KR101575308B1 - Preparation of high elastic and reinforced rubber composition comprising high elastic polymeric fillers - Google Patents
Preparation of high elastic and reinforced rubber composition comprising high elastic polymeric fillers Download PDFInfo
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Abstract
The present invention relates to a method for producing a rubber composition having excellent reinforcement properties and elasticity. More specifically, the present invention relates to a method for producing a rubber composition which is excellent in reinforcing property and which is composed of a styrene-butadiene block copolymer (polybutadiene block copolymer) polybutadiene) to produce a rubber composition excellent in reinforcement and viscoelasticity. The rubber composition is prepared by a first step of preparing a polymer organic filler in the form of a styrene-butadiene copolymer, and a second step of dispersing the styrene-butadiene copolymer and polybutadiene by a physicochemical method do. The present invention relates to an elastic and reinforcing reinforced rubber composition containing a polymeric organic filler, which is excellent in rubber processability, modulus, tensile properties and tear properties, and is excellent in elasticity, Polymer composite material.
Description
The present invention relates to a method for producing a rubber composition having excellent reinforcement properties and elasticity. More specifically, the present invention relates to a method for producing a rubber composition which is excellent in reinforcing property and which is composed of a styrene-butadiene block copolymer (polybutadiene block copolymer) polybutadiene) to produce a rubber composition excellent in reinforcement and viscoelasticity.
Conventionally, the polymer organic filler is composed of a gel composed of a styrene-butadiene-acrylate copolymer by emulsion polymerization or a gel composed of a styrene-butadiene polymer by solution polymerization. A gel composed of a styrene-butadiene-acrylate copolymer was prepared by radical polymerization technique mainly in an emulsion state, and an anionic polymerization technique was used to produce a gel composed of a styrene-butadiene polymer. Such organic fillers are applied to tire treads and the like. Methods for producing styrene-butadiene copolymers or styrene-butadiene-acrylate copolymers by emulsion copolymer techniques are known in various patent inventions.
For example, U.S. Patent Nos. 3575913 and 3563946 disclose that styrene-butadiene or styrene-butadiene-acrylate copolymers are prepared in the form of an emulsion using potassium persulfate or azobisisobutyronitrile .
U.S. Patent No. 4064081 describes a method using emulsion polymerization of a copolymer of butadiene-styrene-itaconic acid, and potassium persulfate is used as an initiator used in polymerization.
U.S. Patent Nos. 5274027 and 5302655 disclose that acrylonitrile-based compounds such as itaconic acid, methylmethacrylic acid and the like are used, and styrene-butadiene-acrylate-based copolymers are emulsion- A method for producing the copolymer through polymerization is described.
U.S. Patent Nos. 5395891, 6127488, 6777500 and 7344752 disclose a polybutadiene or styrene-butadiene copolymer crosslinked by emulsion polymerization for use as an organic filler, And exhibits excellent wet stop capability, but has a problem in that the elasticity is lowered.
In the case of the solution polymerization method, it is possible to control the micro-molecular structure such as the vinyl structure of the conjugated diene and the molecular weight of the styrene molecule, as well as to artificially control the coupling rate and the coupling number which can greatly affect the physical properties of the polymer In addition, the polymers polymerized by the solution polymerization method are superior in terms of the rotational resistance and the wet resistance in comparison with the polymers polymerized by the emulsion polymerization method. Therefore, the properties required at present in environmentally friendly and high efficiency tires And is widely used as a method for producing a polymer that can be satisfactorily used.
This solution polymerization involves not only good dynamic properties but also other advantages in the polymerization process. For example, it is possible not only to control the cold flow at room temperature by introducing chemical functionalities into the polymer in the organolithium catalyst and the terminal modified product generally used as an initiator, but also to control the workability and the bonding force It is possible to improve the dispersibility of the reinforcing material and improve compatibility with carbon black and silica, which are reinforcing materials used in tires, to improve the tread wear characteristics and reduce the rolling resistance And also has an effect of improving the wetting resistance. Conventional methods using a functional initiator and a terminal modified product in a solution polymerization method are as follows.
