiene) based on the polymer.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 8

The prepared catalyst complex contained tris-[bis(2-ethylhexyl)phosphate]neodymium (NdP3), butadiene (BD), and diisobutyl aluminum hydride (DIBAH), and ethyl aluminum sesquichloride (EASC) was A procedure similar to Example 5 was used, except that it was used as a chlorinating agent. The molar ratio of the BD:Nd:DIBAH:EASC components of the catalyst complex was 10:1:15:2.7. The aging time of the catalyst composite was 22 hours at a temperature of 25 °C.

1,1-diphenyl-3,3,5,5-tetramethylaminotriphosphoronitrile (DPP) was used as branching agent in step 2 in an amount of 0.5 mmol per mole of neodymium.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 9

The prepared catalyst complex contained tris-[bis(2-ethylhexyl)phosphate]neodymium (NdP3), butadiene (BD), and diisobutyl aluminum hydride (DIBAH), and ethyl aluminum sesquichloride (EASC) was A process similar to Example 7 was used, except that it was used as a chlorinating agent. The molar ratio of the BD:Nd:DIBAH:EASC components of the catalyst complex was 10:1:15:2.7. The aging time of the catalyst composite was 22 hours at a temperature of 25 °C.

1,1-diphenyl-3,3,5,5-tetramethylaminotriphosphoronitrile (DPP) was used as branching agent in step 2 in an amount of 1.5 mmol per mole of neodymium. Liquid polyisoprene LIR 30 was used as plasticizer in step 3 in an amount of 1.0 mass % (10 g per kg of polybutadiene) based on the polymer.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 10

Similar to Example 8, except that the prepared catalyst complex contained praseodymium versatate (PrV3), butadiene (BD), diisobutyl aluminum hydride (DIBAH) and ethyl aluminum sesquichloride (EASC) process was used. The molar ratio of BD:Nd:DIBAH:EASC components of the catalyst complex was 10:1:11:2.2. The aging time of the catalyst composite was 19 hours at a temperature of 22 °C.

HCF was used as the branching agent in an amount of 2.0 moles per mole of praseodymium. Liquid polyisoprene LIR 30 was used as plasticizer in step 30 in an amount of 1.5% by mass based on polymer (15 g per kg of polybutadiene).

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 11

A process similar to Example 8 was used, except that HCF was used as the branching agent in an amount of 1.8 moles per mole of neodymium (step 2). Liquid polybutadiene Polyvest EP-ST-E 80 functionalized with triethoxysilane to have a degree of silanization of 80% was used as a plasticizer in an amount of 1.0% by mass (10 g per kg of polybutadiene) based on the polymer. .

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 12

Liquid polybutadiene Polyvest EP-ST-E 80 functionalized with triethoxysilane to have a degree of silanization of 100% was used as a plasticizer in an amount of 1.5% by mass (15 g per kg of polybutadiene) based on the polymer A process similar to Example 10 was used, except that

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 13

Except for the difference that the amount of the branching agent used was 1.2 moles per mole of neodymium, and the maleinized liquid rubber Ricon 131 MA 10 was used as a plasticizer in an amount of 0.8% by mass (8 g per 1 kg of polybutadiene) based on the polymer. , a process similar to Example 10 was used.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 14

A process similar to Example 8 was used, except that the amount of branching agent DFF used was 5.0 moles per mole of neodymium. Nonfunctionalized liquid polybutadiene Polyvest EP-ST-E 130 was used as plasticizer in an amount of 2% by mass (20 g per kg of polybutadiene), based on the polymer.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 15

A procedure similar to Example 13 was used, except that thionyl chloride (SOCl ₂ ) was used as the branching agent in an amount of 5 moles per mole of neodymium.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 16

Thionylchloride was used as a branching agent in an amount of 7.0 moles per mole of neodymium, and a maleinized liquid rubber Ricon 130 MA 8% as a plasticizer in an amount of 1.5% by mass (15 g per 1 kg of polybutadiene) based on the polymer A procedure similar to Example 11 was used, with the difference that it was used.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 17