U.S. Patent No. 2011/0207879 discloses a technique developed for the purpose of reducing the workability and rotational resistance of a carbon black compounding property by using a diphenylethylene-based polymerization initiator. However, in the case of the diphenylenylene type, , It is difficult to produce a rubber suitable for a silica tire which is attracting attention as an environmentally friendly tire. In addition, since the initiating efficiency tends to be lower than that of general organolithium initiator in the polymerization of conjugated diene system, it also has disadvantages in terms of economy. The styrene-butadiene copolymer or the styrene-butadiene-acrylate copolymer produced by the conventional emulsion polymerization is not only large in the phenomenon that the particles and the particles adhere to each other due to radical reaction and also crosslink in the particle, In addition to the difficulty of producing silica coatings or nanocomposites, emulsion polymerization has been difficult to produce nanoporous copolymers and silica nanocomposites.
United States Patent US 5395891 US 6747095 B2 discloses a patent for a rubber composition comprising a crosslinked polybutadiene particle gel and crosslinked rubber gel particles using butadiene, a styrene monomer, a crosslinking agent, and a functional monomer. In U.S. Pat. Nos. 6,470,050 and 7,553,909, butadiene-styrene copolymers were polymerized using a free lithium initiator by solution polymerization to produce nanoparticles. The tensile strength and tear strength of the prepared nanoparticles were increased by more than 30%. Especially, it improved the mechanical properties, especially the reinforcement, through the formulation composition suitable for tire tread and sidewall rubber material.
U.S. Patent No. US2012 / 0132346A1 polymerized butadiene-styrene copolymers by solution polymerization and produced more uniform and stabilized nanoparticles through a particle stabilizer. In addition, functional functional groups such as N-vinyl carbazole, pyrolidone, polyethylene glycol and polypropylene oxide were introduced and balanced mechanical properties and dynamic characteristics were shown through the composition of suitable tire rubber. However, the mechanical strength and the hardness of the tire are improved by applying the tire to the tire through the actual compounding, but the limit of expressing the characteristics of the high efficiency fuel material having a low hysteresis and a small heat generation characteristic has been shown at the same time. Accordingly, there is a growing demand for new rubber composites which can be used for the production of existing tires and high performance run flat tires and improve their physical properties.
Accordingly, the present inventors have made efforts to solve the problems of the conventional organic-inorganic composite material, and as a result, have devised a butadiene styrene block copolymer having a controlled block content through the high stiffening property of the butadiene styrene copolymer and the low hysteresis effect. The prepared block copolymer polymer was physically and chemically dispersed in cis polybutadiene in the form of polymer organic filler to maximize the reinforcing effect and to produce a hysteresis reduced rubber composition. Introduction of isocyanate and isocyanurate-based functional functional groups aims at uniform particle dispersion and stabilization, and at the same time promotes cross-linking through functional chemical group bonding to enable effective physicochemical dispersion with cis-polybutadiene.
(a) preparing a styrene-butadiene block copolymer in the form of a polymeric organic filler into which a functional group is introduced and adjusting the block,
(b) producing at least 95% high-cis polybutadiene, to which functional functional groups have been introduced,
(c) uniformly dispersing the polymeric organic filler in the form of styrene-butadiene block copolymer prepared in step (a) and the high-cis-polybutadiene prepared in step (b)
The present invention provides a method of manufacturing a rubber composition comprising
The present invention relates to a method for producing a rubber composition having excellent reinforcement properties and elasticity. More specifically, the present invention relates to a method for producing a rubber composition which is excellent in flexibility and viscoelasticity in a styrene-butadiene block copolymer Characterized in that the rubber composition is physically and chemically dispersed in an excellent polybutadiene. The rubber composition is prepared by a first step of preparing a polymer organic filler in the form of a styrene-butadiene block copolymer, a second step of dispersing the styrene-butadiene block copolymer and polybutadiene by a physicochemical method . The present invention relates to an elastic and reinforcing reinforced rubber composition containing a polymeric organic filler, which is excellent in rubber processability, modulus, tensile properties and tear properties, and is excellent in elasticity, Polymer composite material. Physicochemical dispersion bonding through the block copolymer in the form of an organic filler induces the chemical urethane bond including the isocyanate and isocyanurate groups at the terminal functional moiety, and the binding of the polymer organic filler to the polybutadiene in the second step Strengthen. It improved physical properties, hardness, modulus and viscoelasticity through particle dispersion and physico - chemical crosslinking of organic filler polymer. The polymerization reaction was controlled and the odor of the polymer was improved.
The rubber composition of the present invention described above maximizes the elasticity and reinforcing effect of the polymer organic filler and the compatibility of the high sheath polybutadiene, thereby exhibiting excellent processability, modulus and tensile properties, and excellent fuel economy. Therefore, it is expected that the present invention can reduce the reinforcing effect and the hysteresis when applying the rubber composition of the tire, and improve the fuel efficiency and weight of the tire.
According to the present invention,
(a) preparing a styrene-butadiene block copolymer in the form of a polymeric organic filler into which a functional group is introduced and adjusting the block,
(b) producing at least 95% high-cis polybutadiene, to which functional functional groups have been introduced,
(c) uniformly dispersing the polymeric organic filler in the form of styrene-butadiene block copolymer prepared in step (a) and the high-cis-polybutadiene prepared in step (b)
The present invention provides a method of manufacturing a rubber composition comprising
The functional functional group may be an isocyanate-based or isocyanurate-based functional group, and the styrene-butadiene copolymer of the step (a) may be a styrene-based monomer; Butadiene-based monomer; An anionic polymerization initiator; Terminal modifier, and solvent. It is preferable that the monomer includes a conjugated diene monomer, and the conjugated diene monomer is an unsaturated hydrocarbon having 4 to 12 carbon atoms, and 4 to 8 are used for one polymer molecule.
The details will be described below.
The present invention relates to (a) preparing a butadiene styrene block copolymer in the form of a polymeric organic filler in which a functional group is introduced and (b) preparing a cis-polybutadiene having a functionality of 95% It is characterized by uniform dispersion of polymeric organic fillers in the form of copolymers and hi-cis-polybutadiene. The block content is made to exhibit a well-balanced mechanical reinforcement effect and viscoelastic properties by producing a copolymer with a sloping regulated form. Introduction of isocyanate and isocyanurate functional functional group-introducing functional groups leads to (a), (b) inducing physicochemical bonding between the two polymers and enhancing the dispersibility and the particle stability of the polymer organic filler, b) maximize the compatibility and dispersibility of the polymers, minimize hysteresis and maximize the reinforcing effect. The hardness, reinforcement and viscoelasticity were enhanced by strengthening the physico - chemical dispersion bond through the block copolymer of organic filler type, and the physical properties were demonstrated through particle dispersion and physicochemical crosslinking of the organic filler polymer. The polymerization reaction was controlled and the polymer odor was improved.
In the step (a) which is one of the constituent materials of the present invention, the styrene-butadiene copolymer may be a styrene-based monomer; Butadiene-based monomer; Anionic initiators; A terminal modifier and a solvent. Of the monomers forming the polymer, the conjugated diene monomer is an unsaturated hydrocarbon having 4 to 12 carbon atoms, and 4 to 8 numbers are widely used in one molecule. Monomers of conjugated dienes include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (1,3 pentadiene and octadiene. Vinyl aromatic styrene monomers are styrene, 2-methylstyrene, 3-methylstyrene, 3-methylstyrene, 4-methylstyrene,? -Methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene (2,4- diisopropylstyrene, 4-tert-butylstyrene, divinylstyrene, tert-butoxystyrene, vinylbenzyldimethylamine, (4) (4-vinylbenzyl) dimethylaminoethyl ether, N, N-dimethylaminoethylstyrene, 2-tert-butylstyrene, 3-tert-butylsty 3-tert-butylstyrene, 4-tert-butylstyrene, vinylpyridine or a mixture thereof may be used.