A procedure similar to Example 14 was used, except that tin tetrachloride (SnCl ₄ ) was used as the branching agent in an amount of 2.5 moles per mole of neodymium.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 18

Tin tetrachloride (SnCl ₄ ) was used as a branching agent in an amount of 5.0 moles per mole of neodymium, and a liquid polybutadiene Polyvest EP-ST-E 80 functionalized with triethoxysilane to a degree of silanization of 100% Polyvest EP-ST-E 80 A process similar to Example 14 was used, with the difference that it was used as a plasticizer in an amount of 5% by mass (50 g per kg of polybutadiene) on a standard basis.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 19

A catalyst complex was prepared based on tris-[(2-ethyl)hexanoate]neodymium (NdEh3), the amount of DFF used was 15 moles per mole of neodymium (step 2), and the amount of plasticizer LIR 30 in step 3 was polymer A process similar to Example 9 was used, except that it was 0.5% by mass (5 g per kg of polybutadiene) based on .

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 20

The catalyst complex was prepared based on tris-[bis(2-ethylhexyl)phosphate]neodymium, the amount of tin tetrachloride used as a branching agent was 20 moles per mole of neodymium, and Ricon 131 MA 10 as a plasticizer based on the polymer A process similar to that of Example 18 was used, except that it was used in an amount of 0.5 mass% (5 g per 1 kg of polybutadiene).

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Example 21

A process similar to Example 19 was used, except that the catalyst composite was prepared based on neodymium neodecanoate. The molar ratio of BD:Nd:DIBAH:EASC components of the catalyst complex was 10:1:13:2.0. The aging time of the catalyst composite was 19 hours at a temperature of 22 °C. The amount of the branching agent SiCL ₄ used was 1.0 mole per mole of neodymium; Polyvest EP-ST-E MA75 was used as a plasticizer in an amount of 0.5% by mass (5 g per kg of polybutadiene) based on the polymer.

The physical and mechanical properties, and molecular weight properties of the polymers obtained in various steps are shown in Table 3.

Samples of the polymers obtained in Examples 1 to 22 were tested in the formulation of rubber compositions (ASTM 3189), and the test results are shown in Table 4.

Table 2: Properties of liquid rubbers used according to the invention

Remark:

Polyvest EP-ST-E 60 - Liquid polybutadiene functionalized with triethoxysilane, 60% degree of silanization

Polyvest EP-ST-E 80 - Liquid polybutadiene functionalized with triethoxysilane, degree of silanization 80%

Polyvest EP-ST-E 100 - Liquid polybutadiene functionalized with triethoxysilane, 100% degree of silanization

Polyvest 130 (S) - non-functionalized liquid polybutadiene (S) with antioxidants

Polyvest EP-ST-E MA75 - Liquid polybutadiene functionalized with maleic anhydride

LIR 30 - liquid polyisoprene, 30% silanization

LIR 50 - liquid polyisoprene, 50% silanization

Ricon 130 MA 8 - Liquid polybutadiene having 8 maleic groups functionalized with maleic anhydride

Ricon 131 MA 10 - Liquid polybutadiene having 10 maleic groups functionalized with maleic anhydride

Table 3: Properties of Polymers

Remark:

* - for branching agents, the amount used is given in moles per mole of lanthanide; For plasticizers, the amount used is given in mass % based on 100% polymer.