As the hydrocarbon solvent used in the polymerization, n-hexane, n-heptane, iso-octane, cyclohexane, methylcyclopentane, benzene, toluene and the like are used, and particularly, n-hexane, n-heptane, Or mixed use. The monomer is preferably contained in the hydrocarbon solvent in an amount of 5 to 40% by weight, more preferably 10 to 25% by weight. When the content is less than 5% by weight, the solvent used in the production is excessively used, When it contains weight%, problems of solution viscosity and reaction heat control are caused.
As the polymerization initiator used in the formation of the living polymer, mainly organic lithium such as n-butyllithium or s-butyllithium is activated after being activated under a polar solvent such as tetrahydrofuran. In the case of a functional lithium initiator, it is possible to use an amine functional initiator and a lithium initiator substituted with an alkylamine or a cyclamine group.
The Lewis base compound used for controlling the microstructure of the polymer may be selected from the group consisting of tetrahydrofuran, N, N, N, N-tetramethylethylenediamine (TMEDA), di-n-propylether, Di-isopropyl ether, di-n-butyl ether, ethyl butyl ether, triethylene glycol, 1,2-dimethoxybenzene (1 2-dimethoxybenzene, trimethylamine, triethylamine and tetrahydrofuryl propane are generally used. Of these, di-tetrahydrofuryl propane, tetrahydrofuran, N, N, N, N-tetramethyl Ethylenediamine, ethyltetrahydrofurfuryl ether is mainly used. Typical polymerization reaction temperatures are in the range of about 10 to 100 DEG C, preferably 20 to 90 DEG C, and the reaction pressure is 0.5 to 10 kgf / cm < 2 >. [ cm < 2 & gt ;. Sodium 3,7-dimethyl-3-octylate, and 3,3-dimethyl-3-octylate can be used together with initiators and Lewis base compounds to control the microstructure of the polymer and improve the polymerization initiating activity.
The termination used to terminate the polymerization reaction may be selected from the group consisting of alcohol based methyl, ethyl, propane, isopropanol, amine methyl, ethyl, propyl, isopropylamine, MeSiCl 3 , Me 2 SiCl 2 , SiCl 4 , MeSnCl 3 , Me 2 SnCl 2 , SnCl 4, and the like. At the same time as the termination of the reaction, it is possible to carry out a substitution reaction by adding a compound including functional groups such as hydroxyl, carboxy, amino, formyl, epoxy, imide, malimde, alkoxysilane, thiol and amide.
[Chemical Formula 1]
[A - B] n X
(2)
[(AB) a- (AB) b ] n X
The styrene-butadiene copolymer is prepared as in the above formula (1) or (2) in the step (a).
A represents a conjugated diene monomer, B represents an aromatic vinyl monomer, and [A - B] represents a block copolymer comprising a conjugated diene-based monomer and an aromatic vinyl monomer.
(AB) a is a block copolymer containing a conjugated diene monomer A and a small amount of an aromatic vinyl monomer B, and the total weight ratio of the conjugated diene monomer is 60 to 100%. (AB) b is a block copolymer containing a small amount of a conjugated diene monomer A and an aromatic vinyl monomer B, wherein the total weight ratio of the aromatic vinyl monomer is 60 to 100%.
n represents an integer of 2 to 10 and is controlled through crosslinking and coupling with 1,4-divinylbenzene. The total weight-average molecular weight of the copolymer to which the functional group is attached after crosslinking by 1,4-vinylbenzene is about 600,000 to 2,500,000. A and b are from 5 to 100, and the sum is 100 in total. It is possible to prepare a uniform and stabilized polymer organic filler on a hydrocarbon solvent used in polymerization.
X is a residue of a terminal functional group, and as the terminal functional group, a compound such as a thiol group, a silane group, an amine group or a glycidyl amino group is used. Among the terminal functional functional group used, isocyanate and isocyanurate type include thiol type, amine type, epoxy type, and alcohol type silane type, which leads to an additional urethane reaction of isocyanate. Tris [2- (3-mercaptopropionyloxy) ethyl] isocyanurate, which is an isocyanurate compound containing a thiol group, is used to induce cross-linking through physical addition of a polar functional group and a chemical addition reaction with a sulfur compound during rubber compounding.
1) mole of a rare earth compound or a transition metal compound and 1 to 10 molar ratio of a compound containing a halogen, based on the amount of the compound to be used, and 3) an organoaluminum compound 1,4-cis-polybutadiene is prepared by polymerizing 1,3-butadiene or a butadiene derivative in a catalyst system containing 10 to 100 molar ratio of a compound and a non-polar solvent. As the rare earth compound and transition metal compound, a rare earth salt or a transition metal salt composed of an organic acid or an inorganic acid can be used, and an organic acid salt having an excellent solubility in an organic solvent is preferable, and a carboxylate is more preferably used. The carboxylic acid salt has a saturated, unsaturated, cyclic or linear structure having 8 to 20 carbon atoms. Specifically, octanoic acid, naphthenic acid, bassate acid and stearic acid may be used. The rare earth carboxylate may be specifically selected from the group consisting of niodum bathate, nioodimium octoate, nioium naphthenate and the like. More preferably, the monodentate sodium nioxide is selected from the group consisting of the activity and the polymer properties It is the best in terms of. The transition metal carboxylate salt may be nickel octoate, nickel naphthenate, cobalt octoate, cobalt naphthenate or the like.
The halogen-containing compound is a halogen compound which can easily produce a Lewis acid containing a halogen and a halogen. Polymerization with " living properties " such as rare earth and alkali metal catalyzed polymerization can be carried out by further containing an isocyanate compound represented by the general formula (3).
(3)
R 2 - (NCO) n
Wherein R 2 is an aryl group or alkyl group having 4 to 100 carbon atoms, and n is the number of isocyanates substituted in R 2 , and is an integer of 2 to 10. The isocyanate compound may be selected from alkyl triisocyanates having 4 to 100 carbon atoms, alkyl tetraisocyanates having 4 to 100 carbon atoms, aromatic triisocyanates, and aromatic tetraisocyanate compounds. Specific examples include hexyl diisocyanate, octyl diisocyanate, methylenediphenyl diisocyanate, hexyl triisocyanate, octyl triisocyanate, dodecyl tetraisocyanate, methylene triphenyl triisocyanate, 1,2,5,7-tetraisocyanate naphthalene, 3,7-triisocyanate naphthalene, tris- (p-isocyanatophenyl) -thiophosphate, carbodiimide-isocyanate cyclic derivative compounds, methylene diphenyl diisocyanate and polystyryl isocyanate.
Each of the polymeric compounds obtained in steps (a) and (b) is prepared by mixing physicochemically. (A) 5 to 50% by weight of the block copolymer (a) substituted with a functional group and (b) 50 to 95% by weight of the high-cis-polybutadiene are mixed to maximize mutual compatibility and dispersibility through physicochemical bonding And minimize hysteresis to maximize balanced mechanical reinforcement and viscoelastic properties.