Abbreviations used in Table 3:

NdP3 - tris-[bis(2-ethylhexyl)phosphate]neodymium

NdV3 - Neodymium neodecanoate

GdV3 - gadolinium versatate

NdEh3 - tris-[(2-ethyl)hexanoate]neodymium

DEAC - diethyl aluminum chloride

EASC- Ethyl Aluminum Sesquichloride

HCP - 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine

TCP - 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene

DPP - 1.1-diphenyl-3,3,5,5-tetramethylaminotriphosphoronitrile

SiCL4 - Silicon Tetrachloride

SOCl2 - Thionyl chloride

Δ ML 2/1 (%) - increase in viscosity of the polymer obtained in step 2 compared to the polymer obtained in step 1, calculated by the formula given in the section "Content of the Invention"

Δ tgδ 1200% 2/1 (%) - change in branching index of the polymer obtained in step 2 compared to the polymer obtained in step 1, calculated by the formula given in the section "Content of the Invention"

Δ ML 3/2 (%) - drop in Mooney viscosity of the branched polymer obtained in step 2 after plasticizer introduction (step 3), calculated by the formula given in the section "Content of the Invention"

Δ tgδ 1200% 3/2 (%) - change in the branching index of the polymer obtained in step 3 compared to the polymer obtained in step 2, calculated by the formula given in the section "Content of the Invention"

Table 4 - Plasto-elastic properties of rubber compositions

As can be seen from Table 4, the proposed method for preparing branched polydiene can improve the processability of the rubber composition by 6% to 10% (based on the Mooney viscosity index), and also the dispersion of the filler in the polymer matrix (Pain effect). (as assessed by the Payne Effect parameter);

Using only modifiers and no plasticizers, the desired branching index tgδ (1200%) range of about 4.7 to about 5.3 is not achieved, and thus the processability of the rubber composition and dispersion of fillers in such polymers suffer.

Accordingly, the technical solution according to the present invention has a Mooney viscosity of about 40 MU to about 49 MU; and a branching index characterized by a mechanical loss angular tangent tgδ (1200%) of about 4.7 to about 5.3; The polydiene prepared according to the present invention has improved processability and improved dispersion of fillers in the polymer matrix, and rubber compositions based thereon have improved elastic-hysteresis properties (eg, Mooney viscosity). ) ML(1+4), MU, a Payne effect Δ(G'1%-G'50%), kPa, tgδ 60ºC (at 10% deformation).

Claims (17)