Production Example 1. [A - B] n X
3 g of heptane, 130 g of 1,3-butadiene, 9.0 mmole of N-tetramethylethylenediimine, and 0.5 mmole of sodium 3,7-dimethyl-3-octylate are sequentially introduced into the 2G polymerization reactor filled with argon or nitrogen. After the completion of the addition, the internal temperature of the reactor is maintained at 40 ° C while the agitator is turned. When the internal temperature of the reactor reaches the set temperature, 10.0 mmol of n-butyllithium is introduced into the reactor to initiate the reaction. After 10 minutes after the reaction temperature reaches the maximum temperature, 270 g of styrene and 40 g of 1,3-divinylbenzene are added. After 10 minutes from the peak polymerization temperature, add 8.0 mmole and 4.0 mmole of hexamethylene diisocyanate and Tris [2- (3-mercaptopropionyloxy) ethyl] isocyanurate, respectively. The degree of polymerization reaction was determined by observing the change of reaction temperature. A small amount of reactants were taken from the reaction at various times to analyze monomer ratio and reaction conversion ratio. The reaction is terminated by the addition of 9.6 mmoles of Butylated Hydroxy Toluene (BHT). The degree of polymerization reaction was determined by observing the change of reaction temperature. During the reaction, a small amount of reactant was taken at any time to analyze monomer ratio and reaction conversion ratio.
Preparation Example 2 [(AB) a- (AB) b ] nX
3 g of 1,3-butadiene, 34 g of styrene, 7.1 mmole of N-tetramethylethylenediimine, and 1.9 mmole of sodium 3,7-dimethyl-3-octylate were placed in a 2G polymerization reactor filled with argon or nitrogen. Sequentially. After the completion of the addition, the internal temperature of the reactor is maintained at 40 ° C while the agitator is turned. When the internal temperature of the reactor reaches the set temperature, 4.0 mmol of n-butyllithium is introduced into the reactor to initiate the reaction. After 10 minutes after the reaction temperature reaches the maximum temperature, 34 g of 1,3-butadiene, 136 g of styrene, and 4.0 g of 1,3-divinylbenzene are further added. After 10 minutes from the peak temperature of polymerization, add 4.0 mmole of hexamethylene diisocyanate and Tris [2- (3-mercaptopropionyloxy) ethyl] isocyanurate, respectively. The degree of polymerization reaction was determined by observing the change of reaction temperature. A small amount of reactants were taken from the reaction at various times to analyze monomer ratio and reaction conversion ratio. After reaction for a certain time, 3.85 mmole of Butylated Hydroxy Toluene (BHT) is added to terminate the reaction.
Preparation Example 3 [(AB) a -B] n X
3 g of 1,3-butadiene, 21 g of styrene, 7.1 mmole of N-tetramethylethylenediimine, and 1.9 mmole of sodium 3,7-dimethyl-3-octylate were sequentially charged in a 2G polymerization reactor filled with argon or nitrogen. . After the completion of the addition, the internal temperature of the reactor is maintained at 40 ° C while the agitator is turned. When the internal temperature of the reactor reaches the set temperature, 4.0 mmol of n-butyllithium is introduced into the reactor to initiate the reaction. After 10 minutes after the reaction temperature reaches the maximum temperature, add 136 g of styrene and 4.0 g of 1,3-divinylbenzene. After 10 minutes from the peak temperature of polymerization, add 4.0 mmole of hexamethylene diisocyanate and Tris [2- (3-mercaptopropionyloxy) ethyl] isocyanurate, respectively. The degree of polymerization reaction was determined by observing the change of reaction temperature. A small amount of reactants were taken from the reaction at various times to analyze monomer ratio and reaction conversion ratio. After reaction for a certain time, 3.85 mmole of Butylated Hydroxy Toluene (BHT) is added to terminate the reaction.
Preparation Example 4. Preparation of [A- (AB) b ] n X
3 g of heptane, 140 g of 1,3-butadiene, 7.1 mmole of N-tetramethylethylenediimine, and 1.9 mmoles of sodium 3,7-dimethyl-3-octylate are sequentially introduced into the 2G polymerization reactor filled with argon or nitrogen. After the completion of the addition, the internal temperature of the reactor is maintained at 40 ° C while the agitator is turned. When the internal temperature of the reactor reaches the set temperature, 4.0 mmol of n-butyllithium is introduced into the reactor to initiate the reaction. After 10 minutes after the reaction temperature reaches the maximum temperature, 30 g of 1,3-butadiene, 170 g of styrene and 4.0 g of 1,3-divinylbenzene are further added. After 10 minutes from the peak temperature of polymerization, add 4.0 mmole of hexamethylene diisocyanate and Tris [2- (3-mercaptopropionyloxy) ethyl] isocyanurate, respectively. The degree of polymerization reaction was determined by observing the change of reaction temperature. A small amount of reactants were taken from the reaction at various times to analyze monomer ratio and reaction conversion ratio. After reaction for a certain time, 3.85 mmole of Butylated Hydroxy Toluene (BHT) is added to terminate the reaction.