A process for preparing a branched polydiene by polymerization of a conjugated diene, comprising the steps of:
preparing a catalyst complex including a lanthanide compound, an organoaluminum compound, a conjugated diene, and a halogen-containing component;
polymerizing the conjugated diene in the presence of the catalyst complex;
performing post-polymerization modification with at least one branching agent selected from the group consisting of halogen-containing compounds, phosphorus-nitrogen compounds, or mixtures thereof;
termination step;
introducing at least one plasticizer into the polymer, wherein the plasticizer is a low molecular weight polymer having a molecular weight of 1500 g/mol to 5000 g/mol; and
Degassing and drying the polymer. The method of claim 1, wherein the branching agent is thionyl chloride, diphenyltin dichloride, phenyltin trichloride, triphenyltin chloride, dibutyltin dichloride, butyltin trichloride, tin tetrachloride, or silicone tetrachloride. from the group comprising, preferably comprising tin tetrachloride, methyltin trichloride, ethyltin trichloride, butyltin trichloride or silicon tetrachloride, most preferably comprising tin tetrachloride or silicon tetrachloride a selected halogen containing compound. The process according to claim 1, wherein the molar ratio of said halogen-containing compound selected as said branching agent to lanthanide is between 1.0 and 20, preferably between 2.0 and 15, most preferably between 5.0 and 10.0. The method according to claim 1, wherein the branching agent is a phosphorus-nitrogen compound having a chemical structure based on repeating units of (-P=N-) _n , wherein n is an integer from 3 to 24, preferably, the wherein the branching agent is a chlorine-containing phosphorus-nitrogen compound comprising 2 to 6 chlorine atoms. 5. The method of claim 4, wherein the branching agent is 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine, 2,4,6 -trichloro-2,4,6-triphenoxycyclotriphosphazene, 2,2,4,4-tetrachloro-6,6-dimethylmercaptocyclotriphosphazatriene, or 4,4,6, Chlorine-containing phosphorus selected from the group comprising 6-tetrachloro-1,3,5-triaza-2,4,6-triphosphocyclohexa-1,3,5-triene-2,2-diamine - a nitrogen compound, the method. The method according to claim 1, wherein the amount of the phosphorus-nitrogen compound selected as the branching agent is 0.5 to 15.0 moles per 1 mole of lanthanide, preferably 1.0 to 5.0 moles per 1 mole of lanthanide. 7. The plasticizer according to any one of claims 1 to 6, wherein the plasticizer is a non-functionalized low molecular weight polybutadiene, a polybutadiene functionalized with maleic anhydride or triethoxy silane, a non-functionalized Low molecular weight polyisoprene, or polyisoprene functionalized with maleic anhydride, preferably nonfunctionalized low molecular weight polybutadiene, or polybutadiene functionalized with maleic anhydride or triethoxy silane. 8. The use according to any one of claims 1 to 7, wherein the amount of the plasticizer used is 0.5 mass% to 5.0 mass%, preferably 0.7 mass% to 2.0 mass%, based on the polymer, most preferably is 0.8 mass % to 1.5 mass %, the manufacturing method. The method according to any one of claims 1 to 8, wherein the lanthanide compound in the catalyst complex is neodymium carboxylate or organophosphate. The method according to claim 9, wherein the lanthanide compound in the catalyst complex is neodymium neodecanoate, tris-[bis(2-ethylhexyl)phosphate]neodymium, or a mixture thereof. 11. The organoaluminum compound according to any one of claims 1 to 10, wherein the organoaluminum compound is trialkyl aluminum, triphenyl aluminum or dialkyl aluminum hydride, alkyl aluminum dihydride, in particular trimethyl aluminum, triethyl aluminum, tri -n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-tert-butyl aluminum, triphenyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum, diethyl aluminum Hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, di-isohexyl aluminum hydride, dioctyl aluminum hydride, di- isooctyl aluminum hydride, phenyl ethyl aluminum hydride, phenyl-n-propyl aluminum hydride, phenyl isopropyl aluminum hydride, phenyl-n-butyl aluminum hydride, phenyl isobutyl aluminum hydride, benzyl ethyl aluminum hydride, group comprising benzyl-n-butyl aluminum hydride, benzyl isobutyl aluminum hydride, and benzyl isopropyl aluminum hydride, preferably triethyl aluminum, triisobutyl aluminum, diisobutyl aluminum hydride or mixtures thereof A method for preparing a compound selected from 12. The method according to any one of claims 1 to 11, wherein the conjugated diene is 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-1,3-octadiene, phenyl-1,3-butadiene, 2, 3-diethyl-1,3-butadiene, 2,3-di -n-propyl-1,3-butadiene, and a compound selected from the group comprising 2-methyl-3-isopropyl-1,3-butadiene, preferably 1,3-butadiene and isoprene. The catalyst complex according to any one of claims 1 to 12, wherein the catalyst complex used for polymerization comprises a lanthanide compound (A), a conjugated diene (B), an organoaluminum compound (C) and a halogen-containing component (D) in 1 :(5 to 30):(8 to 30):(1.5 to 3.0) in a molar ratio of (A):(B):(C):(D), wherein the lanthanide compound (A) is wherein the molar amount is calculated as the molar amount of lanthanide. A branched polydiene prepared by the method according to any one of claims 1 to 13. Mooney viscosity from 40 to 49 Mooney units, and from 4.7 to 5.3, measured using an amplitude range of 10% to 1200%, a frequency of 0.1 Hz, and a variable shear amplitude at a temperature of 100° C. A branched polydiene characterized by a branching index expressed as a mechanical loss angle tangent of tgδ (1200%). 16. The method according to claim 14 or 15, characterized by a Payne effect Δ(G'1%-G'50%) in kPa, and a Tanδ 60°C at 10% deformation. Branched polydiene. The branched polydiene based rubber mixture according to any one of claims 14 to 16.