Preparation Example 5 (Preparation of high-cis-polybutadiene polymerized in step (b)) [
The Ziegler-Natta catalyst used in the polymerization reaction was niobium diisobutate (1.0 wt% cyclohexane solution), diethyl aluminum chloride (1.0 M cyclohexane solution), diisobutyl aluminum hydride (15 wt% cyclohexane solution) and tri-isobutyl and aluminum (1.0 M cyclohexane solution), mole ratio of the catalyst is from 1: 3: 4: 20, and, 1.0 × 10 per 100 g monomer - an Audi you di catalyst of 4 mol was used. 1.5 Kg of cyclohexane polymerization solvent, the catalyst was added to the 5-L polymerization reactor by a predetermined amount, 300 g of butadiene monomer was added, and the mixture was reacted at 70 ° C for 2 hours. After 2 hours of polymerization, add 1.2 x 10 -3 moles of hexamethylene diisocyanate.
Examples 1 to 6
A certain amount of the polymer solution polymerized in Production Examples 1 to 4 with respect to a certain amount of the solution of the gossyp 1,4-polybutadiene polymer polymerized in Production Example 5 was continuously supplied for 24 hours while maintaining the temperature in the agitator at 50 ° C, Respectively.
Compounding properties were measured according to the mixing formula shown in the mixing condition table of Table 2 with respect to 100 parts by weight of the polymer composite mixture prepared in Examples 1 to 6. Comparative Example 1 was prepared by polymerizing high cis 1,4-polybutadiene using an Nd catalyst. After the first compounding step was carried out through zinc oxide, stearic acid, carbon black and process oil using a 500 cc bender at 120 ° C, the sulfur and vulcanization accelerator were mixed and stirred to complete the second blend. Kneaded at 80 DEG C using a roll mill, processed into a flat sheet form on a roll having a thickness of 2 mm, and left for 24 hours. The vulcanization step was carried out at 160 캜 using a press and vulcanization for a crosslinking time measured at rpa to prepare a sheet having a thickness of 2 mm for the measurement of physical properties. The properties of the prepared specimens were measured and the results are shown in Table 3.
As shown in Table 3 below, the modulus and tensile properties were excellent, and the results of the balanced mechanical properties and dynamic characteristics were obtained. Comparative Example 1 is a result of evaluation of the compounding properties of the same polymer used in Examples 1 to 6. [
(kgf / cm 2 )
(kgf / cm 2 )
(kgf / cm 2 )
Claims (9)
(b) producing at least 95% high-cis polybutadiene, to which functional functional groups have been introduced,
(c) uniformly dispersing the polymer organic filler in the form of styrene-butadiene block copolymer prepared in step (a) and the high-cis polybutadiene prepared in step (b)
In the step (c), the styrene-butadiene block copolymer prepared in the step (a) is uniformly dispersed with the high-cis-polybutadiene prepared in the step (b) at a ratio of 5 to 50% ≪ / RTI >
I) 1 mole of a rare earth compound or a transition metal compound,
Ii) 1 to 10 molar equivalents of a halogen-containing compound based on the amount of the rare earth compound or transition metal compound used, and
Iii) a catalyst system containing an organoaluminum compound in an amount of 10 to 100 molar ratio based on the amount of the rare earth compound or the transition metal compound used; And polymerizing 1,3-butadiene or a butadiene derivative in a non-polar solvent to prepare 1,4-cis-polybutadiene.
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